JPS58136413A - Preparation of molded product with picture pattern - Google Patents

Abstract

PURPOSE:To obtain a molded product having a picture pattern and excellent in appearance, by a method wherein a radical curing type resin is closely contacted with the picture pattern on the surface of a film in an uncured stage of said resin and, after the resin is cured and the film is peeled off to transfer the picture pattern to the surface of said resin, the picture pattern surface is painted with a transparent or a translucent paint. CONSTITUTION:In curing a radical curing type resin or a mixture of the radical curing type resin and a fibrous reinforcing material, the surface of said resin or said mixture is closely contacted with the picture pattern surface of a film having a picture pattern printed by a printing ink having compatibility with said resin in an uncured stage of said resin to cure the resin and, after the film is peeled off to transfer the picture pattern printed on the surface of said film to the surface of the cured resin, the picture pattern surface is painted with a transparent or a translucent paint. By this method, a molded product with a picture pattern excellent in appearance can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a molded product with a desired pattern, and particularly relates to a method for manufacturing a molded product with a desired pattern, and in particular FRP, which is molded at room temperature or near room temperature using a radical curing resin. This applies to molded products.

The purpose of the present invention is to create molded products such as FRP and cast products that have rarely been painted in the past, or have only been able to be decorated with simple post-printing or limited hand-drawn patterns. The purpose is to freely apply a desired pattern to the material, thereby completely changing its appearance and significantly improving its commercial value.

Conventionally, methods for painting molded products such as FRP and cast products include methods such as heat transfer, sublimation transfer, and direct printing, methods of inserting printed paper or printed nonwoven fabric into a right wheel during molding, Alternatively, methods such as manually drawing patterns on gel coat have been adopted.

However, the appearance of the molded products obtained by these existing methods is simple and lacks commercial value, lacks depth and gives a cheap feeling, or has disadvantages such as the protrusion of the fibers of the nonwoven fabric. However, it was not always satisfactory.

The present inventors have improved the conventional method of painting molded products such as FRP and cast products, in order to obtain molded products that are superior in appearance to molded products obtained by conventional methods. As a result of various studies, we have completed the present invention.

That is, in the present invention, when curing a radical curable resin or a radical curable resin and a fibrous reinforcing material, a printing ink having an affinity with the resin is applied at an uncured stage when the resin is liquid or sticky. A film with an arbitrary pattern printed on it is brought into close contact with the resin surface so that the pattern side is in contact with the resin surface, and the resin is cured.Then, the film is peeled off and the printed pattern on the film surface is transferred to the cured resin surface. , and further relates to a method for producing a molded article, which is characterized in that the surface of the transferred pattern is coated with a transparent or translucent paint.

The molded product obtained by the method of the present invention has a pattern applied using a method different from conventional post-printing or non-woven fabric painting, so the pattern is sandwiched between the paint and the hardening resin. Moreover, since the transparency, reflectance, and degree of coloring of the upper and lower resin layers can be changed depending on the location, the conventional simple printing method is not as effective as the molded products obtained by this method. It is possible to get rid of the cheap appearance of youth woven fabric, where the fibers are noticeable, and give it a much better appearance.

For example, one example of this is to use a resin mixed with glass beads in either the resin layer above or below the pattern layer, or in both resin layers.

That is, the present invention is not just a method of painting, but focuses on beauty that gives a high-class feel to the molded product.

The radical curable resin used in the present invention can be broadly classified into the following types.

(1) Unsaturated polyester resin Contains α-β unsaturated polybasic acid as one component, modified with any saturated acid and/or unsaturated acid, and unsaturated alkyd obtained by esterification reaction with polyhydric alcohol. The type that is dissolved in nanatsuma.

0:) Vinyl ester resin A type of resin produced by the reaction of an epoxy resin and an unsaturated basic acid dissolved in a monomer.

As the unsaturated basic acid, acrylic acid or methacrylic acid is generally used, and can be said to be a type of unsaturated acrylate resin.

(110 unsaturated acrylate resin 1 minute for acryloyl or methacryloyl groups.

It goes without saying that each of the resins (il-011) can be used in combination as necessary.

Commercially available polyhydric alcohols and polybasic acids, which are raw materials for the synthesis of unsaturated polyester resins, may be used as they are, and there is no need to place any particular restrictions on their components.

Furthermore, the epoxy resin component constituting the vinyl ester resin does not need to be particularly limited, and commonly used bisphenol-diglycidyl ether type, novolac-polyglycidyl ether type, polybasic acid glycidyl ester type, peracetic acid oxidation type, etc. It is selected as necessary from the intramolecular glycidyl group type, etc.

There are limited synthesis methods and raw materials for unsaturated acrylate resins depending on their structure. For example, polyurethane-acrylate (polyurethane-acrylate) is mainly composed of diisocyanate, unsaturated alcohol, and polyol, and polyester-acrylate is made of acrylic acid or methacrylic acid, polyhydric alcohol, and polybasic acid. is preferred. The ratio of radical curing resin and fibrous reinforcing material is General Banko 90.
: 10-50:50.

The filler may or may not be used, but it is often better to use it because it changes the appearance of the molded product and makes molding easier. However, it cannot be used if transparency is required for the molded product.

Typical examples of fillers include calcium carbonate, clay, hydrated alumina, fly ash, and the like.

In order to cure the radical curable resin, a curing agent and, if necessary, an accelerator are naturally added to the resin.

To apply a pattern to the film used in the present invention,
Depending on the type, it is necessary to carefully examine the type of printing ink that makes up the pattern, especially the type of binder (vehicle). For example, if a pattern with clear lines is not formed, such as with a certain type of stone, there is no need to place any particular restrictions on the type of printing ink, but if the pattern cannot be even slightly distorted, , the types of vehicles are limited.

From a practical point of view, it is important to use a vehicle that does not disturb the image even if the uncured resin and printing film are left in contact for a long period of time, or even when the film is dissolved, and that has a higher affinity for the resin than the film. desirable.

With this in mind, preferred polymers or oligos w- constituting the printing ink vehicle include the following types: That is, specific examples thereof include styrene-maleic acid copolymer, polymer or oligomer obtained by adding a third component to styrene-maleic acid, polyamide resin, polybutene, xylene resin, chlorinated rubber, petroleum resin, 100 Thialkyl phenol resin, oil-modified phenol resin, +) resin, ester gum, rosin-maleic acid resin, rosin-modified phenol resin, oil-modified alkyd resin, dry natural oil and polymerized oil, epoxy resin, cellulose derivative, etc. can give. In addition to the above, polymer latex, which is a water-based ink but has a lipophilic dry film, or polymers that are both water-soluble and soluble in organic solvents, such as methylcellulose, hydroxyethyl heptalrose, methylhydroxypropylcellulose, and polyvinyl It is also possible to use pyrrolidone, polyvinyl methyl ether, and the like.

In particular, inks made by adding colorants to organic solvent-soluble polymers, which are not commonly used in printing inks, can be used either by printing or hand-painting.

Furthermore, photocurable vehicles, which have been increasingly used in recent years, can also be used. They are unsaturated acrylate resins, i.e.
It mainly consists of alkyd acrylate, vinyl ester resin (epoxy acrylate), and urethane acrylate, with a necessary amount of polyacrylate of polyhydric alcohol added thereto, and a photosensitizer added.

There are no particular restrictions on the use of the colorant, which is the other component of the ink.

Moreover, printing as used in the present invention means adding a desired pattern to a film by machine or hand-drawing.

The material of the film used in the present invention is not particularly limited as long as it is insoluble in the radical curable resin and printable but does not adhere to the radical curable resin, but generally polyethylene,
Polypropylene, polyethylene terephthalate, polyvinyl chloride, modified polyvinyl alcohol, cellophane, etc. are used. The film with the pattern printed thereon is brought into close contact with the printed surface of the resin while the radical curable resin is in a liquid or sticky state and is in an uncured state, and is peeled off after the resin is cured. In this way, a molded article with a pattern transferred to the cured resin surface is obtained.

Although conventional molding methods can be applied to the method of the present invention, it is preferable to use a mold when producing a molded article.

Although a mold is not necessarily required when manufacturing an FRP molded product using a mold, it is preferable to use a mold when manufacturing a cast product. Any conventional mold can be used, and any shape can be used.

If a mold having an uneven surface is used, a molded product having a corresponding uneven pattern, curved surface, etc. can be obtained.

In the present invention, it is necessary to further coat the patterned cured resin surface with a transparent or translucent paint.

As a paint for this purpose, the same type of resin as the one mentioned above that constitutes the FRP molded product and cast product may be used, but there are also other paints such as polyurethane paint, epoxy resin paint, and acrylic resin. It is also possible to use paints, a group of paints called clear paints such as rose ester paints, and various light-curing paints that can best demonstrate their characteristics. It can be utilized.

It is preferable that painted FRP molded products and cast molded products using radical curable resin be molded mainly at room temperature or at a temperature close to room temperature. Examples of molding methods for painted FRP include lay-up molding, spray-up molding, cold press molding, resin injection molding, and the like.

Next, examples will be shown below to help understand the present invention.

In addition, unless otherwise specified, parts in the examples mean parts by weight.

Example 1 4 s Om+X 450 w ■Revolac 150HR) 100 parts, 10 parts of styrene,
#380 glass mat 3 using a mixture of 2 parts methyl ethyl ketone peroxide and 1 part cobalt naphthenate.
After laminating the ply, the above resin mixture was further impregnated and laminated using a Surf Ace Pine (30'kt-1) device.

When the surface of the resin is sticky and uncured, print your favorite fashion model on a polyethylene terephthalate film using a drying oil-modified alkyd resin printing ink, and place it so that the pattern is in contact with the resin surface. hardened.

When the film was peeled off after curing, the pattern of the fashion model was transferred to the resin surface.

Furthermore, unsaturated spiroacetal acrylate resin (manufactured by Showa Kobunshi ■, Ltd.,
After painting Subiratsuk U-3155) to a thickness of 0.2■,
It was cured by passing 20 crn under the lamp at a speed of 2 m/min using an ultraviolet irradiation device with an output of 30 h.

An FRP molded product with a cement substrate was obtained, which had a depth of hardness of 4H to 5H and featured a pattern of a fashion model.

Example 2 Two cams (solution was used as an adhesive) were laid on aluminum of 600fi
A mold is filled with a mixture consisting of 100 parts of Lipoxy R-802 (manufactured by Showa Kobunshi ■ Co., Ltd.), 150 parts of calcium carbonate, 2 parts of a hardening agent (hardening agent 382 (manufactured by Chemical Industry ■ Inc.), and 1 part of cobalt naphthenate). I injected it so that

While the resin is gelling and the surface is sticky, a Tivoli Marble pattern is printed on a polypropylene film using a rosin-modified alkyd resin printing ink, and the pattern side is brought into contact with the uncured resin. In addition, they were hardened tightly to prevent air from entering from the edges.

After curing, when the film was peeled off, a cast product with a Tivoli marble pattern of light reddish brown shading was obtained.

Acrylic lacquer, shite, acrylic ester and methacrylic acid copolymer (Vinyroll 92T, manufactured by Showa Kobunshi Co., Ltd.) were spray-coated on the patterned surface of this cast product to a thickness of 0°15mm. After drying and finishing with a puff, the result was an artificial marble that was comparable to glossy natural marble.

Example 3 Unsaturated polyester resin (Rigorak 150, manufactured by Showa Kobunshi ■ Co., Ltd.) (R
, BQT) 100 parts, washed and dried fly ash 30
Using a mixture consisting of 0 parts black pigment, 5 parts black pigment, and 1 part methyl ethyl ketoshiba oxide, 3 plies of $380 mat were laminated, and then Surf Ace mat 30p
It was impregnated and laminated.

When the surface of the resin is sticky and uncured, a photocurable resin (manufactured by Showa Kobunshi ■ Co., Ltd.,
A picture of a sea bream was drawn using printing ink made by mixing 100 parts of Lipoxy 5P-1509) with 5 parts of a coloring agent (manufactured by Nippon Kinzoku Powder Company, KAI 5-500G for gold ink), and exposed to sunlight for 2 hours. The ink was adhered onto the layered material.

When the film was peeled off after curing, the sea bream pattern was transferred to the resin surface.

Furthermore, as a top coat, a polyurethane resin clear lacquer (manufactured by Kansai Paint Co., Ltd., Acryk $2026GL Clear, a hardening type using a predetermined amount of isocyanate curing agent) is sprayed onto the pattern surface for 200 ml.
It was coated in layers to give a thickness of μ. After curing, polishing and puffing were performed to obtain a strikingly beautiful lacquer-like FRP with a pattern of sea bream standing out against a black background. □ Patent applicant: Showa Kobunshi Co., Ltd. Agent: Sei Kikuchi, patent attorney

Claims (1)

[Claims] When curing a radical curing resin or a radical curing resin and a fibrous reinforcing material, a printing ink having an affinity with the resin is used to print an arbitrary pattern on the uncured stage when the resin is liquid or sticky. The printed film is placed in close contact with the resin surface so that the pattern side is in contact with the resin surface, and the resin is cured.
Next, the film is peeled off, the printed pattern on the film surface is transferred to the cured resin surface, and the transferred pattern surface is further painted with transparent or semi-transparent paint. .