JPH05318469A - Semicured resin sheet with pattern and preparation thereof and preparation of frp molding with pattern using said semicured resin sheet with pattern - Google Patents

Abstract

PURPOSE:To shorten working time on a mold, to improve productivity and to obtain an FRP molded item with a pattern having high design properties. CONSTITUTION:A method for preparation of a semicured resin sheet 6 with a pattern wherein an uncured resin 2 for forming a surface layer is placed in a bulk shape on one end part of the surface of a base film 1 and an end part side of a face with a pattern 3 of a transfer film 4 one face of which is patterned with an ink being soluble in the resin 2 for forming the surface layer is pushed thereon and then, the transfer film 4 is pressed from one end part side of the surface of the base film 1 by means of a roller 5 and is laminated on the resin 2 for forming the surface layer while the bulk resin 2 for forming the surface layer is uniformly drawn and is made into a semicured condition by curing treatment and the pattern is transferred from the transfer film 4 and in addition, if necessary, this transfer process is repeated to make the pattern into a multilayered pattern, and a method for preparation of an FRP molded item with a pattern wherein the semicured resin sheet 6 with a pattern is laminated with the molding material on a mold and is molded by pressing and heating, are provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a patterned semi-cured resin sheet, a method for producing the same, and a method for producing a patterned FRP molded article using the patterned semi-cured resin sheet.

[0002]

2. Description of the Related Art The following is known as a method for applying a pattern to an FRP molded product. A A method of laminating a woven or non-woven fabric on which a pattern is printed on a mold. A method in which the mold B is masked, the gel coat resin is sprayed, the masking is removed, the molding material is placed on the mold, and integrally molded. C As shown in Japanese Examined Patent Publication No. 3-47183, the end portion of the pattern printing surface of the transfer film is pressed against the uncured transparent resin placed in a block on one end of the mold surface, and then the roller is placed on the transfer film. Stretch the resin uniformly to cure the resin, then peel off the transfer film to transfer the pattern, and further laminate the transparent resin layer, the colored opaque layer and the glass fiber-reinforced resin reinforcement layer to strengthen the glass fiber with the pattern. A method of manufacturing plastic products.

[0003]

The method A involves the work of laminating on the mold, and the method B also applies the gel coat resin directly onto the mold, so that the mold occupy time becomes long. This is not a preferable manufacturing method because the productivity is deteriorated, the working time is increased due to the masking work, and further, in the case of the heating mold, the environment is deteriorated due to long-time work in the vicinity of a high temperature mold. In addition, application of the gel coat resin provided only a monotonous pattern such as a stone tone by monochromatic or multicolor blowing. Next, in the method disclosed in Japanese Patent Publication No. 3-47183 of C, since the patterning is performed by transfer, the pattern is a wood grain,
There are no restrictions such as stone tones and abstract patterns, printing is precise, and more precise patterns can be obtained. However, in order to peel off the transfer film and transfer the pattern onto the surface resin, it is necessary to cure the surface resin, and the work time on the molding die becomes long, so high cycle such as press molding using a heating die is required. It could not be used as a patterning method when required.

The present invention solves such a problem, and the mold occupancy time in molding is short, and the parting line from the patterning portion can be easily worked without masking work. Molding defects such as parting line defects due to outflow and crack breakage due to pressure do not occur, and it is possible to follow the surface pattern of uneven shapes and mold shapes with joints, and intermediate members and manufacturing for efficient molding products The purpose is to provide the law. Another object of the present invention is to obtain a patterned FRP molded product having a high designability that has not been found in a conventional press-molded product having a pattern, that is, a highly accurate pattern having no restrictions on color and pattern. It is a thing.

[0005]

The present invention is directed to the formation of an uncured surface layer in which a curing agent and a chain transfer agent are added in advance to one end of the surface of a base film having a patterned semi-cured resin sheet with a pattern on one side. Resin is placed in a lump, and the end side of the patterning surface of the transfer film having one surface patterned with an ink soluble in the surface layer-forming resin is pressed against the lump-shaped surface layer-forming resin, and then, The transfer film is pressed from one end side of the base film surface, the lumpy surface layer forming resin is evenly stretched while being superimposed on the surface layer forming resin, and the cured surface layer forming resin is cured and stretched. A semi-cured resin sheet having a semi-cured state, a pattern transferred from a transfer film, and a repeating process, if necessary, to form a multi-layered pattern, and a method for manufacturing the semi-cured resin sheet with a pattern are desired. of Cut into Jo, the film was peeled,
The present invention relates to a method for producing a patterned FRP molded product in which a molding material is placed on a molding die in an overlapping manner, and pressure / heat molding is performed to integrate a patterned semi-cured resin sheet into the molding material.

In the invention of claim 2, the surface layer forming resin is not particularly limited, but is a thermosetting resin such as unsaturated polyester resin, vinyl ester resin or acrylic resin having transparency or translucency, A curing agent and a chain transfer agent are added, and the type, combination, addition amount, and proper selection of the curing conditions suppress the polymerization, and as the first stage curing, the polymerization is stopped at an arbitrary degree of curing, It is possible to obtain a semi-cured resin sheet in a cured state. In addition, the resin for forming the semi-cured resin layer of the second and subsequent layers when forming a multilayer may be a colored and opaque thermosetting resin. Arbitrary degree of cure means that the semi-cured resin sheet retains its shape, the surface does not become sticky, and the strength and flexibility are such that spillage or crack destruction does not occur during press molding for the manufacture of patterned FRP molded products. And having a reactive group sufficient for adhesion to the molding material during complete curing, that is, the second stage curing, and the degree of curing is preferably in the range of 75 to 85%.

The transfer film is not particularly limited as long as it has heat resistance and peelability and is insoluble in the surface resin.
Polyethylene resin, polypropylene resin, nylon, polyester resin, fluorine resin or other plastic film, aluminum foil or other metal foil alone or laminated with another film, or paper or plastic film with releasability Use the one coated with resin. The thickness of the film is preferably about 10 to 100 μm in order to uniformly stretch the lumpy surface resin. The patterning ink needs to be soluble in the surface resin, but unsaturated polyester resin, acrylic resin, nitrified cotton (nitrocellulose) -based resin, or the like mixed with a pigment or dye is preferable. The base film is not particularly limited as long as it has heat resistance and peelability and is insoluble in the surface resin, and the same material as the transfer film can be used.

According to the second aspect of the present invention, first, a transparent or translucent uncured surface layer forming resin, to which a curing agent and a chain transfer agent have been added in advance, is placed in a lump form on one end of the surface of the base film. The transfer film is pressed on the base film and the resin for forming a lumpy surface layer, and the transfer film is pressed in one direction by a roller or the like. Thereby, the resin for forming the surface layer is defoamed and uniformly stretched. Next, the surface layer forming resin is cured, the surface layer forming resin is semi-cured by the action of the chain transfer agent, and the pattern of the transfer film ink is transferred onto the surface layer forming resin. The pattern transfer by the transfer film is not limited to wood grain, stone tone, abstract pattern, etc., and printing is precise, and a more precise pattern can be obtained. The method of curing treatment is not limited, but it is generally put in a drying oven or the like and heated to 50 to 80 ° C.

Further, in order to improve the design in combination with the pattern of the surface layer, the transfer film on the surface layer of the resin for forming the surface layer is peeled off if necessary, and the same uncured surface as described above is again peeled to the surface. Transfer the pattern by stacking the layer-forming resin in a lump, pressing another transfer film, pressing and stretching, and repeating the curing process to make the pattern multi-layered and providing transparent, semitransparent, and colored opaque layers. A semi-cured resin sheet with a pattern having a three-dimensional effect, a clear feeling, or a concealing effect is obtained. In this case, the transfer film may be a plain film, a film with a pattern, a film with a colored opaque ink, or the like. An example of a patterned semi-cured resin sheet is one in which the pattern is transferred to a transparent semi-cured resin surface layer (the background color is the molding material when the molded product is used), and A transparent semi-cured resin layer made of a plain transfer film and made into multiple layers (the background color is the molding material, and the transparent resin layer gives a three-dimensional effect to the pattern). A transparent semi-cured resin layer is formed on the patterned surface layer by forming the opaque layer with a plain transfer film (the colored opaque layer is used as the background color to provide a hiding effect regardless of the color of the molding material). Examples include those formed by a transfer film with a colored opaque ink (a transparent resin layer gives a three-dimensional effect, and a colored opaque ink has a concealing effect).

In order to bring the surface layer forming resin into a semi-cured state, the chain transfer agent, preferably 4-methyl-2,4 diphenylpentene-1 (α-methylstyrene dimer), is used to decompose the curing agent. Decrease the exothermic temperature without participating in the reaction, suppress the polymerization reaction by properly selecting the addition amount and type of curing agent, combination, curing conditions, etc., and perform polymerization at an arbitrary degree of cure (polymerization conversion rate). Stop. Here, the semi-cured state of the resin due to the action of the chain transfer agent is SMC or BM.
Unsaturated compared to what is already found in C compound formation, etc., mainly due to metal crosslinking between unsaturated polyester and divalent metal oxides (viscosity decreases due to pressurization and heating, and compound flow is expected) In order to partially form a three-dimensional network structure by a copolymerization reaction of an unsaturated dibasic acid in an alkyd with a monomer, that is, a cross-linking between molecules, a curing degree of 7
In the range of 5 to 85%, the semi-cured resin sheet with a pattern retains its shape, the surface does not become sticky, and the uneven shape and joints of the molding die are pressed and heat-molded by a press for producing a patterned FRP molded product. It has such a strength and flexibility that it follows, does not cause outflow, crack breakage, etc., and leaves a reactive group (crosslinking point) sufficient to allow adhesion to a molding material when completely cured.

The patterned semi-cured resin sheet having a pattern on one side thereof is manufactured in a process different from that of the patterned FRP molded product and can be stored for a certain period of time. This allows efficient production of patterned FRP molded products. The invention of claim 3 cuts the patterned semi-cured resin sheet into a desired shape,
Semi-cured resin with a pattern is placed by stacking it with a molding material at a predetermined position on a mold coated with a release agent, pressurizing and heating, and curing the patterned semi-cured resin sheet as the molding material cures. The sheet is integrated with the molding material to form a patterned FRP molded product.

[0012]

EXAMPLES Next, examples of the present invention will be described. Example 1 Step 1 As shown in FIG. 1, 100 parts by weight of a transparent uncured isophthalic acid-based unsaturated polyester resin (manufactured by Hitachi Chemical Co., Ltd., Polyset 3715T) was preliminarily mixed with perloyl TCP (NOF Corporation) as a curing agent. 1 part by weight of product name manufactured by Co., Ltd. and 4-methyl-2,4 diphenylpentene-1 (α-methylstyrene dimer) as a chain transfer agent
The resin 2 for forming a surface layer, to which 0.5 part by weight of NOFMER MSD manufactured by NOF CORPORATION was added, was placed in a lump shape at one end on the surface of a base film 1 made of a polyester film having a thickness of 50 μm. On the other hand, a wood grain pattern layer 3 is formed by patterning one surface with an ink soluble in the surface layer forming resin.
A transfer film 4 of a polyester film having a thickness of 25 μm was prepared. The end portion side of the patterning surface of the transfer film 4 is pressed against the lumpy surface layer forming resin 2, and then the transfer film 4 is pressed by the roller 5 to the base film 1
While pressing from one end side of the surface to uniformly stretch the lump-shaped surface layer forming resin 2, the lumped surface layer forming resin 2 was superposed on the surface layer forming resin 2.

Next, the stretched surface layer forming resin 2 is added to 60
The resin was allowed to stand for 60 minutes in a drying oven maintained at 0 ° C. to proceed with polymerization of the resin. The polymerization was stopped at a curing degree of 75% by the action of the previously added chain transfer agent, and the first-stage curing was completed in a semi-cured state. Then, when the transfer film 4 was peeled off, a patterned semi-cured resin sheet 6 in which the woodgrain pattern layer 3 was transferred to the upper surface of the semi-cured surface layer forming resin 2 was formed. The patterned semi-cured resin sheet had no stickiness on the surface and was flexible, so that the sheet shape was maintained and the handling was easy.

Step 2 The patterned semi-cured resin sheet 6 formed in Step 1 is set to 200 × 3.
After cutting to 00 mm, the base film 1 is peeled off, and the pattern layer 3 is placed on the upper side, that is, the transparent surface layer 2 side is in contact with the lower molding die 7 as shown in FIG. SMC as the molding material 8 is then stacked on the patterned semi-cured resin sheet 6, and the upper mold 9 is tightened to apply pressure (10
0 kg / cm ² ), heating (lower mold 7; 150 ° C., upper mold 9; 14)
(5 ° C.) and molded. The patterned semi-cured resin sheet 6 was completely cured and integrated with the SMC as the SMC flowed and cured in the molding die, and the second stage curing was completed. The molded product was taken out of the mold and F shown in FIG. 3 with a woodgrain pattern.
RP molded product 10 was obtained.

Example 2 Step 1 In the same manner as in Step 1 of Example, a semi-cured surface layer forming resin 2 having a marble pattern transferred was obtained.

Step 2 The transfer film 4 on the semi-cured surface layer forming resin 2 obtained in Step 1 is peeled off, and one end portion on the surface layer on which the marble pattern layer 3 is transferred is shown in FIG. As described above, transparent uncured three-dimensional layer forming resin (having the same composition as that of the surface layer forming resin in step 1) 11 of Polyset 3715T to which Nofmer MSD was added in advance was placed in a lump. On the other hand, a concealing transfer film (with a white opaque ink) 13 having a concealing layer 12 formed by patterning one surface with an ink soluble in the three-dimensional layer forming resin 11 is prepared, and the pattern of the concealing transfer film 13 is prepared. The end portion side of the attachment surface is pressed against the block-shaped three-dimensional layer forming resin 11, and then the concealment transfer film 13 is pressed by the roller 5 from one end side of the surface layer 2 to form the block-shaped three-dimensional layer forming resin 11. Was uniformly stretched and superposed on the three-dimensional layer forming resin 11.

Next, the stretched three-dimensional layer forming resin 11 is
In the same manner as in Example 1, the resin was allowed to stand for 60 minutes in a drying oven maintained at 60 ° C. to promote polymerization of the resin, and a semi-cured state was obtained by the action of the chain transfer agent. The curing degree of the three-dimensional layer 11 at this time is 75.
%, The curing of the surface layer 2 formed in step 1 progressed slightly, and the degree of curing was about 80 to 85%. Then, the concealment transfer film 13 is peeled off, and the three-dimensional layer 1 in the semi-cured state is removed.
A semi-cured resin sheet 14 having a pattern, in which the white and opaque concealing layer 12 was transferred onto the sheet 1, was obtained.

Step 3 Patterned semi-cured resin sheet 14 formed in Steps 1 and 2
Is cut into 200 × 300 mm, the base film 1 is peeled off, and the hiding layer 12 is placed on the upper side as shown in FIG. 5, that is, the transparent surface layer 2 side is in contact with the lower molding die 15, and It is placed on the mold 15 and subsequently SMC is used as the molding material 8.
Is placed on the patterned semi-cured resin sheet 14, and the upper mold 16 for molding is tightened to apply pressure (80 kg / cm ² ) and heat (lower mold 1
5; 125 ° C., upper mold 16; 135 ° C.) and molded. The patterned semi-cured resin sheet 14 is completely cured and integrated with the SMC as the SMC flows and cures in the molding die. The molded product is taken out of the mold, and the white opaque hiding layer 12
6. The patterned FRP molded product 17 shown in FIG. 6 in which the surface of the molding material 8 is not affected by the hue of the molding material 8 and a clear and three-dimensional marbled pattern is applied to the surface with a clear parting line.
Got

In the above embodiment, the patterned semi-cured resin sheet is not sticky and has flexibility, so that the shape of the sheet can be maintained even if the base film is peeled off, the handling is easy, and the polymerization is stopped. Therefore, it can be stored for a certain period. In addition, it has a strength and flexibility that does not cause outflow or crack destruction even when the SMC flows during press molding, and it is a reactive group (crosslinking point) that enables adhesion to the molding material when completely cured. ), The adhesiveness with the molding material is secured.

[0020]

EFFECTS OF THE INVENTION The patterned semi-cured resin sheet of the present invention can be stored in the semi-cured state for a certain period of time.
RP molded products can be manufactured efficiently. In the production of patterned semi-cured resin sheets, the degree of cure can be easily adjusted by the action of a chain transfer agent, so the surface is not sticky and easy to handle, and the flexibility and strength that can withstand press forming in the production of molded products. And can be integrated with the molding material. In addition, the transfer of the pattern by the transfer film is not limited in terms of colors, patterns such as wood grain, stone tone, and abstract pattern, and printing is precise, and a more precise pattern can be obtained. In the production of a patterned FRP molded product, by using the above-mentioned semi-cured resin sheet with a pattern, compared to the gel coat application work on the molding die, there is no work of providing a parting such as masking, and the occupation time of the mold is short and high. Productivity is possible. In addition, the work near the hot mold can be reduced, and the working environment can be improved. The patterned FRP molded product obtained by the present invention achieves higher productivity and design than the conventional patterned molded product obtained by press molding.

[Brief description of drawings]

FIG. 1 is a diagram showing a method for producing a patterned semi-cured resin sheet in an example of the present invention.

FIG. 2 is a diagram showing a method for producing a patterned FRP molded product in an example of the present invention.

FIG. 3 is a cross-sectional view showing an FRP molded product manufactured in an example of the present invention.

FIG. 4 is a diagram showing a method of manufacturing a patterned semi-cured resin sheet in an example of the present invention.

FIG. 5 is a diagram showing a method for producing a patterned FRP molded product in an example of the present invention.

FIG. 6 is a cross-sectional view showing an FRP molded product manufactured in an example of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Base film, 2 ... Surface layer forming resin, 3 ... Pattern layer, 4 ... Transfer film, 5 ... Roller, 6 ... Patterned semi-cured resin sheet, 7 ... Molding lower mold, 8 ... Molding material, 9 ... Upper mold for molding, 10 ... FRP molded product with pattern, 11 ... Resin for forming three-dimensional layer, 12 ... Concealment layer, 13 ... Concealment transfer film,
14 ... Patterned semi-cured resin sheet, 15 ... Molding lower mold, 1
6 ... Upper mold for molding, 17 ... FRP molded product with pattern

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 17, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

In the invention of claim 2, the resin for forming the surface layer is not particularly limited, but it is a thermosetting resin such as unsaturated polyester resin, vinyl ester resin, acrylic resin or the like having transparency or translucency and cured. Agent and chain transfer agent are added, polymerization is suppressed by appropriate selection of their type, combination, addition amount, and curing conditions, and as the first stage curing, polymerization is stopped at any degree of curing, and semi-cured. It is possible to obtain a semi-cured resin sheet in a state. In addition, the resin for forming the semi-cured resin layer of the second and subsequent layers when forming a multilayer may be a colored and opaque thermosetting resin. Arbitrary degree of cure means that the semi-cured resin sheet retains its shape, the surface does not become sticky, and the strength and flexibility are such that spillage or crack destruction does not occur during press molding for the manufacture of patterned FRP molded products. And having a reactive group sufficient for adhesion to the molding material during the complete curing, that is, the second stage curing, and the degree of curing is preferably in the range of 60 to 90%.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

In order to bring the surface layer forming resin into a semi-cured state, the chain transfer agent, preferably 4-methyl-2,4 diphenylpentene-1 (α-methylstyrene dimer), is used to decompose the curing agent. Decrease the exothermic temperature without participating in the reaction, suppress the polymerization reaction by properly selecting the addition amount and type of curing agent, combination, curing conditions, etc., and perform polymerization at an arbitrary degree of cure (polymerization conversion rate). Stop. Here, the semi-cured state of the resin due to the action of the chain transfer agent is SMC or BM.
Unsaturated compared to what is already found in C compound formation, etc., mainly due to metal crosslinking between unsaturated polyester and divalent metal oxides (viscosity decreases due to pressurization and heating, and compound flow is expected) In order to partially form a three-dimensional network structure by a copolymerization reaction of an unsaturated dibasic acid in an alkyd with a monomer, that is, an intermolecular cross-linking, the curing degree is 6
The semi-cured resin sheet with a pattern retains its shape in the range of 0 to 90%, the surface does not become sticky, and the uneven shape and joints of the mold are pressed and heat-molded by a press for manufacturing a patterned FRP molded product. It has such a strength and flexibility that it follows, does not cause outflow, crack breakage, etc., and leaves a reactive group (crosslinking point) sufficient to allow adhesion to a molding material when completely cured.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location B29L 7:00 4F (72) Inventor Masao Horii 1010 Ippongi, Toyama City, Toyama Prefecture Hitachi Chemical Unit Co., Ltd. (72) Inventor Hirofumi Izumi 4-13-1, Higashi-machi, Hitachi-shi, Ibaraki Yamazaki factory, Hitachi Chemical Co., Ltd.

Claims (3)

[Claims] 1. A patterned semi-cured resin sheet having a pattern on one side. 2. An uncured resin for forming a surface layer, to which a curing agent and a chain transfer agent have been added in advance, is placed in a lump form on one end of the surface of the base film, and an ink soluble in the resin for forming the surface layer is used. The end side of the patterned surface of the transfer film having one surface patterned, is pressed against the lumpy surface layer forming resin,
Next, the transfer film is pressed from one end side of the surface of the base film, and the lumpy resin for forming the surface layer is uniformly stretched and superposed on the resin for forming the surface layer, and is cured and stretched to form the surface layer forming resin. 2. The method for producing a semi-cured resin sheet with a pattern according to claim 1, wherein the semi-cured resin sheet is transferred to a semi-cured state, the pattern is transferred from the transfer film, and the transfer step is repeated as necessary to form a multilayered pattern. .. 3. The pattern-forming semi-cured resin sheet according to claim 1 is cut into a desired shape, the film is peeled off, the molding material is placed on a molding die in an overlapping manner, and pressure / heat molding is carried out to obtain a pattern. A method for producing a patterned FRP molded article, which comprises integrating a semi-cured resin sheet with a molding material into a molding material.