JPS6338069B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition that is used in paints, printing inks, casting molds, fiber-reinforced plastics, and the like, and gives products a shimmering and strikingly beautiful appearance. Conventionally, regardless of the material, for example, artificial molded products that have a shimmering appearance such as lacquered lacquer or opal jewelry are made of organic or inorganic materials. However, it has not been created as a practical matter. Attempts have been made to incorporate scaly colorants, such as aluminum powder, into paints to give the product a slightly shimmering feel. However, it is not satisfactory to say that it imparts a very authentic shimmering iridescent color to the product; rather, it would be more accurate to say that it imparts a dazzling and foreign appearance to the product. In recent years, as aesthetic requirements have increased, it has become difficult to keep up with the increasing sophistication of demand by simply adding color to products, and there has been a significant movement toward products with a superior tactility. For example, taking the above-mentioned raita as an example, as is well known, raita is made by gluing pearlescent shells finished in a desired pattern onto a black lacquer base, but its elegant appearance makes it a luxury item. It has a reputation as such, and you won't find a product like this anywhere else. As a result of various studies in order to obtain a molded product with a beautiful appearance with rainbow-colored sparkles, the present inventors discovered that a resin composition consisting of specific multilayer plastic film strips and a specific liquid resin could be used in paints and printing inks. The present inventors have discovered that when used in applications such as casting and fiber-reinforced plastics, they can give products a beautiful appearance with iridescent sparkles, leading to the completion of the present invention. That is, the present invention provides at least two different refractive indexes.
A multilayer plastic film strip in which 10 or more layers of transparent plastic film are alternately laminated;
The present invention relates to a resin composition comprising a liquid resin that does not swell or dissolve the multilayer plastic film strips. The multilayer plastic film strip used in the present invention has a thickness of each layer of plastic film in microns or less, and has at least 10 layers, preferably 50 layers or more, of at least two types of plastic films having different refractive indexes alternately. It is laminated and cut into desired sizes, and exhibits a beautiful iridescent sparkle caused by the interference of light. If a multilayer plastic strip made of plastic films with the same refractive index is used, the effects of the present invention cannot be obtained. The size to be cut is selected depending on the purpose.
For example, when manufacturing large-sized products such as building materials, if the multilayer plastic film strips are too small, it will not look good, so it is usually preferable to cut the multilayer plastic film into pieces of about 0.3 to 1 mm. In addition, interior parts,
When used for manufacturing decorative items, etc., the suitable size of the multilayer plastic film strips is about 0.1 to 0.5 mm. The type of transparent plastic film constituting the multilayer plastic film strip (hereinafter referred to as the glitter imparting agent) is not particularly limited, but generally polyvinyl chloride (refractive index 1.52 to 1.53) or polystyrene (refractive index 1.59 to 1.60) is used. , polypropylene (refractive index 1.49), polymethyl methacrylate (refractive index 1.48-1.50), methyl methacrylate-styrene copolymer (refractive index 1.56-1.57), polycarbonate (1.58-1.59) and polyester (1.65)
Films made of thermoplastic resins such as The glitter-imparting agent consists of 10 or more alternate layers of at least two types of plastic films with different refractive indexes,
Preferably, as long as 50 or more layers are laminated, the lamination order is not particularly limited. What is meant by alternation here?
For example, the lamination order of the glitter-imparting agent consisting of two types of plastic films with refractive index A and refractive index B is as follows:
ABABAB means that they are stacked in the order of AB. Furthermore, the lamination order of the glitter imparting agent consisting of three types of plastic films with refractive index A, refractive index B, and refractive index C is ABCABC...ABC
may be stacked in the order of
ABCBCACAB...means that they may be stacked in the order of CBA, etc. That is, when three or more types of plastic films having different refractive indexes are used, it means that two or more layers of plastic films having the same refractive index are not successively laminated. If the number of laminated layers of at least two types of plastic films with different refractive indexes is less than 10, it is difficult to give the product a shimmering appearance. In the present invention, examples of the liquid resin used in combination with the glitter-imparting agent include the following. (a) Acryloyl group CH ₂ =CH-CO- or methacryloyl group that cures without the use of monomers

[Formula] An unsaturated (meth)acrylate oligomer having one or more of the following in one molecule. For example, polyester to (meth)acrylates, vinyl ester resin, spiroacetal to (meth)acrylates, urethane to (meth)acrylates, poly(meth)acrylates of polyhydric alcohols with a molecular weight of 200 or more, trishydroxyalkyl isocyan Nurate (meth)acrylate, polyether ~ (meth)acrylates, ether of unsaturated alcohol of methylolmelamine. As vinyl ester resin, epoxy~
(meth)acrylates and poly(meth)acrylates of alkylene oxide adducts of polyhydric phenols or novolaks. The above oligomers can be used in combination freely. Additionally, these oligomers may be used in combination with solvents or monomers that do not dissolve the multilayer plastic film strip. (b) A mixed use system of unsaturated spiroacetal or unsaturated cycloacetal containing two or more allyl ether type unsaturated bonds in one molecule and a polythiol compound. For example, a reaction resin of diarylidene pentaerythrite and tetrathioglycolate of pentaerythrite. (c) Epoxy resins using amines, amine adducts, or liquid polyamides as curing agents. High temperature curing using acid anhydrides is also available, but no particular advantage has been found and prolonged heating at high temperatures tends to impair the sparkle. The present invention consists of using a glitter-imparting agent together with a liquid resin that does not swell or dissolve the glitter-imparting agent, and the resin itself or The objective is to impart iridescent sparkle to the target material or molded product. If a solvent or liquid resin that dissolves the plastic film constituting the glitter-imparting agent is used as a vehicle, this glittering iridescence disappears completely, leaving behind an unattractive appearance that looks like dirt mixed in. For this purpose, aromatic hydrocarbons, esters,
The solvents normally used as vehicles, such as ketones, halogenated hydrocarbons, and nitroparaffins, and the monomers, such as styrene, methacrylates, acrylates, vinyl acetate, etc., are used depending on the type of plastic that makes up the film. Depending on the situation, it is generally not used as a vehicle. Therefore, resins, paints, inks, etc. that contain these solvents or monomers as one component should not be used in combination with glitter-imparting agents, as long as the polymer constituting the plastic film is soluble in these solvents or monomers. It is difficult. However, there are no restrictions on the use of resins in either or both of the upper and lower layers other than the vehicle layer containing the glitter-imparting agent. The amount of glitter-imparting agent added to the liquid resin is
Usually 0.1 to 10% by weight based on the weight of liquid resin
It is. The glitter-imparting agent is used by being mixed with a liquid resin in advance, but when used in paints or printing inks, the glitter-imparting agent may be sprayed after applying the liquid resin. If the amount of glitter-imparting agent added is less than 0.1% by weight,
The effect of the present invention cannot be obtained, and if the amount exceeds 10% by weight, no effect can be observed by increasing the amount. The resin composition of the present invention is used for molding paints, printing inks, cast products, fiber-reinforced plastic molded products, etc., and gives the products a sparkling and beautiful appearance. However, when using the resin composition for the above-mentioned purpose to obtain a product with glitter, it is necessary to avoid high temperatures that would melt the multilayer plastic film strips constituting the glitter-imparting agent. Next, embodiments in which the resin composition of the present invention is used for painting, printing ink, and molding will be shown. (1) Painting The glitter-imparting agent is mixed directly into the liquid resin and applied, or the glitter-imparting agent is sprinkled and fixed on the undried coating film, and then a top coat is applied on top. In this case, the vehicle used in combination with the glitter-imparting agent must satisfy the conditions mentioned above. In the case of multiple coatings, there is no restriction on the resin constituting the coating film other than the glitter-imparting agent-containing layer. As the coating method, existing methods can be used. (2) Printing ink As long as the resin composition of the present invention is used as a printing ink vehicle, there is no need to place any restrictions on the type of ink, printing method, or type of printing substrate, and in particular, it is possible to obtain the desired results by the transfer method. Can be done. (3) Molding Casting, molding of fiber reinforced plastic (FRP),
Both heating and pressure molding using a mold are practical. In any case of casting, heating, or pressure molding, the glitter-imparting agent may be mixed throughout.
Alternatively, it may be mixed only in a portion. In FRP molding, the gel coat layer on the surface is the main component. When using the resin composition of the present invention to give a product a beautiful appearance with iridescent sparkle using any of the methods, additives, colorants, reinforcing materials, etc. commonly used in the resin composition may be added as necessary. Of course, both can be used together. In the resin composition of the present invention, the liquid resin is the above (a),
In the cases of (b) and (c), the resin composition of the present invention can be cured to form a molded product, but the resin composition of the present invention can be applied to the material to give it a sparkling and beautiful appearance. You can also do that. Materials that give glitter include various cement products, gypsum products, slate, calcium silicate boards, wood wool cement boards, magnesium carbonate boards, plywood, hardboards, chipboards, fiber-reinforced plastics, various thermoplastic molded products,
Examples include cloth, paper, and plastic concrete. Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, parts in the examples mean parts by weight unless otherwise specified. Example 1 100 parts of a photocurable resin (Spirac T-502 manufactured by Showa Kobunshi Co., Ltd.) prepared by adding a photosensitizer to a mixed system of unsaturated spiroacetal and a polythiol compound and 0.3 parts of azobisisobutyronitrile Part, glitter-imparting agent (manufactured by MEADOWBROOK INVENTIONS, USA)
Product name Crystaliner #322, an alternating multi-layer laminated film of polymethyl methacrylate (refractive index 1.48-1.50) and polyester (refractive index 1.65) approximately 0.3-0.5
2 parts (cut into mm size) were added. The resulting mixture was poured into a silicone rubber mold with dimensions of 200 mm x 200 mm x 10 mm to a thickness of 0.8 to 1 mm, and then heated 20 cm under an ultraviolet lamp with an output of 10 KW at a speed of 20 mm/min. The mixture was allowed to pass through the gel to form a gel. Next, 100 parts of unsaturated polyester resin (manufactured by Showa Kobunshi Co., Ltd., Rigoratsuku #2004W) was added thereon,
Glass powder (manufactured by Nippon Glass Fiber Co., Ltd., 325 mesh)
A mixture consisting of 100 parts of titanium white, 0.1 parts of titanium white, 2 parts of methyl ethyl ketone peroxide, and 0.5 parts of cobalt naphthenate was injected and cured at room temperature, followed by post-curing at 80° C. for 4 hours. After demolding, the photocurable resin layer on the surface was reapplied 20cm/20cm under the lamp of an ultraviolet irradiation device with an output of 50KW.
Post-cure was carried out by passing at a speed of 100 min. The obtained decorative board exhibited countless iridescent sparkles on a translucent white background, was extremely beautiful, and reproduced an opal tone. In the above method, unsaturated polyester resin is used instead of a photocurable resin (Spirac T-502, manufactured by Showa Kobunshi Co., Ltd.), which is a mixture of unsaturated spiroacetal and polythiol compound with a photosensitizer added. (Showa Kobunshi Co., Ltd., Rigoratsuku #2004W), even if the same amount of glitter-imparting agent is added,
It had no brightening effect and looked like nothing more than black, dust-like floating matter. Example 2 A model model of a bathroom vanity as shown in Fig. 1 (a=
1000mm, b=300mm, c=30mm, d=50mm, e=
100mm, corner part 30R), apply a mold release agent and use epoxy-acrylate type vinyl ester resin (manufactured by Showa Kobunshi Co., Ltd., Lipoxy R-) as a gel coat.
820) 100 parts, methyl ethyl ketone peroxide 2
1 part of cobalt naphthenate.
It was painted to a thickness of 0.5 to 0.7 mm and gelled. Next, a vinyl ester resin (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester, A-BPE-4) was prepared by adding 2 moles of ethylene oxide to bisphenol A and converting the terminal alcoholic hydroxyl group into acrylic ester.
A mixture of 100 parts, 1 part of the same glittering agent as in Example 1 (Crystaliner #322, cut into 0.3-0.5 mm size), 2 parts of benzoyl peroxide, and 0.2 parts of dimethylaniline was added to about 0.5-1 mm. was applied and cured at room temperature. At this time, the surface exposed to air was in a gelatinous state and sticky. Place Surf Ace Mat 30p and add 100 parts of unsaturated polyester resin (manufactured by Showa Kobunshi Co., Ltd., Rigoratsuku 158BQT) as a backing resin, 5 parts of black pigment (Rigoratsuku Color RC-81 Black), and 2 parts of methyl ethyl ketone peroxide. A mixed resin was applied. Thereafter, 5 plies of glass mat #450 were laminated with the same resin. After curing, the mold was removed, the edges were finished, and the surface was polished.The resulting bathroom vanity was extremely beautiful, with a myriad of seven-colored glitter on the black base. Example 3 100 parts of polyester resin (manufactured by Showa Kobunshi Co., Ltd., Rigoratsuku #1608C), 100 parts of calcium carbonate,
A mixed resin consisting of 10 parts of black pigment (Rigorak Color RC81 Black), 2 parts of methyl ethyl ketone peroxide, and 1 part of cobalt naphthenate was applied to a thickness of approximately 1 mm, and after curing was polished. Next, a photocurable resin (Showa Kobunshi Co., Ltd.) is applied on top of it.
company, vinyl ester resin, lipoxy VR-77)
50 parts trimethylolpropane triacrylate
A mixed resin consisting of 50 parts of benzophenone, 1 part of dimethylaminoethanol, and 1 part of dimethylaminoethanol was applied to a thickness of 0.7 to 0.8 mm. 100 parts of a photocurable resin (manufactured by Showa Kobunshi Co., Ltd., Spirac T-502), which is a mixture of unsaturated spiroacetal and polythiol compounds and a photosensitizer added to a 50μ thick polyethylene terephthalate film;
After drawing a peony flower pattern with a mixed resin consisting of 2 parts of the same glittering agent (Crystaliner #322) used in Example 1 and 0.5 parts of benzophenone,
The ink was cured by exposing it to sunlight for 20 minutes. A polyethylene terephthalate film with a peony flower pattern is placed in close contact with the above-mentioned photocurable resin coating, and after defoaming,
Under a UV irradiation device with an output of 50KW, 5 cm of 20cm
It was passed at a speed of m/min. After curing, when the film was removed, the sparkling peony design of Rata was transferred to the paint film. Next, an acrylic lacquer (manufactured by Showa Kobunshi Co., Ltd., Vinyroll 92T) was applied to a thickness of about 70μ. After drying and buffing, a strikingly beautiful decorative board with a blue to red sparkling peony pattern on a black background was obtained. Example 4 A 150 μ thick sheet (manufactured by Oji Yuka Co., Ltd.,
Synthetic paper (YUPO) was adhered with a 1% aqueous solution of carboxymethyl cellulose, and the length of 10 mm square was
A mold for injection was created by placing a 600mm square iron block. To this, 5 parts of polyvinylpyrrolidone, 25 parts of water,
Spray a solution of 70 parts of methanol to a thickness of 30 to 50 μm, and before it dries, apply a glittering agent (manufactured by MEARL CORPORATION, USA).
0.7 part (0.5-1 mm cut) of Crystoliner #322 (based on polyvinylpyrrolidone) was applied in partial shading. After drying the coating, add 100 parts of α-gypsum, 36 parts of water, acrylic emulsion (manufactured by Showa Kobunshi Co., Ltd., AP-
604) 10 parts, black pigment (manufactured by Sanyo Shiki Co., Ltd., Sandai Super), 10 parts, glass fiber for cement (1/4
A mixed slurry consisting of 5 parts (inch cut) was injected and cured. When the mold was removed after curing, a molded product with countless glittering patterns on the black gypsum surface, resembling galaxies, was obtained. 100 parts of liquid epoxy resin with an epoxy equivalent of 187,
A mixture containing 35 parts of xylylene diamine is applied onto the pattern with a brush to a thickness of 0.7 to 0.8 mm.
hardened. Painted gypsum boards obtained by polishing and buffing are
Countless rainbow-colored sparkles could be seen on the black background, making it extremely beautiful. At this time, instead of a mixture consisting of a liquid epoxy resin with an epoxy equivalent of 187 and xylylene diamine,
When a polyester resin or a styrene-containing vinyl ester resin was used, the glitter was completely lost and only a slightly colored pattern appeared, which was incomparably inferior. Example 5 A 300 mm x 300 mm x 3 mm aluminum plate whose surface had been polished with #600 abrasive paper and cleaned with trichlorethylene was
Thoroughly mix 100 parts of vinyl ester resin (manufactured by Showa Kobunshi Co., Ltd., Lipoxy R-806DA), 5 parts of black pigment (Rigorak Color Black, RC-81), 2 parts of methyl ethyl ketone peroxide, and 1 part of cobalt naphthenate. After coating to a thickness of approximately 0.7 mm, a polyethylene terephthalate film with a peony flower pattern similar to that used in Example 3 was adhered and hardened. After curing, the film was removed to obtain an aluminum plate with a glittering black background and a peony flower pattern transferred onto it. As a top coat, unsaturated spiroacetal resin (Spirac U-3155, manufactured by Showa Kobunshi Co., Ltd.)
After coating to a thickness of 0.2 mm, the coating was cured by passing 20 cm under an ultraviolet irradiation device with an output of 30 KW at a speed of 5 m/min. The appearance of the obtained decorative aluminum plate was the same as that of Example 3, except that the base was an aluminum plate, and was extremely beautiful. Example 6 After applying a silicone resin mold release agent to a glass shear dish having a diameter of 100 mm, the following formulation was injected. Photocurable resin (manufactured by Showa Kobunshi Co., Ltd., Spirak T-502) 70 parts trimethylolpropane triacrylate 30 parts benzophenone 0.5〃 Azobisisobutyronitrile 0.3〃 Titanium white 0.01〃 Sparkling agent Crystaliner manufactured by MEARL CORPORATION #322 0.1~0.3mm cut type 3″ Initially, 20cm below the 30KW ultraviolet irradiation device for 5m/
After pass-curing for 1 minute, post-curing was carried out at 80°C for 4 hours and at 100°C for 2 hours. A beautiful opal-like cast product with a surface hardness of 4H, which is hard and translucent, and has countless seven-colored sparkles was obtained. Cast products could be used for buttons, pendants, net dress, etc. Example 7 370 parts of a liquid epoxy resin having an epoxy equivalent weight of 187 and 120 parts of sulfamine were reacted at a temperature of 80° to 120°C to produce an epoxy resin prepolymer having a melting point of 70 to 75°C. To 100 parts of this prepolymer, 2-ethyl-4-
After blending 0.5 parts of methylimidazole, 3 parts of a glittering agent (same type as used in Example 6), 3 parts of zinc stearate, and 1 part of a synthetic wax-based mold release agent, it was rolled at 80 to 90°C. Knead and cool
It was coarsely crushed to about 0.5 to 1 mm. This coarsely crushed material is molded at a mold temperature of 140 to 150℃, and the outer diameter is
It was placed in a concentric ashtray mold with a diameter of 145 mm, an internal diameter of 83 mm, and a depth of 30 mm to form an ashtray. At this time, when the molding temperature exceeded 170°C, there was a tendency for the glitter to disappear. The resulting ashtray had an amber base with countless iridescent sparkles and was extremely beautiful.

[Brief explanation of drawings]

FIG. 1 is a perspective view of a model of the bathroom vanity used in Example 2.

Claims (1)

[Scope of Claims] 1. A multilayer plastic film strip in which ten or more layers of at least two kinds of transparent plastic films having different refractive indexes are alternately laminated, and a curable film that does not swell or dissolve the multilayer plastic film strip. A resin composition comprising at least one type of liquid resin. (b) Contains one acryloyl group or methacryloyl group in one molecule, which cures without the use of monomers.
An unsaturated (meth)acrylate oligomer having 1 or more unsaturated (meth)acrylate oligomers. (b) A mixture of an unsaturated spiroacetal or an unsaturated cycloacetal having two or more allyl ether type unsaturated bonds in one molecule and a polythiol compound. (c) Epoxy resins using amines, amine adducts, or liquid polyamides as curing agents.