JP5049239B2 - Thermoplastic resin extruded body and method for preventing raindrops on thermoplastic resin extruded body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin extruded molding which prevents adhesion of dirt such as raindrop traces over a long period of time. <P>SOLUTION: The thermoplastic resin extruded molding is obtained by extrusion molding a thermoplastic resin composition containing at least one of 0.1-2.0 pts.mass of a silicone oil and 5-30 pts.mass of silica as a silicon component based on 100 pts.mass of a thermoplastic resin having hydrophilic groups. The silicone oil or silica provides the surface of the extruded molding with high water-sliding property. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to a thermoplastic resin extrusion molded article used as an exterior member around a house, for example, a rain gutter, and a method for preventing raindrops on the thermoplastic resin extrusion molded article .

  The exterior members used outdoors such as rain gutters may have raindrops attached to the front, bottom, and back surfaces of the rainwater due to the action of rainwater, and the raindrops may become noticeable as dirt and impair the appearance. In particular, there is a strong demand to improve antifouling properties so that raindrop traces are likely to adhere to molded products produced by molding vinyl chloride resin, etc., and such raindrop traces are less likely to adhere to resin molded products. Has been.

  Therefore, conventionally, in order to improve the antifouling property of the resin molded body, the surface of the resin molded body is lubricated by applying a silicon-based or fluorine-based coating treatment or a film. In order to prevent raindrops from occurring, the rainwater adhering to the surface is prevented from slipping immediately and remaining.

  However, if the surface of the resin molded body is subjected to a paint treatment or a film is applied, the number of man-hours increases and the manufacturing cost increases, and the coating film wears away during long-term use or the film peels off. As a result, the antifouling property is deteriorated, and there is a problem that it is difficult to prevent raindrops from adhering over a long period of time.

Further, for example, there is a proposal that a sliding strip is kept low over a long period of time by molding a weather strip as an exterior member with an olefin-based thermoplastic elastomer containing a silicone-based silicone oil (Patent Document 1). No attempt has been made to prevent dirt such as raindrops from attaching.
JP 2004-306937 A

The present invention has been made in view of the above points, and is capable of preventing the adhesion of dirt such as raindrops over a long period of time . The object is to provide a prevention method .

The thermoplastic resin extrusion-molded article according to the present invention has a silicone oil of 0.1 to 100 parts by weight of a thermoplastic resin having a hydrophilic group and a kinematic viscosity of 50 to 100,000 mm ² / s (25 ° C.) as a silicon component. A thermoplastic resin composition containing 2.0 parts by mass and at least one of 5 to 30 parts by mass of silica is coated by extrusion molding on the surface of a core formed of at least one of a metal and a thermoplastic resin . At the same time, it is characterized in that a water drop having a sharp upper end is formed upward .
The thermoplastic resin extrusion-molded article according to the present invention has a silicone oil of 0.1 to 100 parts by weight of a thermoplastic resin having a hydrophilic group and a kinematic viscosity of 50 to 100,000 mm ² / s (25 ° C.) as a silicon component. A thermoplastic resin composition containing 2.0 parts by mass and at least one of 5 to 30 parts by mass of silica is coated with a base layer of a thermoplastic resin on the surface of a core formed of a metal, and the surface of the base layer It is characterized by being formed by being extruded and coated and having a water drop with a sharp upper end directed upward.

In the thermoplastic resin extrusion molded article, the surface of the inner from the Shino Mizuochi upper is preferably inclined downward toward the inside at an angle of greater than 0 °.

In the thermoplastic resin extrusion molded article, a surface of the outer from the Shino Mizuochi upper is preferably inclined downward toward the outside at an angle greater than the sliding angle of water.

  According to the present invention, by containing silicone oil or silica in a predetermined amount in a thermoplastic resin having a hydrophilic group, the surface of an extrusion-molded body extruded with this thermoplastic resin composition has high water slidability. The antifouling property can be maintained over a long period of time without the need for painting treatment or film sticking.

  Hereinafter, the best mode for carrying out the present invention will be described.

  In the thermoplastic resin composition used in the present invention, those having a hydrophilic group in the molecule are used as the thermoplastic resin as the main component. Examples of this hydrophilic group include esters (—COO—), ethers (—O—), cyano (—CN) and the like, and as thermoplastic resins having such hydrophilic groups, Although not limited, acrylic resin, polycarbonate, ABS (acrylonitrile-butadiene-styrene copolymer), ASA (acrylonitrile-styrene-acrylate), and the like can be used.

  By using a thermoplastic resin having a hydrophilic group in this way, it becomes easy to cause an affinity with water although it is weak on the surface of an extruded product extruded with the thermoplastic resin composition, and the antifouling property of the surface Can be further enhanced.

  The above-mentioned acrylic resin is not particularly limited in molecular weight, but it is preferable to use a resin having a melt flow rate (MFR: measurement conditions of 230 ° C., 37.3 N) in the range of 1 to 35 g / 10 min. Examples of such commercially available acrylic resins include “LG” and “LG2” manufactured by Sumitomo Chemical Co., Ltd., “MF” and “VH5” manufactured by Mitsubishi Rayon Co., Ltd., “GF” and “manufactured by Kuraray Co., Ltd. EH "etc.

It is preferable to add rubber to this acrylic resin. The rubber is not particularly limited, but butadiene rubber, butyl rubber, acrylic rubber, silicon rubber and the like can be used. Moreover, although the addition amount of rubber | gum is not specifically limited, The range of 10-60 mass parts is preferable with respect to a total of 100 mass of an acrylic resin and rubber | gum. By adding rubber, which can enhance the impact resistance compensates for the low elasticity of the acrylic resin, it is those that can be improved the impact resistance of the molded article. If the added amount of rubber is less than 10 parts by mass, the effect of improving the impact resistance due to the addition of rubber cannot be sufficiently obtained. Conversely, if the added amount of rubber exceeds 60 parts by mass, the amount of rubber is excessive. As a result, the weather resistance of the molded article decreases, and the moldability deteriorates.

  In addition, it is desirable to use a rubber in which a silicon compound is coated on a part or the entire surface of the rubber. As this silicon compound, silicon resin, silane coupling agent, or the like can be used. When the surface of rubber is coated with a silicone resin, the silicone resin is preferably grafted and bonded to rubber molecules. Thus, by using the rubber | gum coat | covered with the silicon type compound, the water resistance of rubber | gum can improve and it can suppress deterioration.

  The present invention uses a thermoplastic resin composition prepared by blending silicone oil or silica with the above-mentioned thermoplastic resin having a hydrophilic group.

Any silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil can be used. Among them, dimethyl silicone oil is preferable, and as a commercially available product, for example, “KF96 series” manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Silicone oils having various viscosities are provided. For example, in the “KF96 series”, “KF96-30cs” has a kinematic viscosity of 30 mm ² / s, “KF96-50cs” has a kinematic viscosity of 50 mm ² / s, “ KF96H-1 million in cs "is a kinematic viscosity 10000 mm ² / s," KF96H-10 million in cs "is a kinematic viscosity 100,000 mm ² / s," KF96H-30 million in cs "kinematic viscosity of 300000mm ² / s. These kinematic viscosities are measured values at 25 ° C., and the kinematic viscosities are values measured in accordance with “Crude oil and petroleum products—kinematic viscosity test method and viscosity index calculation method” of JIS K2283.

In the present invention, the silicone oil preferably has a kinematic viscosity in the range of 50 to 100,000 mm ² / s (25 ° C.). When the kinematic viscosity of the silicone oil is less than 50 mm ² / s, the silicone oil becomes easy to bleed on the surface of the molded product obtained by extruding the thermoplastic resin composition to which the silicone oil is added. It becomes difficult to maintain the lubricity over a long period of time. On the other hand, when the kinematic viscosity of the silicone oil exceeds 100,000 mm ² / s, in preparing the thermoplastic resin composition by adding the silicone oil, the dispersibility is deteriorated, and there is a possibility that variation in the provision of the lubricity occurs. is there.

  The compounding quantity of this silicone oil is set to the range of 0.1-2.0 mass parts with respect to 100 mass parts of thermoplastic resins. By blending the silicone oil, it is possible to increase the lubricity of the surface of the extruded product as described later. When the blending amount of the silicone oil is less than 0.1 parts by mass, the lubricity is sufficiently increased. It cannot be increased. On the other hand, when the blending amount of the silicone oil exceeds 2.0 parts by mass, the molding material slips during extrusion molding, resulting in poor moldability such as a reduction in molding speed.

  Further, the silica is not particularly limited, but it is preferable to use a powder having a particle size of about 1 to 10 μm. The amount of silica is set in the range of 5 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin. By blending silica, the water sliding property of the surface of the extrusion-molded product can be increased as will be described later. When the amount of silica is less than 5 parts by mass, the sliding property cannot be sufficiently increased. . On the contrary, when the compounding amount of silica exceeds 30 parts by mass, silica is exposed on the surface of the molded body obtained by extrusion molding, the appearance is impaired, and the product cannot be used.

  In the present invention, either silicone oil or silica may be blended alone, or both may be blended together.

  In addition to the thermoplastic resin, silicone oil, silica, and rubber, the thermoplastic resin composition used in the present invention may contain an ultraviolet absorber or a hindered amine light stabilizer. Thus, by combining the ultraviolet absorber and the hindered amine light stabilizer in combination, it is possible to improve the weather resistance of the resin molded article, and to compensate for the decrease in weather resistance due to the addition of rubber. It can be done.

  Although it does not specifically limit as a ultraviolet absorber, A benzotriazole type, a benzophenone type, a salicylate type, and a triazine type ultraviolet absorber can be used.

  For example, as a benzotriazole ultraviolet absorber, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-octylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenyl Benzotriazole), methyl-3- [3-tert-butyl-5- (2H-benzotria) Condensation product of sol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol (molecular weight 300) (“TINUVIN 1130” manufactured by Ciba Specialty Chemicals Co., Ltd.), isooctyl-3- [3- (2H-benzo Triazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate ("TINUVIN 384" manufactured by Ciba Specialty Chemicals Co., Ltd.), 2- (3-dodecyl-5-methyl-2-hydroxyphenyl) Benzotriazole (“TINUVIN571” manufactured by Ciba Specialty Chemicals Co., Ltd.), 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2 ′ -Hydroxy-3 ', 5'-di-ter -Amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6 '' -Tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl ) Phenol], 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (“TINUVIN900” manufactured by Ciba Specialty Chemicals) can do.

  Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone 2,2′-dihydroxy-4,4′dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxy-2 '-Cal Carboxymethyl benzophenone, and the like can be exemplified 2-hydroxy-4-stearyloxy benzophenone.

  Examples of salicylate ultraviolet absorbers include pt-butylphenyl salicylate and 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.

  Examples of the triazine-based ultraviolet absorber include hydroxyphenyl triazine-based “TINUVIN400”, “TINUVIN411L”, “TINUVIN1577FF” manufactured by Ciba Specialty Chemicals Co., Ltd., and “CYASORB UV- 1164 "and the like.

  The blending amount of the ultraviolet absorber is preferably in the range of 0.1 to 1.0 part by mass with respect to 100 parts by mass of the thermoplastic resin (the total amount with the rubber when blending rubber). The effect which improves the weather resistance of a resin molding cannot fully be acquired as the compounding quantity of a ultraviolet absorber is less than 0.1 mass part. On the other hand, when the amount exceeds 1.0 part by mass, the amount of the ultraviolet absorber becomes excessive, the ultraviolet absorber is bleed on the surface of the resin molded body, and the appearance of the resin molded body is impaired. Therefore, by setting the blending amount of the ultraviolet absorber within the above range, the weather resistance of the resin molded product can be improved while preventing bleeding.

  As the hindered amine light stabilizer, a high molecular weight type hindered amine light stabilizer and a low molecular weight type hindered amine light stabilizer can be used. The high molecular weight type hindered amine light stabilizer has a molecular weight of 2000 or more and less than 5000, and particularly preferably has a molecular weight in the range of 2000 to 3000. The low molecular weight type hindered amine light stabilizer has a molecular weight of 200 or more and less than 2000, and preferably has a molecular weight in the range of 300 to 600. In addition, molecular weight means a number average molecular weight, and is a value measured by a gel permeation chromatography method.

  As the high molecular weight type hindered amine light stabilizer, poly ((6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl) ((2, 2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)), N, N ′, N ″, N ″ '-Tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane -1,10-diamine and a mixture of (dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol), dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6 And tetramethyl-4-piperidyl-1,6-hexamethylenediamine N-(2,2,6,6 Tetoramechireru 4-piperidyl) polycondensates of butylamine and the like can be exemplified.

  Low molecular weight type hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, 1- [2- [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propynyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] -2,2,6 , 6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl Mixture of sebacate (“TINUVIN292” manufactured by Ciba Specialty Chemicals Co., Ltd.), bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, manufactured by Ciba Specialty Chemicals Co., Ltd. “TINUVIN123” and the like can be exemplified.

  The blending amount of the hindered amine light stabilizer is 0 to 0.5 mass of the high molecular weight type hindered amine light stabilizer with respect to 100 parts by mass of the thermoplastic resin (when rubber is blended, the total amount with the rubber). Part, a low molecular weight type hindered amine light stabilizer is set in the range of 0.1 to 1.0 part by mass. The effect of improving weather resistance by blending a hindered amine light stabilizer can be obtained mainly by a low molecular weight type hindered amine light stabilizer, and a high molecular weight type hindered amine light stabilizer is not an essential component. When the resin molding is exposed for a long period of time, the high molecular weight type hindered amine light stabilizer gradually appears near the surface after the low molecular weight type hindered amine light stabilizer is consumed and the effect is reduced. Can compensate for the decrease in the effect of the low molecular weight type. When the blending amount of the low molecular weight type hindered amine light stabilizer is less than 0.1 parts by mass, the weather resistance of the resin molded product cannot be sufficiently improved. On the other hand, when the blending amount of the low molecular weight type hindered amine light stabilizer exceeds 1.0 part by mass, the surface of the resin molding may be bleed and the appearance may be impaired. Moreover, when the compounding quantity of a high molecular weight type hindered amine light stabilizer exceeds 0.5 mass part, there exists a possibility that it may bleed on the surface of a resin molding similarly, and there exists a possibility that a weather resistance may fall on the contrary. As described above, the high molecular weight type hindered amine light stabilizer is not an essential component, but by using the low molecular weight type and this high molecular weight type hindered amine light stabilizer in combination, the weather resistance of the resin molded product can be maintained over a long period of time. Therefore, it is more preferable to add the high molecular weight type hindered amine light stabilizer in the range of 0.05 to 0.5 parts by mass.

  The thermoplastic resin composition used in the present invention may further contain a colorant and, if necessary, an antioxidant and a lubricant. As the lubricant, any hydrocarbons, fatty acids, higher alcohols, metal soaps, and the like can be used.

  A thermoplastic resin composition can be prepared by blending the above components. At this time, the silicone oil is blended by a method of adding silicone oil together with pellets or powders of other materials, a method of adding silicone oil by a side feeder while other materials are being kneaded.

  This thermoplastic resin composition is a molding material suitable for extrusion molding. By extrusion molding, an exterior member around the house used in a place where rainwater acts can be produced.

  Thus, the extrusion molded object shape | molded as an exterior member contains silicone oil and silica as a silicon component. When silicone oil is contained, the surface of the extrusion molded body becomes water-repellent by the action of silicone oil. When rain water acts on the surface of the extrusion molded body, the rain water is repelled into water droplets, and the extrusion molded body It becomes easy to slip off the surface. When silica is contained, the surface of the extruded product becomes hydrophilic due to the action of silica, and when rainwater acts on the surface of the extruded product, the rainwater wets and spreads and slides on the surface of the extruded product. It becomes easy to fall. In this way, even when either silicone oil or silica is contained, the surface of the extruded molded body has high water slidability. It can be prevented from remaining on the surface of the extruded product, and the raindrop can be prevented from attaching to the surface of the extruded product as dirt. Accordingly, it is not necessary to apply a coating treatment or a film to the surface of the extruded molded body, and the lubricity is expressed by the action of silicone oil or silica contained in the extruded molded body. And the antifouling performance by sliding property can be maintained high over a long period of time.

  When producing an extruded product by extruding a thermoplastic resin composition, suitable exterior members include window frames and air conditioner covers that have the same cross-sectional shape, and rain gutter members such as eaves and vertical eaves. ing. FIG. 1A shows eaves A, and is an example in which eaves A is produced by extruding the above-described thermoplastic resin composition containing silicone oil or silica. In the eaves bowl A, a reinforcing ear 2 is provided at the upper end on the outdoor side of the bowl body 1 formed in a U-shaped cross section having an upper surface opened. And the upper end part of this ear | edge part 2 is formed as the water drop 3 in which the upper end sharpened upwards over the full length of the ear | edge part 2. As shown in FIG.

  In the eaves bowl A, the ear part 2 is usually formed as a horizontal surface 2a at the upper end as shown in FIG. For this reason, even if silicone oil or silica is blended as described above to increase the water slidability of the surface of the eaves A, rainwater does not flow easily on the horizontal surface 2a. By dripping the outer surface of the eaves A on the outdoor side, a raindrop is likely to be generated on the outer surface of the eaves A. Therefore, in the above-described FIG. 1A, the horizontal surface 2a is not formed on the upper surface of the ear portion 2 by forming the upper end portion of the ear portion 2 as a water drop 3 that is pointed upward. For this reason, rainwater does not stay on the upper surface of the ear part 2, and raindrops caused by dripping of the accumulated rainwater do not adhere to the outer surface of the eaves A.

Here, when the water drop 3 is formed at the upper end of the ear 2 of the eaves A as described above, the surface from the top of the upper end of the water drop 3 to the inside (indoor side) is inward at an angle exceeding 0 °. It is formed so as to incline downward. In this way, by forming the surface 3a that slopes downward from the upper end of the water drop 3 toward the inside, the rain water that has fallen on the inside from the top of the water drop 3 is outside the eaves A. Without flowing to the (outdoor side), everything flows inward by this inclined surface 3a and flows into the interior of the eaves wall A, and raindrops are attached to the outer surface of the eaves wall A. It can be prevented. The inclination angle theta ₁ of the surface 3a may be any angle more than 0 ° but, more preferably the inclination angle theta ₁ is large, it is more preferable in practice the inclination angle theta ₁ is in the range of 20 to 130 ° .

Moreover, the surface from the upper end of the water drop 3 to the outside (outdoor side) is formed so as to incline downward toward the outside at an angle exceeding the water fall angle. Here, the falling angle of water refers to an angle at which a water droplet starts to slide down when it is gradually tilted after dropping 50 μl of ion-exchanged water on a horizontal surface. In this way, by forming the surface outside the top of the water drop 3 on the surface 3b inclined at an angle exceeding the water fall angle, the rainwater that has fallen on the outside from the top of the water drop 3 becomes dripping. It is possible to prevent the raindrops from occurring on the outer surface of the eaves A on the outdoor side. The eaves A produced in the present invention contains silicone oil and silica and has a high surface slipperiness, so that the falling angle of water is as small as about 40 ° or less. Therefore, the inclination angle theta ₂ of the surface 3b inclined at an angle greater than the sliding angle of the water may be at least about 40 °. The inclination angle θ ₂ is preferably as large as possible, and most preferably θ ₂ = 90 ° at which the surface 3b becomes a vertical surface.

  In the above embodiment, an example is shown in which the drainage 3 is formed at the upper end of the ear 2 of the eaves bowl A. However, the present invention is of course not limited to this, and the drainage is dropped at the upper end. By forming 3, it is possible to make it difficult to cause raindrops on the outer surface facing the outdoor side.

  In performing the extrusion molding, the thermoplastic resin composition is formed into a single layer as shown in FIG. 1 using only the thermoplastic resin composition containing the silicone oil and silica, and the thermoplastic resin composition is integrally extruded on the surface of the core 4. You can also. FIG. 2 (a) shows an example in which this thermoplastic resin composition is integrally extruded on the core 4, while the long core 4 is sent through the extrusion die 5, and from the extruder 6. By supplying the thermoplastic resin composition to the extrusion mold 5 and molding, a coating layer 7 made of a thermoplastic resin composition containing silicone oil or silica is formed on the surface of the core 4 as shown in FIG. The coated extruded product 8 can be obtained. In this case, in addition to forming the coating layer 7 on both surfaces of the core 4 as shown in FIG. 2B, the coating layer 7 can be formed only on one surface of the core 4.

  Further, the core 4 may have an irregular cross-sectional shape in addition to a planar shape. For example, the core 4 having a U-shaped cross section with an upper opening as shown in FIG. 3A or an upper surface as shown in FIG. By using a core 4 having a C-shaped cross section of the opening, a cover layer 7 is formed by integrally extruding a thermoplastic resin composition containing silicone oil or silica on the surface of the core 4 to form an eaves A. A molded body can be produced. In the eaves A of FIGS. 3A and 3B, the coating layer 7 made of a thermoplastic resin composition containing silicone oil or silica is formed only on the outer surface of the eaves A that requires antifouling properties. I have to do it.

  As such a core 4, what was formed with metal materials, such as a steel plate, and what was shape | molded with the thermoplastic resin or the thermosetting resin can be used. As the thermoplastic resin, ABS resin, polyvinyl chloride, polyethylene, polypropylene, polyethylene terephthalate, polyethylene terephthalate and ABS alloy resin, and the like can be used. A recycled resin obtained by recycling the resin can also be used.

  In the embodiment of FIG. 2A described above, the core 4 formed in advance is used, and the thermoplastic resin composition is applied to the surface of the core 4 from the extruder 6 while passing the core 4 through the extrusion mold 5. The surface of the core 4 is coated with the coating layer 7 by extrusion molding. However, in the embodiment of FIG. 4A, the thermoplastic resin containing the silicone oil or silica described above in the extrusion mold 5 is used. An extruder 6 for extruding the composition and an extruder 9 for extruding the resin for the core 4 are connected. In this case, the core 4 formed by extruding the thermoplastic resin composition from the extruder 6 to the extrusion mold 5 while molding the core 4 with the resin extruded from the extruder 9 to the extrusion mold 5. The above-described thermoplastic resin composition can be extruded on the surface of the core, and an extruded product 8 in which the surface of the core 4 is coated with the coating layer 7 can be formed. For example, FIG. ) Can be produced.

  According to the method of FIG. 4A, the core 4 can be molded even if it has a hollow cylindrical shape, and the core 4 is formed into a cylindrical shape by the resin extruded from the extruder 9 to the extrusion mold 5. While molding, a thermoplastic resin composition containing silicone oil or silica is extruded from the extruder 6 onto the surface of the core 4, so that, for example, a round vertical bowl B as shown in FIG. A square-shaped vertical collar B as shown in FIG. 4 (c) can be produced. 4 (b) and 4 (c), the coating layer 7 made of a thermoplastic resin composition containing silicone oil or silica is applied only to the outer surface of the vertical basket B that requires antifouling properties. It is designed to form.

  As a resin for forming the core 4 as shown in FIG. 4A, a thermoplastic resin such as ABS resin, polyvinyl chloride, polyethylene, polypropylene, polyethylene terephthalate, polyethylene terephthalate and ABS alloy resin, and the like can be used. Since the core 4 is not particularly required to have antifouling property or the like, a recycled resin obtained by recycling these resins can also be used.

FIG. 5A shows another example of integral extrusion molding. An extruder 6 for supplying the thermoplastic resin composition containing the silicone oil or silica to the extrusion mold 5 and other moldings are shown. A material, for example, an extruder 10 for supplying a base resin material is connected, and the long core 4 is supplied to the extrusion die 5. And while passing the core 4 through the extrusion die 5 in this way, the thermoplastic resin composition containing silicone oil and silica and the base resin material are supplied from the extruders 6 and 10 to the extrusion die 5 and molded. Thus, as shown in FIG. 5 (b), the surface of the core 4 is coated with a base layer 11 made of a base resin material, and the surface of the base layer 11 is thermoplastic containing silicone oil or silica. It is possible to obtain an extruded product 8 coated with the coating layer 7 made of the resin composition. In this case, in addition to forming the coating layer 7 on both surfaces of the core 4, the coating layer 7 can be formed only on one surface of the core 4.

  As the core 4, for example, a metal core 4 having a U-shaped cross section having an upper surface opened as shown in FIG. 5C is used, and a thermoplastic resin composition and a base resin containing silicone oil or silica on the surface of the core 4. A metal core eaves A can be produced by forming the base layer 11 and the covering layer 7 by simultaneous integral extrusion molding of the material. In the example of eaves A in FIG. 5 (c), the coating layer 7 made of a thermoplastic resin composition containing silicone oil or silica is formed only on the outer surface where antifouling properties are required.

  As the base resin material, a thermoplastic resin molding material such as ABS, polyvinyl chloride, or polyethylene can be used, and the base layer 11 molded with the base resin material has antifouling property and the like. Since it is not particularly required, recycled resin or the like can be used.

  Next, the present invention will be specifically described with reference to examples.

(Examples 1-7)
70 parts by mass of acrylic resin (methacrylic resin “LG” (MFR 10 g / 10 min) manufactured by Sumitomo Chemical Co., Ltd.), silicone resin-coated acrylic rubber (acrylic rubber “S2001” manufactured by Mitsubishi Rayon Co., Ltd.) ))), 30 parts by weight of a benzotriazole UV absorber (“TINUVIN234” manufactured by Ciba Specialty Chemicals Co., Ltd.), hindered amine light stabilizer (high molecular weight type: Ciba Specialty) 0.3 parts by mass of “CHIMASSORB 944FDL” (molecular weight of about 2000 to 3100) manufactured by Chemicals Corporation, hindered amine light stabilizer (low molecular weight type: “TINUVIN765” manufactured by Ciba Specialty Chemicals Co., Ltd. (molecular weight of about 500) ) 0.3 parts by mass, inorganic pigment ( 1 part by weight of iron), and further the silicone oil kinematic viscosity in Table 1, were blended in blending amount of Table 1, by mixing and kneading them to prepare an acrylic resin composition.

Silicone oils with a kinematic viscosity of 30 mm ² / s are “KF 96-30 cs”, those with a kinematic viscosity of 50 mm ² / s are “KF 96-50 cs”, and those with a kinematic viscosity of 10,000 mm ² / s. "KF96H-1 million in cs", the "KF96H-100,000 cs" those having kinematic viscosity of 100,000 ^mm 2 / s, kinematic viscosity of 300000mm ² / s is "KF96H-30 million in cs" (all manufactured by Shin-Etsu chemical Kogyo Co., Ltd.) was used.

  And the extrusion molding board for the test of a single layer structure was produced by extrusion-molding the acrylic resin composition prepared as mentioned above. Extrusion molding was performed under the conditions of an extrusion mold temperature of 220 ° C.

(Examples 8 to 10)
In place of silicone oil, silica (“ACEMATT HK125” manufactured by Evonik Degussa Japan Co., Ltd .: white fine particles, average particle size of 4.0 μm (measured by a particle size distribution meter)) was blended in the blending amounts shown in Table 1. In the same manner as in Examples 1 to 7, acrylic resin compositions were prepared. The acrylic resin composition was extrusion molded to produce a single-layer test extruded plate.

(Comparative Example 1)
An acrylic resin composition was prepared in the same manner as in Examples 1 to 7 except that silicone oil and silica were not blended. The acrylic resin composition was extrusion molded to produce a single-layer test extruded plate.

(Comparative Examples 2 to 5)
An acrylic resin composition was prepared in the same manner as in Examples 1 to 7 except that silicone oil and silica were blended as shown in Table 1. The acrylic resin composition was extrusion molded to produce a single-layer test extruded plate.

(Example 11)
As shown in Table 2, 100 parts by mass of polycarbonate resin (“L-1250Z” manufactured by Teijin Chemicals Ltd.) is mixed with 1 part by mass of silicone oil having a kinematic viscosity of 10,000 mm ² / s, and mixed and kneaded. Thus, a polycarbonate resin composition was prepared.

  The polycarbonate resin composition was extrusion molded to produce a single-layer test extrusion plate.

(Example 12)
As shown in Table 2, 1 part by mass of silicone oil having a kinematic viscosity of 10,000 mm ² / s is mixed with 100 parts by mass of ASA resin (“S310C” manufactured by UMGABS Co., Ltd.), and mixed and kneaded. A resin composition was prepared.

  The ASA resin composition was extrusion molded to produce a single-layer test extrusion plate.

(Example 13)
As shown in Table 2, 100 parts by mass of ABS resin (“TFX450” manufactured by Technopolymer Co., Ltd.) is mixed with 1 part by mass of silicone oil having a kinematic viscosity of 10,000 mm ² / s, and mixed and kneaded. An ABS resin composition was prepared.

  The ABS resin composition was extrusion molded to produce a single-layer test extrusion plate.

(Comparative Example 6)
Extruded plates for test having a single-layer structure were produced by extrusion molding in the same manner as in Example 11 except that a polycarbonate resin not containing silicone oil was used.

(Comparative Example 7)
Extruded plates for test having a single-layer structure were produced by extrusion molding in the same manner as in Example 12 except that an ASA resin not containing silicone oil was used.

(Comparative Example 8)
Except that an ABS resin not containing silicone oil was used, an extrusion-molded plate for test having a single-layer structure was produced by extrusion molding in the same manner as in Example 13.

  In extruding an extruded plate as described above, formability was evaluated. Formability is evaluated based on whether or not there is a filling defect during extrusion molding. “◎” indicates that molding can be performed without any problem. “○” indicates that there is a slight molding defect in part but there is no problem as a product. The case where there was a defect and there was a problem as a product was evaluated as “x”.

  Moreover, about the extrusion-molded board produced as mentioned above, surface sliding property was evaluated by measuring sliding angle and 90 degree sliding water amount.

  The sliding angle is measured by placing the extruded plate horizontally, dropping 50 μL of ion-exchanged water droplets onto the horizontal upper surface of the extruded plate, then tilting the extruded plate gradually, and the water droplets begin to slide down. This was done by measuring the angle.

  The sliding angle was measured in the same manner after the extrusion-molded plate was immersed in 50 ° C. ion-exchanged water for 10 days for elution treatment.

  To measure the amount of water sliding down 90 °, make sure that the surface of the extruded plate has a vertical angle of 90 °, drop a predetermined amount of water droplets on this surface, confirm that water flows down without residual water, The amount of water flowing was gradually increased, and the maximum amount of water droplets when water flowed down on the surface without remaining water was measured.

  The 90 ° sliding water amount was measured in the same manner after the extrusion-molded plate was immersed in ion-exchanged water at 50 ° C. for 10 days for elution treatment.

  In addition, the evaluation of the slipperiness is based on the fact that the sliding angle and the 90 ° sliding water amount after the elution treatment are compared with those in Comparative Example 1 and Comparative Examples 6-8 using a resin not containing silicone oil or silica. In this case, the improvement was indicated as “◯”, the change not so much as “△”, and the deterioration as “X”.

  Moreover, outdoor exposure antifouling property was evaluated by exposing an extrusion-molded board outdoors for one year. The evaluation was made by observing the raindrops on the surface and judging by the state of the dirt. “○” indicates that the dirt is not noticeable, “△” indicates that the dirt is slightly generated, and “X” indicates that the dirt is noticeable. .

  As seen in each example of Tables 1 and 2, using thermoplastic resin having a hydrophilic group such as acrylic resin, polycarbonate, ASA, ABS as the thermoplastic resin, with respect to 100 parts by mass of this thermoplastic resin, By blending silicone oil in the range of 0.1 to 2.0 parts by mass and silica in the range of 5 to 30 parts by mass, it is confirmed that the lubricity can be increased and the antifouling property can be improved.

The eaves bowl of a single layer structure is shown, (a) is a perspective view, (b) is sectional drawing of a conventional shape. (A) is the schematic of the shaping | molding method, (b) is sectional drawing of an extrusion molded object. The eaves of the two-layer structure of a core and a coating layer are shown, (a) (b) is sectional drawing, respectively. (A) is the schematic of the shaping | molding method, (b) (c) is sectional drawing which shows the vertical cocoon of the two-layer structure of a core and a coating layer, respectively. (A) is the schematic of the shaping | molding method, (b) is sectional drawing of an extrusion molded object, (c) is sectional drawing which shows the eaves of the three-layer structure of a core, a base layer, and a coating layer.

Explanation of symbols

3 Draining 4 Core 7 Covering layer 10 Base layer A Eaves B B Vertical

Claims (5)

As a silicon component, 0.1 to 2.0 parts by mass of silicone oil having a kinematic viscosity of 50 to 100000 mm ² / s (25 ° C.) and 5 to 30 parts by mass of silica with respect to 100 parts by mass of the thermoplastic resin having a hydrophilic group. The thermoplastic resin composition containing at least one of the parts is covered by extrusion molding on the surface of the core formed of at least one of a metal and a thermoplastic resin , and the upper end has a pointed water drop upward. A thermoplastic resin extrusion-molded article characterized in that is formed . As a silicon component, 0.1 to 2.0 parts by mass of silicone oil having a kinematic viscosity of 50 to 100000 mm ² / s (25 ° C.) and 5 to 30 parts by mass of silica with respect to 100 parts by mass of the thermoplastic resin having a hydrophilic group. The thermoplastic resin composition containing at least one part is coated with a base layer of a thermoplastic resin on a surface of a core formed of a metal, and is extruded and coated on the surface of the base layer. A thermoplastic resin extrusion-molded article in which a pointed water drop is formed upward . The thermoplastic resin extrusion-molded article according to claim 1 or 2 , wherein the inner surface from the upper end of the water drop is inclined downward inward at an angle exceeding 0 °. The thermoplastic resin extrusion molding according to any one of claims 1 to 3, wherein the outer surface from the upper end of the water drop is inclined downward toward the outside at an angle exceeding a water fall angle. body.   A method of preventing raindrops from adhering to a thermoplastic resin extruded product, wherein the thermoplastic resin extruded product has a kinematic viscosity as a silicon component with respect to 100 parts by mass of a thermoplastic resin having a hydrophilic group. 50-100,000 mm ² / S (25 ° C.) obtained by extrusion molding a thermoplastic resin composition containing at least one of 0.1 to 2.0 parts by mass of silicone oil and 5 to 30 parts by mass of silica. A method for preventing raindrops on an extruded thermoplastic resin article.

Images