JP6401560B2 - Polyvinyl chloride resin products - Google Patents

Description

  The present invention relates to a polyvinyl chloride resin product installed outdoors, such as a rain gutter attached to a house.

  In general, resin products installed outdoors, such as rain gutters attached to houses, are also important in terms of appearance, such as good design, so coloring with various pigments, surface treatment, etc. Is given. In recent years, various designs of houses have been developed. For example, in a rain gutter system or the like attached to a house as described in Patent Document 1, the color scheme or the like is important. Further, in such resin products installed outdoors, a polyvinyl chloride resin or the like that is generally lightweight, inexpensive, and capable of mass production is used as a resin material.

  On the other hand, polyvinyl chloride resin products such as the rain gutter system described above are subject to discoloration as aged deterioration because they are exposed to harsh environments exposed to sunlight, wind and rain, etc. outdoors. In particular, in a polyvinyl chloride resin product in which titanium oxide is contained in a resin material as a white pigment and the surface is a light color system such as a white system, depending on the blending conditions of the polyvinyl chloride resin, for example, When used outdoors for about 3 years, yellowing (discoloration from yellow to brown) may occur on the surface. For this reason, for example, when the above rain gutter system or the like is made of a polyvinyl chloride resin, there arises a problem that appearance characteristics are deteriorated due to yellowing due to aging.

JP 2013-002144 A

  As a method for preventing the yellowing of the polyvinyl chloride resin product as described above, for example, it is conceivable to increase the content of titanium oxide which is a white pigment. However, such a method has a problem that the manufacturing cost increases because a large amount of titanium oxide, which is an expensive pigment, is used. Also, simply increasing the whiteness by increasing the amount of titanium oxide contained in the polyvinyl chloride resin product cannot drastically eliminate yellowing due to aging, just to meet the increase in manufacturing costs. There is a problem that the effect of cannot be obtained.

  In order to prevent yellowing of the polyvinyl chloride resin product, for example, it may be possible to add a UV absorber such as benzophenone, benzotriazole, or salicylic acid ester, an antioxidant, or the like. However, even in such a method, as described above, since an expensive ultraviolet absorber or antioxidant is used, there is a problem that the manufacturing cost increases and yellowing cannot be completely eliminated.

  Here, when adding titanium oxide as a white pigment to a polyvinyl chloride resin product, titanium oxide has a catalytic action. May erode the polyvinyl chloride resin. For this reason, when titanium oxide is used as a white pigment, polyvinyl chloride is conventionally treated by subjecting titanium oxide particles to a surface treatment with an inorganic material before addition to the polyvinyl chloride resin. It is considered that the above-mentioned erosion is suppressed as the surface treatment amount increases and the film thickness increases. However, when the surface treatment amount of the titanium oxide particles is increased, the material decomposition of the titanium oxide particles can be suppressed, but the yellowing of the polyvinyl chloride resin product cannot be eliminated as described above.

  The present invention has been made in view of the above problems, and even when installed in a harsh environment outdoors for a long period of time, yellowing due to secular change is suppressed, the cost is low, and light resistance An object of the present invention is to provide a polyvinyl chloride resin product that is excellent in performance.

  The present inventors repeated intensive experiments in order to solve the above problems. As a result, first, the amount of surface treatment of titanium oxide particles, which has been considered better in the past, is reduced, and the average particle diameter of the filler and the distribution density of the filler on the product surface are regulated within an appropriate range. Thus, it was found that micropores derived from the filler can be formed on the product surface with an appropriate distribution. Thus, by reducing the amount of surface treatment of the titanium oxide particles to moderately generate material decomposition, the surface of the polyvinyl chloride resin product is likely to be moderately eroded by the titanium oxide particles. The filler tends to flow out, and along with this, fine pores are formed, and the average opening diameter and distribution of the fine pores are controlled within an appropriate range, which causes yellowing due to aging of the polyvinyl chloride resin. Even in this case, it was found that white coloration can be maintained by the action of micropores on the product surface. As a result, it was discovered for the first time that the occurrence of yellowing on the product surface can be suppressed as much as possible even when a polyvinyl chloride resin product is installed outdoors for a long time, and the present invention has been completed. is there.

That is, the invention according to claim 1 is a polyvinyl chloride resin product containing at least titanium oxide particles as a white pigment and further containing a filler, wherein the titanium oxide particles are organic materials. And surface treatment with an inorganic material in an amount of more than 0% by mass and 5.0% by mass or less with respect to the added amount of the titanium oxide particles to the polyvinyl chloride resin, and the filler is an average particle The diameter is in the range of 0.1 to 5.0 μm, the distribution density on the product surface in the initial state of the polyvinyl chloride resin product is 30 (pieces / 5 μm ² ) or more, and After the surface of the polyvinyl chloride resin product is irradiated with a laboratory light source for 3000 hours under the conditions in accordance with JIS A 1415, the average opening diameter of the micropores formed from the filler is 0.00. 1-5. with a [mu] m, and wherein the distribution density of the fine pores in the surface is 30 (pieces / 5 [mu] m ²⁾ or more.

  According to the present invention, the surface treatment is performed by limiting the addition amount of the inorganic material with respect to the addition amount of the titanium oxide particles to the above range, and further, by limiting the average particle diameter of the filler to the above range, Since the surface is likely to cause moderate erosion of the polyvinyl chloride resin by the titanium oxide particles on the surface, the filler is likely to flow out over time, and accordingly, fine pores having the same distribution as the filler are formed. It is formed. Further, by defining the distribution density of the filler on the surface of the polyvinyl chloride resin product within the above range, it has an average opening diameter in accordance with the average particle diameter of the filler, and is similar to the filler. Although micropores with a distribution density are formed, these micropores diffusely reflect sunlight and exhibit mainly white color, so even if yellowing occurs on the product surface, The coloration of the system is maintained. Therefore, even when installed in a harsh environment outdoors for a long period of time, yellowing due to secular change is suppressed, a low cost and a polyvinyl chloride resin product excellent in light resistance can be realized.

  Further, the invention according to claim 2 is the configuration of the polyvinyl chloride resin product according to claim 1, in an initial state on the surface of the polyvinyl chloride resin product and a condition in accordance with JIS A 1415. The color difference ΔE from the state after irradiating the laboratory light source for 3000 hours is in the range of 0 ≦ ΔE ≦ 5.

  According to the present invention, since the color difference ΔE between the initial state of the product surface and the state after irradiating the laboratory light source under a predetermined condition is in the above range, the yellowing is suppressed to the minimum, and the white color is displayed. The effect of maintaining the color is remarkably obtained.

  The invention according to claim 3 is the structure of the polyvinyl chloride resin product according to claim 1 or 2, wherein the surface treatment of the titanium oxide particles is aluminum oxide or silicon which is the inorganic material. It is characterized by.

  According to the present invention, since the surface treatment of the titanium oxide particles is performed with an inorganic material such as aluminum oxide or silicon, the thickness of the coating covering the surface of the titanium oxide particles can be controlled appropriately, and the titanium oxide particles can be appropriately treated. By promoting proper material decomposition, it is possible to appropriately generate erosion to the polyvinyl chloride resin, promote the outflow of the filler, and form micropores on the product surface. Therefore, even when yellowing occurs on the product surface, the effect of maintaining the white color can be obtained more significantly.

  The invention according to claim 4 is the configuration of the polyvinyl chloride resin product according to any one of claims 1 to 3, wherein the filler is at least calcium carbonate particles or magnesium oxide particles. It is either.

  According to the present invention, when the filler is calcium carbonate particles or magnesium oxide particles, it is possible to effectively flow out these fillers distributed on the product surface to form micropores. Therefore, even if the product surface is yellowed, the effect of maintaining the white color can be obtained more remarkably.

  As defined in the present invention, “the fine pores formed from the filler after irradiating the surface of the polyvinyl chloride resin product with a laboratory light source for 3000 hours under the conditions in accordance with JIS A 1415” First, after stipulating the irradiation time of a laboratory light source as an alternative to sunlight, which is adopted as an indicator of secular change in light resistance tests, etc., after the filler has flowed out due to changes in the product surface due to this condition The fine pores that become traces derived from the filler are defined.

According to the polyvinyl chloride resin product according to the present invention, as described above, the surface treatment is performed by appropriately limiting the amount of the inorganic material relative to the addition amount of the titanium oxide particles, and the average particle of the filler The diameter and the distribution density of the polyvinyl chloride resin product in the initial state of the product surface are limited, and the average opening diameter and distribution of micropores formed on the product surface after an exposure test under predetermined conditions using a laboratory light source Uses a configuration that regulates the density within an appropriate range. Thus, first, by limiting the surface treatment amount of the titanium oxide particles, it becomes easy for moderate erosion to the polyvinyl chloride resin due to the titanium oxide particles on the product surface. It becomes easy to flow out, and accordingly, fine pores having the same distribution as the filler are formed. Since the micropores are mainly white, even if yellowing occurs on the product surface, white coloration is maintained while suppressing the yellowing. The present invention has a high yellowing suppression effect for vinyl chloride resin products whose surface is white, such as white or cream, but is whitened for those that are dark, such as black or brown. Since it is conspicuous, it is better not to apply it. It is possible to apply a light gray system such as a light gray if it is light enough to satisfy the color difference defined in the present invention.
Therefore, according to the present invention, even when installed in a harsh outdoor environment for a long period of time, yellowing due to secular change is suppressed, the cost is low, and the polyvinyl chloride is excellent in light resistance. -Based resin products can be realized.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which illustrates typically the polyvinyl chloride resin product which is one Embodiment of this invention, and is the schematic which shows the case where the polyvinyl chloride resin product which concerns on this invention is applied to a rain gutter system. It is a figure explaining the polyvinyl chloride resin product which is one Embodiment of this invention, and is a scanning electron microscope (SEM) photograph which shows distribution of the micropore in the surface of a polyvinyl chloride resin product. It is a SEM photograph which shows distribution of the micropore in the surface of the conventional polyvinyl chloride-type resin product. It is a graph which shows the relationship between the irradiation time of a laboratory light source, and the color difference (DELTA) E of the Example of the polyvinyl chloride resin product which is one Embodiment of this invention, and the comparative example which is a conventional polyvinyl chloride resin product. is there.

  Hereinafter, in addition to the rain gutter system to which the present invention shown in FIG. 1 is applied, one embodiment of a polyvinyl chloride resin product according to the present invention with reference to the drawings is shown in FIG. 2 (Example) and FIG. 3 (Comparative Example). ) And the graph showing the relationship between the irradiation time and the color difference of the laboratory light source in FIG. 4 will be described as appropriate. In addition, the material, dimension, etc. which are illustrated in the following description are an example, Comprising: This invention is not limited to them, It can change suitably in the range which does not change the summary.

  The polyvinyl chloride resin product of the present embodiment is a resin product installed outdoors, such as a rain gutter attached to a house and a resin pipe that accommodates various communication lines. As an example of such a polyvinyl chloride resin product, as shown in FIG. 1, an eaves bowl 11 that receives rainwater flowing down from a roof, and a water collector 13 that is attached to the eaves bowl 1 to form a drop opening 12. There is a rain gutter system 1 including a gutter 14 having an upper end connected to the outlet 12 of the eaves gutter 11 and arranged vertically along an outer wall of a house or the like.

  Since the polyvinyl chloride resin product as described above is placed in an environment exposed to sunlight or wind and rain outdoors, good light resistance and appearance characteristics are required. In the present embodiment, as described in detail below, in the polyvinyl chloride resin product, by optimizing the average particle diameter of the filler added to the resin material and the distribution density thereof on the product surface, Even when yellowing occurs on the product surface under the severe environment as described above, the yellowing can be suppressed and white coloration can be maintained.

That is, the polyvinyl chloride resin product of the present embodiment contains at least titanium oxide particles as a white pigment, and at least one of calcium carbonate particles or magnesium oxide particles as a filler. The surface of the titanium particles is surface-treated with an inorganic material in an amount of more than 0% by mass and not more than 5.0% by mass with respect to the added amount of the titanium oxide particles to the polyvinyl chloride resin. The particle diameter is in the range of 0.1 to 5.0 μm and the initial state of the polyvinyl chloride resin product, that is, the distribution density on the product surface immediately after production is 30 (pieces / 5 μm ² ) or more. Yes.
The polyvinyl chloride resin product of the present embodiment becomes susceptible to erosion due to material decomposition of the titanium oxide particles on the product surface with use over time, so that the filler flows out from the product surface. It becomes easy and a micropore is formed in connection with this.
That is, the polyvinyl chloride resin product of the present embodiment has micropores formed on the surface after irradiating the surface with a laboratory light source for 3000 hours under conditions conforming to JIS A 1415 as an index of secular change. Specifically, the average opening diameter and distribution density of the particles are optimized. Specifically, the average opening diameter of the micropores formed as traces (traces after outflow) derived from the filler is 0.1 to 5.0 μm. In addition, the distribution density on the surface is 30 (pieces / 5 μm ² ) or more.

  As the polyvinyl chloride resin material used for the polyvinyl chloride resin product of the present embodiment, the resin material conventionally used for rain gutters, polyvinyl chloride resin pipes, etc. can be used without any limitation. As an example, the following composition may be mentioned.

  In the polyvinyl chloride resin material used in the present embodiment, the polyvinyl chloride resin (PVC) used as the main agent may be, for example, a homopolymer of vinyl chloride or copolymerized with vinyl chloride. It may be a copolymer with other possible monomers. Examples of such other copolymerizable monomers include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate; acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; Methacrylic acid esters such as ethyl methacrylate; Maleic acid esters such as dibutyl malate and diethyl malate; Fumarate esters such as dibutyl fumarate and diethyl fumarate; Vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether Vinyl cyanides such as acrylonitrile and methacrylonitrile; olefins such as ethylene, propylene and n-butene; vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide It can be mentioned vinyl halides, and the like.

Moreover, as said polyvinyl chloride-type resin, what was manufactured by conventionally well-known methods, such as a suspension polymerization method and an emulsion polymerization method, can be used, for example.
Also, the average degree of polymerization of the polyvinyl chloride resin is not particularly limited, but is preferably in the range of 500 or more and 1500 or less, and about 1000 can be used. When the average degree of polymerization of the polyvinyl chloride resin is less than 500, the impact resistance is lowered, and when it exceeds 1500, the melt viscosity is increased and the workability is lowered.

  Further, in the polyvinyl chloride resin material of the present embodiment, pigments and fillers are added to the above-mentioned main component polyvinyl chloride resin, and if necessary, stabilizers, lubricants, processing agents are further added. Various additives such as auxiliary materials are blended.

  In this embodiment, titanium oxide particles are added as a pigment. Titanium oxide particles are used as white pigments, especially in light-colored polyvinyl chloride resin products, and may be used by mixing with other pigments. For example, rutile titanium oxide is used. Can do.

  In the present embodiment, it is preferable that the average particle diameter of the titanium oxide particles is in the range of 0.1 μm to 0.5 μm. If the average particle diameter of the titanium oxide particles is within the above range, the material of the titanium oxide particles will be appropriately decomposed over time on the surface of the polyvinyl chloride resin product. Easier to erode. Thereby, the filler described later distributed on the product surface is likely to flow out, and accordingly, micropores having an average opening diameter of 0.1 to 5.0 μm derived from the filler are easily formed on the product surface. . If the average particle diameter of the titanium oxide particles exceeds the above upper limit or falls below the lower limit, there is a possibility that desired micropore formation efficiency cannot be obtained on the product surface. Moreover, in this embodiment, it is more preferable that the average particle diameter of a titanium oxide particle is the range of 0.2-0.25 micrometer.

  In the present embodiment, the surface of the titanium oxide particles is surface-treated with an inorganic material in an amount of more than 0% by mass and 5.0% by mass or less with respect to the addition amount of the titanium oxide particles to the polyvinyl chloride resin. Adopted configuration. In this way, by treating the surface of titanium oxide particles with a relatively small amount of inorganic material, compared to the case of surface treatment with a large amount of inorganic material as in the past, the material of titanium oxide particles that accompanies aged use Decomposition tends to occur. Thereby, appropriate erosion of the polyvinyl chloride resin material is likely to occur on the surface of the polyvinyl chloride resin product, and the filler distributed on the product surface is likely to flow out. Therefore, the effect | action which becomes easy to form a micropore with an average opening diameter derived from a filler of 0.1-5.0 micrometers is acquired.

If the inorganic material used for the surface treatment of titanium oxide particles exceeds 5.0% by mass with respect to the added amount of titanium oxide particles, the material will not decompose properly over time, and polyvinyl chloride resin products It may be difficult to form micropores on the surface of the film. In addition, if the surface of the titanium oxide particles is not surface-treated with an inorganic material, the material decomposition of the titanium oxide particles becomes too large, and the erosion of the polyvinyl chloride resin material becomes transient and causes a large yellowing. In the present invention, the lower limit of the inorganic material relative to the amount of titanium oxide particles added is specified to be more than 0% by mass.
In this embodiment, the surface of the titanium oxide particles is surface-treated with an inorganic material in an amount of more than 0.05% by mass and 1.0% by mass or less with respect to the added amount of the titanium oxide particles. It is particularly preferable that the surface treatment is performed with an inorganic material in an amount of more than 0.1 mass% and 0.5 mass% or less.

  In the present embodiment, the inorganic material used for the surface treatment of the titanium oxide particles is not particularly limited, but for example, a surface treatment with aluminum oxide or silicon is preferable. Thus, by making the surface treatment of the titanium oxide particles with aluminum oxide or silicon, the thickness of the coating covering the surface of the titanium oxide particles can be properly controlled, and appropriate material decomposition of the titanium oxide particles can be achieved. It is promoted, and the erosion to the polyvinyl chloride resin can be appropriately generated. Thereby, the outflow of the filler from the product surface is promoted, and it becomes possible to effectively form micropores derived from the titanium oxide particles.

  In the present embodiment, as the surface treatment of the titanium oxide particles, the above can also be made of an organic material in addition to the inorganic material. In such a case, as an organic material, for example, an organic polyol, an organic polysiloxane, or the like can be used. The amount of the organic material used can also be the same as that of the inorganic material described above.

  Next, the filler used in the present embodiment is not particularly limited. For example, it is preferable to use at least one of calcium carbonate particles and magnesium oxide particles. By using calcium carbonate particles or magnesium oxide particles as fillers, these fillers distributed on the surface of the polyvinyl chloride resin products are effectively discharged with the passage of time to form micropores. It becomes possible to make it.

  In the present embodiment, the average particle size of the filler is in the range of 0.1 to 5.0 μm. By restricting the average particle diameter of the filler composed of calcium carbonate particles or magnesium oxide particles to the above range, the filler that appears on the surface of the polyvinyl chloride resin product flows out with use over time. In addition, fine pores having the same average opening diameter, that is, an average opening diameter of 0.1 to 5.0 μm are formed. Even if the polyvinyl chloride resin material is yellowed by forming such fine pores with an average opening diameter on the product surface, white coloration is produced by the action of the fine pores on the product surface. Can be maintained. If the average particle diameter of the filler exceeds the upper limit of the above range, the size of the micropores formed may be too large, and it may be difficult to obtain a white color, and is below the lower limit of the above range. However, there is a possibility that the fine pore size necessary to maintain the white coloration cannot be obtained. Moreover, in this embodiment, it is more preferable that the average particle diameter of the filler and the average opening diameter of the fine pores on the product surface derived therefrom are in the range of 0.2 μm or more and 0.25 μm or less.

In this embodiment, the distribution density of the filler on the surface of the polyvinyl chloride resin product is 30 (pieces / 5 μm ² ) or more. Thereby, in this embodiment, it derived from the filler after irradiating the surface of a polyvinyl chloride-type resin product for 3000 hours using a laboratory light source as an alternative of sunlight used as an index of aged use. The distribution density of micropores formed as traces can be 30 (pieces / 5 μm ² ) or more. When the distribution density of the filler on the surface of the polyvinyl chloride resin product, that is, the distribution density of micropores after aged use is less than 30 (pieces / 5 μm ² ), the white color is maintained. It can be difficult. Moreover, in this embodiment, it is more preferable that the distribution density of the filler on the surface of the polyvinyl chloride resin product and the distribution density of micropores derived from the filler are 50 (pieces / 5 μm ² ) or more. .

  As described above, in the polyvinyl chloride resin product of the present embodiment, moderate material decomposition occurs by reducing the surface treatment amount of the titanium oxide particles, and moderate erosion occurs on the surface of the polyvinyl chloride resin product. Adopts a configuration that allows the filler to flow out by making it easy to occur, and to form micropores along with this, and then control the average opening diameter and distribution of these micropores to an appropriate range doing. As a result, even when yellowing occurs due to aging of the polyvinyl chloride resin, white coloration can be maintained by the action of micropores on the product surface.

  Here, the conditions conforming to JIS A 1415 described in the present embodiment are, for example, using a sunshine carbon arc lamp or the like as a laboratory light source instead of sunlight, and a test object (polychlorinated) at a predetermined illuminance and time. This is a standard used in various light resistance tests. As such a testing machine for performing an irradiation test, a commercially available sunshine weather meter (for example, S80 manufactured by Suga Test Instruments Co., Ltd.) can be used.

  In the polyvinyl chloride resin product of the present embodiment, the color difference ΔE between the initial state on the product surface and the state after 3000 hours of irradiation with a laboratory light source under conditions in accordance with JIS A 1415 is 0 ≦ It is preferable that ΔE ≦ 5. The surface of the product is yellowed by optimizing the surface treatment with the inorganic material of the titanium oxide particles and the average particle diameter of the filler and the distribution density on the product surface so that the color difference ΔE is within the above range. Is suppressed to a minimum, and the effect of maintaining the white coloration is remarkably obtained.

  FIG. 2 is a scanning electron microscope (SEM) photograph showing the distribution of micropores on the surface of the vinyl chloride resin product having the structure according to the present invention, and FIG. 3 shows the surface of a conventional polyvinyl chloride resin product. The distribution of micropores in is shown by an SEM photograph. Here, both FIG. 2 and FIG. 3 are those obtained by performing an exposure test using a laboratory light source. Specifically, under the conditions in accordance with JIS A 1415 described above, a sunshine weather meter (stock of Suga Test Instruments) The sample which performed irradiation for 3000 hours using company make: S80 etc. is shown.

In the exposure test using the above sunshine weather meter, the irradiance by the sunshine carbon arc lamp: 255 W / m ² ± 10% (300 to 700 nm), the black panel temperature: 63 ° C., the rain cycle: 12 minutes / 60 minutes As a test.
The color difference ΔE on the product surface was measured using a commercially available spectrocolorimeter (Konica Minolta Co., Ltd .: CM-2600d) under the condition of a 10 ° visual field.

In the example shown in FIG. 2, 0.1 to 5.0 μm micropores are formed on the product surface with a distribution density of 30 (pieces / 5 μm ² ) or more, and therefore after exposure to sunlight for 3000 hours. The color difference on the product surface was ΔE = 3.3, and it was confirmed that yellowing was not noticeable.
On the other hand, in FIG. 3, since the distribution density of fine pores of 0.1 to 5.0 μm on the product surface is less than 30 (pieces / 5 μm ² ), the color difference on the product surface after 3000 hours exposure to sunlight. Was as large as ΔE = 14.8, confirming that the yellowing of the product surface was conspicuous compared to the example shown in FIG.

Examples of processing aids added to the polyvinyl chloride resin include acrylic resins.
Moreover, as a lubricant, a polyethylene-type resin etc. are mentioned, for example.
Moreover, Sn (tin) etc. can be mentioned as a stabilizer.

  The polyvinyl chloride resin material of the present embodiment includes a polyvinyl chloride resin as a main component, titanium oxide particles of a white pigment as an essential component, calcium carbonate particles or magnesium oxide particles as a filler, and further if necessary. Each of the above additives to be added is mixed, heated and melted, kneaded and homogenized.

  In addition, the method of molding the polyvinyl chloride resin product of the present embodiment using the above polyvinyl chloride resin is not particularly limited. For example, when manufacturing rain gutters as a polyvinyl chloride resin product. May employ a conventional rain gutter extruder. Also, the resin temperature and molding conditions at this time are not particularly limited.

In addition, in a vinyl chloride resin product, in order to provide weather resistance, a layer made of a weather resistant resin such as AES or ABS may be provided on the outermost surface, but in the present invention, the filler in the vinyl chloride resin flows out. Therefore, it is desirable not to provide these weather resistant resin layers.
In addition, adding a light-proofing aid such as UVA or HALS to vinyl chloride resin prevents deterioration of the vinyl chloride resin due to sunlight and suppresses the outflow of the filler. Since it cannot be suppressed, it is desirable not to add these light-proofing aids.

As described above, according to the polyvinyl chloride resin product according to the present invention, the following effects can be obtained by the above-described configuration.
That is, according to the polyvinyl chloride resin product according to the present invention, the surface treatment is performed by appropriately limiting the amount of the inorganic material relative to the addition amount of the titanium oxide particles to the polyvinyl chloride resin. The average particle size and the distribution density on the product surface in the initial state of the polyvinyl chloride resin product are limited, and after irradiating the laboratory light source for 3000 hours under the conditions specified in JIS A 1415, The structure which prescribed | regulated the average opening diameter and distribution density of the micropore formed to the appropriate range is employ | adopted. Thus, first, by limiting the surface treatment amount of the titanium oxide particles, it becomes easy for moderate erosion to the polyvinyl chloride resin due to the titanium oxide particles on the product surface. It becomes easy to flow out, and accordingly, fine pores having the same distribution as the filler are formed. Since the micropores are mainly white, even when yellowing occurs on the product surface, the white color is maintained while suppressing the yellowing.
Therefore, even when installed in a harsh environment outdoors for a long period of time, yellowing due to secular change, etc. is suppressed, and it is possible to realize a low-cost polyvinyl chloride resin product with excellent light resistance. .

  Next, the present invention will be described in detail by the following examples, but the present invention is not limited only to these examples.

<Preparation of sample>
[Example 1]
In Example 1, with the conditions and procedures shown below, the compounding conditions shown in Table 1 below, that is,
100 parts by mass (average polymerization degree: 1000) of the main resin (polyvinyl chloride resin, Shin-Etsu Chemical Co., Ltd., SS-10),
Pigment (titanium oxide particles): 3.5 parts by mass
Filler (calcium carbonate particles and magnesium oxide particles; mixing ratio 1: 1): 5 parts by mass
Stabilizer (Nitto Kasei, TVSKK-6476, Sn content 15%): 0.6 parts by mass,
Lubricant (polyethylene resin): 0.9 parts by mass
Processing aid (acrylic resin): 1.0 part by mass,
Were mixed under each condition.

  And the sample of the polyvinyl chloride resin product of Example 1 which was extrusion-molded using the extruder for rain gutters conventionally used, and was made into the shape like the eaves bowl 11 shown in FIG. Was made. The molding conditions at this time were: screw: biaxial different direction, cylinder temperature: 130 to 175 ° C., mold temperature: 185 to 220 ° C., resin temperature: 180 to 195 ° C.

Further, in Example 1, as the titanium oxide particles, those having an average particle diameter of 0.20 to 0.25 μm are used as shown in Table 1 below. The amount was 3.5 parts by mass with respect to parts by mass. In Example 1, the surface of the titanium oxide particles is formed by adding inorganic materials such as aluminum oxide (Al ₂ O ₃ ), silicon (SiO ₂ ), and organic materials such as polyol to titanium oxide. What carried out surface treatment using the quantity of 0.5 mass% with respect to the compounding quantity of particle | grains was used.

  Moreover, in Example 1, about the calcium carbonate particle | grains and magnesium oxide particle which were used as said filler, what each has an average particle diameter of the range of 0.1-5.0 micrometers was used.

[Example 2]
In Example 2, the used amount of aluminum oxide (Al ₂ O ₃ ) and silicon (SiO ₂ ), which are inorganic materials used for the surface treatment of the titanium oxide particles, was set to 0. 0 with respect to the blending amount of the titanium oxide particles. A sample of a polyvinyl chloride resin product was produced under the same conditions and procedures as in Example 1 except that the amount was 5% by mass.

[Example 3]
In Example 3, polyvinyl chloride was used under the same conditions and procedure as in Example 1 except that polysiloxane was used in the same amount instead of the polyol of the organic material used for the surface treatment of the titanium oxide particles. A sample of a resin resin product was produced.

[Comparative Example 1]
In Comparative Example 1, the compounding conditions shown in Table 2 below, that is, the amounts of aluminum oxide (Al ₂ O ₃ ) and silicon (SiO ₂ ), which are inorganic materials used for the surface treatment of titanium oxide particles, were oxidized. A sample of a polyvinyl chloride resin product was produced under the same conditions and procedures as in Example 1 except that the amount was 3.5% by mass with respect to the blending amount of the titanium particles.

[Comparative Example 2]
In Comparative Example 2, a polyvinyl chloride resin product was prepared under the same conditions and procedures as in Comparative Example 1 except that the blending conditions shown in Table 2 below, ie, the content of titanium oxide particles was 4.0% by mass. A sample of was prepared.

[Reference Example 1]
In Reference Example 1, the blending conditions shown in Table 2 below, that is, 0.1 mass of UV absorber (UV A wave) absorbing UVA as a weathering assistant with respect to the blending amount of titanium oxide particles. A sample of a polyvinyl chloride resin product was produced under the same conditions and procedures as in Example 1 except that the amount was added in an amount of%.

[Reference Example 2]
In Reference Example 2, the blending conditions shown in Table 2 below, that is, HALS (light stabilizer) as a weathering assistant was added in an amount of 0.1% by mass with respect to the blending amount of the titanium oxide particles. A sample of a polyvinyl chloride resin product was prepared under the same conditions and procedures as in Example 1 except for.

[Comparative Example 3]
In Comparative Example 3, a sample of a polyvinyl chloride resin product was produced under the same conditions and procedures as in Example 1 except that the surface treatment of the titanium oxide particles was not performed at all.

<Evaluation test>
[Distribution density of micropores]
About the sample of the polyvinyl chloride resin product of each example obtained under the above conditions, after cutting out to a predetermined size, a sunshine carbon arc lamp was used as a laboratory light source to replace sunlight according to the conditions in accordance with JIS A 1415. And irradiated for 3000 hours. At this time, a sunshine weather meter (product number: S80) manufactured by Suga Test Instruments Co., Ltd. was used as a test apparatus. The test conditions at this time were as follows: Irradiance by sunshine carbon arc lamp: 255 W / m ² ± 10% (300 to 700 nm), black panel temperature: 63 ° C., rain cycle: 12 minutes / 60 minutes.
Thereafter, the distribution density of micropores on the product surface was confirmed by SEM observation, and the results are shown in Tables 1 and 2 below.

[Color difference]
About the sample of the polyvinyl chloride resin product of each example obtained on the said conditions, after cutting out to a predetermined | prescribed magnitude | size, it irradiated for 3000 hours with the sunshine carbon arc lamp which is a laboratory light source by the same apparatus and conditions as the above. . Thereafter, using a spectrocolorimeter (manufactured by Konica Minolta Co., Ltd .: CM-2600d), the color difference ΔE from the sample surface before the test was measured under the conditions of a 10 ° field of view, and the results are shown in Tables 1 and 2 below. Indicated.

<Evaluation results>
As shown in Table 1, the samples of the polyvinyl chloride resin products of Examples 1 to 3 having the configuration according to the present invention were irradiated with a sunshine carbon arc lamp for 3000 hours, and then the surface had micropores of 30 to 50 ( It was confirmed that it was formed with a distribution density of 5 pieces / 5 μm ² ).
In addition, the samples of Examples 1 to 5 had a color difference ΔE in the range of 3.1 to 4.1 after the irradiation with the sunshine carbon arc lamp for 3000 hours, and almost no color change was observed. It was confirmed that the white color was maintained.

On the other hand, in the samples of Comparative Examples 1 and 2, the amount of aluminum oxide and silicon used for the surface treatment of the titanium oxide particles exceeded the upper limit defined in the present invention. The distribution density of micropores formed on the surface of the sample after irradiation was less than 30 (pieces / 5 μm ² ), and the color difference ΔE before the test was as large as 14.8. This is presumably because the surface treatment amount of the titanium oxide particles was too large, so that the material decomposition of the titanium oxide particles did not proceed and the erosion into the polyvinyl chloride resin material did not proceed, so that it was difficult to form micropores.

Further, the sample of Reference Example 1 was formed on the surface of the sample after being irradiated with a sunshine carbon arc lamp for 3000 hours, although the specifications such as titanium oxide particles and fillers satisfy the conditions defined in the present invention. The distribution density of the micropores was less than 30 (pieces / 5 μm ² ), and the color difference ΔE before the test was as large as 12.5. This is presumably because, in Reference Example 1, since the ultraviolet absorber was added, the erosion of the polyvinyl chloride resin material did not proceed and the formation of micropores on the surface was difficult to proceed.

In addition, the sample of Reference Example 2 is also the sample after irradiation with a sunshine carbon arc lamp for 3000 hours, although the specifications of titanium oxide particles and fillers satisfy the conditions defined in the present invention as in Reference Example 1. The distribution density of micropores formed on the surface of the film was less than 30 (pieces / 5 μm ² ), and the color difference ΔE before the test was as large as 12.8. In Reference Example 2, since the light stabilizer was added, the erosion of the polyvinyl chloride resin material did not proceed and the formation of micropores on the surface was difficult to proceed as in Reference Example 1. Possible cause.

Further, the sample of Comparative Example 3 is an example in which the surface treatment of the titanium oxide particles was not performed at all, but the distribution density of micropores formed on the surface of the sample after irradiation with the sunshine carbon arc lamp for 3000 hours was The color difference ΔE was less than 30 (pieces / 5 μm ² ), and the color difference ΔE with respect to that before the test was also slightly large at 7.3. This is considered to be because, when the surface treatment of the titanium oxide particles is not performed at all, the erosion of the polyvinyl chloride resin material has advanced remarkably and yellowing due to the titanium oxide particles has occurred remarkably. .

  Here, the following Table 3 and FIG. 4 are graphs showing the relationship between the irradiation time by the sunshine carbon arc lamp and the color difference ΔE in the samples of Examples 1 and 2 and Comparative Example 1 described above.

As shown in Table 3 and FIG. 4, in the samples of the polyvinyl chloride resin products of Examples 1 and 2 having the configuration according to the present invention, the change in the color difference ΔE until the irradiation time reaches 3000 hours is slightly increased. On the other hand, in Comparative Example 1 , it can be seen that the color difference ΔE increases rapidly after the irradiation time exceeds 1000 hours.

  In addition, each structure in those embodiment and each Example demonstrated above, those combinations, etc. are examples, and addition, omission, substitution, and other change of a structure are possible in the range which does not deviate from the meaning of this invention. . Further, the present invention is not limited by each embodiment, and is limited only by the scope of the claims.

  The polyvinyl chloride resin product according to the present invention can be widely applied to resin products installed outdoors, such as rain gutters, sashes, deck materials, resin pipes that accommodate various communication wires, etc. Is possible.

1 ... Rain gutter system 11 ... Eaves 12 ... Dropper 13 ... Water collector 14 ... Reed.

Claims (4)

At least a titanium oxide particle as a white pigment, and further a polyvinyl chloride resin product containing a filler,
The titanium oxide particles, organic materials, and the surface treated by 0 mass percent 5.0 wt% or less of the amount of inorganic material to the amount of the polyvinyl chloride resin of the titanium oxide particles And
The filler has an average particle diameter in the range of 0.1 to 5.0 μm, and a distribution density on the product surface in the initial state of the polyvinyl chloride resin product is 30 (pieces / 5 μm ² ) or more. And
And the average opening diameter of the micropore formed from the said filler after irradiating the laboratory light source on the surface of the said polyvinyl chloride-type resin product for 3000 hours on the conditions based on JISA1415. A polyvinyl chloride resin product having a size of 0.1 to 5.0 μm and a distribution density of the micropores on the surface of 30 (pieces / 5 μm ² ) or more.   The color difference ΔE between the initial state on the surface of the polyvinyl chloride resin product and the state after irradiating the laboratory light source for 3000 hours under the conditions in accordance with JIS A 1415 is in the range of 0 ≦ ΔE ≦ 5. The polyvinyl chloride resin product according to claim 1.   The polyvinyl chloride resin product according to claim 1 or 2, wherein the surface treatment of the titanium oxide particles is performed by aluminum oxide or silicon which is the inorganic material.   The polyvinyl chloride resin product according to any one of claims 1 to 3, wherein the filler is at least one of calcium carbonate particles and magnesium oxide particles.