JPS5922746A - Resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 which gives products a shimmering and strikingly beautiful appearance.

Traditionally, regardless of the material, for example, artificial molded products that have the appearance of a lacquer coating or a sparkling appearance such as that seen in gemstone opals, whether they are inorganic or organic. 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 always satisfactory to give a product a very authentic shimmering iridescent color, but rather it would be more accurate to say that it gives a completely foreign appearance to the product.

In recent years, as aesthetic demands 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 superior sensibilities.

For example, taking the above-mentioned nakude as an example, as is well known, nakude is made by gluing pearlescent seashells 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 give products a beautiful appearance with iridescent sparkles, and have completed the present invention.

That is, the present invention relates to a multilayer plastic film strip in which at least two types of plastic films having different refractive indexes are alternately laminated, and a resin composition comprising a liquid resin that does not swell or dissolve the multilayer plastic film strip.

The multilayer plastic film strip used in the present invention has a thickness of one layer of plastic film in microns or less, and at least 10 layers, preferably 500 layers or more, of at least two types of plastic films having different refractive indexes. It is made by laminating two layers and cutting it to the desired size, and exhibits a beautiful iridescent sparkle due to 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 products such as building materials,
If the multilayer plastic film strips are too small, they will not look good, so it is usually preferable to cut them into pieces of about 0.3 to 1 mm. However, when used for manufacturing interior parts, decorative items, etc., the size of the multilayer plastic film strips is preferably about 0.1 to 0.5 mm.

The type of plastic film constituting the multilayer plastic film strip (hereinafter referred to as the glitter-imparting agent) is not particularly limited, but it is generally made of polyvinyl chloride (with a refractive index of 1
．． 52-1. '53), polystyrene (refractive index 159~
1.60), polypropylene (refractive index 1.49), polymethyl methacrylate (refractive index 1.48-1.50),
Methyl methacrylate-styrene copolymer (refractive index 1.
56~ts7), polycarbonate (1,58~
Films made of thermoplastic resins such as polyester (159) and polyester (1,65) are used.

The lamination order of the glitter-imparting agent is not particularly limited as long as at least two types of plastic films having different refractive indexes are alternately laminated in IO0 or more layers, preferably in 50 or more layers. The alternation here means, for example, that the lamination order of the glitter-imparting agent consisting of two types of plastic films with refractive index A and refractive index B is ABABAB...A
This means that they are laminated in the order of B. In addition, the lamination order of the glitter imparting agent, which is made up of three types of plastic films with refractive index A, refractive index B, and refractive index C, is ABCA.
They may be stacked in the order of BC......ABC, or they may be stacked in the order of ABCCACAB...
This means that they may be stacked in the order of CBA or the like.

That is, when three or more types of plastic films having different refractive indexes are used, it means that two or more plastic films having the same refractive index are not laminated in succession.

It is difficult to give a shiny appearance.

In the present invention, examples of the liquid resin used in combination with the glitter-imparting agent include the following.

(a) Unsaturated (meth)acrylate oligomer having one or more acryloyl group CH2=CH-C0-1 or methacrylic group CH3=C-C0- in one molecule, which cures without the use of monomers. .

For example, polyester to (meth)acrylates, vinyl ester It fat, spiroacetal to (meth)acrylates, urcitane to (meth)acrylates, poly(meth)acrylates of polyhydric alcohols with a molecular weight of 200 or more, l. (meth)acrylates of hydroxyalkyl isocyanurates, polyethers to (meth)acrylates, ethers of unsaturated alcohols of methylolmelamine.

Vinyl ester resins include epoxy to (meth)acrylates and poly(meth)acrylates containing alkylene oxide additives of polyhydric phenols or novolaks. You are free to use the above I7 pieces in combination. Additionally, these oligomers may be used in combination with solvents or monomers that do not dissolve the multilayer plastic film strips.

(b) A mixed use system of an unsaturated spiroacetal or an unsaturated nocroacetal containing two or more allyl ether type unsaturated bonds in one molecule and a polythiol compound.

For example, a reaction resin of diarylidene pentaerythrinot and pentaerythritol with tetrathioglycole-1.

(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.

ii) Products obtained by dissolving, for example, rosin esters, long oil alkyd resins, or polyvinyl butyral in aliphatic lower alcohols or aliphatic hydrocarbons.

(e) For example, polyvinyl pyrrolidone, polyvinyl methyl ether, or methyl cellulose dissolved in water.

The present invention consists of using a glittering bird agent together with a liquid resin that does not swell or dissolve the glittering agent 1 and i, and using methods such as casting, thermoforming, painting, printing, or spraying. The objective is to give the resin itself or the target material an iridescent sparkle to the molded product.

When a solvent or liquid resin is used as a vehicle to dissolve the plastic filler that makes up the shimmering power agent, this shimmering iridescent color completely disappears, leaving behind a completely unattractive appearance that looks like dirt has been mixed in. do not have.

For this purpose, solvents commonly used as vehicles such as aromatic hydrocarbons, esters, ketones, halogenated hydrocarbons, nitroparaffins, styrene, methacrylic esters, acrylic esters, vinyl acetate, etc. Nododo monomer is generally not used as a vehicle, although it depends on the type of plastic that makes up the film.

Therefore, resins, paints, inks, etc. that contain these solvents or monomers as one component may also be used in combination with glittering agents, as long as the polymer constituting the plastic film is soluble in these solvents or monomers. That 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-improving agent.

The amount of the glitter-improving agent added to the liquid resin is usually 01 to 10 parts by weight based on the weight of the liquid resin.

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 the glitter-imparting agent added is less than 0.1 part by weight, the effects of the present invention cannot be obtained, and if it 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 sparkle, it is necessary to avoid high temperatures that would melt the multilayer glass film strips constituting the glitter-improving 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: Either directly mix a glitter-imparting agent into the liquid resin and paint.
Alternatively, a glitter-imparting agent is sprinkled and fixed on the undried coating film, and a top coat is further applied thereon.

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 that constitutes the coating film other than the glitter-imparting agent-containing layer.

Various existing methods can be used as the coating method.

(2) Printing Ink As long as the resin composition of the present invention is used as a vehicle for printing ink, 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 desired results using a transfer method. I can do it.

(3) Molding Casting, fiber reinforced plastic (FRP) molding, heating using a mold, and pressure molding are all practical.

In any case of casting, heating, or pressure molding, the glitter-imparting agent may be mixed into the entire product or only in a portion thereof.

In FRP molding, the surface gel coat layer is the main component. Using the resin composition of the present invention, by each method,
If you want to give your product a beautiful appearance with iridescent shimmer, you can add conventional additives, colorants,
Of course, reinforcing materials and the like can also be used together.

In the resin composition of the present invention, the liquid resin is as described in (a) and (b).
In the case of , (c), the resin composition itself can be cured to form a molded product, but the resin composition of the present invention can also be applied to the material to give it a sparkling and beautiful appearance. .

Materials that add sparkle include various seven-metal products,
Gypsum products, V-1-1 calcium silicate boards, wood wool cement boards, magnesium carbonate boards, plywood, hardboards, chipboards, fiber reinforced plastics, various thermoplastic molded products, cloth, paper, plastic concrete, etc. can give.

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 0.0 parts of ambisisobutyronitrile were added. Part 3, glitter-imparting agent (USA MEADOW
Manufactured by BROOK INVENTIONS, product name: Cry
Using a staliner #322, a cross-pressure multilayer laminate film of polymethyl methacrylate (refractive index 1.48-1.s o ) and polyester (refractive index 1.6 s ) was calcined to approximately 0.3-0.5-dimensions. Added 2 parts. The obtained mixture was molded into a rubber mold with dimensions of 200 mm x 200 mm, and the thickness was 0.8 to 1 mm.
After pouring the mixture in the same order, the mixture was passed through a 20 m path under an ultraviolet lamp with an output of 10 KW at a speed of 20 wn 7 minutes to once form a gel.

Next, unsaturated polyester resin (Revolac 4t2004W, manufactured by Showa Kobunshi ■) was applied thereon.

100 parts of glass powder (manufactured by Nippon Glass Fiber ■, 325 meso7 units), 0.1 part of titanium white, 2 parts of notyl ethyl ketone peroxide, and 0.5 parts of cobalt nanthenate. After curing at room temperature, post-curing was performed at 80° C. for 4 hours.

After demolding, the photocurable resin layer on the surface was again passed through the lower lamp 20 (7) of the ultraviolet irradiation device having an output of 50 KW at a speed of 2 m/min for post-curing. .

The resulting decorative board exhibited countless iridescent sparkles on a semi-transparent white background, was extremely beautiful, and reproduced an opal tone.

In the above method, an unsaturated polyester resin (Showa Kobunshi Co., Ltd., Spirasoku T-502), which is a mixture of unsaturated spiroacetal and a polythiol compound and a photosensitizer added thereto, is used instead of a photocurable resin (Spirasoc T-502, manufactured by Showa Kobunshi ■ Co., Ltd.). When using Kobunshi ■ Co., Ltd., Rivolak #, 2004 W), even if the same amount of glitter-imparting agent is added, there is no effect at all, and it only looks like black dust-like suspended matter. Met.

Example 2 A model type of a bathroom vanity as shown in Fig. 1 (a=1,000
mm, b = 300 mm, c = 30 mm, d-50 throat, e-1OO throat, corner part 30R), apply a mold release agent, and use epoxy-acrylate type vinyl ester resin (manufactured by Showa Kobunshi ■) as a gel coat. Lipoxy R-820)
100 parts of methyl ethyl ketone peroxide, and 1 part of cobalt naphthenate.
It was coated to a thickness of mm and allowed to gel.

Next, a vinyl ester resin (manufactured by Shin Nakamura Kagaku ■, NK
ester, A-BPE-4) to 100 parts of the same glittering agent as in Example 1 (Crystaliner #32).
2. Cut into 0.3-0.5 mm dimensions) 1 copy,
A mixture containing 2 parts of benzoyl peroxide and 0.2 parts of dimethylaniline was applied to a thickness of about 0.5 to 1 mm and cured at room temperature. At this time, the surface exposed to air was in a gelatinous state and sticky.

Place Surf Ace Pine l-30p, and add 100 parts of unsaturated polyester resin (manufactured by Showa Kobunshi ■, Rivolac 158BQT) as a backing resin, 5 parts of black pigment (Rigorac Color RC-81 Black), and 2 parts of methyl ethyl ketone peroxide. A mixed resin consisting of was applied. Thereafter, 5 plies of Glass Mano L-#450 were laminated with the same resin.

After curing, the mold was demolded, the edges were finished, and the surface polished.The resulting bathroom vanity was extremely beautiful, with a myriad of seven-colored glitter on the black base.

Example 3 On a waterproof plywood board with a thickness of 12 m + n and a size of 450 mm x 450 fi, 100 parts of polyester resin (manufactured by Showa Kobunshi ■, Rivolac #1608 C), 100 parts of calcium carbonate, 1 part of black pigment (Rigora Sok Color RC81 Black)
A mixed resin consisting of 0 parts methyl ethyl ketone peroxide, 2 parts cobalt naphthenate, and 1 part cobalt naphthenate is applied to a thickness of about 1 fin.
Polished after curing.

Next, a mixed resin consisting of 50 parts of a photocurable resin (manufactured by Showa Kobunshi ■, vinyl ester resin, Lipoxy VR-77), 50 parts of trimethylolpropane triacrylate, 1 part of benzophenone, and 1 part of dimethylaminoethanol was added thereon. Apply it to a thickness of 0.7 to 0.8 mm and make a circle.

100 parts of a photocurable resin (manufactured by Showa Kobunshi ■ Co., Ltd., Spiranok T-502) made by adding a photosensitizer to a mixed system of unsaturated spiroacetal and a polythiol compound on a 50μ thick polyethylene terephthalate I film; The same shimmering agent (Crystaline) used in Example 1 was used.
r#322) After drawing a peony flower pattern with a mixed resin consisting of 2 parts of benzophenone and 0.5 parts of benzophenone, it was exposed to sunlight for 2 parts.
The ink was cured for 0 minutes.

A polyethylene terephthalate film with a peony flower pattern drawn on it was placed in close contact with the above-mentioned photocurable resin coating, and after degassing, it was exposed to a UV irradiation device with an output of 50 kW at a distance of 20 cm at 5 m/min. passed at a speed of

After curing, when the film was removed, a pattern of fireflies with a spiral-like sparkle was transferred to the coating.

Next, acrylic lacquer (manufactured by Showa Kobunshi ■, Vinyroll 92T) was applied to a thickness of about 70μ.

After drying, a puff finish was applied to obtain a strikingly beautiful decorative board with a blue to red sparkling peonies design on a black background.

Example 4 On a 600 mm x 600 mm aluminum honeycomb sandwich board, 150 μ thick 7-1 (manufactured by Oji Yuka Co., Ltd., synthetic paper Yupo) was coated with Calhokitsu methyl cellulose 1.
The length of 10 parts m square is 600 mm by adhering through an aqueous solution.
A mold for injection was created by placing a square piece of iron.

A solution consisting of 5 parts of polyvinylpyrrolidone, 25 parts of water, and 70 parts of methanol was spray-painted on this to a thickness of 30 to 50 μm, and before it dried, a glitter-imparting agent (US ME
Manufactured by ARL CoRPORATION, Crysto
liner 1322 05~1 mm
) 07 parts (based on polyvinylpyrrolidone)
It was sprayed partially in different shadings.

After drying the coating, 100 parts of 0-gypsum, 36 parts of water, 10 parts of acrylic emulsion (manufactured by Showa Kobunshi ■, AP-604)
Part, black pigment (manufactured by Sanyo Shiki ■ Co., Ltd., Zandai Super) 1
0 parts, glass fiber for cement (l/4 inch cut) 5
A mixed slurry consisting of 50% was injected and cured.

When the mold was removed after curing, a molded product with countless glittering patterns, like galaxies, was obtained on the black surface.

A mixture of 100 parts of liquid epoxy resin having an epoxy equivalent of 187 and 35 parts of xylylene diamine was applied onto the pattern with a brush to a thickness of 0.7 to 0.8 wvn and cured.

The painted cloth board obtained by polishing and buffing was extremely beautiful, with countless iridescent sparkles visible on the black background.

At this time, when a polyester resin and a styrene-containing vinyl ester resin were used instead of a mixture of liquid epoxy/resin with an epoxy equivalent of 187 and xylylene diamine, the glitter was completely lost and a slightly colored pattern appeared. It was incomparably worse than anything else.

Implementation example 5 One surface! After polishing with I6og abrasive paper, a 300 ram x 300 M
100 parts of Lipokino R-806DA), 5 parts of black pigment (Rigora Sok Color Black, RC-81), 2 parts of methyl ethyl ketone peroxide, and 1 part of cobalt nanthenate were mixed well and painted to a thickness of about 0.7 cm. Thereafter, a polyethylene terephthalate film with a peony flower pattern similar to that used in Example 3 was adhered and cured.

After curing, the film was removed to obtain an aluminum plate with a glittery black background and a peony flower pattern transferred onto it.

After applying top coat resin (Spirasoku U-3155, manufactured by Showa Kobunshi ■ Co., Ltd.) to a thickness of 0.2 fl, the top coat was passed through a 20 on ultraviolet irradiation device with an output of 30 KW at a speed of 5 m/min. hardened.

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 it was extremely beautiful.

Example 6 After applying a silicone resin mold release agent to a glass petri dish with a diameter of 100 mm, the following formulation was injected.

Photocurable resin (manufactured by Showa Kobunshi Mari Co., Ltd., Spiranok T-50
2) 70 parts trimethylolpropane triacrylate 3
0 parts benzophenone 0.5'' azobisisobutyronitrile 0.3 n titanium white 0.0 1 lI glitter imparting agent Post-cured for 2 hours at °C.

A hard, semi-transparent cast product with a surface hardness of 4H and an extremely beautiful Au/Gard-like cast product with countless sparkles was obtained. Cast products could be used for buttons, pendants, necklaces, etc.

Example 7 370 parts of a liquid epoxy resin having an epoxy equivalent 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.

100 parts of blend polymer, 0.5 part of 2-ethyl-4-methylimidazole, 3 parts of a glitter agent (same type as used in Example 6), 3 parts of zinc stearate, and synthetic wax. After adding 1 part of mold release agent, 80 to 90
℃ roll crosstalk and cooling. , coarsely crushed into 5- to 1-position particles.

This coarsely crushed material was molded at a mold temperature of 140 to 150'C, with an outer diameter of 1
The mixture was placed in a concentric ashtray mold having a diameter of 45 mm, an internal diameter of 83 mm, and a depth of 30 yyn 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 the drawing]

FIG. 1 is a perspective view of a model of the bathroom vanity used in Example 2. Patent applicant Showa Kobunshi Co., Ltd. agent Patent attorney Sei Kikuchi - Figure 1 ρ a-family

Claims (6)

[Claims] (1) A resin composition comprising multilayer glass film strips in which at least two types of plastic films having different refractive indexes are alternately laminated, and a liquid resin that does not swell or dissolve the multilayer plastic film strips. (2) A patent for an unsaturated (meth)acrylate oligomer having one or more acryloyl or methacryloyl groups in one molecule, which is a liquid resin that does not swell or dissolve multilayer plastic film strips and cures without the use of monomers. The resin composition according to claim 1. (3) The liquid resin that does not swell or dissolve the multilayer plastic film strips is an unsaturated spiroacetal, or a mixture of an unsaturated cycloacetic compound having two or more allyl ether type unsaturated bonds in one molecule and a polythiol compound. A resin composition according to claim 1. (4) The resin composition according to claim 1, wherein the liquid resin that does not swell or dissolve the multilayer plastic film strips is an epoxy resin using an amine, an amine adduct, or a liquid polyamide as a curing agent. (5) The liquid resin that does not swell or dissolve the multilayer plastic film strips is an aliphatic lower alcohol solution or aliphatic hydrocarbon solution of rosin esters, long oil alkyd resins, or polyvinyl butyral. resin composition. (6) The resin composition according to claim 1, wherein the liquid resin that does not swell or dissolve the multilayer plastic film strips is an aqueous solution of polyvinyl pyrrolidone, polyvinyl methyl ether, or methyl cellulose.