JP2018193474A - Resin composition and article - Google Patents

Abstract

To provide a technology capable of maintaining an effect of an additive added to a resin over a long period.SOLUTION: A roofing material 10 which is an example of an article includes on the surface, an antifouling layer 12 formed of a resin composition. The resin composition contains a substrate containing a resin depressed by an ultraviolet ray, and an additive added to the substrate in order to impart a prescribed characteristic or function to a substrate surface. The resin is a resin depressed as much as 0.2-20 μm when being irradiated with light by a sunshine carbon arc lamp as long as 2,000 hours.SELECTED DRAWING: Figure 5

Description

  The present invention relates to a resin composition, and in particular, to a resin composition containing an additive and an article formed from the resin composition.

  Synthetic resins are relatively inexpensive and excellent in processability, and are therefore widely used for manufacturing various products. Additives having desired characteristics and functions are added to the synthetic resin in order to impart the characteristics required for products in each field to the synthetic resin (see, for example, Patent Document 1).

  In Patent Document 1, a surface resin decorative layer and a back resin layer are provided on both sides of a decorative board substrate mainly composed of gypsum containing reinforcing fibers, and the surface resin decorative layer, the back resin layer, and the decorative board substrate are provided. It is described that an antifungal agent is internally added to at least one, or an antifungal agent is applied to the surface of the decorative board substrate.

JP 2000-145007 A

  When the decorative board described in Patent Document 1 is used for an outdoor building or the like, if the fenders exposed on the surface of the surface resin decorative layer are washed away by rainwater or the like, the expected fender effect is lost. End up. Moreover, since the anti-mold agent internally added to the surface resin decorative layer is not exposed on the surface of the surface resin decorative layer, the anti-mold effect cannot be exhibited.

  Therefore, there is a need for a technology that can maintain the expected effect over a long period of time even for products used in environments such as outdoors.

  This invention is made | formed in view of such a subject, The objective is to provide the technique which makes it possible to maintain the effect of the additive added to resin over a long period of time.

  In order to solve the above problems, a resin composition according to an aspect of the present invention is added to a base material containing a resin that is depleted by ultraviolet rays and a predetermined property or function on the surface of the base material. And additives. The resin is a resin that wears out by 0.2 to 20 μm when irradiated with light by a sunshine carbon arc lamp for 2000 hours.

  Another aspect of the present invention is an article having a surface formed with a layer formed of a resin composition. An article comprising a surface formed of a layer formed of the resin composition includes a base material containing a resin that is depleted by ultraviolet rays, and a base material for imparting a predetermined property or function to the surface of the base material. And an additive to be added. The resin is a resin that wears out by 0.2 to 20 μm when irradiated with light by a sunshine carbon arc lamp for 2000 hours.

  ADVANTAGE OF THE INVENTION According to this invention, the technique which makes it possible to maintain the effect of the additive added to resin over a longer period can be provided.

It is a figure which shows the result of the accelerated weather resistance test about various materials. It is a figure which shows the surface of the molding by the resin composition which concerns on an Example. It is a figure which shows the quantity of the additive eluted from the surface of the molding by the resin composition which concerns on an Example. The quantity of the additive eluted from the surface of the molding by the resin composition which concerns on an Example and a comparative example is shown. It is a figure which shows roughly sectional drawing of the roof material which is an example of the articles | goods formed with the resin composition which concerns on an Example.

  The present applicant provides carports, terraces, and garden rooms in which roofing materials or wall materials are made of transparent resin that transmits visible light as garages (carports), terraces, and garden rooms installed in houses and the like. ing. Such carports, terraces, and garden rooms can ensure internal lighting while appropriately preventing adverse effects caused by rainwater. However, when a long period of time elapses, mold, algae, etc. may propagate on the top surface of the roofing material. In this case, since the roof is transparent, molds and algae generated on the top surface of the roof are visible from the inside, and there is a problem that daylighting is hindered by the propagated molds and algae. An antifouling product has also been developed in which a hydrophilic photocatalyst layer is provided on the upper surface of the roofing material, and the upper surface can be washed away with rainwater to keep the upper surface clean. As in the case of the present invention, if the photocatalyst itself is washed away by rainwater or the like, the antifouling effect cannot be expected thereafter. Similarly, when an antifungal agent or an algae-proofing agent is applied to the top surface of the roofing material, if the applied anti-fungal agent or the like is washed away by rainwater, an antifungal or anti-algae effect is expected thereafter. Can not. Therefore, the development of technology that makes it possible to maintain the effect of the additive for a longer period of time has been promoted.

  On the other hand, since resin deteriorates or wears out due to the influence of ultraviolet rays, rain and snow, humidity, temperature, ozone, etc., development of resin products having high weather resistance in the use environment has been promoted.

  In such a situation, the present inventors have changed the way of thinking and thought that the effect of the additive can be expressed over a long period of time by taking advantage of the fact that the resin is depleted in the usage environment. In other words, if an additive for imparting properties and functions to the resin is added to the resin that is depleted in the usage environment, the resin used as the base material is gradually depleted so that it is kneaded inside. Since the additive is exposed on the outermost surface, the effect of the additive can be expressed continuously. Even if an additive is internally added to a highly weather-resistant resin that does not wear out in the usage environment, the additive that has been exposed to the surface from the beginning only exhibits its function, and the additive kneaded inside is exposed to the surface. However, if the additive is added to the resin that is depleted at an appropriate rate in the usage environment, the additive can be exposed to the surface at all times, so it can be added over a long period of time. The effect of the agent can be maintained.

  Therefore, the resin composition according to the embodiment of the present invention includes a base material (base material) containing a resin that is depleted in a use environment, and an additive added to the base material in order to impart a predetermined property or function to the base material. Agent. The base material includes a resin such as polycarbonate resin, acrylic resin, and vinyl chloride resin that gradually wears out due to ultraviolet rays or the like in a use environment. Additives are formed by base materials such as antibacterial, antifungal, antialgae, and antiviral agents that have the effect of suppressing the growth of microorganisms, as well as water repellents, snowproof agents, hydrophilic agents, and water slide agents. A substance having an effect of imparting desired characteristics or functions to the surface of the article or coating film.

  The substrate may be any material that can be depleted in the environment of use. For example, the base material of the resin composition for forming a building material, a structural material, an article, etc. used outdoors may be a polycarbonate resin, an acrylic resin, a vinyl chloride resin, or the like that is depleted by ultraviolet rays contained in sunlight. . Also, synthetic resins used in paints such as alkyd resins, polyester resins, melamine resins, urea resins, phenol resins, epoxy resins, acrylic urethane resins, urethane resins, silicone resins, acrylic silicone resins, fluorine resins, etc. Also good. In addition to ultraviolet rays, the factors that cause the substrate to wear out include heat, temperature differences, moisture, salt, moisture, oxygen, corrosive gases such as ozone and sulfur dioxide, organic solvents, other chemicals, friction, and machinery. It may be a mechanical impact, wind or the like.

  The amount of wear of the base material depends on the type, amount, particle size of the additive, the density and distribution of the additive in the base material, the characteristics required for the article formed by the resin composition, the use environment of the article, etc. It only has to be selected. The amount of wear of the resin can be evaluated by an accelerated weather resistance test using an artificial light source. FIG. 1 shows the results of an accelerated weathering test for various materials. With respect to the resin molded product, a 10% compound was produced, and then a 2 mm thick plate was prepared with an extrusion molding machine under the standard molding conditions for each resin, and was cut into an evaluation body. For the coating film, an additive was blended in a paint containing a resin as a constituent component, kneaded and cured under the recommended curing conditions of each paint, and then cured at room temperature for 1 week to obtain an evaluation body. "Sunshine weather 2000 hours" is a test result of 2000 hours accelerated deterioration using S80-H-BBR made by Suga Test Instruments as a sunshine carbon arc lamp (Sunshine weather meter: SWOM) in accordance with JIS K 7350-4. Show. The amount of depletion of the substrate is, for example, 0.1 μm or more, preferably 0.2 μm in the accelerated weathering test described above, in order to always expose an appropriate amount of the additive present in the substrate to the surface of the substrate. More preferably, it may be 1 μm or more, more preferably 1.7 μm or more, and even more preferably 2 μm or more. Moreover, in order to suppress the deterioration of the surface of the article formed of the resin composition, for example, in the accelerated weather resistance test, it is 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less, and further preferably 8 μm or less. Also good. Although the measurement value of the amount of wear may vary depending on the test method, any test method may be adopted. The above numerical range may be based on, for example, a measurement value by an accelerated weathering test using a sunshine carbon arc lamp. When measuring by another accelerated weather resistance test, the accelerated weather resistance using a sunshine carbon arc lamp is used. You may convert into the measured value by a test. Moreover, it is good also considering the value when the articles | goods formed with the resin composition were actually exposed outdoors.

  The type of additive may be selected according to the characteristics or functions to be imparted to the base material in order to satisfy the characteristics or performance required in the product. For example, as described above, when used in an article that is installed outdoors and requires transparency, a fungicide, an algae, or an antibacterial agent having an effect of suppressing the growth of microorganisms is used as an additive. Also good. The microorganisms may be molds, algae, fungi or the like. Such an additive may be an inorganic substance, for example, silver, zinc, copper, nickel or the like. When organic materials are decomposed or modified by heating when processing a resin composition, they are generally unsuitable as additives for resins, but when using a material with a low glass transition temperature as a substrate In addition, when an article is molded or processed by a method that does not require high heat, an organic substance may be used as an additive. For example, Biomessenger (registered trademark) R2 from Sumika Environmental Science Co., Ltd., TZA-100 from Fuji Chemical Co., Ltd. It is. Moreover, a mixture of an organic substance and an inorganic substance may be used as an additive. As each additive, a known arbitrary substance that is generally used can be used. For example, you may add additives, such as a ultraviolet absorber, antioxidant, a heat ray absorber, a heat ray reflective agent, and a light stabilizer, which are generally added to resins used outdoors. Moreover, you may add the additive containing a component which accelerates | stimulates depletion of resin to a base material further. For example, an additive such as titanium oxide that is known to degrade the resin may be added to the base material. You may use together these additives and additives, such as an antifungal agent, an algaeproof agent, and an antibacterial agent.

  The amount of the additive only needs to be an amount necessary for effectively expressing the characteristics or functions to be imparted to the base material. The type of additive, the particle size of the additive, the type of base material, the base material May be selected according to the amount of wear, the characteristics required of the article formed of the resin composition, the use environment of the article, and the like. The amount of the additive may be, for example, 0.01 to 10% by weight, more preferably 0.1 to 3% by weight, based on the total weight of the resin composition. In applications where transparency is required, when an additive having a colored component is used, the amount of additive may be selected so that the required transparency is achieved.

  The particle size of the additive may be a particle size necessary for effectively expressing the characteristics or functions to be imparted to the base material, and the type of additive, the particle size of the additive, the type of base material, What is necessary is just to select according to the amount of depletion of a base material, the characteristic requested | required of the articles | goods formed with the resin composition, the use environment of articles | goods, etc. In order to smooth the surface of the layer formed of the resin composition, the particle diameter of the additive may be, for example, 200 nm or less, preferably 50 nm or less, more preferably 40 μm or less. In applications where transparency is required, the particle size of the additive may be selected so that the required transparency is achieved. For example, it is preferably 1 μm or less.

  FIG. 2 shows the surface of a molded product made of the resin composition according to the example. The molded product shown in FIG. 2 is a molded product of a resin composition in which 0.5% by weight of a commercially available zinc oxide having a particle size of the order of several tens of nm is added to a polycarbonate resin as an additive. FIG. 2A shows the surface immediately after molding. A small amount of additive is exposed on the surface. FIG.2 (b) shows the surface after irradiating light with the sunshine carbon arc lamp for 200 hours. More additives are exposed on the surface than immediately after molding. FIG.2 (c) shows the surface after irradiating light with a sunshine carbon arc lamp for 600 hours. Many more additives are exposed on the surface. As described above, since the resin serving as the base material is depleted, the internally added additive is exposed to the surface, so that the effect of the additive can be expressed over a long period of time.

  The additive for imparting characteristics or functions to the surface of the base material can exert its effect on the surface exposed to the surface, so that a predetermined amount of the additive is continuously exposed to the surface. The type of substrate, the amount of wear of the substrate, the type of additive, the amount of additive added, the particle size of the additive, etc. may be selected. The amount of the additive exposed on the surface is, for example, the area of the additive in the surface photograph taken by a transmission electron microscope (TEM), a scanning electron microscope (SEM), a scanning transmission electron microscope (STEM) or the like. May be measured based on. Whether or not a predetermined amount of the additive is continuously exposed on the surface is determined by, for example, photographing the surface at a predetermined interval in the accelerated weather resistance test, and the average value of the area of the additive exceeds the predetermined amount. It may be determined by whether or not there is. Conditions such as the type of base material, the amount of wear of the base material, the type of additive, the amount of additive added, and the particle size of the additive can be related to each other, but the additive exposed on the surface of the molded product The combination of the respective conditions may be appropriately selected so that the amount is continuously greater than or equal to the predetermined value.

  FIG. 3: shows the quantity of the additive eluted from the surface of the molding by the resin composition which concerns on an Example. A sample piece in which a resin composition in which a nickel-based alloy was blended with polycarbonate resin in an amount of 1% by weight was molded into a 50 mm square was used. A sample piece immediately after molding, a sample piece after irradiation with light using a sunshine carbon arc lamp for 600 hours and 2000 hours, and a sample piece whose surface has been polished are immersed in water at 40 ° C. for 3 days. The eluted components were analyzed by ICP mass spectrometry (ICP-MS). As shown in FIG. 3, more nickel-based alloy components were eluted from the sample piece after the accelerated weathering test than the sample piece immediately after forming. This experiment showed that the nickel-based alloy additive was exposed on the surface as the polycarbonate resin was depleted in the usage environment, and the effect was expressed by elution with rainwater or the like.

  FIG. 4 shows the amount of the additive eluted from the surface of the molded product by the resin composition according to the example and the comparative example. In order to confirm the difference in the elution amount of the additive due to the difference in the amount of resin depletion, between the outdoor paint based on Lumiflon (registered trademark), which is hard to be depleted by ultraviolet rays, and the polycarbonate resin, which is easily depleted by ultraviolet rays A comparative test was conducted. The amount of wear of polycarbonate in the experiment shown in FIG. 1 is 2.4 μm, and the amount of wear of Lumiflon is 0.1 μm. 0.5% of commercially available zinc oxide was added as an additive to polycarbonate as an example and Lumiflon as a comparative example, and molded by a general method. A 50 mm sample was put into a sealed container together with 40 mL of pure water and placed in a dryer set at 40 ° C. for 3 days to confirm the water elution of the zinc component from the molded product. Water analysis was performed with ICP-AES having a lower limit of quantification of 4 ppb. In order to confirm the sustainability, extraction was repeated 5 times while changing the pure water each time (from the first to the fifth). Then, after irradiating light with the sunshine carbon arc lamp for 200 hours, similarly, extraction was repeated 5 times while changing pure water every time (6th to 10th). Then, after further irradiating light with a sunshine carbon arc lamp for 200 hours, similarly, extraction was repeated twice while changing pure water every time (11th to 12th times). Zinc oxide blended with Lumiflon, which is hard to be depleted by ultraviolet rays, was not exposed to ultraviolet rays even after being exposed to ultraviolet rays after being exposed to the surface after molding. It was confirmed that the zinc oxide blended in the polycarbonate which is easy to do is exposed to ultraviolet rays and the resin is depleted so that the zinc oxide inside is newly exposed on the surface and continuously released into water. Thus, according to the resin composition according to the examples, when the additive is practically used outdoors, the additive is gradually released from the depleted resin, so that the effect of the additive, for example, the effect of inhibiting microbial growth is permanently exhibited. Can be expected.

  FIG. 5 schematically shows a cross-sectional view of a roof material that is an example of an article formed of the resin composition according to the example. The roof material 10 includes a substrate 14 and an antifouling layer 12 provided on the surface of the substrate 14. The substrate 14 is formed of a transparent polycarbonate resin. The antifouling layer 12 is formed of the resin composition according to the example. The substrate 14 includes an ultraviolet absorber, a near infrared absorber, and the like as additives in order to reduce the amount of ultraviolet rays and heat rays irradiated to the inside of the roof. The antifouling layer 12 contains an additive contained in the resin composition according to the example, and in this example, an additive such as an antifungal agent and an antibacterial agent.

  When a carport, a terrace, a garden room or the like equipped with the roofing material 10 is used outdoors, components of additives such as fungicides and antibacterial agents on the surface of the antifouling layer 12 are eluted by rainwater, and then rainwater When dried, a high concentration layer of additive is formed on the surface. Thereby, the function of an additive is exhibited effectively. Further, even if the high-concentration layer of the additive is subsequently washed away by rainwater or the like, the base material of the antifouling layer 12 is depleted, so that the additive present inside is released and the additive is added to the surface. A high concentration layer is formed. Thereby, the function of an additive is exhibited continuously.

  This roofing material 10 can be formed into a multilayer by coextrusion molding of the resin constituting the substrate 14 and the resin composition according to the example constituting the antifouling layer 12. Conventionally, a roof material is manufactured by co-extrusion molding of a resin constituting a substrate and a resin containing an additive for improving weather resistance. However, the roof material according to the example is an antifouling layer 12. The roofing material 10 can be manufactured at low cost without greatly changing the process because it can be manufactured by coextrusion molding just like the conventional product, by simply adding the desired additive to the resin for forming Can do. In addition, since the amount of additive used can be reduced by molding the roofing material 10 by coextrusion molding, the appearance changes such as discoloration and deterioration of transparency while suppressing the cost of expensive additives. Can be suppressed.

  The thickness of the antifouling layer 12 is such that all of the base material does not wear out and all the additives are washed away until the useful life of the article on which the antifouling layer 12 is formed elapses. It only has to be selected. For example, when the useful life of the article is 10 years, the layer made of the resin composition may be formed to be thicker than the thickness at which the resin used as the base material is worn out in 10 years in the usage environment. Further, when the layer of the resin composition is molded, it is desirable to mold it by a method in which the additive is uniformly distributed in the molded product.

  As mentioned above, although this invention was demonstrated based on embodiment, embodiment only shows the principle and application of this invention. In the embodiment, many modifications and arrangements can be made without departing from the spirit of the present invention defined in the claims.

  10 roofing material, 12 antifouling layer, 14 substrates.

Claims (6)

A base material containing a resin that is depleted by ultraviolet rays;
An additive to be added to the base material in order to impart a predetermined property or function to the surface of the base material;
Including
The resin composition is a resin that wears out by 0.2 to 20 μm when irradiated with light by a sunshine carbon arc lamp for 2000 hours.   The resin composition according to claim 1, wherein the resin is a polycarbonate resin, an acrylic resin, or a vinyl chloride resin.   The resin composition according to claim 1, wherein the additive is an inorganic substance.   4. The resin composition according to claim 1, wherein the amount of the additive is 0.01 to 10% by weight based on the total weight of the resin composition.   The resin composition according to claim 1, wherein the additive has a particle size of 40 μm or less. A base material containing a resin that is depleted by ultraviolet rays;
An additive to be added to the base material in order to impart a predetermined property or function to the surface of the base material;
Including
An article comprising a layer formed of a resin composition on the surface, wherein the resin is a resin that is depleted by 0.2 to 20 μm when irradiated with light by a sunshine carbon arc lamp for 2000 hours .