JPS5931117A - Thermosetting resin molded piece having deep pattern and manufacturing method thereof - Google Patents

Abstract

PURPOSE:To obtain a resin molded piece excellent in depth by a method wherein print pattern is applied to fiber base member having a thickness 0.1-10mm. after it is impregnated with resin liquid and the whole is impregnated with thermosetting resin and then set. CONSTITUTION:A print pattern is given by gravure or silk-screen printing or other means to a fibrous base member that is composed of natural or synthetic fibrous unwoven fabric, etc. having a thickness 0.1-10mm. after it is impregnated with resin liquid and has 25-500gr/m<2> as a weight per unit area. On the other hand, stabilizer, hardener, diluent, solution etc. are added to thermosetting resin as the maincomponent such as unsaturated polyester resin etc. to prepare thermosetting resin liquid. The above-said thermosetting resin liquid is added by a coating method etc. such as roll coating or a well-known impregnation to fibrous base member the above-said print pattern is added to and then the resin is hardened by heating, ultraviolet radiation, etc. to obtain a molded piece.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin molded product having a deep pattern χ.

Conventionally, an attempt has been made to provide a pattern on a thermosetting resin molded product by applying a printed pattern 7 to a fibrous base material using a reinforcing material for the thermosetting resin molded product.

Such thermosetting resin molded products generally lack a sense of depth in the pattern, lacking the so-called "depth" (Z). Conventionally, in order to avoid such monotony, there have been methods of not only printing but also embossing the fibrous base material to create a three-dimensional effect, and improving the color tone, gloss, or light reflectivity of the printed pattern. 'a[Although methods have been used to create a pseudo three-dimensional presence and absence representation, sufficient depth has not yet been achieved.

In view of the drawbacks of the conventional techniques described above, the inventors of the present invention have investigated and found that the thickness of the resin after gold is Q, /~i.

The present invention was based on the discovery that a Jy crystal with a fine depth can be obtained by applying a printed pattern to a fibrous base material of tnm.

That is, the present invention provides a deep pattern in which a printed pattern is applied to a fibrous base material having a thickness of 0, 1 to 10,000 mm after resin molding, and the entire surface is impregnated with a thermosetting resin liquid and hardened. This is a thermosetting resin molded product having χ.

A detailed description of the invention follows.

First, to explain the fibrous base material used in the present invention, examples of the fibrous base material include non-woven fabrics made of natural or synthetic fibers, and the non-woven fabrics may be of any type, dry-type, wet-type, or spunbond. Quantity! ;”
Tan? ~k O'OfAi is used. When using the above-mentioned felt-type non-woven fabric in which fibers are entangled in the thickness direction of the non-woven fabric, the non-woven fabric compressed once during the formation of the printed pattern can be This is preferable because it restores the thickness to .

Furthermore, if the nonwoven fabric is selected so that the optical refractive index of the fibers constituting the nonwoven fabric matches the refractive index of the impregnating resin, the resulting thermosetting resin molded product will have high transparency. From a similar point of view, the transparency of thermosetting resin molded products obtained by using non-binder-type dry or spunbond fabrics is higher than that of wet-type nonwoven fabrics that contain resins other than fibers.

As the fibrous base material, one made of glass fiber 7 may be used, and a nonwoven fabric made of glass fiber or a pinewood made of glass fiber can also be used. Chopped strand mats, continuous strand mats 1, and combination mats can be used as glass fiber mats, but chopped strand mats or combination mats can be used in view of the transparency of the resulting thermosetting resin molded product. Combination mats are preferred. When the fibrous base material 7 is made of glass fiber, it preferably has a basis weight of about 2A--j001Δn1.

In the fibrous base material described above, the thickness of the fibrous base material portion after being impregnated with the resin liquid described later is 0. / trrm-/ Otrr
It is preferable that the thickness is about 0.7 mm, and if it is less than 0.7 mm, the depth will not be sufficiently expressed, and even if it exceeds torrrm, the depth effect will not improve much.

The thickness of the fibrous base material used in the present invention in the μ range described above may be such a value vr after being impregnated with the resin liquid,
Therefore, it may be a material that is originally bulky and collapses when it is compressed once during formation of a printed pattern, or a material that recovers its thickness after being impregnated with a resin liquid. Note that it goes without saying that materials whose thickness recovers immediately after being compressed can also be used.

Next, to explain the printed pattern applied to the fibrous base material as described above, such a printed pattern has better adhesion to the fibrous base material than known ink compositions, and adhesion between the formed printed pattern and the thermosetting resin. The ink composition can be applied to the fibrous base material by printing using a known printing method using an ink composition selected with consideration given to its properties and insolubility in the thermosetting resin liquid. In addition to the above-mentioned selection conditions for the ink composition, it may also be necessary to take into consideration discoloration and fading due to chemical reaction with the thermosetting resin liquid, weather resistance, and especially ultraviolet ray resistance and fire resistance. Binders for the ink composition used include cellulose conductors such as ethyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, cellulose cellulose, and cellulose acetate, styrene resins such as Holistine, polyalpha methylstyrene, and styrene resins. polymeric resin,
Polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, etc. σ),
Acrylic or Methac IJ) resin alone or copolymer resin, rosin, rosin-modified maleic acid tree 11J Rosin-modified phenol resin, rosin ester resin with polymerized rosin, polyvinyl acetate resin, coumarone resin, vinyl toluene resin, vinyl chloride Resin, polyester resin, Boliu V
One or more of tan resin, butyral resin, polyamide resin, vinyl chloride-1 vinyl acetate copolymer resin, etc.; More than one species can be selected and used. Among the above, polyester-based alkyd resins, cellulose-based resins, butyral resins, etc. are included! ``-'' is preferable because the impregnating resin liquid has excellent impregnating properties with them.

The colorant in the ink composition may be selected from a wide range of dyes and pigments, taking into account fading due to chemical reaction with the thermosetting resin liquid, weather resistance, and especially ultraviolet resistance. In addition to the above-mentioned binder and colorant, additives that are commonly used in ink compositions are appropriately added and kneaded to form an ink composition.

As for ink compositions, the above-mentioned relatively common ink compositions, especially ink compositions commonly used in the field of building materials, or paint compositions, can be used as they are, but they can be further heated. In order to increase the depth of the pattern of the curable resin molded product, the following techniques may be used.

For example, attempts to express a pseudo three-dimensional effect7 by adjusting the color tone, gloss, or light reflectance of a printed pattern are as described above. 2 large particle size 5S-tooμm,
Preferably, shiny metal pieces in the form of thin flakes with a particle size of SOμm or more and a thickness, such as aluminum flakes or similar flakes obtained by grinding aluminum vapor-deposited film (e.g. Oike Kogyo Kanji, a commercial product) It is recommended to use ink compositions containing such pigments (available under the name "Elgy") as pigments. stays relatively close to the surface of the fibrous base material,
It is preferable that the ink composition does not penetrate into the interior of the substrate and effectively adheres to the surface of the fibrous base material.It should be noted that the ink composition containing metal powder of small to small particle size is used to print patterns and print on the fibrous base material. Because the base material is compressed during printing and penetrates into the interior between the tangles of fibers, it is difficult to effectively attach the glossy metal powder only to the surface of the fibrous base material. [The above flakes σ] In addition, natural resins or synthetic resins, crushed pieces obtained by crushing inorganic materials, whitebait balloons, glass balloons, etc. with large particle sizes, l-, / Q Q 0 μm, preferably so)t
Particles with a diameter of m or more and V-ri made of a highly glossy metal other than aluminum can also be used.

As mentioned above, it is recommended to use a glossy colorant with a relatively large particle size, more preferably in the form of flakes, and to attach it to the surface of the fibrous base material during printing. From this point of view, the particle size is Sθμη! It is preferable that it is above.

If a fibrous base material is to be marked using the following ink composition, gravure printing or silk screen printing is preferred. Even more! Transfer printing method Z, which utilizes transfer paper, is a more preferable method in that it performs clear printing without causing ink smearing on the L'l In substrate. As the transfer paper to be used, publicly known σ) materials can be used, but the metal paper V-
Even when using a coloring material with a comparatively large particle diameter such as Compared to the method of printing directly on the surface of thick colorants and fibrous materials, it can be applied more efficiently without degrading the design appearance due to ink bleeding, etc.

Next, a method for creating a transfer paper using a colorant having a relatively large particle size such as metal flakes, the materials used, and the transfer method will be described.

First, the base materials for transfer paper include paper such as tissue paper, bleached kraft paper, titanium paper, linter paper, paperboard, polyethylene film, polypropylene film, polyvinyl chloride film,
Polyvinylidene chloride film, polyvinyl alcohol film, polyethylene terephthalate film, polycarbonate film, nylon film, folistin film, ethyl vinyl acetate copolymer film, ethyl vinyl alcohol copolymer film, ionomer Although plastic films such as cellulose diacetate, cellulose triacetate, polysulfone film, and polyimide film can be used, from the viewpoint of heat resistance, economical efficiency, etc., they usually have a thickness of, for example, IQ μm or more.
soμm polyethylene terephthalate film and 23
~50 f/i tissue paper should be used.

The above base material should be provided with a releasable layer to impart releasability as necessary. The releasable layer is the ink composition σ) selected from among the synthetic resins and natural resins that have been praised as binders, adhesion to the base, IJ, retention of the printed pattern described later, diluent during transfer, and other factors. The releasable varnish 7 prepared by mixing with suitable additives can be applied to the surface of the substrate by a known printing method or coating method.

Next, the surface of the base material, or as described above! When a releasable layer is provided on the surface of the N material, a printed pattern containing the coloring material 7 with a large particle diameter is formed on the surface of the releasable layer. As the colorant for the ink composition that forms such a printed pattern, use a colorant Z having a relatively large particle size, such as the metal flakes mentioned above.

From the perspective of stabilizing the ink and transferring the colorant during printing, the particle size of the colorant should be adjusted appropriately depending on the printing method.
For example, in an ink composition used in a gravure printing method, it is desirable that the particle diameter be less than or equal to the maximum plate depth of the gravure plate used.
- For example, it is desirable that J is 00 μm or less. As the components other than the coloring material of the ink composition, the same components as those for the ink composition for printing patterns described above may be used as appropriate.

In addition to the above-mentioned printing pattern to be formed on the transfer paper, it is also possible to use a conventional ink composition to form a pattern and mix the pattern with it.
The pattern formed using a conventional ink composition adheres to a relatively inner part of the fibrous base material during transfer, giving a sense of depth.

To transfer onto a fibrous base material using the above transfer paper, overlap the paper so that the printed pattern side is in contact with the fibrous base material, and heat to about 0'C-y, 00℃. ,t
This is done by applying pressure at a pressure of K9/cnt, and then basin-peeling the transfer paper. Heating and pressure conditions vary depending on the structure of the transfer device and the material of the fibrous base material. However, if the heating and pressure conditions are excessive, the thickness of the fibrous base material may decrease due to impregnation with resin liquid. Restoration is original line 1
However, these conditions can be determined through appropriate preliminary experiments. −For example, a heated steel roller and a flat roller are placed opposite each other, and the pressure χ is applied between both rollers.
When the transfer paper and fibrous base material are passed through while applying the heat, the surface temperature of the heated steel roller is 120℃~tg.
O'C1 Linear pressure between both rollers l~t o t/cm
It is.

Next, to explain the thermosetting resin liquid used in the present invention, a typical thermosetting resin liquid consists mainly of unsaturated polyester resin, and further contains stabilizers, curing agents, diluents, solvents, etc. It is possible to have something like this.

The above-mentioned thermosetting resin liquid is impregnated into the above-described printed patterned fibrous base material and cured.

Impregnation can be carried out using a known coating method, such as roll coating, or a known impregnation method, and curing can be carried out by leaving to stand, heating, ultraviolet irradiation, electron beam irradiation, or the like.

The present invention basically consists of the above configuration, but
Furthermore, the following application 2 can also be performed.

The first application example is the application to the field of known polyester decorative laminates. The polyester decorative board is made of a crystalline material such as plywood or particle board, and is adhered to a titanium paper with a basis weight of g 051' / 2 degrees, a decorative paper with an appropriate printing pattern, and unsaturated on the surface of the decorative paper. polyester resin,
Furniture and kitchen cabinets are obtained by applying an unsaturated polyester resin solution containing additives and hardening agents, etc., covering it with vinylon film, etc., and curing it at room temperature.It has a neat appearance and is durable. It is used as a surface material. When the present invention is applied to the above-mentioned polyester decorative board, it is sufficient to use a fibrous base material with a printed pattern 7 instead of the decorative paper and produce the same material. When the refractive index of the resin liquid used for impregnation is equal to the light refractive index of the resin, the entire surface becomes transparent and the underlying plywood or particle board is visible, making it unsightly.To avoid such unsightliness, use white titanium paper, for example. It is advisable to use a material with good concealment properties and attach it to the surface of plywood or verticle board in advance.

The second application example is an application to the hand lay-up method, which is one of the molding methods. In the hand lay-up method, for example, a release layer is applied to the mold, a gel coat is applied on top of the unsaturated polyester resin, and two layers of the fibrous base material with the printed pattern 7 used in the present invention are formed. On top of that, transparent polynisder resin for the intermediate layer is impregnated, air bubbles are removed using a defoaming roller, colored unsaturated polyester resin is applied for the backing, and a glass fiber mat such as chopped strand mat is layered. The molded product 7 can be obtained by a series of methods such as hardening. At this time, if you use a material that can be shaped as a fibrous base material, you will be able to create patterns on objects with three-dimensional shapes.

The above-described thermosetting resin molded product of the present invention has a deep, so-called deep pattern 2. Furthermore, it is possible to emphasize the depth by using a colorant with a large particle size such as metal flakes, and in particular, the depth can be further emphasized by using a colorant with a high gloss such as metal flakes. It is. In addition, coloring materials with different particle sizes are used in stages.
Expression of depth by the horizontal 'a?' Variegated [row r, c5. Nido can also do it.

Examples to more specifically demonstrate the present invention are listed below.

Example 1 Transfer base paper (manufactured by Sanko Paper, basis weight 3, air permeability 100)
The coating was coated on the surface of a polyamide resin vehicle using a gravure coating method, and the density was 3f/711' Ic.
Coating to form a release layer, then particle size /, 0
Using an unbleached gravure ink and a normal gravure ink for decorative plates as the vehicle, when using the former ink 2, the number of lines is 3Q lines/inch, and the gravure depth is OOPM. When using regular gravure ink for decorative plates, the number of lines is 1.
After printing using a gravure plate with a S line/inch and a plate depth of 30 μm to create a transfer paper, the printed surface of the resulting transfer paper was placed on a chopped strand mat and the surface temperature was 1 gO ℃.
χ pressure lt/m, speed Fft/0 between a heated steel roller and a cotton roller facing the roller
After that, the transfer base paper 7 was removed and a pattern was placed on the surface of the chopped strand mat.

The chopped strand matte YPVA having the pattern 2 obtained above was coated on a smooth glass plate with a mold release layer.
1, OM) 100 parts by weight of methyl ethyl ketone peroxide (sr%) was added to 1 part by weight of Z. After draining some of the polyester, apply a chopped strand mat, drain the remaining polyester (1 layer), remove any air bubbles inside with a defoaming roller, and smooth and harden the surface with a finishing roller. After curing, when peeled from the glass plate, a polyester plate with excellent transparency, a smooth optical surface, and a pattern on the intermediate layer was obtained.

The thickness of the resulting molded strand mat is approximately 2t+un, and the thickness is very deep, with normal ink distributed over almost the entire thickness and a pattern containing aluminum V-ri near the surface. A transparent decorative board with a certain color was obtained.

Example 1 Same as Example 1, except for 1. 10 yen/n in advance instead of a glass plate? The thickness of the attached titanium paper with a basis weight of
Seven moldings were carried out on plywood, and as in Example 1, a decorative polyester plywood with deep holes was obtained.

Claims (1)

[Claims] (11) A printed pattern is applied to a fibrous substrate whose thickness after impregnation with a resin liquid is 0./n to lO, and the entire surface is impregnated with a thermosetting resin liquid and hardened. (2) The fibrous base material is a felt-type nonwoven fabric of natural or synthetic fibers. Claim No. (1) The thermosetting resin molding according to the present invention. (3) The thermosetting resin molded product according to claim (1), characterized in that the fibrous base material is made of glass fiber. (4) The printed pattern is flakes with a particle size of 271 to 7000 μtn. (5) Printed pattern is the particle size of SOμtrt-OOμm
- The thermosetting resin molded product according to any one of claims (1) to (3), characterized in that it also includes a pattern made of an ink containing a pigment. (6) The thermosetting resin molded product according to any one of claims (1) to 5), wherein the thermosetting resin liquid is an unsaturated polyester resin liquid. (7) Thickness after resin gold sinking is 0. / mm~io1. I
Thermosetting with a deep pattern characterized by forming a printed pattern on the fibrous base material B, and then immersing a thermosetting resin molded product into the fibrous base material on which the printed pattern was formed and curing it. Characteristics: Production method for lQJ resin molded products. (8) The printed pattern is a grain size Sμm, 7000μm V-
The manufacturing method according to claim (7), characterized in that the manufacturing method is formed using an ink containing a pigment. (9) The printed pattern is formed using ink Z containing a pigment with a grain size of SOPM-00 pm. The manufacturing method according to any one of claims (7) to (9), characterized in that the grate and flame are formed by a gauze transfer instant printing method.