JP4773917B2 - Monolithic extruded body and building material - Google Patents

Description

  The present invention relates to an integrally extruded body containing an aluminum core material and a building member.

  Conventionally, as a method for producing a synthetic resin product with a core material, a synthetic resin product with a core material is obtained by lamination molding and / or extrusion molding with a synthetic resin using a metal core material having a resin adhesive applied to the surface. A method characterized by this is known (Patent Document 1). Specifically, a phenol-modified acrylic adhesive, a modified urethane adhesive, an adhesive composed of a silane coupling agent, etc. is applied to an aluminum core in advance, and the core is put into an extrusion molding machine to contain the core. A synthetic resin molding is obtained. However, in such a method, since it is necessary to apply an adhesive to the core in advance, the manufacturing is complicated and there is a problem in productivity.

Therefore, as a method with excellent productivity, in particular, as a method for manufacturing a plate material for construction, a metal plate having a predetermined thickness dimension, a width dimension, a longitudinal dimension, a uniform cross section in the longitudinal direction, and a corrugated plate shape is formed. Is a method of manufacturing a building plate material including a core material and a resin containing the core material, and a corrugated plate having a uniform cross section in the longitudinal direction, while transporting the metal strip material in the longitudinal direction. The first step of continuously forming the core material, the second step of continuously forming the resin molded product including the core material by the resin extrusion molding method, and the resin molded product formed in the second step have a predetermined length. And a third step of obtaining a unit plate material by cutting each unit (Patent Document 2). Specifically, composite extrusion molding (coextrusion molding) is performed on the surface of a corrugated core material having a thickness of about 0.3 to 1.0 mm together with a resin raw material. However, in such a method, the productivity is certainly improved, but since the synthetic resin is directly coated on the metal core material, the metal core material and the synthetic resin cause poor adhesion.
JP-A-62-13315 JP 2003-13543 A

In order to improve the adhesiveness, it is conceivable to emboss the surface of the metal core material in the technique of Patent Document 2. However, the processing is very complicated and it is extremely difficult to cope with an irregularly shaped core material other than a flat plate shape or a hollow core material.
Usually, an aluminum core material is subjected to a surface treatment called alumite treatment in order to improve corrosion resistance and wear resistance. In the anodizing treatment, an oxide film is formed on the surface of aluminum by electrolysis with an anode in an electrolytic solution that satisfies certain conditions. Since the aluminum film obtained by the treatment has fine pores, it adsorbs pollutants and corrosive substances, has insufficient corrosion resistance, and is easily contaminated. Therefore, a sealing treatment such as pressurized steam or Sealing treatment using nickel acetate is performed.
The present inventor has found that the adhesion performance is improved by paying attention to the alumite treatment process and specifying the presence or absence of the sealing treatment and the resin used for the coating layer, in particular, the adhesion performance after the water immersion treatment. The improvement was found. Furthermore, the present inventors have found that an integral extrusion molded article and a building member having sufficient adhesion between the coating layer and the aluminum core material and excellent in productivity are provided.

According to the present invention, the following inventions are provided.
1. An integral extruded body in which at least two or more coating layers made of synthetic resin are formed along the longitudinal direction of the core material on a part or all of the outer surface of the aluminum core material, In the covering layer, the synthetic resin layer in contact with the core material is a polyester-based resin layer, and the core material is subjected to an alumite treatment that does not involve a sealing treatment at least in the coating layer forming region. Integral extrusion molding.
2. 2. The integral extrusion molded article according to 1 above, wherein the polyester resin layer contains an epoxy resin and / or an inorganic filler.
3. A building member comprising the integrally extruded article according to any one of the above 1 or 2.

The integrally extruded product of the present invention improves the adhesion between the aluminum core material and the coating layer, particularly the adhesion between the core material after the water immersion treatment and the coating layer. Furthermore, when the coating layer has a multilayer structure, the adhesion performance of each layer is also extremely excellent.

  The integrally extruded product of the present invention is formed by forming a coating layer made of a synthetic resin on the outer surface of an aluminum core material. For example, as shown in FIG. 1, the coating layer 2 is continuously formed in the longitudinal direction L of the core material 1. In the circumferential direction C of the cross section of the core material 1, for example, the coating layer 2 may be formed continuously in the whole circumferential direction C as shown in FIG. 1 or may be formed in a part of the circumferential direction C. May be. FIG. 1 is a schematic sketch showing an example of the integrally extruded product of the present invention. In the present specification, the integral extrusion means that the resin for the coating layer is extruded and at the same time the layer is sequentially coated on the fed core material to be integrated, and is formed by such a method. This is called a monolithic extrusion.

  An aluminum core material is used for the core material of the present invention. Here, “made of aluminum” has a hollow or solid form made of aluminum or an aluminum alloy, and its overall shape is not particularly limited, and may be, for example, a flat plate shape, a rod shape, or the like. Usually, the core material is formed by extrusion molding of aluminum or aluminum alloy. In the present invention, “made of aluminum” includes “made of aluminum alloy” in its category.

  In the case where the core material has a hollow form, the thickness of the aluminum portion is preferably 1.0 mm or more, particularly 1.1 to 5.0 mm. Moreover, the whole dimension in case a core material has a hollow or solid form is not restrict | limited in particular, What is necessary is just to set suitably according to the use of the integral extrusion molding obtained.

  The core material of the present invention is subjected to an alumite treatment to form an alumite layer before forming a coating layer described later. The alumite treatment is a so-called anodizing treatment and is a treatment for obtaining an oxide film on the aluminum surface. In the present invention, the principle of a general anodizing method can be adopted as it is. As an example, a method of degreasing and cleaning a predetermined aluminum material, performing electrolytic polishing, washing with water, and then performing an anodic oxidation treatment in an electrolytic bath. As the electrolytic solution, a phosphoric acid solution, a sulfuric acid solution, a sulfamic acid solution, an oxalic acid solution, or the like can be used. The anodic oxidation treatment is performed by electrolytic treatment using an aluminum material as an anode in an electrolytic solution at 20 to 40 ° C. In a normal anodizing process, a sealing process is performed as a subsequent process. Sealing treatment is intended to prevent adverse effects such as a decrease in corrosion resistance due to the fine pores produced in the anodizing treatment, and uses treatment in pressurized water vapor or an aqueous solution of nickel acetate / cobalt acetate. It has been. However, in the present invention, the core material that is not subjected to the sealing treatment is used as the core material. This is because the adhesive force with the polyester resin is greatly improved due to the fine pores on the surface of the oxide film.

  The aluminum core material of the present invention preferably has a groove having a depth of about 0.03 to 1.0 mm along the longitudinal direction. It is because the further improvement of adhesiveness is seen by providing the said groove | channel. The depth and pitch of the grooves are shown as average values of values measured at arbitrary three locations per 1 m in the longitudinal direction of the core material. The measurement method is not particularly limited, but a method using a micro gauge is simple. The said groove | channel gives the core material which has a very uniform groove | channel by giving desired groove shape to the extrusion die of aluminum, for example, and extruding aluminum from the said die | dye. In addition, this invention does not prevent that a core material has the unevenness | corrugation by a groove | channel and embossing of a direction substantially perpendicular | vertical with respect to the said longitudinal direction other than the groove | channel of a core material longitudinal direction, for example.

In the present invention, at least two coating layers made of synthetic resin are formed along the longitudinal direction of the core material.
In the present invention, the synthetic resin layer (2A) in contact with the core material is a polyester resin layer.
Examples of the polyester resin include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexadimethylene terephthalate, copolymerized polyesters thereof, and saturated copolymerized polyester resins. As long as the adhesiveness is not impaired, the above polyester resins are mixed with polyolefin resins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene and acrylic acid derivatives, etc. May be.

These polyester resins show very favorable adhesiveness with the aluminum core material. As described above, since the aluminum core material is not subjected to the sealing treatment after the alumite treatment, it has an oxide film having fine pores on the surface. Because of the presence of these micropores, for example, EVA resin or the like improves the adhesion due to the anchor effect, but due to the presence of the micropores, the adhesive strength under submerged conditions decreases. In addition, even if a polyethylene resin with low water absorption has a micropore in an aluminum core material, adhesiveness is very weak. That is, by using a polyester-based resin, it has an adhesive force with respect to the aluminum core material and can maintain the adhesive performance even under water immersion treatment conditions. Further, the polyester resin is bonded to an acrylic resin such as a polymethyl methacrylate resin (hereinafter referred to as PMMA resin) or a methyl methacrylate-styrene copolymer resin (hereinafter referred to as MS resin) that is usually used as the coating layer (2B). Excellent in properties. Therefore, an integrally extruded product having excellent adhesion to both the core material and the coating layer (2B) can be obtained.

It is preferable to mix an inorganic filler such as epoxy resin, talc, barium sulfate, barium carbonate, mica, and titanium oxide with the polyester resin. This is because the polyester-based resin has a low viscosity, is difficult to be laminated on the aluminum core material with a uniform thickness, may cause uneven adhesion, and is extremely difficult to mold. If it is a method of applying to the core material as in the prior art, it is preferable that the viscosity is low. Since the resin flows, molding becomes very difficult. Therefore, by mixing an epoxy resin and an inorganic filler and increasing the viscosity, it becomes easy to laminate a polyester-based resin on the aluminum core material to a uniform thickness, and adhesion unevenness is unlikely to occur and molding is easy. is there. In addition, as for the melt index (based on JIS-K-7210: 190 degreeC, 2.16 kg) of a polyester-type resin layer, 10-50 g / 10min is preferable.

  The material of the synthetic resin layer (2B) that does not come into contact with the core material in the coating layer is not particularly limited. For example, polyvinyl chloride resin (hereinafter referred to as PVC resin), acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as PVC resin). , ABS resin), acrylonitrile-styrene-acrylic rubber copolymer resin (hereinafter referred to as ASA resin), polystyrene resin, high-impact polystyrene resin, acrylonitrile-styrene copolymer resin (hereinafter referred to as AS resin), silicone composite rubber modified Acrylonitrile-styrene copolymer resin (hereinafter referred to as SAS resin), modified polyphenylene ether resin, polyethylene resin, polypropylene resin, polymethyl methacrylate resin (hereinafter referred to as PMMA resin), methyl methacrylate-butyl acrylate copolymer resin Methyl methacrylate - styrene copolymer resin (hereinafter, referred to as MS resin) acrylic resin or polyester resin or a mixed resin or the like of these and the like. Particularly preferred from the viewpoints of moldability, toughness, and economy are PVC resin, ABS resin, SAS resin, AS resin, ASA resin, and PMMA resin, and these resins themselves are harder. These synthetic resins include fillers such as calcium carbonate, talc, mica, and shirasu balloons, lightweight materials, reinforcing materials such as glass fibers and cellulose fibers, flame retardants, other heat stabilizers, and synthetic resins such as lubricants. Various additives added to the molded body can be included.

A preferred configuration of the coating layer is shown below. However, it is not limited to the following configurations. In addition, the layer described at the beginning is a layer in contact with the core material, and shows a layer approaching the outermost surface layer in order, and the layer described at the end is the outermost surface layer;
(1) Layer made of polyester resin containing epoxy resin and / or inorganic filler-Transparent protective layer made of PMMA resin;
(2) A layer made of a polyester resin containing an epoxy resin and / or an inorganic filler-a surface decoration layer made of a colored SAS resin having a seed agent;
(3) Layer made of polyester resin containing epoxy resin and / or inorganic filler-Decorative layer made of PMMA resin having seed material or decorative powder-Surface layer made of PMMA resin

The coating layer 2 formed on the outer surface of the core material is made of a synthetic resin. Usually, it is a non-foamed layer, but it may be a low-foamed layer of twice or less.
The total thickness of the coating layer is preferably 0.3 mm or more, more preferably 0.5 mm or more, from the viewpoints of hardness, wearability, and production stability. The thickness of the layer in contact with the core material (so-called inner layer) is extremely preferably at least greater than the groove depth of the core material from the viewpoint of adhesiveness. In particular, when the thickness of the coating layer is 0.6 mm or more, when the surface decoration layer is formed, stable decoration expression is possible. The upper limit of the thickness is not particularly limited, but is 3 mm or less, preferably 2 mm or less, in view of excessive resin pressure during integral molding, productivity and cost.

  The monolithic extruded product of the present invention is manufactured by a so-called monolithic extrusion method in which the coating layer is integrated with the core material simultaneously with the extrusion molding of the coating layer from the viewpoint of productivity, long product molding, and constant product characteristics. The In particular, in the case of producing an integral extrusion molded body having a coating layer composed of two or more synthetic resin layers, it is produced by a coextrusion type integral extrusion machine as shown in FIG. Specifically, the resin extruded from each of the extruders 21 and 22 for melting and kneading the resin forming each synthetic resin layer is laminated in one die 23, and at the same time, the layer is fed in the longitudinal direction. The core material 1 having the grooves is sequentially coated and integrated. Once integrated, it is usually cooled and cut to the desired dimensions. Although two extruders are used in FIG. 2, the present invention is not limited to this, and it may be appropriately installed according to the number of synthetic resin layers constituting the coating layer.

  The integral extruded body of the present invention does not need to cover the entire surface of the aluminum core with a synthetic resin. For example, as long as it has a substantially rectangular cross section as shown in FIG. 1, the upper and lower surfaces may be covered, and the side surfaces may be covered such that the core material is exposed. In addition, the present invention includes a case where only a portion that appears as an external appearance is covered if it is a building member.

[Core]
The following three types of aluminum alloy core materials were used.
Core material A: Anodized (no sealing treatment)
Core material B: Anodized (sealed)
Core material C: No alumite treatment The alumite treatment is performed using a general sulfuric acid method. Further, the sealing treatment uses a method using nickel acetate. Furthermore, a groove having a depth of 0.1 mm is provided along the longitudinal direction by so-called knurling on the entire circumference. Each of the aluminum cores has a rectangular parallelepiped shape and has a total width of 40 mm, a total height of 15 mm, and a total length of 3 m. The thickness of the aluminum part is 1.2 mm. In order to prevent deformation due to resin pressure during molding, the hollow has two ribs.

[Material of inner layer]
Three types of inner layer resins shown below were used.
Inner layer a: polyester resin (“Aron Melt” manufactured by Toagosei Co., Ltd., melting point 115 ° C., melt index 35 g / 10 min, EVA resin 10%, epoxy resin 20%, inorganic filler 10%)
Inner layer b: polyester resin (“Aron Melt” manufactured by Toagosei Co., Ltd., melting point 125 ° C., melt index 40 g / 10 min, containing about 15% polyethylene resin)
Inner layer c: polyester resin (“Aron Melt” manufactured by Toagosei Co., Ltd., melting point 135 ° C., melt index 60 g / 10 min)
Inner layer d: Ethylene-based resin (Mitsui / DuPont Polychemical's “High Milan”, melting point 91 ° C., melt index 5 g / 10 min)

[How to create an evaluation sample]
Example 1
Two integrally extruded samples were produced by the coextrusion type integral extruder shown in FIG. Specifically, the synthetic resin of the outer layer 2B (outermost surface layer) and the inner layer 2A (layer in contact with the core material) is simultaneously extruded from the outer layer extruder 22 and the inner layer extruder 21, respectively, and the aluminum core material in the die 23. 1 was laminated and coated to produce an integrally extruded body having a two-layer coating layer on the entire outer surface of the aluminum core material in the circumferential direction. In addition, extrusion conditions, extrusion resin, and core material conditions are as follows.
Outer layer extruder: 40φ, single screw extruder (extrusion temperature about 180 ° C)
Inner layer extruder: 40φ, single screw extruder (extrusion temperature about 150 ° C)
Inner layer resin: The inner layer a was used. The inner layer thickness after cooling is 0.3 mm.
Outer layer resin: PMMA resin (“Acrypet” manufactured by Mitsubishi Rayon Co., Ltd.) was used. The outer layer thickness after cooling is 0.5 mm.
Core material A is used as the aluminum core material. Preheating (about 100 ° C.) is performed immediately before insertion into the die.

(Examples 2-3 and Comparative Examples 1-3)
An integrally extruded product was produced in the same manner as in Example 1 except that the aluminum core material and the inner layer resin shown in Table 1 were used.

[Evaluation methods]
-Adhesiveness after normal temperature storage First, after preparing a sample, it was stored at normal temperature for 24 hours, and an adhesiveness test was conducted according to the JISK5400: 1990 8.5.2 cross cut tape test. Specifically, a grid was created on the sample surface. The grids were created with a cutter knife, the interval between the cuts by the cutter knife was 2 mm, and the total number of grids was 100. The method of applying the tape and the method of removing the tape were performed according to the JIS method. In the evaluation results in Table 1, the numerator is the number of grids that did not peel, and the denominator is the total grid number.
The adhesion test was performed at the center in the longitudinal direction of the integrally extruded body. In addition, when there is even one peeling grid, the integral extrusion molded body is not preferable.

-Adhesiveness after immersion test Further, another sample was stored at room temperature for 24 hours after sample preparation, and then immersed in water at room temperature for 30 days. After the immersion, it was stored and dried again at room temperature for 24 hours, and the same adhesion test as described above was performed. The results are shown in Table 1.

-Formability About the Example sample, the ease of occurrence of thickness unevenness during extrusion molding was confirmed, and the formability was evaluated as follows.
A: Thickness unevenness hardly occurs and molding is easy.
○: Some unevenness in thickness is seen, and it takes some time for molding.
(Triangle | delta): Thickness nonuniformity is seen, shaping | molding is difficult, and shaping | molding requires time considerably.

  The integrally extruded body with an aluminum core material of the present invention is useful as a building material such as a decorative material for construction, a handrail for construction, a face grid for security, a deck material, and a balcony louver.

It is a general | schematic sketch showing an example of the integral extrusion molding of this invention. It is a schematic sectional drawing of the coextrusion type integral extrusion molding machine for manufacturing the integral extrusion molding of this invention.

Explanation of symbols

1: Core material, 2: Coating layer, 21:22: Extruder, 23: Dice.

Claims (3)

  An integral extruded body in which at least two or more coating layers made of synthetic resin are formed along the longitudinal direction of the core material on a part or all of the outer surface of the aluminum core material, In the covering layer, the synthetic resin layer in contact with the core material is a polyester-based resin layer, and the core material is subjected to an alumite treatment that does not involve a sealing treatment at least in the coating layer forming region. Integral extrusion molding.   The monolithic extruded product according to claim 1, wherein the polyester resin layer contains an epoxy resin and / or an inorganic filler. A building member comprising the integrally extruded product according to claim 1.

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