JP5531686B2 - Decorative sheet for thermoforming and method for producing decorative molded body - Google Patents

Description

  The present invention relates to a decorative sheet used for thermoforming such as a vacuum forming simultaneous decorating 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. There is known a method in which a molding sheet that has been physically roughened in advance by contact pressure is mounted in an injection molding mold, and is peeled after injection molding to mold the irregularity. This is because the sheet manufacturing process requires an embossing device and a special printing process, resulting in high costs, and unevenness has already occurred in the sheet before use stored in a roll shape, and winding misalignment is likely to occur. This may cause problems in terms of handling, such as a tendency to cause gauge band defects due to superposition of convex parts, and embossed parts exposed to high resin temperatures during injection molding, causing plastic deformation due to orientation return. There was a problem that the unevenness of was not obtained.

  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. (For example, refer to 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 is poor in reproducibility, and it has been difficult to reproducibly obtain large irregularities that can withstand a desired design in recent years. 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 a decorative molded body having irregularities on the decorative surface after decoration without requiring a physical method such as embossing in thermoforming such as vacuum forming simultaneous decoration method. It is to provide a method for obtaining a good reproduction.

  The present inventors use a decorative sheet in which a pattern is provided with an infrared absorbing ink or an infrared reflecting ink on a heat-shrinkable resin sheet crystallized by heat setting, as a decorative sheet for thermoforming. This solved the above problems.

  The heat-shrinkable resin sheet shrinks by heating to restore the sheet to the state before stretching. The force (orientation return strength) indicated at this time varies depending on the heating temperature. The present inventors have found that the heat-shrinkable resin sheet that has been subjected to crystallization treatment absorbs energy from electromagnetic waves, particularly infrared irradiation, and the melting phenomenon of crystals proceeds rapidly, so that the shrinkage phenomenon can be expressed more greatly. Heading, heat treatment by electromagnetic waves in a state of holding a decorative sheet that is provided with a pattern with infrared absorbing ink or infrared reflecting ink that is an ink that reacts to infrared rays on a heat-shrinkable resin sheet that has been crystallized. For example, when irradiated with infrared rays, the portion printed with the infrared absorbing ink or the infrared reflecting ink is different from the portion not printed or the portion with different printing density or ink concentration. It has been found that it makes a difference. The present invention succeeded in intentionally producing a film thickness difference, that is, unevenness by utilizing the temperature difference of the sheet.

  That is, the present invention is for thermoforming, in which a pattern is provided with infrared absorbing ink or infrared reflecting ink on a heat-shrinkable resin sheet that has been crystallized, and irregularities appear by thermoforming using a heating method using electromagnetic waves. Provide a decorative sheet.

  In addition, the present invention provides a decorative surface on which the thermoforming decorative sheet is held, and is subjected to decorative thermoforming at a temperature equal to or higher than the temperature at which the resin sheet having heat shrinkability is amorphousized by infrared irradiation. Provided is a method for producing a decorative molded body.

According to the present invention, in a thermoforming such as 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. it can.
In the decorative sheet of the present invention, the irregularities appear at the site where the pattern is provided with infrared absorbing ink or infrared reflecting ink. The ink can be printed by a general-purpose printing method such as gravure printing, and does not require a physical method for imparting unevenness, and thus the cost can be suppressed without requiring an excessive apparatus in the sheet manufacturing process.

  In addition, since the decorative thermoforming is performed at a temperature equal to or higher than the temperature at which the sheet is amorphized by infrared irradiation while holding the sheet, the vacuum forming method in a state in which unevenness is evenly generated on both surfaces of the sheet and a difference in sheet thickness is generated. Thus, sharp irregularities can be obtained with good reproducibility even on an adherend having a deep drawing shape that requires a high spreading magnification.

  If the sheet is irradiated with infrared rays in a state where the sheet is held under a vacuum without heat conduction, a temperature difference applied to the sheet can be more clearly generated, and sharper unevenness can be obtained.

In the present invention, the infrared absorbing ink is an ink containing an infrared absorbent and the like, and absorbs the irradiated infrared rays to generate heat. That is, when a resin sheet printed with infrared absorbing ink is irradiated with a heating method using electromagnetic waves, for example, with infrared rays, a heat amount equal to or greater than the amount of heat applied by 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 a resin sheet printed with infrared reflective ink is irradiated with a heating method using electromagnetic waves from the resin sheet side (that is, the surface opposite to the printed surface of the resin sheet), for example, infrared rays, the infrared rays that have passed through the resin sheet are converted into the infrared rays. By reflecting with the reflective ink, the amount of heat more than the amount of heat applied by infrared irradiation is applied only to the printed part where the infrared transmission part and reflection part overlap (this is specifically compared to the part where no pattern is provided) However, it is estimated that the portion provided with the pattern can supply heat 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.

As described above, the present invention is different from the portion printed with the infrared absorbing ink or the infrared reflecting ink and the portion not printed or the portion with different printing density or ink concentration, as a result of different shrinkage behavior. Although it discovers that it arises and utilizes this, the following aspects (1)-(3) are mentioned to this.
(Hereinafter, a portion having a relatively high surface temperature is referred to as a portion A, and a portion having a relatively low surface temperature is referred to as a portion B. In addition, a case where infrared irradiation is performed is taken as an example.)

(1) On the resin sheet which has heat shrinkability, it has the site | part A which provided the pattern with the said infrared rays absorption ink or infrared reflective ink, and the site | part B which does not provide a pattern.
When performing vacuum forming simultaneously, infrared irradiation is performed so that the part A and the part B have different surface temperatures. Since the amount of heat equal to or greater than the amount of heat applied by infrared irradiation is applied only to the part A, the surface temperature of the part A becomes higher than the part B that is not printed, unevenness occurs, and the sheet is attached to the resin molded body. The decorative molded body which has an unevenness | corrugation is obtained by making it convert.

(2) A pattern is provided on a heat-shrinkable resin sheet so as to have a portion A having a high ink concentration and a portion B having a low ink concentration with infrared absorbing ink or infrared reflecting ink.
When performing vacuum forming simultaneously, infrared irradiation is performed so that the portion A having a high ink concentration and the portion B having a low ink concentration 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, and irregularities are generated. By attaching the sheet to the resin molded body and integrating them, a decorative molded body having irregularities can be obtained.

(3) A pattern is provided on a resin sheet having heat shrinkability with a plurality of infrared absorbing inks or infrared reflecting inks having different infrared absorptivity or reflectance.
When performing vacuum forming simultaneously, 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 have different surface temperatures. Like that.
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, and irregularities are generated. By attaching the sheet to the resin molded body and integrating them, a decorative molded body having irregularities can be obtained.

  In the present application, since a crystallized sheet is used as the heat-shrinkable resin sheet, the shrinkage phenomenon can be expressed more greatly, and irregularities are evenly formed on both sides of the sheet. Therefore, by sticking to the adherend by vacuum forming simultaneous molding, it is possible to obtain sharp unevenness with good reproducibility even for an adherend having a deep drawing shape that requires a high spreading magnification.

(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.

  Industrially, the resin sheet is fixed with a clamp attached to a single-type vacuum molding machine, etc., or a clip attached to a continuous molding machine, etc., and the periphery is held, starting from the clamp part Since the unevenness can be easily caused by causing the expansion and contraction behavior, an existing molding machine can be preferably used.

An example in which the unevenness is formed is shown in FIGS. Figure 1 shows an infrared heater applied to a heat-shrinkable resin sheet printed with a pattern using three types of ink, high-concentration infrared absorption ink, low-concentration infrared absorption ink, and color ink (which does not absorb infrared rays). It is a figure which shows the one aspect which showed the state which uses and irradiates infrared rays, and FIG. 2 showed the state of the said resin sheet after irradiating infrared rays in the state which hold | maintained the said resin sheet in FIG. FIG. 3 is a view showing a state in which the resin sheet in FIG. 2 is attached to an adherend by vacuum forming and integrated.
By irradiating the resin sheet with infrared rays as shown in FIG. 1, as shown in FIG. 2, the printed portion 4 of the high-density infrared absorbing ink, that is, the portion A is most thinned or becomes a concave portion, and the low-density infrared absorbing ink. 5 is a thicker film than the printing unit 4) but is a thin film than the color ink printing unit 6, and is a convex part when viewed from the printing unit 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 is a concave part, and the low-concentration infrared-absorbing ink printing part is a low convex part or non-printing part. Is the highest protrusion. (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, the means (1) to (3) can be printed or handwritten, and the means (4) can express irregularities by laser irradiation. Any irregularities are possible.
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. The black part is a part printed with an infrared absorbing ink or an infrared reflecting ink. 4 represents a stripe, FIG. 5 represents a dot, FIG. 6 represents a geometric pattern, and FIG. 7 represents a grain.

(Surface temperature)
As described above, the unevenness in the present invention is presumed to occur not only on the surface of the part A and part B of the resin sheet but also in a state where the temperature is evenly applied to the inside. However, since there is no means for measuring the internal temperature, the difference in surface temperature was confirmed in the present invention. In the present invention, the surface temperature used was "Thermo Tracer 9100" manufactured by NEC / Avio.

(Heat-shrinkable resin sheet that has been crystallized)
The heat-shrinkable resin sheet (hereinafter abbreviated as “resin sheet S”) used in the present invention is crystallized by a method such as heat setting, and exhibits a spreadability by heating and can be formed into a film. It is a resin and a resin sheet having 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 crystallization treatment is generally performed by heat setting after the stretching treatment. Usually, it is 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, a polyester resin containing a glycol component, which is a soft component that is preferably used in the present invention, starts to generate a sheet drawdown before the temperature at which unevenness occurs unless heat setting is performed, and has sufficient unevenness in the molding region. There is a possibility that a decorative molded body cannot be obtained.

  A resin sheet that has been sufficiently heat-set and subjected to crystallization treatment is preferable because it can express larger irregularities. This is because, as described above, since the crystal melting phenomenon proceeds abruptly, the strength difference generated at the inflection point temperature T of the orientation return strength inflection point T of the part A and the part B becomes clearer in the crystallized sheet. I guess. 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.

  Since the resin sheet S has a good balance between infrared heating and heat dissipation, the film thickness of the thermoforming sheet normally used for vacuum forming is preferably 0.04 mm or more. 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.

(Infrared absorbing ink or infrared reflecting ink)
The infrared absorbing ink or infrared reflecting ink used in the present invention will be described.
The infrared absorbing ink 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 irradiated electromagnetic waves, particularly 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.

The vacuum forming method is a method in which a resin sheet to be vacuum formed is heated by an electromagnetic wave heating method, mainly by a method such as infrared irradiation, and the resin sheet is formed into an elastic region suitable for thermoforming. Also in the present invention, the temperature of the resin sheet S itself is raised by a heating method using electromagnetic waves 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 9 ° C. or higher, and further preferably 13 ° 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, quinoneimine dyes, methine dyes, cyanine dyes, carbon black, titanium black, titanium oxide, Cu-Cr complex oxides, phthalocyanine, naphthalocyanine, cyanine and other pigments and dyes, Methine pigments and dyes, red absorbers such as squarylium dyes, near infrared absorbing agent, infrared absorbing agent.

  Infrared reflective materials contained in the infrared reflective ink include metals such as aluminum, gold, silver, copper, brass, titanium, chromium, nickel, nickel chrome, and stainless steel, Fe-Cr complex oxides, antimony trioxide, and antimony dichromate. Etc.

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.

In the means of (1) to (3), the method of providing a pattern on the resin sheet S with infrared absorbing ink or infrared reflecting ink includes handwriting, coating, printing, etc., but printing is preferred 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 this irradiation method is used, the infrared reflection ink reflects the infrared rays before passing through the resin sheet, that is, the infrared rays are transmitted to 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.

  In the above means (1), the portion A provided with a pattern with infrared absorbing ink or infrared reflecting ink is heated to a temperature higher than the irradiation amount of infrared rays or the like, so the surface temperature becomes relatively high and becomes a recess. On the other hand, since only the heat of the infrared irradiation amount is applied to the part B where the pattern is not provided, the surface temperature becomes relatively lower than the part A and becomes a convex part.

In the means of (2), both the part A and the part B are applied with heat exceeding the irradiation amount such as infrared rays, but the part A is heated more than the part B because the part A has a higher ink density than the part B. . Therefore, the surface temperature of the part A is relatively higher than that of the part B, so that the part A becomes a concave part and the part B becomes a convex part.
Specifically, the means (2) is provided with the portion A and the portion B using inks having different ink concentrations, or the amount of ink is increased in the portion A although the ink is one kind. The ink density can be adjusted by this method.
Further, it is not necessary that the portion A is one. For example, when three types of ink having different ink concentrations are used, the portion using the ink having the lowest density becomes the portion B and becomes a convex portion, and the ink having the highest concentration. The portion using the is the portion A ″ which is the deepest recess. Of course, it is also possible to adjust by the ink deposit amount.

In the means (3), heat is applied to the part A and the part B at a dose higher than the irradiation amount such as infrared rays. However, the part A is provided with ink having higher infrared absorption or reflectance than the part B. More heat is applied than at site B. Therefore, the surface temperature of the part A is relatively higher than that of the part B, so that the part A becomes a concave part and the part B becomes a convex part.
The absorptivity of the infrared absorbing ink or the reflectance of the infrared reflecting ink cannot be generally compared, but as a rough guide, when using an infrared reflecting ink using aluminum and an infrared absorbing ink using carbon black in combination The ink using aluminum becomes a concave portion, and the ink using carbon black becomes a convex portion. When an infrared absorbing ink using carbon black and an infrared absorbing ink using titanium oxide are used in combination, the ink using carbon black becomes a concave portion, and the ink using titanium oxide becomes a convex portion.
Therefore, specifically, when the part A is printed with ink containing aluminum and the part B is printed with ink containing carbon black, the part A becomes a concave part and the part B becomes a convex part. Further, if the part A is printed with an ink containing carbon black and the part B is printed with an ink containing titanium oxide, the part A becomes a concave part and the part B becomes a convex part. As described above, the heat generating material can be appropriately selected in consideration of a desired uneven design and a design having visibility.

It is also possible to mix the means (1) to (3). For example, when the resin sheet S is printed with infrared absorbing ink so that a portion of one plate printing and a portion of multiple printing are generated and a non-printing portion is provided, the portion of the multiple printing is deepest. It is a concave portion, and the portion of general printing is a convex portion when viewed from a plurality of portions to be printed, and a concave portion when viewed from a non-printing portion, and an unevenness such that the non-printing portion is a convex portion can be provided.
In addition, when printing is performed using an infrared absorbing ink having a low concentration and a high concentration, and a non-printing portion is provided, the printed portion of the high concentration ink is the deepest concave portion, and the concentration The printing part using a low-density ink is a convex part when viewed from the printing part of the ink with the above high density, and is a concave part when viewed from a non-printing part, and the non-printing part is a convex part. Can do.

(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 the present invention, since a sheet having an orientation return strength inflection point by heating and exhibiting heat shrinkability is used, a resin layer that does not inhibit the shrinkage and exhibits plasticity at a lower temperature than the resin sheet S is provided. It is possible to add. Further, even a 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 difference in film thickness between the part A and the part B to some extent. From such a point of view, it is preferable to provide an adhesive layer such as an adhesive or a pressure-sensitive adhesive made of a resin layer exhibiting plasticity because the adhesion force to the adherend is further increased. The adhesive layer can be appropriately selected from materials that adhere to the resin sheet S and the adherend.
The adhesive layer is preferably provided on the surface of the resin sheet S that should adhere to the adherend. In many cases, since the resin sheet S also has the purpose of protecting the decorated surface after decoration, if an ink containing a heat-generating substance is provided,
It is preferable that the resin sheet S / the ink containing the heat generating substance / the adhesive layer is laminated in this order.

  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.

  In the resin sheet S used in the present invention, the film thickness as a whole including the infrared absorbing ink or infrared reflecting ink layer or other layers is a film thickness usually used for a thermoforming sheet used for vacuum forming. If there is no particular limitation.

(Manufacturing method)
Specifically, the method for producing a decorative molded body having irregularities on the decorative surface of the present invention,
With the decorative sheet for thermoforming of the present invention held,
Adjacent part A and part B 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 temperature of the part A changes the orientation return strength of the resin sheet. Irradiation with infrared rays so that the surface temperature is equal to or higher than the bend point temperature T, and a step (1) for causing a difference in film thickness between the part A and the part B and the resin sheet are attached to the adherend by a vacuum forming method. It can obtain by the process (2) of attaching and integrating.

  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 means a state where only a part of the outer periphery of the resin sheet S or the entire outer periphery is fixed, that is, a state where the surface of the sheet S attached to the adherend is not supported at all by the substrate or the like. Point to. 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 Heating method using electromagnetic waves Infrared)
In the state where the resin sheet S is held, the part A is irradiated with electromagnetic waves, preferably infrared rays, so that at least the surface temperature of the part A becomes a surface temperature equal to or higher than the orientation return strength inflection point temperature T of the resin sheet. And the part B are heated at different surface temperatures, resulting in a difference in film thickness between the part A and the part B. Heating in this case is performed by radiant heating using electromagnetic waves that are energy having a wavelength. The principle is that an electromagnetic wave is irradiated onto a film, infrared absorbing ink, etc., and only a substance that resonates with the wavelength of the electromagnetic wave absorbs energy resonantly, causing vibration at the molecular level and being heated by the frictional heat. .
As the electromagnetic wave used in the present invention, an infrared ray capable of efficiently heating a plastic can be preferably used. In particular, by combining infrared absorbing ink that resonates with infrared rays, the ink part can be selectively heated in addition to the heating of the entire film, and furthermore, different absorption rates can be realized depending on the ink concentration and type, etc. The temperature distribution of the pattern can be expressed on the film. Further, by arranging the infrared reflecting ink on the back surface of the film, it is possible to efficiently raise the temperature of only that portion by reflecting the infrared light once transmitted through the film and further heating the film.
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. It is preferable that the temperature of the highest part of the material be 0.5 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 irradiation amount so that the pressure is preferably 1 MPa or more.
In many cases, it is possible to use an existing indirect heating type thermoforming machine that is specifically used for a compressed air vacuum forming method. Infrared irradiation equipment that heats sheets needs to irradiate wavelengths that can be absorbed only by heat-generating substances, so halogen heaters, short wavelength heaters, carbon heaters with strong wavelength peaks in the mid-infrared to near-infrared region It is preferable to use a mid-infrared heater or the like. 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 a surface temperature equal to or higher than the orientation return strength inflection point T of the resin sheet and is equal to or higher than the temperature at which the resin sheet S becomes amorphous. Is preferable because large irregularities can be generated. This is because the elastic modulus of the sheet sharply decreases as seen from E ′ measured by dynamic viscoelasticity measurement at the temperature at which amorphousization begins, that is, when the temperature at which the melting of the crystal starts. It is presumed that the vicinity of the temperature is most easily influenced by the orientation relaxation stress of the part A and the part B. 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.

  In addition, the infrared irradiation is not particularly problematic even when performed under atmospheric pressure, but is preferably performed under vacuum because it can efficiently generate unevenness. 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 as long as it is transparent or opaque and has a surface design. Specifically, various shapes such as resin, metal, glass, wood, paper, and carbon can be used. Even if the shape is decorated by a regular decoration method such as painting, plating, and scratching. Good.

  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 resin 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 such as styrene resin, styrene-butadiene-styrene resin, ionomer resin, polyacrylonitrile, nylon, etc. Polyamide resin, ethylene-vinyl acetate resin, ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene-vinyl alcohol Coal 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., olefin elastomer, vinyl chloride Thermoplastic elastomers such as 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.

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

(Resin sheet S)
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. result,
Sheet S1 orientation return strength inflection point temperature T: 188 ° C.
It is.

(Infrared absorbing ink or infrared reflecting ink)
The following inks were used as the infrared absorbing ink or the infrared reflecting ink and the color ink.
Ink P1: “Paint Marker” black manufactured by Mitsubishi Pencil Co., Ltd. Used as infrared absorbing ink.
Ink P2: “Pencil Marker” silver manufactured by Mitsubishi Pencil Co., Ltd. Used as an infrared reflective ink.
Ink P3: “Paint Marker” blue color ink manufactured by Mitsubishi Pencil Co., Ltd.
Ink G1: Gravure printing ink “XS-756” produced by DIC, black Including carbon black, used as an infrared absorbing ink.
Ink G2: Gravure printing ink “XS-756” manufactured by DIC, which contains silver aluminum paste and is used as an infrared reflecting ink.
Ink GH1: Ink for gravure printing “XS-756” manufactured by DIC, used as red ink.
Ink GH2: Gravure printing ink "XS-756" manufactured by DIC Blue Ink used as color ink GH3: DIC gravure printing ink "XS-756" Yellow Used as color ink GH4: DIC gravure printing ink "XS-756" Pearl color Used as color ink

In the ink G1 and the ink G2, the surface temperature of G2 is higher.

(Picture printing method)
A pattern having a thickness of 3 μm was printed on the resin sheet S using a gravure four-color printer using the inks G1 to G4 and GH1 to GH4.
A straight line was drawn on the resin sheet S by hand using the inks P1 to P3.

(Confirmation of expression of difference in film thickness in step (1))
A sheet S1 was used as the resin sheet S, and a straight line having a width of 2 mm was drawn using the inks P1 to P3 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, in the state where the periphery of the sheet is completely clamped and fixed in a vacuum, the resin sheet S Was indirectly heated from the side opposite to the surface on which the straight line was drawn.
After confirming that the surface temperature of the resin sheet S had risen to the heater set temperature with an FT-H30 radiation thermometer manufactured by Keyence Corporation, the sample was cooled to room temperature and the clamp was removed to prepare a sample.
The surface temperature of the part A where the ink is drawn and the part B where the ink is not drawn is determined by using the thermotracer TH9100 manufactured by NEC / Avio, and the part A changes the orientation return strength of the resin sheet S used. When the bending point temperature T is reached, the temperature difference between the part A and the part B / ° C., and the surface temperature of the resin sheet S to be used rises to the heater set temperature (this temperature is usually determined by thermoforming). The temperature of the part A and the part B was measured).
Moreover, the measurement of the film thickness of the said part A and the said part B uses K351C made from Anritsu, and the height difference measurement uses the surface roughness system of Surfcom ver1.71 made by Tokyo Seimitsu Co., Ltd. The maximum film thickness difference was measured.
As a result, Reference Example 1 was able to express good irregularities.

(Vacuum forming simultaneous pasting method)
Thermoforming was performed using “NGF-0709 molding machine” manufactured by Fuse Vacuum Co., Ltd.
After completely clamping the periphery of the resin sheet S printed with a 3μm thick pattern on a gravure four-color printing machine, the upper and lower boxes of the molding machine are closed, and the inside of the box is almost completely vacuumed. The resin sheet S is indirectly heated from the upper surface using a mid-infrared heater. 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 is placed in the upper box. Then, the resin sheet S was attached to the adherend and integrally molded.
Since the surface temperature distribution measurement of the resin sheet S at the time of vacuum molding cannot be performed in a vacuum state, an opening was made in the box under the molding machine, and the surface temperature distribution measurement was performed using a thermotracer TH9100 manufactured by NEC / Avio. 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.
In addition, the distance of a heater and the resin sheet S was about 250 mm, and the adherend used the flat plate of length 80mm * width 150mm * thickness 2mm so that a film thickness difference could be measured.

(Examples 1 to 4) A decorative sheet for thermoforming and a method for producing a decorative molded body
The sheet S1 was used as the resin sheet S. Predetermined pattern printing was performed by gravure printing using any of inks G1, G2, and GH1 to GH4 to obtain decorative sheets (1) to (4). (For the pattern printing plate, Example 1: See FIG. 8, Example 2: See FIG. 10, Example 3: See FIG. 12, Example 4: See FIG. 14)

(Manufacturing method of decorative molded body)
The decorative sheet for thermoforming (1) to (4) was used, and decorative molding to a flat plate was performed by the vacuum forming simultaneous pasting method. The maximum value of the unevenness difference of the obtained decorative molded body was measured. The results are shown in Tables 2 and 3.
In either case, a decorative molded body in which clear unevenness was observed in the pattern portion using the ink G1 and the ink G2 was obtained.

  Decorative sheet for thermoforming (1) printed on sheet S1 with two versions of ink G1 and ink GH2 (this is a part A provided with a pattern with the infrared absorbing ink or infrared reflecting ink and a part B provided with no pattern. In this example, only the printing portion of the ink G1 containing carbon black, which is the heat generating material T1, is concave.

  Further, a decorative sheet for thermoforming (2) printed using two versions of ink G2 (this is an example having a portion A having a high ink concentration and a portion B having a low ink concentration, and The overlapping portion corresponds to the portion A, and the portion printed on one plate corresponds to the portion B), and the portion A that is the overlapping portion of each plate has a recess.

  Further, a decorative sheet for thermoforming (3) printed on the sheet S1 with four plates of inks G1, GH1, GH2, and GH4 (this is not provided with the part A and the pattern A provided with the infrared absorbing ink or the infrared reflecting ink) In the example having the part B), only the printing part of the ink G1 is concave.

  Further, a decorative sheet for thermoforming (4) printed with four plates of inks G1, GH1, GH2, and GH3 (this is an example having the portion A having a high ink concentration and the portion B having a low ink concentration, 14, a part of the ink G1 is overprinted (8-2 in Fig. 14), and 8-2 in Fig. 14 corresponds to the portion A and was printed in one plate. In FIG. 14, 8 corresponds to the portion B), and only the printing portion of the ink G1 is concave, and the portion (8-2 in FIG. 14) where the ink G1 is overprinted is deeper.

  When the DSC measurement of the sheet after thermoforming of the decorative sheet for thermoforming (1) to (4) was performed, a peak due to recrystallization was observed near 132 ° C., unlike the sheet before thermoforming. It was confirmed that the material was amorphous.

(Examples 1-2, 1-3 Manufacturing method of a decorative molded product in which the expansion ratio is changed)
The decorative sheet (1) obtained in Example 1 was used, and the expansion ratio was changed to perform decorative molding on a flat plate by the vacuum forming simultaneous pasting method. The maximum value of the unevenness difference of the obtained decorative molded body was measured. The results are shown in Table 4. All obtained the decorative molded body which has clear unevenness | corrugation.
The expansion ratio is set to 100% (unstretched), 160%, and 290% by placing the adherend in a female box-shaped mold and changing the depth. did.

(Example 5) A decorative sheet provided with a surface protective layer and a method for producing a decorative molded body
On the surface opposite to the surface protective layer (hereinafter referred to as TP) of the sheet S1 coated with the surface protective layer, a predetermined pattern is printed by gravure printing using ink G1 or ink GH2, and a decorative sheet ( 5) was obtained.

The decorative sheet (5) was subjected to decorative molding on a flat plate by the vacuum forming simultaneous pasting method. The results are shown in Table 5.

(Surface protective layer)
The surface protective layer used was a mixture of a hydroxyl group-containing copolymer and a polyisocyanate compound in a ratio of 1: 1.

(Hydroxyl-containing copolymer)
A mixed solution of 850 parts of butyl acetate and 1 part of perbutyl Z (trade name, manufactured by NOF Corporation, t-butyl peroxybenzoate) was heated to 110 ° C. to obtain 660 parts of methyl methacrylate, 150 parts of t-butyl methacrylate, 2- A mixed solution of 190 parts of hydroxyethyl methacrylate, 200 parts of isobutyl acetate, 9 parts of perbutyl O (trade name, manufactured by NOF Corporation, t-butylperoxy-2-ethylhexanoate), perbutyl Z (trade name, Japan) A mixed solution of 2 parts (manufactured by Yushi Co., Ltd., t-butylperoxybenzoate) was dropped and mixed over about 5 hours in a nitrogen atmosphere, and then stirred for 15 hours to obtain a hydroxyl group-containing copolymer having a solid content of 60%. Obtained. The weight average molecular weight of the obtained resin was 100,000, the hydroxyl value of the solid content was 79 KOH mg / g, and the glass transition temperature Tg was 95 ° C. Here, the weight average molecular weight is a polystyrene equivalent value measured by GPC, the hydroxyl value is a calculated value as a KOH neutralization amount from the monomer charge composition, and the polymer Tg is a value measured by DSC.

(Polyisocyanate compound)
As a polyisocyanate compound, an isocyanurate ring-containing polyisocyanate “BURNOCK DN-981” (trade name, manufactured by DIC Corporation, number average molecular weight of about 1000, non-volatile content 75% (solvent: ethyl acetate), functional group number 3, NCO concentration 13 ~ 14%) was used.

(Example 6) A decorative sheet provided with an adhesive layer and a method for producing a decorative molded body
A double-sided tape “DAITAC ZB7011W” manufactured by DIC Corporation having a pressure-sensitive adhesive thickness of 25 μm was laminated as an adhesive layer on the decorative sheet (1) to obtain a decorative sheet (6). The laminating conditions were performed by using a hull made by MCK at a nip pressure of 0.3 MPa and a speed of 4 m / min.
The decorative sheet (6) was decoratively molded into a flat plate having a thickness of 3 mm by the vacuum forming simultaneous pasting method. The results are shown in Table 6. In addition, since the adhesive was provided, the film thickness measurement was performed with the thickness including the flat plate and the release film.

(Comparative Examples 1-3 A decorative sheet and a method for producing a decorative molded body)
Predetermined pattern printing was performed by gravure printing using the inks GH1 to GH4 on the sheet S1, and decorative sheets (H1) to (H3) were obtained (Comparative Example 1: see FIG. 8, Comparative Example 2: FIG. 10 and Comparative Example 3: see FIG.

A decorative molded body was obtained in the same manner as in Example 1 except that the decorative sheets (H1) to (H3) were used. As a result, it was not possible to obtain a molded article having irregularities.

(Comparative example 4 manufacturing method of a decorative sheet and a decorative molded body)
The periphery of the decorative sheet (1) was fixed with a metal frame, and after holding, left in a thermostatic bath at 185 ° C. for 5 minutes to obtain a decorative sheet (H4) subjected to an amorphous treatment. (Comparative example 4: see FIG. 14)

Molding was performed in the same manner as in Example 1 except that the decorative sheet (H4) was used. As a result, drawdown occurred and tearing occurred, and a decorative molded body could not be obtained.
In addition, when decorative molding was performed at a lower molding start set temperature of 170 ° C., molding was possible, but a molded article with irregularities could not be obtained (Comparative Example 5).

: 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) : It is a schematic diagram of the decorating sheet (1) of Example 1. FIG. The upper part is a plan view, and the lower part is a cross-sectional view of the black frame of the plan view. : It is a schematic diagram of sectional drawing of the decoration molded object which uses the decorating sheet (1) of Example 1 (Example 1). : It is a schematic diagram of the decorating sheet (2) of Example 1. FIG. The upper part is a plan view, and the lower part is a cross-sectional view of the black frame of the plan view. : It is a schematic diagram of sectional drawing of the decorative molded body using the decorative sheet (2) of Example 2 (Example 2). : It is a schematic diagram of the decorative sheet (3) of Example 3. The upper part is a plan view, and the lower part is a cross-sectional view of the black frame of the plan view. : It is a schematic diagram of sectional drawing of the decorative molded body using the decorative sheet (3) of Example 3 (Example 3). : It is a schematic diagram of the decorating sheet (4) of Example 4. The upper part is a plan view, and the lower part is a cross-sectional view of the black frame of the plan view. : It is a schematic diagram of sectional drawing of the decorative molded body which uses the decorating sheet (4) of Example 4 (Example 4). : 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. .

1: Infrared heater 2: Infrared 3: Resin sheet having heat shrinkability
4: High-concentration infrared absorption ink printing unit 5: Low-concentration infrared absorption ink printing unit 6: Color ink printing unit 7 (does not absorb infrared rays) 7: Substrate 8: Ink G1
8-2: Overprinted portion of ink G1 9: Ink G2
10: Ink GH1
11: Ink GH2
12: Ink GH3
13: Ink GH4

Claims (4)

For thermoforming, characterized in that a pattern is provided with infrared absorbing ink or infrared reflecting ink on a heat-shrinkable resin sheet that has been crystallized, and irregularities are manifested by thermoforming using an electromagnetic heating method. Decorative sheet. The decorative sheet for thermoforming according to claim 1, wherein the resin sheet having heat shrinkability is biaxially stretched. The decorative sheet for thermoforming according to claim 1 or 2, wherein the resin sheet having heat shrinkability is a polyester sheet containing a glycol component. The decorative thermoforming decorative sheet according to any one of claims 1 to 3 is subjected to decorative thermoforming at a temperature equal to or higher than a temperature at which the resin sheet having heat shrinkability is amorphousized by infrared irradiation. A method for producing a decorative molded body having irregularities on a decorative surface, which is characterized.

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