JP2622273B2 - Three-dimensional printed matter comprising shape memory polymer sheet and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention relates to a shape in which the expression content of a pattern, a pattern, a photograph, an illustration, a character, etc. is printed, and a concavo-convex shape corresponding to the expression content is revealed. The present invention relates to a three-dimensional print of a memory polymer sheet and a method for producing the same. This three-dimensional printed matter can be widely used for advertising plates, various signs, business cards, masks, and the like.

(Prior Art) Numerous methods are used for printing, and all methods employ a method of transferring an ink pattern corresponding to the expression content onto a printing material via a plate. The substrate is
In most cases, ink is transferred on a flat or cylindrical rotating roll surface. Even in curved printing such as pencil printing, bin printing, and ampoule printing, the print material is a cylindrical surface or at most a hexagonal prism surface, and the shape is simple even when using a plate corresponding to the shape of the print material. Limited,
It was impossible to transfer in a complicated shape.

On the other hand, there is a method of giving a concavo-convex shape to a printed matter printed on a flat surface. The molding method differs depending on the material of the printed matter or the holder of the printed matter, for example, paper, plastic, metal, etc., but all are formed by mechanical external force, and in many cases, a mold is used. However, with such a molding method, it is extremely difficult to mold without damaging the printed surface.

(Problems to be Solved by the Invention) According to the present invention, by using a shape memory polymer sheet, it is possible to print by a conventional printing method, and to obtain a three-dimensional shape which can be formed into various shapes without using a mechanical external force. An object of the present invention is to provide a printed material and a method for manufacturing the same.

(Means for Solving the Problems) The present invention provides (1) spreadability on a flat shape-memory polymer sheet that stores an uneven shape corresponding to the expression contents of patterns, designs, photographs, illustrations, characters, and the like. And, paste a sheet with excellent printability and print the above expression content on it, or paste a pre-printed sheet on the above shape memory polymer sheet, to the initial memory shape Three-dimensional printed matter characterized by being returned, and (2)
A shape-memory polymer sheet is formed into an uneven shape corresponding to the expression content of a pattern, a pattern, a photograph, an illustration, a character, etc., and the shape is memorized. Heated to deform into a plate, cooled to a temperature below the glass transition temperature while holding its shape and fixed, and, on the plate-shaped shape memory polymer sheet, has spreadability, And paste a sheet with excellent printability and print the above expression content on it, or paste a pre-printed sheet on the above shape memory polymer sheet, and then again temperature above the glass transition point A three-dimensional printed matter manufacturing method characterized by raising the temperature to return to the original memory shape.

(Function) The present invention relates to a three-dimensional printed matter formed of a shape memory polymer sheet that stores a concave-convex shape corresponding to an expression content such as a pattern, a design, a photograph, an illustration, and a character.

A shape memory polymer is a memory that stores the original molding shape, then deforms at a temperature equal to or higher than the glass transition point of the polymer and lower than the molding temperature, and then cooled to a temperature below the glass transition point while maintaining that shape. By fixing the deformed shape, and recovering the original formed shape by heating to a temperature equal to or higher than the glass transition and lower than the forming temperature, the deformed shape and the formed shape can be used properly by temperature operation is there.

In the present invention, the above shape memory polymer is used as a sheet, and is formed in advance into an uneven shape corresponding to a specific expression content. The polymer sheet remembers this shape. The molding of the polymer sheet is performed by a usual plastic molding method such as injection molding.

The polymer sheet is heated to a temperature equal to or higher than the glass transition point of the polymer and equal to or lower than the molding temperature, deformed into a flat plate shape, and fixed by cooling to a temperature equal to or lower than the glass transition point while maintaining the shape.

Next, the above-mentioned expression content is printed directly on the flat polymer sheet or printed on a spreadable sheet having excellent printability and attached to the polymer sheet. When a printed sheet is used, printing may be performed after the sheet is attached to the polymer sheet, or a separately printed sheet may be attached to the polymer sheet. In addition, as a material of the printing sheet that can be used here, paper, a soft plastic film, a cloth, and the like can be cited, but the material and form are not limited as long as the material has excellent spreadability and printability.

As described above, the flat polymer sheet on which the expression content is printed can be restored to the original uneven shape by heating the polymer sheet to a temperature equal to or higher than the glass transition point, and a three-dimensional printed material having the uneven shape corresponding to the expression content can be obtained.

The polymer that can be used in the three-dimensional printed matter of the present invention has shape memory properties and can maintain a flat shape when printing on a polymer sheet or when attaching a printed sheet to a polymer sheet. It does not matter what kind it is. Usable polymers include urethane-based polymers, styrene-butadiene-based polymers, crystalline diene-based polymers, norbornene-based polymers, and the like.

Among them, a bifunctional diisocyanate, a bifunctional polyol and a bifunctional chain extension containing an active hydrogen group are present at a molar ratio of 2.00 to 1.10: 1.00: 1.00 to 0.10, preferably 1.80 to
1.20: 1.00: Polyurethane synthesized by the prepolymer method, blended at 0.80 to 0.20, and containing approximately equal amounts of [NCO] and [OH] at the polymer terminals, and having a glass temperature in the range of -50 to 60 ° C. Shape memory polymers having a transition point and a crystallinity of 3 to 50% by weight are particularly suitable because of their excellent moldability.

Since this polymer does not substantially contain excess [NCO] at the terminal, allophanate bonds forming rigid crosslinks can be avoided, and a plastic chain polymer having a degree of freedom in processability can be obtained. In addition, by giving an appropriate degree of crystallinity, a required elastic modulus can be imparted to the chain polymer.

Here, the crystallinity is preferably in the range of 3 to 50% by weight. When the crystallinity is 3% by weight or less, the rubber elasticity decreases at a temperature above the glass transition point, and when the crystallinity is 50% by weight or more, the rubber elasticity increases at a temperature above the glass transition point, and the glass transition point increases. The ratio of the elastic modulus before and after ± 10 ° C decreases.

The raw materials that can be used for this polymer are illustrated below, but are not limited thereto.

First, as an example of a bifunctional isocyanate, OCN-R-NCO can be represented by a general formula, and R includes one having one or two benzene rings and one having no benzene ring.
Any of them can be used, and specific examples thereof include 2.4-toluene diisocyanate, 4.4'-diphenylmethane diisocyanate, carbodiimide-modified 4.4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate.

As an example of a bifunctional polyol, HO-R '
-OH, and R 'has a benzene ring of 1,
Any of those having two or not, and further, a product obtained by reacting a difunctional carboxylic acid or a cyclic ether with the above-mentioned difunctional polyol can be used. , 1.4-butane glycol adipate, polytetramethylene glycol, polyethylene zulicol, bisphenol-A +
Propylene oxide and the like can be mentioned.

An example of a bifunctional chain extender containing an active hydrogen group can be represented by HO—R ″ —OH in the general formula, where R ″ is a (CH ₂ ) _n group and one or two benzene rings. Any group can be used, such as ethylene glycol, 1.4-butane glycol, bis (2-hydroxyethyl) hydroquinone, bisphenol-A + ethylene oxide, bisphenol-A + propylene oxide, and the like. .

Polyurethane synthesized from these raw materials can be represented by the following general formula.

HOR ″ OCONH (RNHCOOR′OCONH) _n RNHCOOR ″ OCONH− (R
NHCOOROCONH) _m RNHCOOR "OH m = 1-16, n = 0-16.

Production examples of these polyurethanes are shown below. The isocyanate component and the polyol component are blended as shown in Table 1 and reacted without a catalyst to synthesize a prepolymer. The chain full-length agent is added in the blend of Table 1 and cured by heating. Thus, a shape memory polyurethane was obtained. The basic properties of this polyurethane are as shown in the table below. In the table
Tg indicates a glass transition point (° C.), and E / E ′ indicates (tensile elastic modulus at a temperature lower by 10 ° C. than the glass transition point) / (tensile elastic modulus at a temperature higher by 10 ° C. than the glass transition point). The crystallinity (% by weight) was measured by an X-ray diffraction method.

(Example) The character shown in FIG. 3 was created on a relief by the method for producing a three-dimensional printed matter of the present invention. FIG. 1 is a polymer sheet in which the shape of a character is stored. FIG. 1A is a plan view of the sheet, and FIG. 1B is a cross-sectional view taken along line II of FIG. FIG. 2 is a view showing a state in which characters are printed on the sheet of FIG. 1 after the sheet is flattened, and FIG.
FIG. 2B is a sectional view taken along the line II-II of FIG. FIG. 3 is a diagram showing a completed drawing of the relief in which the shape of the character has been recovered after printing, FIG. 3A is a plan view, and FIG. 3B is a sectional view taken along the line III-III of FIG.

Sheet 1 used here is sample No. 38 in Table 1.
Using a polymer (Tg = 35) synthesized by the prepolymer method with the raw material mixture, a sheet having a thickness of 3 mm is formed by extrusion molding, cut into A4 size, and then heated to about 180 ° C. higher than the melting point of the sheet 1. It was heated and molded on a character-shaped mold in FIG. 1 to memorize the three-dimensional shape.

Then, the sheet 1 was heated to about 50 ° C. higher than the glass transition point, pressed between flat plates, cooled to about 20 ° C. lower than the glass transition point, and fixed in a planar shape. then,
The printed matter 3 of the character 2 was printed on the flat sheet 1 so as to match the above three-dimensional shape and position as shown in FIG.

Thereafter, the character was heated to about 50 ° C. higher than the glass transition point to recover the original three-dimensional shape of the character, thereby completing a relief as shown in FIG.

(Effect of the Invention) According to the present invention, by adopting the above configuration, a predetermined printing can be performed by a conventional printing method on a sheet deformed into a planar shape, and thereafter, the sheet is stored in advance in the sheet. By returning to the three-dimensional shape, a three-dimensional print was easily obtained.

[Brief description of the drawings]

1 to 3 are views for explaining a procedure for producing a three-dimensional printed matter of the present invention, wherein A is a plan view of each figure, and B is a cross-sectional view of A in FIG.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G09F 7/16 G06K 19/00 Z

Claims (2)

(57) [Claims] 1. A flat, shape-memory polymer sheet that stores irregularities corresponding to the expression contents of patterns, designs, photographs, illustrations, characters, etc., and has excellent spreadability and excellent printability. A three-dimensional object characterized by attaching a sheet and printing the above-mentioned expression contents thereon, or attaching a pre-printed sheet onto the above-mentioned shape memory polymer sheet and returning to the original memory shape. Printed matter. 2. A shape memory polymer sheet is formed into a concave and convex shape corresponding to the expression content of a pattern, a pattern, a photograph, an illustration, a character, etc., and the shape is memorized. It is heated to a temperature below the molding temperature, deformed into a flat plate shape, cooled to a temperature below the glass transition temperature while fixing its shape, fixed, and then spread on the flat shape memory polymer sheet. Ductile,
And paste a sheet with excellent printability, and print the above expression content on it, or paste a pre-printed sheet on the shape memory polymer sheet,
A method for producing a three-dimensional print, wherein the temperature is raised again to a temperature equal to or higher than the glass transition point to restore the original memory shape.