JP5587545B2 - Manufacturing method of injection laminated molded body - Google Patents

Description

The present invention, by the film insert molding, to a manufacturing method of an injection molded laminate obtained by transferring a fine unevenness of the die surface.

  As a method of patterning and decorating the surface of synthetic resin molded products, a printing material such as a resin sheet or film that has been pre-printed is set in a molding die, and the synthetic resin is injected into the die and resin is injected. A synthetic resin molding method (film insert molding) for integrating a sheet and a synthetic resin is known.

  This method has a feature that even a molded product having a shape that is difficult to directly print or color on the surface of the molded product can be patterned on the surface of the synthetic resin molded product. In film insert molding, a pattern layer formed by printing or the like on a resin sheet can be formed between the resin sheet and the synthetic resin molded product, so that the surface of the synthetic resin molded product is printed. In comparison, it has the advantage that it is excellent in scratch resistance and hardly changes over time, and is often used for decorating the surfaces of various devices.

  Molded articles obtained by film insert molding have a wide variety of uses. For example, they can be used for bathroom components. Moreover, in recent bathroom constituent materials, in order to improve the designability etc., the molded article with a pattern which provided the pattern on the surface is proposed (refer patent document 1). Such bathroom components are given importance to the design of the surface, but their drainage (quick drying) is insufficient, and the material of the bathroom components is thermoplastic with relatively high water repellency. Since many plastics such as resin and FRP are used, the hot water on the bathroom constituent material after bathing forms a polka dot with a large contact angle on the bathroom constituent material. Residual water is difficult to dry and remains without being naturally dried.

  Therefore, a molded product that can be dried in a short time by natural drying is proposed by providing the surface with fine irregularities that show hydrophilicity to prevent water aggregation and to form a water film. (See Patent Document 2).

Furthermore, in order to prevent reflection and reflection of light, a film insert molded product having a surface with fine irregularities has been proposed (see Patent Documents 3 to 5).
JP 2002-54295 A Japanese Patent No. 3991277 JP 2000-158479 A JP 7-156196 A JP 7-156197 A

  The bathroom constituent materials have been subjected to fine unevenness processing, fine drainage groove processing, and the like according to customer requirements such as drainage, dryness, and non-slip properties (preventing toppling). Along with this, the shape of the surface mold is also changed to a finer unevenness and matte shape than the conventional mold.

  However, with the conventional film insert molding method, even if the above-described fine irregularities and fine and complicated mold shapes are to be transferred, the transfer cannot be sufficiently performed, and the surface thereof cannot be hydrophilized.

  Also, in order to prevent light reflection and reflection, film insert molded products with fine irregularities on the surface have been proposed, but the outermost layer needs to be made of a material with a low softening temperature, due to insufficient heat resistance of the surface There was a problem of insufficient durability of stickiness and fine irregularities.

  The present invention has been made in view of the above problems, and is a laminated molded article having excellent design properties, and has a high adhesive strength between the laminated sheet and the molding resin, and can be peeled even in an environment using hot water, such as a bathroom. The residual water on the surface of the laminated molded body can be naturally dried and dried in a short time, and the laminated molded body and the laminated molded body can prevent light reflection and reflection. An object is to provide a manufacturing method.

The present invention relates to the following.
(1) A transfer sheet layer, a pattern layer, a laminated sheet having an acrylic binder layer, and a base material layer made of a thermoplastic resin,
The transfer sheet layer is a fine unevenness for hydrophilizing all or part of the surface, a 60 ° gloss value is 10 or less, and a method for producing an injection laminated molded article having fine unevenness,
The injection layered molded article uses an injection mold that can alternately heat and cool the mold cavity surface, heat the mold cavity and inject, and after the injection, the mold cavity surface temperature is subjected to weighted deflection of the thermoplastic resin. A method for producing an injection laminated molded article obtained by using a heat cycle method according to the following steps in which the injection laminated molded article is repeatedly moved up and down so as to be demolded after lowering the temperature.
(Step 1) A step of setting a laminated sheet having a transfer sheet layer, a pattern layer, and an acrylic binder layer on the mold side having fine irregularities on the surface and clamping the mold.
(Step 2) The surface of the mold cavity is heated using steam as a heating medium, and is maintained at a temperature at which the dynamic viscoelastic modulus of the laminated sheet is 500 MPa or less and a dynamic elastic modulus is 10 MPa or more. Injecting the thermoplastic resin into a mold.
(Step 3) After completion of injection, the mold cavity surface is cooled by using water as a cooling medium, and the temperature at which the thermoplastic resin becomes less than the deflection temperature under load and the dynamic viscoelastic modulus of the laminated sheet becomes less than 500 MPa. Then, after cooling to a temperature at which cooling and solidification can be promoted, the 60 ° gloss value is 10 or less, the transfer rate is 70% or more, and fine irregularities for hydrophilization are formed on the surface of the transfer sheet layer. A step of demolding all or part of the injection laminated molded body.

  According to the present invention, fine irregularities for hydrophilizing the surface by film insert molding can be formed at a high transfer rate, so that drainage, drying, non-slip, durability, productivity, and cleanliness can be achieved. In addition, it is possible to provide a laminate molded body and a method for producing the laminate molded body that are excellent and can efficiently prevent reflection and reflection of light.

The present invention will be described below with reference to the drawings.
As shown in FIG. 1, the laminated molded body provided with fine irregularities for hydrophilizing the surface in the present invention or fine irregularities having a 60 ° gloss value of 10 or less includes a transfer sheet layer 1, a pattern layer 2, This is a structure including a laminated sheet 4 having a binder layer 3 and a base material layer 5.

  The fine unevenness 1a for hydrophilization in the present invention or the fine unevenness 1a having a 60 ° gloss value of 10 or less is an evaluation length of 20 mm, a measurement speed of 0.6 mm / s, and a cut. The average value of arithmetic average roughness Ra (JIS B0601-1994) is 0.5 μm or more when three or more arbitrarily selected points are measured with an off value of 0.08 mm, filter type Gaussin, and a cutoff ratio of 300. And more preferably 0.7 μm or more.

  The fine irregularities 1a are formed in advance on all or part of the mold surface, and are formed on all or part of the outer surface of the transfer sheet layer 1 by transferring the shape of the mold during film insert molding.

  As the transfer sheet layer 1 in the present invention, a thermoplastic resin sheet that can be processed into a three-dimensional shape can be used. For example, various resins such as polyethylene terephthalate, acrylic, polypropylene, polyethylene, nylon, polyester, fluorine, vinyl chloride, polycarbonate, polycarbonate polybutylene terephthalate, amorphous polyethylene terephthalate, polyacrylonitrile A sheet can be used, and can be selected and used according to the use environment and application.

  The resin sheet used for the transfer sheet layer 1 preferably has a thickness of 25 μm to 5000 μm, and if it is thinner than 25 μm, it cannot follow the stretching when transferring the three-dimensional shape, and is liable to be broken or wrinkled. . On the other hand, if it is thicker than 5000 μm, it may be impossible to follow the bent portion of the molding die, and it becomes gradually difficult to manufacture a highly accurate laminated molded body.

The resin sheet used for the transfer sheet layer 1 is subjected to physical or chemical adhesion treatment on one or both sides of the resin sheet using a coating apparatus or a printing machine in order to increase the adhesive force with the pattern layer or the binder layer. Can be applied to general adhesive treatment methods, epoxy resin adhesives, cyanoacrylate adhesives, polyurethane adhesives, urea resin adhesives, melamine resin adhesives, acrylic modified silicone resin systems Adhesives, phenolic resin adhesives, vinyl acetate resin adhesives, chloroprene rubber solvent adhesives, synthetic rubber latex adhesives, isocyanate adhesives, emulsion adhesives, hot melt adhesives, silane cups Apply various adhesives such as ring agent, corona treatment, sanding treatment, plasma treatment, flame treatment, ozone treatment It can be subjected to treatment of an acid treatment or the like.
In addition, various additives such as fillers, foaming agents, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, and the like can be added to the adhesive treatment agent and coloring processing can be performed as needed during the adhesion treatment.
The resin sheet used for the transfer sheet layer 1 can contain an antifungal / antibacterial agent, and a commercially available antibacterial agent can be used. In general, industrial antibacterial agents are roughly classified into inorganic antibacterial agents and organic antibacterial agents, and any antibacterial agent can be used for the transfer sheet layer 1 of the present invention.
The resin sheet used for the transfer sheet layer 1 may be a color sheet processed with a pigment or a dye.

The pattern layer 2 in the present invention can be formed by gravure printing, inkjet printing, screen printing, sublimation transfer printing, spray spraying, vapor deposition, or the like. There are two types of printing modes: normal printing in which the pattern is formed on the side opposite to the clear sheet when printing is completed, and reverse printing in which the pattern is formed on the side of the clear sheet. Either form can be used.
The ink used for the pattern layer 2 is a pigment or dye on various resins such as urethane, vinyl acetate, acrylic, vinyl chloride / acrylic, polyester, epoxy, and nitrified cotton (nitrocellulose). Can be used, and may be a conductive material, an ink using a metal, or the like. The pattern may be any of wood grain, stone tone, abstract pattern, metal tone, and the like, and is not particularly limited.

The binder layer 3 in the present invention is a layer for adhering the laminated sheet 4 and the resin to be the base layer 5, and is made of acrylic, urethane, polyester, polyamide, ethylene butyl alcohol, ethylene vinyl acetate. In addition to various binders such as polymer system and vinyl chloride / vinyl chloride, epoxy resin adhesive, cyanoacrylate adhesive, polyurethane adhesive, urea resin adhesive, melamine resin adhesive, acrylic modified silicone resin adhesive , Phenolic resin adhesive, vinyl acetate resin adhesive, chloroprene rubber solvent adhesive, synthetic rubber latex adhesive, isocyanate adhesive, emulsion adhesive, hot melt adhesive, silane coupling agent Various adhesives such as can be used.
In addition, the binder layer 3 can be added with various additives such as a filler, a foaming agent, an antioxidant, a heat stabilizer, an ultraviolet absorber, and a light stabilizer, and can be colored as necessary.
Two or more binder layers may be provided.
The binder to be used can be selected from those having heat sensitivity and pressure sensitivity suitable for the resin.
The binder layer 3 can be formed by gravure printing, ink jet printing, screen printing, sublimation transfer printing, spraying, roll coater, or the like, and a film-like binder can also be used.
In order to protect the pattern layer from the flow pressure of the resin at the time of insert molding, the binder layer 3 can also contain a fibrous reinforcing material, for example, polyester fiber, nylon fiber, glass fiber, natural fiber, metal fiber, Various fibers such as ceramic fibers can be used, and an adhesive treatment or the like can be applied to the fibers as necessary. The form of the fiber may be any form such as plain weave, satin weave, non-woven fabric, and mat.
Two or more reinforcing layers may be provided, and different types of reinforcing materials can be used in combination.

Patterning can be performed on paper used as a reinforcing material, woven fabric of organic fibers such as polyester resin and acrylic resin, or non-woven fabric of inorganic fibers such as glass, etc. An ink fixing process can be performed.
Also, the basis weight of the fiber ^{is preferably, 30g / m 2 ~100g / m} 2 and more preferably 15g / ^{m 2} ~250g / m 2 approximately. If the weight per unit area is less than 15 g / m ² , the ink adhesion area on the fiber surface is small, and the pattern gradually becomes rough and the sharpness tends to decrease. If it exceeds 250 g / m ² , adhesion to other layers Tend to be gradually damaged.

  The base material layer 5 in the present invention is a layer formed of a resin injected at the time of injection molding, and the resin used for the base material layer 5 is an ABS resin, a polystyrene resin, an acrylic resin, a polycarbonate resin, or a polypropylene resin. Resin, polyethylene resin and the like can be used.

The cross section of the laminated molded body obtained by film insert molding the resin to be the laminated sheet 4 and the base material layer 5 in the present invention can be considered as shown in FIG. 1, and the laminated molded body has the following steps as shown in FIG. Can be produced.
(Step 1) A step of setting the laminated sheet 4 on the mold (movable mold 6) side having fine irregularities on the surface and clamping the mold.
(Step 2) The thermoplastic resin 8 is injected into a mold in a state where the mold cavity surface is maintained at a temperature at which the dynamic viscoelastic modulus of the laminated sheet 4 is 500 MPa or less and a dynamic elastic modulus is 10 MPa or more. Process.
(Step 3) After completion of injection, the surface of the mold cavity is cooled to a temperature at which the dynamic viscoelastic modulus of the laminated sheet becomes less than 500 MPa and a deflection temperature under load of the thermoplastic resin, which can promote cooling and solidification. The process of demolding the laminated molded body.

  The laminated sheet 4 can be trimmed as necessary. Trimming may be performed in advance according to the size of the laminated molded body before injection molding, or may be trimmed after injection molding and trimming the excess laminated sheet 4.

  The laminated molded body is an injection mold provided with fine irregularities for hydrophilization, or fine irregularities having a 60 ° gloss value of 10 or less, and a resin that becomes the laminated sheet 4 and the base layer 5 is formed by film insert molding. The shape of the mold is then transferred to the transfer sheet layer 1 of the laminated sheet.

The injection mold used when producing the laminated molded body includes, for example, a movable mold 6 and a fixed mold 7. Of the fixed mold 6 and the movable mold 7, the movable mold 6 on the side in contact with the transfer sheet layer 1 has fine irregularities 6 a for making the entire surface or part of it hydrophilic, or a fine whose 60 ° gloss value is 10 or less. Concavities and convexities 6a are provided.
Further, the movable die 6 can be provided with a vacuum suction hole and a clamp member for fixing the laminated sheet.

  The laminated sheet 4 used at the time of producing the laminated molded body can be set between the movable mold 6 and the fixed mold 7, and the laminated sheet 4 can be fixed by a vacuum suction hole or a clamp member. By setting the laminated sheet 4 and then injecting the thermoplastic resin 8 into the cavity, the laminated sheet 4 can be bonded and integrated with the resin simultaneously with the injection molding in the cavity to form a laminated molded body.

  The injection molding method at the time of production of the laminated molded body is such that when the thermoplastic resin is injection-molded, the cavity surface temperature of the mold is repeated using an injection mold in which the mold cavity surface is alternately heated and cooled. Molding is performed by applying a heat cycle injection molding method that moves up and down. For example, a heat cycle injection molding method in which the cavity surface is heated and cooled in a short time by a combination of steam and water as shown in Japanese Patent No. 39756565 is applied.

  The injection molding conditions at the time of producing the laminated molded body are as follows: injection is performed at a resin temperature higher by +120 to 200 ° C. than the deflection temperature under load of the plastic resin, and the thermal deformation temperature elastic modulus of the laminated sheet 4 is 500 MPa or less on the mold cavity surface. The mold cavity surface is heated to a temperature body, preferably a temperature body of 200 MPa or less to maintain the temperature, the transfer sheet layer 1 is softened, and a thermoplastic resin is injected into the mold. After injection filling, the mold cavity surface is cooled at a temperature lower than the deflection temperature under load of the thermoplastic resin, preferably at a temperature 10 ° C. to 50 ° C. lower than the deflection temperature under load, and the laminated molded body is demolded.

Hereinafter, the present invention will be described by way of examples.
( Test Example 1)
Using urethane-based ink (manufactured by Chiyoda Gravilla Co., Ltd.) on the easy-adhesion treated surface of polyester film A-1532 (manufactured by Toyobo Co., Ltd.) that has been subjected to easy adhesion treatment of 200 mm long, 200 mm wide and 0.18 mm thick. A pattern layer was printed by gravure printing, and a binder layer was further formed to obtain a laminated sheet. The obtained laminated sheet is attached to a mold of an injection molding machine in which fine irregularities are formed, and an ABS resin (manufactured by Asahi Kasei Chemicals Co., Ltd.) is used as a resin for the base layer at a resin temperature of 230 ° C. and a mold temperature of 140 ° C. After bonding and integrating the laminated sheet and the ABS resin as the base material by injection molding under the conditions, the mold temperature was cooled to 40 ° C. and then demolded, and the surface was 200 mm long and 200 mm wide with fine irregularities. A laminated molded body was obtained. In addition, the metal mold | die used the average value of arithmetic average roughness Ra of a fine unevenness | corrugation being 1.1 micrometers.

( Test Example 2)
Gravure printing using urethane-based ink (manufactured by Chiyoda Gravilla Co., Ltd.) on the corona-treated surface of polyester film A-1538 (manufactured by Toyobo Co., Ltd.) subjected to corona treatment of 200 mm long, 200 mm wide and 0.18 mm thick The printed layer was printed and a binder layer was formed to obtain a laminated sheet. The obtained laminated sheet is attached to a mold of an injection molding machine in which fine irregularities are formed, and an ABS resin (manufactured by Asahi Kasei Chemicals Co., Ltd.) is used as a resin for the base layer at a resin temperature of 230 ° C. and a mold temperature of 140 ° C. After bonding and integrating the laminated sheet and the ABS resin as the base material by injection molding under the conditions, the mold temperature was cooled to 40 ° C. and then demolded, and the surface was 200 mm long and 200 mm wide with fine irregularities. A laminated molded body was obtained. In addition, the metal mold | die used the average value of arithmetic average roughness Ra of a fine unevenness | corrugation being 1.1 micrometers.

(Example 3)
A vinyl chloride / acrylic ink (manufactured by Chiyoda Gravilla Co., Ltd.) is applied to the corona-treated surface of a polyester film A-1538 (manufactured by Toyobo Co., Ltd.) having a corona treatment of 200 mm long, 200 mm wide and 0.18 mm thick. Using this, a pattern layer was printed by gravure printing, and a binder layer was further formed to obtain a laminated sheet. The obtained laminated sheet is attached to a mold of an injection molding machine in which fine irregularities are formed, and an ABS resin (manufactured by Asahi Kasei Chemicals Co., Ltd.) is used as a resin for the base layer at a resin temperature of 230 ° C. and a mold temperature of 140 ° C. After bonding and integrating the laminated sheet and the ABS resin as the base material by injection molding under the conditions, the mold temperature was cooled to 40 ° C. and then demolded, and the surface was 200 mm long and 200 mm wide with fine irregularities. A laminated molded body was obtained. In addition, the metal mold | die used the average value of arithmetic average roughness Ra of a fine unevenness | corrugation being 1.1 micrometers.

(Comparative Example 1)
Using urethane-based ink (manufactured by Chiyoda Gravilla Co., Ltd.) on the easy-adhesion treated surface of polyester film A-1532 (manufactured by Toyobo Co., Ltd.) that has been subjected to easy adhesion treatment of 200 mm long, 200 mm wide and 0.18 mm thick. A pattern layer was printed by gravure printing, and a binder layer was further formed to obtain a laminated sheet. The obtained laminated sheet is mounted on a mold of an injection molding machine in which fine irregularities are formed, ABS resin (manufactured by Asahi Kasei Chemicals Co., Ltd.) is used as a resin for the base layer, and the mold temperature is 50 ° C. After the injection molding is performed in a state of being kept constant, the laminated sheet and the ABS resin as the base material layer are bonded and integrated, and then cooled and demolded in the state of the mold temperature kept constant, and the surface is finely formed. A laminated molded body having a height of 200 mm and a width of 200 mm was obtained. In addition, the metal mold | die used the average value of arithmetic average roughness Ra of a fine unevenness | corrugation being 1.1 micrometers.

(Comparative Example 2)
Print a pattern layer by gravure printing using urethane-based ink (manufactured by Chiyoda Graviya Co., Ltd.) on a polyester film (manufactured by Toyobo Co., Ltd.) that is 200 mm long, 200 mm wide, and has a thickness of 0.18 mm. A binder sheet was formed to obtain a laminated sheet. The obtained laminated sheet is mounted on a mold of a mirror-type injection molding machine, and ABS resin (manufactured by Asahi Kasei Chemicals Co., Ltd.) is injected as a resin for the base layer at a resin temperature of 230 ° C. and a mold temperature of 140 ° C. After molding and integrating the laminated sheet and the ABS resin to be the base material layer, the mold temperature is cooled to 40 ° C., and then the mold is removed, and the laminated molded body having a vertical unevenness of 200 mm and a width of 200 mm having fine irregularities on the surface. Got.

(Test method)
(1) Evaluation of transferability The surface of the obtained laminated molded product having a length of 200 mm and a width of 200 mm was evaluated with a surface roughness profile measuring machine Surfcom 130A (manufactured by Tokyo Seimitsu Co., Ltd.), an evaluation length of 20 mm, and a measurement speed of 0.6 mm / s. The cut-off value is set to 0.08 mm, the filter type is Gaussin, and the cut-off ratio is 300. The average value of the arithmetic average roughness Ra (JIS B0601-1994) when three or more arbitrarily selected points are measured is determined. The transfer rate was evaluated by calculating the transfer rate with respect to. The case where the transfer rate was 90% or more was rated as ◯, the case where it was 70% or more and less than 90%, and the case where it was less than 70%.
(2) Evaluation of hydrophilicity When water was applied to the transfer sheet layer side of the obtained laminated molded product having a length of 200 mm and a width of 200 mm, the water aggregation phenomenon was prevented and a water film was formed. The case where the water was aggregated was evaluated as Δ, and the case where the water was aggregated was evaluated as x.
(3) Evaluation of drying property When water was poured on the obtained molded product having a length of 200 mm and a width of 200 mm, drying times by natural drying were compared.
(4) Evaluation of hot water resistance When a test was conducted in which the obtained laminated molded product, a sample having a length of 50 mm and a width of 50 mm was immersed in hot water at 50 ° C. for 24 hours, the case where the laminate sheet did not peel after the test The case of partial peeling was indicated by Δ, and the case of complete peeling was indicated by ×.
(5) Glossiness The specular glossiness (JIS Z8741 60-degree specular gloss) of the obtained molded product having a length of 200 mm and a width of 200 mm was measured.

  As a result, in the above examples, the laminated molded body having fine irregularities for hydrophilizing on the surface or fine irregularities having a 60 ° gloss value of 10 or less, and having excellent design properties, is a laminated sheet and a molding resin. The adhesive strength was high, peeling did not occur even in an environment using warm water, and it could be dried in a short time by natural drying. In addition, since a film insert molded product having an extremely low surface glossiness can be obtained at low cost, it is also suitable for automobile interior parts and home appliance parts.

It is sectional drawing which shows the structure of the laminated molded object in this invention. It is sectional drawing which shows the manufacturing method of the laminated molded object in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transfer sheet layer 1a Fine unevenness 2 Pattern layer 3 Binder layer 4 Laminated sheet 5 Base material layer 6 Movable type 7 Fixed type 8 Thermoplastic resin

Claims (1)

A transfer sheet layer, a pattern layer, a laminated sheet having an acrylic binder layer, and a base material layer made of a thermoplastic resin,
The transfer sheet layer is a fine unevenness for hydrophilizing all or part of the surface, a 60 ° gloss value is 10 or less, and a method for producing an injection laminated molded article having fine unevenness,
The injection layered molded article uses an injection mold that can alternately heat and cool the mold cavity surface, heat the mold cavity and inject, and after the injection, the mold cavity surface temperature is subjected to weighted deflection of the thermoplastic resin. A method for producing an injection laminated molded article obtained by using a heat cycle method according to the following steps in which the injection laminated molded article is repeatedly moved up and down so as to be demolded after lowering the temperature.
(Step 1) A step of setting a laminated sheet having a transfer sheet layer, a pattern layer, and an acrylic binder layer on the mold side having fine irregularities on the surface and clamping the mold.
(Step 2) The surface of the mold cavity is heated using steam as a heating medium, and is maintained at a temperature at which the dynamic viscoelastic modulus of the laminated sheet is 500 MPa or less and a dynamic elastic modulus is 10 MPa or more. Injecting the thermoplastic resin into a mold.
(Step 3) After completion of injection, the mold cavity surface is cooled by using water as a cooling medium, and the temperature at which the thermoplastic resin becomes less than the deflection temperature under load and the dynamic viscoelastic modulus of the laminated sheet becomes less than 500 MPa. Then, after cooling to a temperature at which cooling and solidification can be promoted, the 60 ° gloss value is 10 or less, the transfer rate is 70% or more, and fine irregularities for hydrophilization are formed on the surface of the transfer sheet layer. A step of demolding all or part of the injection laminated molded body.

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