JP6342102B2 - Method for producing molded product with wrinkle pattern and molded product with wrinkle pattern formed - Google Patents

Description

  The present invention relates to a method for producing a molded product on which a texture pattern is formed, and a molded product on which a texture pattern is formed.

  Molded articles obtained by extruding materials such as thermoplastic resins and thermoplastic elastomers into sheets or films are used for various purposes for construction, civil engineering, daily necessities, and agriculture. Moreover, the molded product extruded into the cylindrical body is used for a tube or the like for filling a garbage bag, cosmetics, food, or the like. These molded articles can be produced by extruding a molten thermoplastic resin, thermoplastic elastomer, or other material from the discharge port of the extrusion mold.

  However, materials such as thermoplastic resins and thermoplastic elastomers have a problem that, depending on the type, a blocking phenomenon occurs in which the materials adhere to each other when stacked and cannot be easily peeled off. Therefore, a natural organic material having at least one selected from silk powder, wool powder and chitin powder and having an average particle size of 30 μm or less and a water content of 10 wt% or less as a material such as a thermoplastic resin or a thermoplastic elastomer. A method of containing 1 to 40 wt% of fine powder and 5 wt% or less of a heat stabilizer is known (see Patent Document 1).

  In addition, it is also known that it has a high-grade appearance by forming a textured pattern on the molded product, and in the case of a thin film-like molded product such as a garbage bag, it is easy to peel off the films. Yes. A method of forming a texture pattern on a molded product is known in which a thermoplastic resin film after extrusion is pressed with a pair of rollers, at least one of which is a textured roller (see Patent Document 2).

Japanese Patent No. 3014585 JP-A-5-309730

  The method of pressing with a wrinkled roller described in Patent Document 2 can be suitably used for a planar molded product extruded by the T-die method. However, when a molded product is manufactured by an inflation method, the molded product is extruded into a cylindrical shape. Therefore, when the molded product extruded into a cylindrical shape is pressed with a roller with a texture, there is a problem that the molded product is bonded. At present, there is no known method for forming a texture pattern on a molded product extruded by the inflation method.

  On the other hand, in the T-die method, when the thickness of the extruded molded product is different, it is necessary to adjust the interval between the wrinkled rollers according to the thickness. Moreover, when a part of the embossed roller is worn or missing, it is necessary to replace the entire roller. A simpler production method is also required in the production of a molded product on which a texture pattern is formed by the T-die method.

  The present invention has been made to solve the above-mentioned problems, and as a result of extensive research, when glass wool is added to a melt-kneaded product for extrusion molding, it is surprisingly pressed with a roller with a texture. A texture pattern is formed on the surface of an extruded molded product without performing a process such as the following (hereinafter, a process of forming a conventional texture pattern may be referred to as “texture processing”). Newly found.

  That is, the objective of this invention is providing the manufacturing method of the molded article in which the wrinkle pattern was formed, and the molded article in which the wrinkle pattern was formed, without implementing wrinkle processing.

  The present invention relates to a method for producing a molded product on which a wrinkle pattern is formed, and a molded product on which a wrinkle pattern is formed, as shown below.

(1) A melting step for producing a melt-kneaded material including at least a thermoplastic resin and / or a thermoplastic elastomer and glass wool,
Extrusion process for producing the molded product by extruding the melt-kneaded product from the discharge port of the extrusion mold by an extrusion molding method,
A cooling step for cooling the molded product extruded in the extrusion step,
The manufacturing method of the molded article in which the wrinkle pattern was formed including this.
(2) The glass wool content is 1 to 20% by weight.
The manufacturing method of the molded article in which the wrinkle pattern as described in said (1) was formed.
(3) The extrusion molding method is an inflation method or a T-die method, and the molded product is a film, a sheet, or a cylindrical body.
The manufacturing method of the molded article in which the embossed pattern as described in said (1) or (2) was formed.
(4) The extrusion molding method is a coextrusion method,
The molded product is formed as a laminated multilayer product,
At least one of the outer layers of the multilayer article is a layer formed by extruding a melt-kneaded material containing at least the thermoplastic resin and / or thermoplastic elastomer and glass wool.
The manufacturing method of the molded article in which the embossed pattern as described in said (1) or (2) was formed.
(5) The extrusion molding method is coextrusion by an inflation method or coextrusion by a T-die method,
The molded product is formed as a multilayer product,
At least one of the outer layers of the multilayer article is a layer formed by extruding a melt-kneaded material containing at least the thermoplastic resin and / or thermoplastic elastomer and glass wool.
The manufacturing method of the molded article in which the wrinkle pattern as described in said (3) was formed.
(6) including at least a thermoplastic resin and / or a thermoplastic elastomer, and glass wool,
Molded product with wrinkle pattern.
(7) The content of the glass wool is 1 to 20% by weight,
A molded article on which the embossed pattern described in (6) above is formed.
(8) The molded product is a film, a sheet, or a cylindrical body.
A molded article on which the embossed pattern according to (6) or (7) is formed.
(9) The molded product is a multilayer product,
At least one of the outer layers of the multilayer article is a layer containing at least the thermoplastic resin and / or thermoplastic elastomer and glass wool.
A molded article on which the texture pattern according to any one of (6) to (8) is formed.
(10) The thickness of the molded product is 3 μm to 300 μm.
A molded article on which the embossed pattern according to (8) or (9) is formed.

  In the present invention, a texture pattern is formed on the surface of an extruded molded article simply by adding glass wool to the melt-kneaded product for extrusion molding. Therefore, since the embossing process is not necessary, a molded product on which the embossed pattern is formed can be manufactured by various extrusion methods including the inflation method.

FIG. 1 is a drawing substitute photograph, FIG. 1 (A) is a photograph of glass wool, and FIG. 1 (B) is a photograph of glass fiber. FIG. 2 is a drawing-substituting photograph, FIG. 2 (A) is a photograph of the bag produced in Example 1, and FIG. 2 (B) is a photograph of the bag produced in Comparative Example 1. FIG. 3 is a photograph substituted for a drawing and a photograph of the bag produced in Example 2. FIG. 4 is a drawing-substituting photograph, FIG. 4 (A) is a photograph of the layer side containing glass wool of the two-layer film produced in Example 3, and FIG. 4 (B) is a photograph of the layer side not containing glass wool. FIG. 5 is a drawing-substituting photograph, FIG. 5 (A) is a photograph of the layer side containing glass wool of the two-layer film produced in Example 4, and FIG. 5 (B) is a photograph of the layer side not containing glass wool. FIG. 6 is a drawing-substituting photograph, FIG. 6 (A) is a photograph of the film produced in Example 5, and FIG. 6 (B) is a photograph of the film produced in Comparative Example 2. FIG. 7 is a drawing-substituting photograph, FIG. 7 (A) is a photograph of the tubular body produced in Example 6, FIG. 7 (B) is a photograph of the tubular body after printing, and FIG. 7 (C). Is a photograph in which a spiral for fastening a cap is formed on a cylindrical body. 8 is a drawing-substituting photograph, FIG. 8A is an X-ray transmission image of the film produced in Example 1, and FIG. 8B is an X-ray transmission image of the film produced in Example 5.

  Hereinafter, a method for producing a molded article on which a texture pattern of the present invention is formed (hereinafter sometimes simply referred to as “manufacturing method”) and a molded article on which a texture pattern is formed (hereinafter simply referred to as “molded article”). Will be described in detail.).

  The production method of the present invention includes a thermoplastic resin and / or a thermoplastic elastomer (hereinafter sometimes referred to as “resin etc.”) and a melting step for producing a melt-kneaded material containing at least glass wool, At least an extrusion process for producing a molded product by extrusion from a discharge port of an extrusion mold, and a cooling process for cooling the molded product extruded in the extrusion process. A texture pattern can be formed on a molded product by a melting step, an extrusion step, and a cooling step. Moreover, the manufacturing method may include other processes as required, such as a printing process for printing on the surface of the molded product after the cooling process. Other steps such as a printing step may be performed by a known method.

  The thermoplastic resin is not particularly limited as long as it can be mixed with glass wool. For example, conventionally used thermoplastic resins such as general-purpose plastics, engineering plastics, and super engineering plastics can be mentioned. Specifically, as general-purpose plastic, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE) , Acrylonitrile butadiene styrene resin (ABS resin), styrene acrylonitrile copolymer (AS resin), acrylic resin (PMMA), and the like. As engineering plastics, polyamide (PA), polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE, modified PPE, PPO) represented by nylon, polybutylene terephthalate (PBT), polyethylene terephthalate ( PET), syndiotactic polystyrene (SPS), cyclic polyolefin (COP) and the like. As super engineering plastics, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polysulfone (PSF), polyethersulfone (PES), amorphous polyarylate (PAR), polyetheretherketone (PEEK), Examples thereof include thermoplastic polyimide (PI) and polyamideimide (PAI). These resins may be used alone or in combination of two or more.

  The thermoplastic elastomer is not particularly limited as long as it can be mixed with glass wool. For example, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene-diene block copolymer, styrene-diene-styrene block copolymer, and hydrogenated ones of these can be used, and these are used in combination. It is also possible to do. It is also possible to use the above thermoplastic resin and a thermoplastic elastomer in combination.

  In the present invention, glass wool means a glass fiber having a fiber diameter of about 1 to 7 μm in a cotton shape. FIG. 1A is a photograph of glass wool. On the other hand, a glass fiber (long glass fiber) having a fiber diameter of 10 to 18 μm is also known as a reinforcing material added to a thermoplastic resin or the like (see FIG. 1B). Glass fibers are generally used as chopped strands in which 50 to 200 fibers are collected and cut into a predetermined length. As shown in FIGS. 1A and 1B, glass wool and glass fiber are completely different in production method and purpose of use. In addition, when glass fiber is added to resin, etc., it cannot be extruded by the inflation method, and even if it is extruded by the T-die method, the glass fiber protrudes from the surface of the molded product such as a sheet, so it is easily broken. End up. On the other hand, when glass wool is added, a texture pattern can be formed on the surface of the molded product as shown in the examples described later.

  Glass wool is produced by spraying molten glass by rotating a spinner having a large number of small holes of about 1 mm around at high speed. This manufacturing process is generally called a centrifugal method, and fine glass wool of about 1 to 7 μm can be economically manufactured by adjusting the viscosity and rotation speed of molten glass. Glass wool can be produced by the above method, but a commercially available product may be used.

  In the melting step, glass wool may be added to molten resin or the like to prepare a melt-kneaded product, but a master batch pellet containing a large amount of glass wool is prepared in advance, and the master batch pellet and a pellet not containing glass wool are mixed. May be.

  What is necessary is just to produce the masterbatch pellet containing glass wool by a well-known method. Glass wool is an inorganic material, while resin or the like is an organic material. Therefore, simply bonding glass wool to resin or the like weakens the adhesiveness between glass wool and resin or the like. Therefore, glass wool may be surface-treated with a silane coupling agent and then added to a resin or the like.

  The silane coupling agent is not particularly limited as long as it is conventionally used, and may be determined in consideration of reactivity with a resin and the like, thermal stability, and the like. Examples thereof include silane coupling agents such as aminosilane, epoxysilane, allylsilane, and vinylsilane. As these silane coupling agents, commercially available products such as Z series manufactured by Toray Dow Corning, KBM series manufactured by Shin-Etsu Chemical Co., Ltd., KBE series, and JNC manufactured may be used.

  The silane coupling agent can be surface treated on glass wool by dissolving in a solvent and spraying and drying on glass wool. The weight percentage of the silane coupling agent with respect to the glass wool is 0.1 to 2.0 wt%, preferably 0.15 to 0.4 wt%, and more preferably 0.24 wt%.

  Glass wool may be surface-treated with a lubricant. The lubricant is not particularly limited as long as the glass wool is kneaded into a resin or the like so that the glass wool can be easily slipped and easily filled into the resin, and a conventionally used lubricant such as silicon oil is used. Although calixarene is particularly preferred. Since silicon is an oil, it has poor affinity with resins, etc., but calixarene is a phenolic resin, which improves slipping of glass wool, while having excellent affinity with resins, etc. The resin can be filled while maintaining the length.

  The surface treatment of glass wool is performed by spraying and drying a solution in which calixarene is dissolved on glass wool. The solution in which the calixarene is dissolved can be produced by a known production method, but for example, a plastic modifier nanodaX (registered trademark) manufactured by Nanodax Corporation may be used. The weight percentage of the plastic modifier nanodaX (registered trademark) with respect to glass wool is preferably 0.001 to 0.5 wt%, and more preferably 0.01 to 0.3 wt%.

  Glass wool may be treated with the silane coupling agent or lubricant, or may be treated with the silane coupling agent and the lubricant.

  In addition to the surface treatment with the above silane coupling agent and / or lubricant, glass wool is surfaced with a known film forming agent such as epoxy resin, vinyl acetate resin, vinyl acetate copolymer resin, urethane resin, acrylic resin, etc. It may be processed. These film forming agents can be used alone or in admixture of two or more, and the weight percentage of the film forming agent is preferably 5 to 15 times that of the silane coupling agent.

  In the melting step, resin and the like, glass wool, and various additives that are added as necessary, using a known melt kneader such as a single-screw or multi-screw extruder, a kneader, a mixing roller, a Banbury mixer, etc. What is necessary is just to melt-knead at the temperature of -400 degreeC.

  The content of glass wool is preferably 1 to 20% by weight, more preferably 1 to 10% by weight, and particularly preferably 2 to 5% by weight. When the glass wool content is less than 1% by weight, it is difficult to form a texture pattern. On the other hand, if the content of glass wool exceeds 20% by weight, the strength of the molded product is unfavorable. In the present invention, the “glass wool content” means the weight of glass wool / (weight of thermoplastic resin and / or thermoplastic elastomer).

  Further, in the melting step, known ultraviolet absorbers, stabilizers, antioxidants, plasticizers, colorants, color adjusters, flame retardants, antistatic agents, fluorescent whitening agents, as long as the object of the present invention is not impaired. Additives such as matting agents and impact strength improvers can also be blended.

  The extrusion process is not particularly limited as long as it can produce a molded product by extruding the melt-kneaded material produced in the melting process from the discharge port of the extrusion mold by an extrusion molding method. For example, a slightly thick cylindrical shaped product can be extruded by extruding the melt-kneaded product from an annular discharge port. This manufacturing method is useful for tubes filled with cosmetics, foods, and the like.

  Alternatively, the melt-kneaded product may be extruded from an annular discharge port by an inflation method to produce a molded product. The molded product manufactured by the inflation method may be cut into one end before winding to form a flat film, or may be a cylindrical body. When the cylindrical body is pressed with a roller with a crimp, the thin film constituting the cylindrical body is bonded, and conventionally, a cylindrical body with a crimp cannot be manufactured by an inflation method. However, in the present invention, since a texture pattern is formed on the molded product without performing texture processing by adding glass wool to a resin or the like, it is particularly useful for producing a cylindrical body by an inflation method. When a garbage bag or the like is manufactured from a cylindrical body, since the texture pattern is formed on the surface, the bag can be easily opened.

  In the extrusion process, a die (T-die method) in which a die having a linear discharge port called a T-die is installed at the tip of the extruder and the material is continuously extruded to produce a molded product. Also good. In the T-die method, the film is cooled through a mirror-finished cooling roller (chilled roller), and the width of the film is adjusted by cutting off the end part until it is finally wound. Conventionally, a texture pattern is formed by using a part of the roller as a textured roller. However, in the present invention, a grain pattern is formed on the surface of the film by adding glass wool to a resin or the like, and therefore it is not necessary to use a roller with a grain. In addition, when it is desired to further increase the depth of the texture (unevenness), the film on which the texture pattern is formed may be further pressed with a roller with a texture.

  The molded product may be a single layer or multiple layers. In the case of multilayering, coextrusion, which is a technique of extruding a plurality of materials at a time and stacking them at the time of the extrusion process, may be performed. For example, in the case of the inflation method, a die pre-lamination method in which each molten resin is contacted in a feed block in front of the mold, an in-die laminating method in which the molten resin is contacted by a route inside the mold, and discharge by contact from a plurality of concentric discharge ports. And die outer lamination method.

  In the case of the T-die method, a single manifold method and a multi-manifold method in which a feed block is installed immediately before a die and a plurality of extruders are connected to the feed block via an adapter may be used. In the single manifold method, a resin is contacted in a feed block and then a film is formed through a die. The number of layers can be set by changing the adapter, and a multilayer film can be obtained relatively easily. In the multi-manifold method, a T die having a plurality of manifolds is used, and the resins supplied from a plurality of extruders are brought into contact with each other immediately before the discharge port and laminated. A material having a large physical property difference such as a viscosity difference can be coextruded, and the thickness of each layer can be easily adjusted.

  The above-described coextrusion of the inflation method and the T-die method is a typical example of a method for producing a laminated molded product. If a final laminated product such as a laminating method is obtained, another production method may be used. It may be. In general, when a molded product is produced by an extrusion molding method, the physical properties of the molded product often differ between the extrusion direction and the vertical direction. However, as shown in the examples described later, the molded product of the present invention has an effect that the difference in physical properties between the extrusion direction and the vertical direction can be reduced by adding glass wool.

  When the molded product is a laminated multilayer product, it is preferable that at least one of the outer layers of the multilayer product is a layer obtained by extruding a molten kneaded product of resin or the like and glass wool. By adding glass wool, a texture pattern is formed on the outer layer, which gives a high-class feeling and prevents the molded product from sticking. In the case of a multilayer product, a layer obtained by extruding a melt-kneaded product of resin or the like and glass wool may be formed as an internal layer of the multilayer product. When formed as an inner layer, the specific surface area is increased by the embossed pattern, so the adhesion with the upper and lower layers is improved.

  The cooling step may be performed by cooling the extruded melt-kneaded product by a known method, for example, by air cooling or the like.

  The shape of the molded product is preferably a film, a sheet, or a cylindrical body. In the present invention, based on JIS (Japanese Industrial Standards), “film” is “a plastic film having a thickness of less than 250 μm”, and “sheet” is “a thin plastic plate having a thickness of 250 μm or more”. Means "thing". The thickness of the molded product (film, sheet, cylindrical body) is not particularly limited as long as it is thicker than the diameter of glass wool to be added and can be formed by an extrusion molding method, but is preferably about 3 μm to 300 μm, About 5 to 275 μm is more preferable, and about 8 to 250 μm is more preferable. When the thickness is about 3 μm or less, the molded product is too thin and easily broken. On the other hand, when the thickness is about 300 μm or more, there is less merit that a texture pattern is formed and the film is difficult to adhere and the difference in physical properties between the extrusion direction and the vertical direction of the molded product can be reduced.

  In the present invention, the “molded product” means a product obtained by extruding a melt-kneaded product by an extrusion molding method, regardless of whether it is a single layer or multiple layers. Therefore, the thickness of the molded product of about 3 μm to 300 μm means the thickness of the sheet, film, or cylindrical body itself produced by the extrusion molding method, and the thickness of the product obtained by attaching them to a plate or the like. It doesn't mean.

  By the way, the present inventor has filed a patent application for a composite forming material in which glass wool is filled in a thermoplastic resin (see Japanese Patent No. 5220934). However, the composite forming material described in Japanese Patent No. 5220934 is an invention for increasing the fiber length of glass wool to be filled in a thermoplastic resin and increasing the filling amount of glass wool. Only the pellets and injection-molded products are described. On the other hand, the molded product of the present invention is formed by extrusion from the discharge port of the extrusion mold. In the case of injection molding, since the composite forming material is injected into a mold, a texture pattern is not formed on the molded product. Therefore, the manufacturing method of the molded product on which the embossed pattern is formed and the molded product on which the embossed pattern is formed are different from the manufacturing method and the injection molded product described in Japanese Patent No. 5220934.

  Applications of the molded article of the present invention include waterproof sheets, concrete molded waterproof materials, roof base materials, decorative decorative materials for decorative boards, underfloor waterproof materials, etc .; for civil engineering such as waterproof sheets and pipe protective materials; Materials, interior materials, etc. for vehicles; waterproof sheets, interior materials, etc. for ships; cosmetic bottles, product bottles, shopping bags, plastic bags, garbage bags, etc .; For agriculture such as bags, etc. What is necessary is just to process a molded article for various uses by cutting, heat sealing, etc. as needed.

  The present invention will be described in detail with reference to the following examples, which are provided merely for the purpose of illustrating the present invention and for reference to specific embodiments thereof. These exemplifications are for explaining specific specific embodiments of the present invention, but are not intended to limit or limit the scope of the invention disclosed in the present application.

[Preparation of master batch pellets]
Polypropylene (PP, AZ564 manufactured by Sumitomo Chemical Co., Ltd.) was used as the thermoplastic resin. Glass wool was produced by centrifugation, and the average fiber diameter was about 3.6 μm.

  The surface treatment of glass wool was performed by spraying a solution containing a silane coupling agent from a binder nozzle onto glass wool fiberized from a spinner. As the silane coupling agent, aminosilane coupling agent S330 (manufactured by JNC) was used. The weight percentage with respect to glass wool was 0.24 wt% for the silane coupling agent.

  Thereafter, the glass wool was dried at 150 ° C. for 1 hour, and then pulverized to an average fiber length of 850 μm by a cutter mill. Using the same-direction twin-screw kneading extruder ZE40A ((φ43 L / D = 40), manufactured by Berstorf Co.) as an extrusion molding machine, and a gravimetric screw feeder S210 (manufactured by K-Tron) as a measuring device, Glass wool was added and kneaded so that the content of glass wool was 40% by weight. The kneading conditions were as follows: screw rotation speed 150 rpm, resin pressure 0.6 Mpa, current 26-27 A, feed amount 12 Kg / hr. Moreover, the resin temperature of the polypropylene at the time of kneading | mixing heated 190-280 degreeC, and glass wool was heated and added to 100 degreeC. After kneading, master batch pellets were prepared.

[Production of bag by inflation method]
<Example 1>
As the inflation device, CO-MP manufactured by Sumitomo Heavy Industries Modern Co., Ltd. was used. First, a master batch pellet and high-density polyethylene (HDPE; HI-ZEX7000F manufactured by PRIME POLYMER) were blended so that the glass wool content was 4.5% by weight to prepare a resin mixture. Next, the resin mixture was melted and kneaded at 180 ° C. to 230 ° C. to prepare a melt-kneaded product. Next, a cylindrical body (molded product) was produced by extruding the melt-kneaded material from the annular discharge port. Next, the cylindrical body was cut into an appropriate size, and a part of the cut cylindrical body was heat sealed to prepare a bag. The bag thickness was about 35 μm. 2A is a photograph of the bag produced in Example 1. FIG.

<Comparative Example 1>
A bag was produced in the same manner as in Example 1 except that the master batch pellet was not added. The thickness of the bag was about 28 μm. FIG. 2 (B) is a photograph of the bag produced in Comparative Example 1.

  As is clear from FIGS. 2A and 2B, the bag produced in Example 1 had a wrinkle pattern formed on the entire surface. On the other hand, the surface of the bag produced in Comparative Example 1 was smooth.

<Example 2>
Instead of the high-density polyethylene of Example 1, low-density polyethylene (LDPE; Sumikasen F200-0 manufactured by Sumitomo Chemical Co., Ltd.) was used so that the glass wool content was 2% by weight, and the amount of air blown during inflation was set. By adjusting, a bag was produced in the same procedure as in Example 1 except that the thickness was about 9 μm. FIG. 3 is a photograph of the bag produced in Example 2. As is apparent from FIG. 3, the bag produced in Example 2 had a wrinkle pattern formed on the entire surface. Moreover, the opening of the bag could be easily opened.

<Example 3>
Next, a two-layer film was produced by coextrusion by an inflation method. One layer is blended with master batch pellets and low density polyethylene (LDPE; Sumikasen F200-0 manufactured by Sumitomo Chemical) so that the glass wool content is 10% by weight, and the resin mixture is melted and kneaded at 210 ° C. Thus, a melt-kneaded product was produced. For the other layer, a melt-kneaded material was prepared in the same procedure as that for one layer except that the master batch pellet was not added. Next, by using a CO-RD die rotating method (in-die lamination method in which contact is made by a route inside the mold) manufactured by Sumitomo Heavy Industries Modern Co., Ltd., two layers are formed by co-extrusion of the melt-kneaded material from an annular discharge port. A cylindrical laminated film was produced. The thickness of each layer was 75 μm.

  FIG. 4A is a photograph of the layer side containing glass wool, and FIG. 4B is a photograph of the layer side not containing glass wool. As is clear from FIGS. 4A and 4B, the layer to which glass wool was added had a texture pattern on the entire surface. On the other hand, the surface of the layer to which glass wool was not added was smooth. Moreover, each layer was firmly bonded without peeling.

<Example 4>
2 in the same manner as in Example 3 except that butyl rubber (Butyl 065 manufactured by JSR Corporation), which is a thermoplastic elastomer, was used instead of the low density polyethylene of Example 3 and the content of glass wool in one layer was 2% by weight. A laminated film of layers was produced. The thickness of each layer was 75 μm.

  FIG. 5A is a photograph of the layer side containing glass wool, and FIG. 5B is a photograph of the layer side not containing glass wool. As is clear from FIGS. 5A and 5B, the layer to which glass wool was added had a texture pattern on the entire surface. On the other hand, the surface of the layer to which glass wool was not added was smooth. Moreover, each layer was firmly bonded without peeling.

  From the above results, when producing a molded article by the inflation method, a grain pattern was formed on the surface without adding a special process by adding glass wool to the thermoplastic resin and / or thermoplastic elastomer. It became clear that molded articles could be manufactured.

[Production of film by T-die method]
<Example 5>
An SPS7000 manufactured by Sumitomo Heavy Industries Modern Co., Ltd. was used as the T-die device. First, a master mixture pellet and high-density polyethylene (HDPE; HI-ZEX7000F manufactured by PRIME POLYMER) were blended so that the glass wool content was 4% by weight to prepare a resin mixture. Next, the resin mixture was melted and kneaded at 230 ° C. to prepare a melt-kneaded product. Next, a film was produced by extruding the melt-kneaded material from a T die. The thickness of the film was 30 μm. FIG. 6A is a photograph of the film produced in Example 5.

<Comparative example 2>
A film was produced in the same procedure as in Example 5 except that the master batch pellet was not added. The film thickness was about 23 μm. FIG. 6B is a photograph of the film produced in Comparative Example 2.

  As is apparent from FIGS. 6A and 6B, a texture pattern was formed on the surface of the film produced in Example 5. On the other hand, the surface of the film produced in Comparative Example 2 was smooth. From the above results, by adding glass wool to the thermoplastic resin and / or thermoplastic elastomer, it is possible to produce a molded product having a texture pattern formed on the surface without adding any special process even in the T-die method. Became clear. Therefore, even in a T-die apparatus in which no wrinkled roller is arranged, a molded product on which a wrinkled pattern is formed can be produced.

[Production of cylindrical body by extrusion method]
<Example 6>
The extrusion device used was a tube device P-50 manufactured by Mars Seiki Co., Ltd. First, a master mixture pellet and high-density polyethylene (HDPE; HI-ZEX5000SF manufactured by PRIME POLYMER) were blended so that the glass wool content was 2.5% by weight to prepare a resin mixture. Next, the resin mixture was melted and kneaded at 235 ° C. to prepare a melt-kneaded product. Next, a cylindrical body was produced by extruding the melt-kneaded material from an extruded circular die. In addition, unlike the inflation method, the method of Example 6 does not send compressed air when extruding the melt-kneaded material. The thickness of the cylindrical body was 60 μm. FIG. 7A is a photograph of the extruded cylindrical body. As is apparent from FIG. 7A, a texture pattern was formed on the surface of the produced cylindrical body.

  FIG. 7B is a photograph of the cylindrical body after printing. In the conventional method, since the surface of the cylindrical body produced by the extrusion method is mirror-like, it is difficult to print directly on the extruded cylindrical body, and thus the printed seal is pasted on the cylindrical body. By adding glass wool to the resin or the like, a textured pattern is formed on the surface of the cylindrical body, so that it is possible to print directly on the cylindrical body.

  FIG. 7C is a photograph in which a spiral for tightening the cap is formed on the cylindrical body by a heat press. By filling the contents such as cosmetics and then heat-sealing, a cylindrical molded product can be produced.

[Tensile properties of film produced by inflation method]
<Example 7>
One layer is mixed with masterbatch pellets, butyl rubber (Butyl065 manufactured by JSR Corporation), and HDPE (HI-ZEX7000F manufactured by PRIME POLYMER) so that the glass wool content is 2% by weight. A two-layer laminated film is produced in the same procedure as in Example 3, except that master batch pellets and high-density polyethylene (HDPE; HI-ZEX7000F manufactured by PRIME POLYMER) are mixed so that the glass wool content is 2% by weight. did. The thickness of each layer was 75 μm.

<Comparative Example 3>
One layer is made of only high density polyethylene (HDPE; HI-ZEX7000F made by PRIME POLYMER), and the other layer is made of high density polyethylene (HDPE; HI-ZEX7000F made by PRIME POLYMER) and LDPE (NEO-ZEX2006H made by PRIME POLYMER). A two-layer laminated film was produced in the same procedure as in Example 3 except for mixing. The thickness of each layer was 75 μm.

  Next, the tensile strength of the film produced in Example 7 and Comparative Example 3 was examined. The tensile tester was KS D 3001: 2001 made by Galdavini under the experimental conditions of KSM4394. The test results are shown in Table 1.

  As is apparent from Table 1, the film added with the glass wool of Example 7 had substantially the same strength in the extrusion direction and in the vertical direction. On the other hand, the film to which the glass wool of Comparative Example 3 was not added had different strengths in the extrusion direction and the vertical direction. The inflation method is a method that can form a large number of films and sheets at a low cost, and it has been cited as one of the problems that the strengths in the vertical and horizontal directions of the produced films and sheets are different. However, it has become clear that this problem can be solved by adding glass wool to a resin or the like.

[X-ray transmission image of the produced film]
X-ray transmission images of the film produced by the inflation method in Example 1 and the film produced by the T-die method in Example 5 were taken. X-ray transmission images were taken using a HITACHI CS-SEMCS 4800 under the condition of 30 kV 180 μA. 8A is an X-ray transmission image of the film produced in Example 1, and FIG. 8B is an X-ray transmission image of the film produced in Example 5. As apparent from FIG. 8A, it was confirmed that the glass wool was dispersed in a random direction in the film. In Example 7 above, it was confirmed that the difference in strength between the longitudinal direction and the lateral direction of the produced film or sheet can be reduced by adding glass wool to the resin or the like. This is thought to be due to the dispersal. Further, as apparent from FIG. 8B, the glass wool was dispersed in a random direction even in the film produced by the T-die method. Therefore, the molded product produced by the T-die method can also reduce the difference in strength between the vertical direction and the horizontal direction.

  According to the method for manufacturing a molded product with a texture pattern according to the present invention, a molded product with a texture pattern can be manufactured using a conventionally used apparatus and without performing the texture processing. . Therefore, it is useful for the production of films, sheets, cylindrical bodies and the like.

Claims (12)

A method for producing a molded article on which a wrinkle pattern is formed, the production method comprising:
A melting step for producing a melt-kneaded material including at least a thermoplastic resin and / or a thermoplastic elastomer and glass wool;
Extrusion process for producing the molded product by extruding the melt-kneaded product from the discharge port of the extrusion mold by an extrusion molding method,
A cooling step for cooling the molded product extruded in the extrusion step,
Including
The texture pattern of the molded product is formed by the melting step, the extrusion step, and the cooling step.
A method for producing a molded article on which a wrinkle pattern is formed. The glass wool content is 1 to 20% by weight,
The manufacturing method of the molded article in which the embossed pattern of Claim 1 was formed. The extrusion method is an inflation method, and the molded product is a film, a sheet, or a cylindrical body,
The manufacturing method of the molded article in which the embossed pattern of Claim 1 or 2 was formed. The extrusion molding method is a T-die method, and the molded product is a film, a sheet, or a cylindrical body.
The manufacturing method of the molded article in which the embossed pattern of Claim 1 or 2 was formed. The extrusion molding method is a coextrusion method,
The molded product is formed as a laminated multilayer product,
At least one of the outer layers of the multilayer article is a layer formed by extruding a melt-kneaded material containing at least the thermoplastic resin and / or thermoplastic elastomer and glass wool.
The manufacturing method of the molded article in which the embossed pattern of Claim 1 or 2 was formed. The extrusion molding method is coextrusion by an inflation method,
The molded product is formed as a multilayer product,
At least one of the outer layers of the multilayer article is a layer formed by extruding a melt-kneaded material containing at least the thermoplastic resin and / or thermoplastic elastomer and glass wool.
The manufacturing method of the molded article in which the embossed pattern of Claim 3 was formed. The extrusion molding method is coextrusion by a T-die method,
The molded product is formed as a multilayer product,
At least one of the outer layers of the multilayer article is a layer formed by extruding a melt-kneaded material containing at least the thermoplastic resin and / or thermoplastic elastomer and glass wool.
The manufacturing method of the molded article in which the wrinkle pattern of Claim 4 was formed. A molded product on which a wrinkle pattern is formed,
Including at least a thermoplastic resin and / or a thermoplastic elastomer, and glass wool,
The glass wool content is 1 to 20% by weight,
The thickness of the molded product is 3 μm to 300 μm,
The glass wool is dispersed in a random direction in the molded article,
Molded product with wrinkle pattern. The molded article is a film, a sheet, or a cylindrical body,
A molded article on which the texture pattern according to claim 8 is formed. The molded product has a thickness of 3 μm to 250 μm,
The molded article is a film or a cylindrical body,
A molded product on which the texture pattern according to claim 9 is formed. The molded product has a thickness of 3 μm to 75 μm.
A molded article on which the texture pattern according to claim 10 is formed. The molded product is a multilayer product,
At least one of the outer layers of the multilayer article is a layer containing at least the thermoplastic resin and / or thermoplastic elastomer and glass wool.
A molded article on which the texture pattern according to any one of claims 8 to 11 is formed.