JPS62184824A - Manufacture of plastic molded body with thermally reversibly color-changeable pattern - Google Patents

Abstract

PURPOSE:To obtain a plastic molded body equipped with thermally reversibly color- changeable pattern by a method wherein thermoplastic resin powder is poured under heat and pressure in a mold in the state that the non-printeed surface of a transparent plastic film, onto which a color-changing design pattern layer is formed in printing ink containing temperature sensitively color-changeable particulates and, after that, over the whole surface of which a protective layer is formed, is brought into close contact with the inner surface of the molding die in order to mold integrally. CONSTITUTION:First, a color changing design pattern layer 2 is formed onto a transparent plastic film 1. Secondly, a protective layer 3 is formed in printing ink which contains bonding agent same as that used in forming the color changing design pattern layer 2 onto said color changing design pattern layer 2 in order to obtain a transparent plastic film 1 with thermally reversibly color-changeable pattern applied. Thirdly, the non-printed surface of the film 1 is electrostatically adhered onto the inner wall of a molding die. Fourthly, thermoplastic molding resin powder such as powder of polyethylene, polypropylene, polystyrene or the like is poured under heat and pressure from an injection molder in the molding die in order to obtain a plastic molding body 6 with termally reversibly color-changeable pattern by simultaneous integral molding.

Description

[Detailed Description of the Invention] [Industrial Application De? ] The present invention is directed to the production of a thermoreversible color-changing patterned plastic molded body, which is novel and has great industrial applicability, and is provided with a pattern that sharply changes color in the t+j reverse direction in response to temperature changes. It is about law.

[Conventional technology] Traditionally, plastic molded products have been considered industrial supplies.

It is used in a wide range of applications, including parts, electrical appliances, household goods, miscellaneous goods, and leisure goods.

If necessary, a design pattern is applied by simultaneous molding with a design film. However, the designs were made from common dyes and pigments, had an rB tone, lacked fashion and functionality, and did not have a high commercial value.

By the way, in the near future, desired designs are applied to paper, 4i, leather, film, etc. using ink containing various temperature-sensitive color-changing substances, and the colors reversibly change and fade due to changes in the temperature of the outside world. This method is widely practiced, and the thermochromic substance used in this case has excellent coloring power in one color and is relatively mild at temperatures of -20°C to 70°C. Electric IJ may be advantageously used in the environment:
, sex 1. 3% of chromatic dyes, electron f-accepting substances and solvents
Component IIJ compounds are well known, and if such a temperature-sensitive color-changing substance can be used to form a heat-reverse color-changing pattern when painting plastic molded objects, it will be possible to apply a wide range of plastic molded objects. It is clear that, in combination with various uses, it will be possible to demonstrate industrial applicability far beyond anything previously thought of.

However, the temperature-sensitive color-changing substance that is the three-component mixture is
The thermochromic properties are exhibited only when the three components are in a strictly constant ratio, but when a mixture of the three components is used in printing ink, these components physically dissolve and dissolve.
The problem is that the ink easily flows out of the system due to the evaporation atmosphere, and at the same time, the solvent, plasticizer, or low-boiling point additives contained in the ink enter the system and have an adverse effect. Particularly when integrally molding a decorative film and plastic powder by heating in painting a plastic molded body, however, there were many cases in which thermosensitive discoloration was not exhibited.

Therefore, in recent years, a method has been generally adopted in which the above-mentioned three-component mixture is made to coexist as an encapsulation of a polymer-resin, etc. However, in reality, it is difficult to encapsulate the three components, and the surface It tends to form a significantly porous solid solution. However, in any case, it is impossible to maintain the three components stably, and the discoloration function is easily lost. Therefore, the plastic molded product Conventionally, it was impossible to paint with a temperature-sensitive color-changing substance.

[Problems to be Solved by the Invention] The inventors of the present invention have conducted various researches on how to effectively impart a thermally discolored pattern to a plastic molded body. 56-131753 (#+i Kaisho 5
8-32671), in which a thermochromic granular material, that is, an electron flammable coloring pigment, an electron f-accepting substance, and a solvent are co-encapsulated in a non-thermal EIf+7ilj resin. A thermochromic granular material obtained by coating the surface of a granular material with a hydrophilic polymer compound is used as a printing ink for plastic transparent film, and the entire surface of the color-changing pattern layer formed with the printing ink is used. Niho 1. (1) If a layer is formed, the tough film of the thermochromic granules provides excellent solvent resistance, plasticity resistance, and monomer resistance during printing of the ink, and n. The design pattern is extremely stable even when heated and pressurized during drying and integral molding with plastic powder, and these effects are due to the presence of the protective layer.In this way, the plastic molded product The present invention was completed based on the discovery that the conventional problems that had hindered the use of thermochromic substances in the designs of the invention could be completely solved.

[Means for Solving the Problems] The method of the present invention involves applying three components: an electron-f donating seven-color dye, an electron r-accepting substance, and a solvent to the entire surface or part of the surface of a plastic transparent film (1). A color-changing pattern layer (2) is created using a printing ink containing temperature-sensitive color-changing granules, which are formed by coating the surface of granules to be co-incorporated in a non-thermal IIf-yilj resin with a hydrophilic polymer compound. 1. Next, a protective layer (3) made of synthetic component F resin was formed on the entire surface of the color-changing pattern layer (2), and then the non-printing surface of the plastic transparent film (1) was placed on the inner surface of the mold for molding. ', let me look at you six times,
Thermal fif plastic resin powder is injected into the mold under pressure and heat to simultaneously mold a plastic molded body (4) with a reverse discoloration pattern for 1 s. The present invention relates to a method for producing a thermoreversibly color-changing patterned plastic molded article.

[Function] In the plastic molded body manufactured by the method of the present invention, one design pattern changes to 11 by temperature change due to the above structure.
For example, as shown in Figure 2, in a washbasin with a man and a woman and a heart drawn on it, the large heart part is used as a temperature-sensitive color-changing part that changes color at 40°C, and at room temperature, As shown in Figure 2, the coloring surface pattern (21) hides the small eyu, which is the normal dye and pigment pattern (5), and when hot water is added, as shown in Figure 3.

The normal dye pigment pattern (5) is created by the pattern (22) that opens when decoloring.
) If the configuration is such that a lamb appears, an extremely interesting change in the design pattern will occur (11).Incidentally, the male and female figures in Figures 2 and 3 are 1 normal dye and pigment pattern. (5).

[Example] Examples of the plastic transparent film (1) used in the method of the present invention include plastic films such as polyethylene, polypropylene, polystyrene, chlorinated polypropylene, polyvinyl chloride, and polycarbonate.

Next, the plastic transparent film (1) h has a temperature-sensitive color-changing granular component contained in the printing ink forming the color-changing pattern layer (2). As color pigments, 3φ3゛dimethoxyfluorane (
yellow), 3 chlor-6 phenylaminofluorane (yellow-orange)
, 3-diethylamino, 6-methyl, 7-chlorofluoran (
Zhu), 3 ethyl, 7 san, 8 pennful sai ten (challenge), 3
・3°・3゛°Tris (P-dimethylaminophenyl)
Phthalide C+'+"?), 3 m 3゜ screw (P
-dimethylaminophenyl) phthalide (M), substituted phenylmethane and fluora 7 derivatives such as 3-diethylamino, 6-methyl, 7-phenylaminofluoran (black), various indolylphthalides, spiropyrano, coumarins, etc. In the present invention, one of these
Used in combination of seeds or two in one.

Next, the electric power supply I7. Electron-accepting substances that combine with monocrystalline color pigments to develop color include P-phenylphenol, hisphenol A, cresol, renlucine,
Fertilizers such as chloroglycino, phenolic resin oligomers, β-naphthol, etc., and these metals! , ammonyl, 5-chlorhentrianol, 4-laurylaminosulfobenzotriazole, 5-butylbenztrisole, dihenzotrianol.

Henzytriazoles and metal salts thereof such as 2-oxybenzotriazole, 5-carfoethoxyhenzotrianol, etc., ammonium salts, and resorcinic acid, erosive r-acid, benzoic acid.

Organic acids such as pyromellitic acid, stearic acid, para-toluene sulfone, 1.5 phthalein disulfonic acid and substituted derivatives thereof, metal i'&! Among these, triazoles are particularly effective in the present invention.

Next, the solvent which is a component to be coexisted with the electron-donating, amorphous color pigments and the corresponding electron-accepting substance according to the present invention has a boiling point of 150°C or higher at room temperature. First, alcohols such as octyl alcohol, dodecyl alcohol, oleyl alcohol, myristyl alcohol, and geraniol, esters such as stearin, lauryl, lanolin, and palmitylic acid chrycerite, benzylideneaniline, benzylidenetheurylamine, etc.
Amides such as nmethines, acetamide, and stearamide, and other solvents include coconut oil, oil, naphthalene, and percrene.What are these solvents? ! ! +
i (Determine the color change temperature of the reverse color changing granules.

In addition, solvents with a boiling point of 150'C or higher at room temperature generally volatilize easily, are difficult to coexist with other components, and have too large a dissolving power, so they cannot be heated to a high temperature. The three components of 6-like, which have the disadvantage of being difficult to exhibit, are non-8i'+7
Using fijI resins such as polyester resins, polyurethane resins, melamine resins, benzoguanamine resins, and epoxy MLH as wall materials, interfacial resins, ins
By using a known encapsulation method such as the ite+7j method, the granules are made into granular materials, which are then immersed in water, and polyvinyl alcohol, which is a hydrophilic polymer compound,
Polyacrylic 111! , gelatin, methylcellulose,
By coating the surface of the granules with alginic acid or the like, even better granules can be obtained.

,) 11. The temperature-sensitive color-changing granules are adhesives, such as polyolefin resins, for adhering to printing inks, ie, plastic transparent films (1) h.

Halogenated olefin resins, polyacrylic ester resins, polyester resins, nylon fence resins, polyurethane resins, vinyl resins, cellulose resins, etc. alone or in combinations thereof.

Mixture 9 is mixed into a printing ink made into a solvent solution emulsion or dispersion, and the printing ink forms a discolored pattern layer (2) on the plastic transparent film (1)L.
) is formed.

Further, a protective layer (3) is formed on the color-changing pattern layer (2) using a printing ink made of the same adhesive as that used to form the color-changing pattern layer (2), and a thermoreversible color-changing pattern is formed on the color-changing pattern layer (2). A plastic transparent film (1) is then obtained by electrostatically adhering the non-printing side of the film (1) to the inner wall of a molding die, and then adding a molding thermoplastic resin powder, such as polyethylene.

A thermoreversible color-changing patterned plastic molded body (6 ).

It should be noted that ordinary chemicals such as viscosity modifiers,
Drying regulators, ultraviolet absorbers, antioxidants, dyes, pigments,
Fluorescent pigments, optical brighteners.

Even if surfactants, water agents, antifoaming agents, oils and fats, waxes, crosslinking agents, catalysts, resins, etc. are added, this does not depart from the gist of the present invention.

Next, a practical example of the present invention will be described.

Example 1 A polypropylene film (thickness 150 p-) was coated with 25 parts by weight of heat 0f reverse color changing granules (hereinafter referred to as 'F' j-1).
), 25 parts of Pylon 300 (saturated polyester resin, manufactured by Toyobo Co., Ltd.), 0.5 parts of Tinuvin 328 (ultraviolet absorber, manufactured by Ciba Geigy), and 50 parts of ethyl cellosolve acetate. A large heart pattern as shown in FIG. 2 was printed using a screen plate and air-dried thoroughly. Next is a regular pigment, Pylon 300 (
Using a printing ink consisting of saturated polyester resin (manufactured by Toyobo Co., Ltd.) and ethyl cellosolve acetate, men and women as shown in Figures 2 and 3 and s'r-rules as shown in Figure 3 were printed in multiple colors using a screen plate. , air-dried well. Furthermore, 30 parts of Pylon 300 (saturated polyester resin, manufactured by Toyobo Co., Ltd.),
Using a screen plate, the entire surface of the pattern was printed using a printing ink containing 70 parts of ethyl cellosolve acetate, and allowed to dry naturally.

After electrostatically adhering the non-printed side of the obtained film to the inner surface of a basin-shaped mold, 150 parts of Tubatex P-4700J (polypropylene resin, manufactured by Mitsubishi Chemical Industries, Ltd.) was introduced into the hopper of an injection molding machine. It was injected into a mold by heating and pressurizing, and after cooling, it was taken out from the mold to obtain an 8n (polypropylene washbasin with a reverse discoloration pattern).

Thus, at room temperature, the basin depicts a man and a woman and hearts of different sizes as shown in Figure 2, but when it is filled with hot water of about 37°C or higher, it becomes a large heart as shown in Figure 3. disappeared, and a small η clearly appeared, and this phenomenon could be repeated any number of times depending on temperature changes.

The composition and manufacturing method of the thermochromic granules used in this example are as follows. ) 2 parts, 5 parts of putobenzotriazole, 50 parts of myristyl alcohol, Epicote 802 (epoxy resin,
18 parts (manufactured by Yuka Shell Epoxy Co., Ltd.) were heated and dissolved in advance, and 50 parts of a 10% gelatin aqueous solution was heated to 60°C.
0 part, and adjust the stirring speed to obtain a uniform particle size l.
After dispersing it in the form of oil droplets, 5 parts of Epicure Z (curing agent for epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) was added, the temperature was raised to 90°C, and the mixture was heated and stirred for 1 hour. was collected by filtration and dried to obtain 72 parts of light red granules having an average particle size of 10p.

Next, 72 parts of the granules were stirred and added into 500 parts of a 10% polyvinyl alcohol/styrene maleic acid co-dimensions (4/1) aqueous solution, and then 50 parts of a lO% alginic acid sorter aqueous solution was added.
After adding 00 parts of borax to separate the two layers, it was gelled with 25 parts of borax, precipitated in a saturated bath, and decanted to give about 200 parts of borax.
A light red thermosensitive discoloration f'1 granular material was obtained.

Example 2 Polystyrene transparent film (thickness: 150 mm), 20 parts of Chromic Color 5-18 Blue (thermoreversible color changing granules, manufactured by Matsui Shiki Kagaku C Gyosho Co., Ltd.), Glow Color PinkM
A one-point floral pattern was created using a printing ink consisting of 3 parts of F2G (fluorescent pigment, manufactured by Matsui Shiki Kagaku Chogyosho Co., Ltd.), 20 parts of Dianal BR107 (acrylic resin, manufactured by Mitsubishi Chemical Industries, Ltd.), and 60 parts of ethyl cellosolve acetate. Pattern screen version (
100 mesh) to form one pattern layer and dry for 1 minute.
A protective layer was formed on a whole blood screen plate using a printing ink consisting of 725 parts of O and 75 parts of ethyl cellosolve acetate, and further dried for 1 minute. Next, the non-printing side of the film was placed on the inner wall V of a cup-shaped mold with a static mark A, and the film was made of Dialex HF55 (polystyrene resin).

80 copies (manufactured by Mitsubishi Kasei) were put into the hopper of an injection molding machine, injected into the mold under heating and pressure, and after cooling, taken out from the mold to form a polystyrene cup with a thermoreversible color-changing pattern. I got it. Thus, the pedicel of the cup is a blue color at temperatures above about 18°C, but when cooled to below about 12°C or poured with cold water, it turns purple.

This phenomenon could be reversibly repeated any number of times by changing the temperature.

[Effect of the invention] Next, the effects of the present invention will be listed.

(a) The thermal T+7 reverse color-changing patterned plastic molded article of the present invention can have a color-changing pattern that is completely different from conventional patterns, and can also be used in combination with conventional colors. It is possible to create products that are innovative, fashionable, functional, and playable.

(b) By combining the three components used in the color-changing pattern layer (2) of the present invention to any desired value.

It is possible to obtain any desired color and color change temperature,
Its range of use is extremely wide.

(c) The thermochromic granular material used in the color-changing pattern layer (2) of the present invention has a tough film and contains three components: an electron f-cogamma coloring pigment, an electron-accepting substance, and a solvent. It can be effectively maintained and has excellent durability.

(d) By keeping the protective layer (3) of the present invention wrapped around the temperature-sensitive color-changing granules, the color-changing function of the granules can be exhibited even more effectively.

[Brief explanation of drawings]

The drawings all show one embodiment of the thermoreversibly color-changing patterned plastic molded article according to the present invention, in which Fig. 1 is an enlarged cross-sectional view, Fig. 2 is a perspective view at Y temperature compensation, and Fig. 3 is a perspective view at the time of Y temperature compensation. is a perspective view when hot water is being charged. In the figure, (1) is a plastic transparent film, (2) is a color-changing design pattern layer, (21) is a design pattern when coloring, (22)
) is a design pattern when decolored, (3) is a protective layer, (4) is a plastic molded body, (5) is a normal dye and pigment pattern, (6) is a heat 0
f It is a plastic molded body with a reverse color changing pattern.

Claims (1)

[Claims] A hydrophilic polymer is further added to the entire surface or part of the surface of the plastic transparent film (1) with granules in which the three components of an electron-donating coloring dye, an electron-accepting substance, and a solvent are co-encapsulated in a non-thermoplastic resin. A color-changing pattern layer (2) is created using a printing ink containing thermochromic granules whose surface is coated with a compound.
A protective layer (3) made of synthetic polymer resin is then formed on the entire surface of the color-changing pattern layer (2), and then the non-printing surface of the plastic transparent film (1) is tightly attached to the inner surface of the mold. 1. A method for producing a thermoreversibly color-changing patterned plastic molded body, comprising: injecting thermoplastic resin powder into the mold under pressure and heat, and integrally molding the same at the same time.