JPH0221389B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a powder colorant with a laminated structure exhibiting an iris color, and in particular to a powder colorant of this type that does not contain harmful dyes.

Conventional metallic luster coloring pigments include aluminum powder,
Bronze powder, pearl essence, etc. are also used, and a powder called glitter, which is made by coloring a metal-deposited film with dye and cutting it finely, is also used. However, the colors of aluminum powder, bronze powder, and pearl essence are limited to a single color of silver, gold, or white silver, respectively.

Glitter can be colored into any desired color, but it has poor light resistance and the darker the color, the poorer the luster.
It has drawbacks such as the need to use dyes containing metals such as cobalt that are harmful to the human body.

Therefore, an object of the present invention is to provide a powder coloring material that exhibits complex and beautiful colors without using dyes that are harmful to the human body.

A further object of the present invention is to provide a powder coloring material that has excellent light resistance and does not fade over a long period of time.

The object of the present invention is to provide a thin layer of synthetic or natural resin;
a thin layer of metal on both sides of the thin resin layer, a thin layer of a mixture of an alkyl metal compound and a synthetic or natural resin on two sides of the two thin layers of metal not in contact with the thin resin layer, and a thin layer of a mixture of an alkyl metal compound and a synthetic or natural resin; This is achieved by the iris powder coloring material of the present invention, which has a seven-layer stacked structure of two thin metal layers and a translucent vapor-deposited layer of metal on two sides that are not in contact with each other.

FIG. 1 of the accompanying drawings is a schematic diagram showing the laminated structure of the seven-layer laminate of the present invention, and FIGS. 2 to 5 are diagrams showing the manufacturing order thereof.

In Figure 1, 1 is a thin layer of synthetic or natural resin;
2,2 is a thin layer of metal, 3,3 is a thin layer of a mixture of an alkyl metal compound and a synthetic or natural resin, and 4,
4 is a semi-transparent vapor deposited layer of metal.

The synthetic or natural resin constituting the center layer 1 is a heat-adhesive resin that is easily crushed, such as terpene resin, petroleum resin, ketone resin, phenolic resin, maleic resin, acrylic resin, polystyrene resin, etc. One type or a mixture of two or more types can be used. The thickness of this layer is between 5 and 20 microns, preferably between 7 and 15 microns.

The thin metal layers of layers 2 and 2 consist of vapor-deposited layers of aluminum, silver or copper, or foils of these metals, with a thickness of 400 to 800 angstroms in the case of vapor-deposited layers.
Preferably it is 400 to 600 angstroms, and for foils 5 to 10 microns, preferably 5 to 7 microns.

Examples of alkyl metal compounds constituting layers 3 and 3 are alkyl titanates such as tetra-n-butoxytitanium, tetraisopropoxytitanium, tetraethylhexoxytitanium, tetrastearoxytitanium, etc.; tetra-n-butoxyzirconium and Alkyl zirconates such as tetra-isopropoxyzirconium; alkyl silicates such as tetra-n-butoxysilane, tetra-
Alkyl germanates such as n-butoxygermanium and tetraisopropoxygermanium; and alkyl aluminates such as tetraisobutoxyaluminum, and one kind or a mixture of two or more of these compounds can be used. Alkyl titanates are preferred, and quickly hydrolyzed compounds such as tetrapropoxytitanium and tetra-n-butoxytitanium are more preferred.

Examples of resins used in combination with the above alkyl metal compounds are natural resins, petroleum resins, terpene resins, ketone resins, phenol resins, polyamide resins, epoxy resins, melamine resins, alkyd resins, urethane resins, polybutadiene resins, and xylene resins. resin, urethane-modified acrylic resin that can be cured by ultraviolet light, polyester-modified acrylic resin,
These include styrene-modified acrylic resin, epoxy-modified acrylic resin, etc., and one or a mixture of two or more of these can be used.

The component ratio of the alkyl metal compound-resin mixture in this layer is 2 to 0.05 parts by weight, preferably 0.5 to 0.1 parts by weight of the resin to 1 part by weight of the alkyl metal compound.

Examples of metals used in the semi-transparent deposited layers of layers 4,4 are aluminum, silver and copper, which may be the same or different from the metal of layers 2,2. The thickness of this layer is greater than or equal to 100 angstroms and less than 400 angstroms, preferably between 200 and 300 angstroms.

The seven-layer laminate powder of the present invention can be manufactured as follows.

In FIG. 2, reference numeral 5 denotes a supporting film, on one side of which a semitransparent metal vapor deposition layer 4 is formed by vapor deposition, and on top of the semitransparent vapor deposition layer 4, an alkyl metal compound-resin mixture layer 3 is further formed. will be established. It is preferable to apply a release agent in advance to the side of the supporting film on which the metal translucent vapor deposited layer is vapor deposited using a gravure printing machine or a reverse roll coater. Any known mold release agent, such as polyvinyl acetate with a low degree of polymerization,
Acrylic resin or the like with a low degree of polymerization can be used. Layer 3 can be easily provided by coating layer 4 with a solution in which the alkyl metal compound and resin in a predetermined ratio are dissolved in a solvent. Any solvent commonly used as a solvent for resins such as aromatic hydrocarbons such as toluene, acetic esters such as ethyl acetate, etc. can be used. The dissolved concentration of the alkyl metal compound-resin mixture in the solution is preferably 30 to 70%, preferably 40 to 60%.

The solution can be applied using any known coating machine such as a roll coater, but a gravure printing machine with 150 to 300 meshes is usually used.

When using a roll coater, a layer 3 of substantially uniform thickness is obtained, but when using a gravure printing machine,
Due to the unevenness of the plate surface, a layer 3 having a non-uniform thickness can be formed, and due to this non-uniform thickness, the final product exhibits an extremely varied iris color. A printing plate with a deep engraved or etched surface provides a greater variety of iris colors, and plates with patterns such as stripes, checkers, dots, swirls, etc. give better results.

The thickness of layer 3 is 2000 ~ if the thickness is uniform.
9000 angstroms, preferably 3000-7500 angstroms.

In the case of gravure printing, the amount of coating is determined by the number of meshes and the depth of engraving, and the amount of coating after drying is 0.2 to 0.9 grams per square meter, preferably 0.3 to 0.8 grams.

After the alkyl metal compound-resin mixture layer 3 is formed, a metal layer 2 is deposited thereon, and the layer 2
A resin layer 1 serving as a center layer is provided on top of the resin layer 1.

Resin layer 1 is provided by applying a solvent solution of one or more resins as exemplified above onto the vapor deposited metal layer of layer 2. 1/1. Any of the same solvents and coating equipment used to form the alkyl metal compound-resin mixture layer 3 can be used. The resin concentration of the solution is preferably 30-70%, preferably 40-60%.

Two five-layer laminated films, in which the metal semitransparent vapor deposited layer 4, the alkyl metal compound-resin mixture layer 3, the metal vapor deposited layer 2, and the resin layer 1 were formed in this order on the support film 5 as described above, were As shown in the figure, the respective resin layers 1 are made to face each other to form the form shown in FIG. A film having an iris color having a seven-layer laminated structure as shown in FIG. 1 is obtained.

The thin film exhibiting an iridescent color having a seven-layer laminated structure formed as described above is crushed to a required degree and, if necessary, shaken off to obtain a product. Grinding can be done using any grinder.

The metal layer 2 of the seven-layer film can also be formed of metal foil.

When using metal foil, on one side,
An alkyl metal compound-resin mixture layer 3, a semi-transparent metal vapor deposited layer 4 on top of the layer 3, and a resin layer 1 on the other side of the metal foil to make a five-layer laminated film. A product can be obtained by thermal bonding and pulverization in the same manner as described above.

The powder coloring material of the present invention has a beautiful iris color due to the interference of light, and the iris color does not fade over a long period of time, and is safe for the human body. Suitable as a pigment for coloring resin molded products.

The present invention will be explained in more detail with reference to Examples below.

Example 1 A 25% resin concentration solution of polymethyl methacrylate with a polymerization degree of about 800 dissolved in methyl ethyl ketone was coated on one side of a 12 micron support polyester film using a 200 mesh, 20 micron deep striped pattern etching plate gravure machine. After drying with warm air at 60°C, aluminum is deposited to a thickness of approximately 200 angstroms on this coated surface.

Next, a solution of 40 parts by weight of tetra-n-butoxytitanium and 10 parts by weight of oil-modified polyurethane resin dissolved in 150 parts by weight of a mixed solvent of toluene-butyl acetate (1:1) was applied to this translucent vapor deposition surface using the same plate as above. The coating amount after drying is 0.35 when applied with a gravure printing machine.
g/m ² , and aluminum is deposited on the coated surface to a thickness of 500 angstroms.

A solution of 60 parts by weight of a ketone resin (HIRATSU 111 manufactured by Hitachi Chemical Co., Ltd.) in 40 parts by weight of methyl ethyl ketone was applied onto the surface of this vapor-deposited aluminum layer using a reverse roll coater. The coating amount was such that the film thickness after drying was 7 microns.

A laminated film in which a laminated film consisting of four layers: a translucent vapor-deposited aluminum layer, a tetra-n-butoxytitanium-polyurethane mixture layer, a vapor-deposited aluminum layer, and a ketone resin layer is formed on a support film as described above. is obtained.

The two laminated films on this support were stacked so that the ketone resin layers faced each other, heated and pressed through a pair of hot rolls at a temperature of 130°C, and after cooling, the support film was peeled off. The 7-layer laminated film was crushed, sifted through an 80-mesh sieve, and dried in a dryer at 80°C for about 1 hour to obtain an iridescent powder with no solvent odor.

Example 2 A solution prepared by dissolving 10 parts by weight of low polymerization degree polyvinyl acetate (polymerization degree 500) in 90 parts by weight of alcohol was coated on one side of a 25 micron thick polyester film in the same manner as in Example 1, and silver was deposited to a thickness of 100 angstroms.

40 parts by weight of tetra-n-butoxyzircon and 15 parts of epoxy resin (50%) on this semi-transparent vapor deposited layer of silver.
Parts by weight, 10 parts by weight of toluene, methyl ethyl ketone
A solution consisting of 20 parts by weight and 15 parts by weight of butyl acetate is applied as in Example 1.

Thereafter, an iris-colored powder coloring material was obtained in the same manner as in Example 1.

Example 3 A polypropylene film with a thickness of 25 microns is used as the support film, 35 parts of tetraisopropoxygermanium is used as the alkyl metal compound-resin mixture solution, and a polyamide resin (a 1:1 mixture of toluene and isopropyl alcohol is used as the solvent) A solution consisting of 9 parts of 50% solution), 30 parts of toluene, 20 parts of ethyl alcohol (anhydrous), and 6 parts of butyl acetate (all parts by weight), and 60 parts by weight of petroleum resin as the central resin layer forming solution. An iris-colored powder coloring material was obtained in the same manner as in Example 1, except that a solution of 40 parts by weight of methyl ethyl ketone was used and the temperature of the hot press roll was 120°C.

[Brief explanation of drawings]

FIG. 1 of the accompanying drawings is a diagram schematically showing an example of the structure of a layer of the powder coloring material of the present invention, and FIGS. 2 to 4 are diagrams showing an example of the manufacturing order thereof. 1... Synthetic or natural resin layer, 2... Metal layer, 3
...Alkyl metal compound-resin mixture layer, 4...
Metal translucent vapor deposited layer, 5...Supporting film.

Claims (1)

[Scope of Claims] 1. A thin layer of thermoadhesive synthetic or natural resin, a thin layer of metal on both sides of the thin resin layer, and two sides of the two thin layers of metal that are not in contact with the thin resin layer. Mixtures of the above alkyl metal compounds and synthetic or natural resins (however,
The amount of the resin per 1 part by weight of the alkyl metal compound is from 0.5 to 0.1 part by weight) and the thickness of the metal on the two sides not in contact with the thin metal layer of the two layers of the mixture 100 An iris-colored powder coloring material having a seven-layer laminated structure of translucent vapor-deposited layers of angstrom or more and less than 400 angstrom. 2. The coloring material according to claim 1, wherein the metal of the metal thin layer and the metal semitransparent vapor deposited layer is aluminum, silver, or copper, and the metal of each layer may be the same or different. 3 The alkyl metal compound is an alkyl titanate,
1 selected from the group consisting of alkyl zirconates, alkyl silicates and alkyl aluminates
The coloring material according to claim 1, which is a species or a compound of two or more species. 4 Resins that form a mixture with alkyl metals include rosins, natural resins, petroleum resins, terpene resins, ketone resins, phenolic resins, polyamide resins,
Epoxy resin, melamine resin, alkyd resin,
The coloring material according to claim 1, which is one or more compounds selected from the group consisting of urethane resins, polybutadiene resins, xylene resins, and modified acrylic resins that can be cured by ultraviolet light. 5 The resin of the layer in contact with the metal thin layer on both sides is one or more selected from the group consisting of terpene resin, petroleum resin, ketone resin, phenol resin, maleic acid resin, acrylic resin, and polystyrene resin. Claim 1, which is a thermoadhesive resin
Colorants listed in section. 6 Step of vapor depositing a metal translucent vapor deposited layer on a plastic film for a support, coating an organic solvent solution of an alkyl metal compound and a synthetic or natural resin on the metal semitransparent vapor deposition layer and drying the alkyl metal compound. a step of forming a layer of a mixture of and a resin, a step of vapor depositing a metal vapor deposited layer on the layer of the mixture, and a step of applying an organic solvent solution of a synthetic or natural heat-bondable resin on the metal vapor deposit layer. , a step of drying to form a heat-adhesive resin layer; two 4-layer laminated films on the obtained support film are placed in such a way that one heat-adhesive resin layer is in contact with the other heat-adhesive resin layer; 1. A method for producing an iris-colored powder coloring material, which comprises the steps of stacking and heat-pressing to integrate, then peeling off a support film, and pulverizing the obtained seven-layer laminated film. 7. The method according to claim 6, wherein the support film is previously treated with a release agent.