JP2019108411A - Hard vinyl chloride-based resin molded body - Google Patents

Abstract

To provide a hard vinyl chloride-based resin molded body suppressing temperature rise or deformation by irradiation of sunlight, hardly discoloring even after outdoor exposure under sunshine for long time.SOLUTION: There are provided a hard vinyl chloride-based resin molded body containing a vinyl chloride resin and a composite oxide-based inorganic pigment of 0.05 to 5 pts.mass based on 100 pts.mass of the vinyl chloride resin, and having median diameter based on area of the composite oxide-based inorganic pigment of 1.0 to 100 μm, and a hard vinyl chloride-based resin molded body consisting of a multilayered structure having a layer consisting of the hard vinyl chloride-based resin molded body in an outer surface side.SELECTED DRAWING: None

Description

  The present invention relates to a rigid polyvinyl chloride resin molded article that can be used as a water pipe, drainage pipe, joint, material for fluid transportation such as mass, gutter, window frame, material for outdoor building such as roofing material, and the like.

  The use as a water pipe is widely known as a rigid polyvinyl chloride resin molded article used outdoors, but besides that, it is for drainage pipes and joints, for fluid transportation such as mass, gutters, window frames, roofs There are many applications that are exposed to sunlight outdoors, such as for outdoor building materials such as materials, especially in summer, the surface temperature of the molded product irradiated with intense sunlight becomes high and irreversible thermal deformation occurs Is a problem.

  In Patent Document 1, a vinyl chloride resin hard molded article in which calcium chloride having an average particle diameter of 1.0 μm or less is blended with a vinyl chloride resin for outdoor building materials together with an organic colorant excellent in infrared permeability It is disclosed that since it can permeate | transmit without scattering, the raise of the surface temperature of a molded article is suppressed and the molded article for outdoor construction materials which is hard to be thermally deformed is obtained.

  Patent Document 2 discloses an invention relating to a hard vinyl chloride resin tube, but also from the viewpoint that it is difficult to absorb infrared rays, the hard vinyl chloride resin tube using an organic black pigment is irradiated with infrared rays. It is also disclosed that the surface temperature of the tube is difficult to increase.

  However, against the problem that these organic colorants are easily deteriorated by weathering and are discolored by exposure to sunlight, Patent Document 3 discloses hard vinyl chloride using an inorganic pigment comprising a complex oxide. A system resin pipe is disclosed.

JP 2001-139698 A JP 2003-329176 A JP, 2013-159774, A

However, also in Patent Document 3, in Example 1 in which discoloration does not easily occur, the effect of suppressing the rise in the tube temperature is not sufficient, and in Example 2 in which the effect of suppressing the temperature rise is more excellent than that, Δb ^* value is better than Comparative Example 1 In addition, the effect of suppressing the deformation of the pipe is also insufficient.

  An object of the present invention is to provide a hard vinyl chloride resin-based molded article which suppresses temperature rise and deformation due to irradiation of sunlight and is hardly discolored even after being exposed to the sun for a long time.

The present invention
[1] A hard vinyl chloride resin molded article containing a vinyl chloride resin and 0.05 to 5 parts by mass of a composite oxide inorganic pigment with respect to 100 parts by mass of the vinyl chloride resin, wherein the complex oxidation is performed Solid vinyl chloride resin molded article having a median diameter of 1.0 to 100 μm on an area basis of the inorganic inorganic pigment, and the hard vinyl chloride resin molded article according to the above [1] on the outer surface side The present invention relates to a hard vinyl chloride resin molded product having a multilayer structure having a layer.

  The hard vinyl chloride resin-based molded article of the present invention suppresses the temperature rise and deformation due to the irradiation of sunlight, and exhibits an excellent effect that it is difficult to discolor even after being exposed outdoors under a long time sunlight.

  The hard vinyl chloride resin molded article of the present invention contains a vinyl chloride resin and a large particle size composite oxide inorganic pigment, and reflects infrared rays by the large particle size composite oxide inorganic pigment. Even when the molded body of the present invention is exposed to sunlight, the temperature of the molded body does not easily rise, and thermal deformation is suppressed. In addition, the large particle size complex oxide inorganic pigment has high durability, and can suppress discoloration due to photodegradation.

  Light is a type of electromagnetic wave, and while electromagnetic waves with a wavelength of 380 to 750 nm are called visible light, electromagnetic waves with a wavelength longer than visible light and an upper limit of 1 mm are called infrared rays, and are invisible to the eye The power to warm up is strong. When a substance is irradiated with an electromagnetic wave, the electromagnetic wave produces at least one of reflection, absorption, and transmission, but when the particle size of the substance is sufficiently smaller than the wavelength of the electromagnetic wave, the electromagnetic wave tends to be transmitted. Therefore, conventionally, in a resin molded article containing a pigment, infrared rays contained in sunlight transmit through the resin composition molded article by using a pigment having a small particle diameter in order to avoid heat deformation due to sunlight. It was technical common sense to keep products from heating. On the other hand, in the present invention, by using a composite oxide inorganic pigment having a large effect of reflecting infrared rays and having a larger area (large particle diameter), the infrared rays are reflected on the surface to heat the molded article. Differs from the prior art in that it employs a mechanism to prevent

  In the present invention, an area-based median diameter is employed as the particle diameter of the complex oxide pigment exhibiting the effects of the present invention as described later. The reason for this is that the composite oxide inorganic pigment is produced through the process of grinding the sintered body, so the particle shape differs depending on the wet or dry type, the difference in the grinding mechanism, etc. This is because the area has the most influence. Although many pigments produced and sold in industry display the value of the average particle diameter by a laser diffraction type particle size distribution meter as a representative value of the particle diameter, the diameter is usually assumed that the particles are spherical. Is a number average, so the tendency does not necessarily coincide with the infrared reflection effect.

  As the vinyl chloride resin in the present invention, a vinyl chloride homopolymer, a copolymer of a vinyl chloride monomer and a monomer copolymerizable with vinyl chloride (usually, a copolymer of 50% by mass or more of vinyl chloride) And graft copolymers obtained by graft copolymerizing a vinyl chloride monomer to an arbitrary polymer, and chlorinated vinyl chloride copolymers obtained by chlorinating at least a part of a vinyl chloride resin.

  Examples of monomers copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid esters such as acrylic acid and ethyl acrylate, and methacrylic esters such as methyl methacrylate and ethyl methacrylate. And olefin monomers such as ethylene and propylene; monomers having an unsaturated bond copolymerizable with vinyl chloride monomers such as acrylonitrile, styrene, and vinylidene chloride; and the like.

  The average degree of polymerization of the vinyl chloride resin is preferably 600 to 2,500, and more preferably 800 to 1,400, from the viewpoint of elongation characteristics at molding, impact resistance, and moldability. The average degree of polymerization of the vinyl chloride resin can be measured in accordance with JIS K 6720-2.

  The complex oxide inorganic pigment in the present invention is a complex of a plurality of metal oxides known as commonly known as CIPC (Complex Inorganic Color Pigment), and has a stable and uniform crystal structure.

  Specific examples of the complex oxide-based inorganic pigment include the Society of Dyes and Dyeing and Colourists (SDC) and the American Association of Textile Chemists and Colorists (AATTC). Pigment Yellow 53 (Ti-Ni-Sb system), Pigment Yellow 119 (Fe-Zn, Fe-Zn-Ti system), Pigment Yellow 157 (Ti-Ba-Ni system) as a color index number defined by Pigment Blue 28 (Co-Al system), Pigment Blue 36 (Co-Cr-Al system), Pigment Green 19 (Ti-Co-Ni-Zn system), Pigment Green 26 (Co-Zn-Cr-Ti system), Pigment Green 50 (Co-Zn-Ni-Ti system), Pigment Brown 24 (Ti-Cr-Sb system), Pigment Brown 29 (Cr-Fe system), Pigment Brown 33 (Fe-Zn-Cr system), Pigment Black 17 (Fe-Cr system), Pigment Black 27 (Co-Fe-Cr type | system | group), Pigment Black 28 (Cu-Cr-Mn type | system | group), etc. are mentioned, 1 type or multiple complex oxide type pigments can be used.

The complex oxide inorganic pigment in the present invention is characterized in that it has a large particle size from the viewpoint of infrared reflection and durability, and it is 1.0 to 10 as an area-based median diameter (D ₅₀ ). It is 100 μm, preferably 1.4 to 60 μm, more preferably 1.8 to 30 μm, and still more preferably 1.8 to 10 μm. The median diameter on an area basis can be obtained by length measurement analysis with a scanning electron microscope.

  The content of the composite oxide inorganic pigment is 0.05 to 5 parts by mass, preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

The molded article of the present invention may contain an inorganic pigment other than the complex oxide inorganic pigment, and since it has a high infrared reflectance, it is an inorganic pigment not containing two or more metal elements, that is, one metal element. It is preferable to contain an inorganic pigment. As such inorganic pigments, Pigment White 4 (ZnO), Pigment White 6 (TiO ₂ ), Pigment Red 101 (Fe ₂ O ₃ ), Pigment Green 17 (Cr ₂ O ₃ ), Pigment Black 11 (Fe ₃ O ₄ ) And the like, and these may be used alone or in combination of two or more. Although both are excellent view to easily available at low cost, preferable one is a cheaper and more infrared reflectance at a high Pigment White 6 (TiO _2). For titanium oxide (TiO ₂ ), crystal systems such as anatase, rutile, brookite and the like are known, but preferred as a pigment is chemically stable rutile.

The inorganic pigment other than the complex oxide inorganic pigment preferably has a large area similarly to the complex oxide inorganic pigment, but since the crystals are often harder than the complex oxide pigment, especially with titanium oxide, etc. When a large area is used, the resin molding die is easily scratched, so the area-based median diameter (D ₅₀ ) is preferably 0.05 to 10 μm, more preferably 0.1 to 6 μm, and still more preferably 0. 2 to 3 μm. Here, the area-based median diameter is calculated from image analysis with an electron microscope.

  More inorganic pigments containing one kind of metal element can be more inexpensive and can enhance the effect of infrared reflectance, but it is preferable if too much to affect the color of the whole molded object too much to the color of this inorganic pigment, depending on the application. There is also no case. Therefore, the content of the inorganic pigment containing one metal element is preferably 20 times by mass or less, more preferably 0.1 to 10 times by mass, still more preferably 0.5 to 5 times that of the complex oxide inorganic pigment. It is mass doubling.

  In addition, the molded article of the present invention may contain an organic pigment, and the color tone of the molded article can be freely adjusted by blending an organic pigment having a much wider variety of colors compared to the inorganic pigment. can do. Organic pigments are generally more expensive than inorganic pigments, do not contribute much to infrared light reflection, and are inferior in light resistance to inorganic pigments, but phthalocyanine pigments are exceptionally light resistant among organic pigments. Because it is excellent. Specific examples of the phthalocyanine based pigment include Pigment Green 15 (copper phthalocyanine), Pigment Blue 15 (copper phthalocyanine blue), Pigment Green 7 (copper phthalocyanine green), and Pigment Green 36 (brominated copper phthalocyanine green). Two or more of these may be used in combination.

  Since the organic pigment is an additive for the purpose of toning the molded body to the last, its content is preferably 10 parts by mass or less, preferably 100 parts by mass in total of the inorganic pigment including the complex oxide inorganic pigment. Preferably it is 0.05-5 mass parts.

  The molded article of the present invention may contain additives such as heat stabilizers, fillers, and lubricants.

  As a heat stabilizer, lead-based stabilizers such as tribasic lead sulfate and lead (II) stearate; tin-based stabilizers such as dibutyltin malate, dibutyltin mercapto and dioctyltin malate polymers; stearic acid, lauric acid And metal soaps which are metal salts of higher fatty acids such as ricinoleic acid; lead whites; lead compounds such as basic lead sulfite and tribasic lead maleate; organotin compounds, antimony compounds, epoxy compounds, phosphites, β-diketones And polyols, phenolic antioxidants, etc. Among them, lead-based stabilizers and tin-based stabilizers having high effects as heat stabilizers are preferable, and stearic acid having a combined effect of heat stabilizers and lubricants is preferred. Lead (II) is more preferred.

  The content of the heat stabilizer is preferably 0.3 to 10 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, from the viewpoint of molding processability and mechanical properties of the molded article. It is a department.

  Examples of fillers include inorganic fillers such as calcium carbonate, talc, clay, mica and silica.

  Inorganic fillers may also have some infrared reflection effect, but since they are originally colorless, the effect of discoloration resistance by selecting large particle size such as complex oxide type inorganic pigments can not be expected very much. Therefore, inorganic fillers having a relatively small particle size are preferable from the viewpoint of dispersibility. Judging criteria of the particle diameter concerning dispersibility are widely judged by the value of number average particle diameter, and the average particle diameter measured by the method of Coulter counter etc. is displayed in the catalog value of the commercial product It is easy to select from The number average particle size of the inorganic filler is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm.

  The content of the filler is preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin from the viewpoint of flowability improvement of the composition compound and smoothness and mechanical strength of the molded article surface. Preferably it is 0.5-5 mass parts.

  Examples of the lubricant include aliphatic hydrocarbons such as polyethylene wax and paraffin wax, higher aliphatic alcohols such as stearyl alcohol, higher fatty acids such as stearic acid, calcium stearate and hydroxystearic acid, and mono esters such as butyl stearate Examples thereof include lubricants of polyhydric alcohol fatty acid esters such as alcohol fatty acid esters, glycerin monostearate and glycerin tristearate.

  The lubricant may be added alone to the vinyl chloride resin, or may be added once it has been complexed with the pigment, filler, etc., but from the viewpoint of preventing the scattering of the solid component and enhancing the dispersibility in the molten resin. Therefore, it is preferable to use in combination with a pigment, a filler and the like.

  The content of the lubricant is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the vinyl chloride resin, from the viewpoint of moldability and economy.

  Other additives include plasticizers such as di-2-ethylhexyl phthalate and 2-ethylhexyl adipate, CPE-based tougheners, MBS-based tougheners, modifiers such as acrylic-based tougheners, antistatic agents, A flame retardant, an ultraviolet absorber, an antioxidant, a foaming agent etc. are mentioned.

  The molded article of the present invention is produced by mixing and kneading raw material components including the above-mentioned vinyl chloride resin and composite oxide inorganic pigment, and other pigments and additives which are optionally used, according to a conventional method. be able to.

  When concentration distribution of the raw material component exists on the surface and inside of the compact, the complex oxide is near the outer surface of the compact when the compact has an outer surface mainly receiving light and an inner surface which is relatively hard to receive. It is preferable that the concentration of the system inorganic pigment is high, and it is more preferable that the concentration of both the complex oxide inorganic pigment and the inorganic pigment containing one metal element be high in the vicinity of the outer surface of the molded body. Such concentration distribution may be a single phase structure or a multilayer structure. Also, the outer surface may be coated with a protective layer that does not inhibit the effects of the present invention.

  When the molded body has a multilayer structure, it is preferable to have a layer formed of the molded body of the present invention on the outer surface side, and the inner layer is a vinyl chloride resin layer not having a composite oxide inorganic pigment May be

  The molded article of the present invention is molded into a shape according to its use, and can be suitably used as a pipe, a joint, a mass, a plate, a rod or the like.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples.

Production Example 1 of Complex Oxide-Based Inorganic Pigment
800 g of iron oxide (Fe ₂ O ₃ ) and 200 g of chromium oxide (Cr ₂ O ₃ ) were weighed and uniformly mixed using a Kawata super mixer SMV-20A. Then, the obtained mixture was placed in a mortar and calcined at 1000 ° C. for 6 hours in an electric furnace to crystallize and colorize black, thereby producing Pigment Brown 29. The fired product is put into a ball mill made of alumina together with alumina balls, ground at a rotational speed of 300 rpm for 60 minutes with a vibration mill, and then classified with a Nisshin Engineering air flow classifier AC-20, and particle sizes shown in Table 1 (D ₅₀ ) classified into three types of fine powder, medium powder and coarse powder.

Production Example 2 of Complex Oxide-Based Inorganic Pigment
750 g of titanium oxide (TiO ₂ ), 100 g of antimony oxide (Sb ₂ O ₃ ) and 150 g of chromium oxide (Cr ₂ O ₃ ) were weighed and uniformly mixed using a Kawata super mixer SMV-20A. Then, the resulting mixture was placed in a mortar and calcined at 1000 ° C. for 6 hours in an electric furnace to cause crystallization and color development, whereby Pigment Brown 24 was produced. The fired product is put into a ball mill made of alumina together with alumina balls, ground at a rotational speed of 300 rpm for 60 minutes with a vibration mill, and then classified with a Nisshin Engineering air flow classifier AC-20, and particle sizes shown in Table 1 (D ₅₀ ) classified into three types of fine powder, medium powder and coarse powder.

Production Example 1 of Organic Pigment
238.5 g of coarsely pulverized β-type copper phthalocyanine, 12.5 g of oxovanadyl phthalocyanine and 250 g of sodium sulfate are put into a ball mill made of alumina together with alumina balls and pulverized with a vibration mill at a rotational speed of 300 rpm for 180 minutes. The crushed material is poured into 5 liters of deionized water at 80 ° C., stirred for 1 hour, centrifuged three times, centrifuged and discarded, and the solid is dried at 120 ° C. for 6 hours to produce Pigment Blue 15 did. After crushing with a Fritsch rotor speed mill P-14, it is classified with an air classification machine AC-20 type manufactured by Nisshin Engineering Co., Ltd., fine powder having a particle size (median diameter D ₅₀ ) shown in Table 1, medium powder, It was classified into three types of coarse powder.

The particle size is obtained by ultrasonically dispersing the obtained pigment in cyclohexane (100 W, 5 minutes), and then using a scanning electron microscope (manufactured by Hitachi High-Technologies Corp., model: SU-1510), with an accelerating voltage of 10 kV. In the enlarged photograph taken, 50 primary particles on the two-dimensional image are randomly selected, and the major diameter (maximum length) and minor diameter (minimum length) of each particle are measured, and the median diameter of area based ( D ₅₀ ) was calculated.

Examples 1 to 10 and Comparative Examples 1 to 4
The raw material shown in Table 2 was used to produce a single layer tube. Moreover, about Example 1, 2, 4 and the comparative example 1, the two-layer pipe was manufactured further.

  The raw materials shown in Table 2 were supplied to a Super Mixer LMI-P manufactured by Kawata Co., and uniformly mixed while raising the temperature to 110 ° C. to obtain a vinyl chloride resin composition.

  The measurement of the weight average polymerization degree of vinyl chloride resin was performed based on JISK-6720-2. 200 mg of a sample is dissolved in 40 mL of nitrobenzene and then diluted to 50 mL using a special grade nitrobenzene as the solvent, and viscosity measurement is performed using a Ubbelohde viscometer in a 30 ° C. constant temperature water bath to calculate the weight average degree of polymerization. did.

(1) Production of Single-Layer Pipe The vinyl chloride resin composition for a single-layer pipe obtained in Examples 1 to 10 and Comparative Examples 1 to 4 was subjected to a twin-screw extruder (rotation in opposite directions, L / D = 28, It was formed into a pipe with an outer diameter of 114 mm, a pipe body thickness of 3.3 mm, and a length of 2.5 m according to a tip temperature setting of 190 ° C.

(2) Production of double-layered pipe A vinyl chloride resin composition for an inner layer was obtained using the same raw material except that the pigment composition was not used in Table 2.
The vinyl chloride resin composition for the double layer pipe is coaxially rotated in the opposite direction using the vinyl chloride resin composition for the inner layer by using an oblique axis different direction rotating twin screw extruder (KMD-60K manufactured by Mitsubishi Heavy Industries, Ltd.). Machine (Role Pearl Co., Ltd., REX400), respectively knead | mixing and introduce | transducing into a two-layer shaping | molding die, Two-layer extrusion molding is performed by 200 degreeC of mold part temperature, and 200 kg / hr of total extrusion quantities. , The pipe body thickness was formed into a pipe of 3.3 mm and a length of 2.5 m. The pipe has a two-layer structure of an outer surface layer (thickness: 0.7 mm) made of a vinyl chloride resin composition for a two-layer pipe and an inner layer of the vinyl chloride resin composition for an inner layer.

  The heating test, pipe deformation test, and color change test of the obtained single-layer pipe and double-layer pipe were performed. The results are shown in Tables 3 and 4. The heating test was performed on all single-layer tubes and two-layer tubes, and the color change test was performed on the single-layer tubes of Examples 1, 2 and 4 and Comparative Examples 1 and 4 and the two-layer tubes of Example 2 and Comparative Example 1. I went to each.

[Heating test]
Place two pipes with an outer diameter of 114 mm, a pipe body thickness of 3.3 mm, and a length of 2.5 m in parallel on a flat aluminum substrate, and equalize 10 floodlights (100 V-300 W) to a height of 400 mm from the pipe surface. Each tube is irradiated with light, and the pipe surface temperature is measured at 5 points on the pipe surface temperature using an infrared type surface thermometer (non-contact handy thermometer IT2-80 manufactured by Keyence Corporation), and the maximum temperature is the surface temperature (° C) did. The initial value of the surface temperature of the pipe was 23.0 ° C., and in the case of a single-layer tube, the surface temperature became almost constant 30 minutes after the start of irradiation, so it was measured 60 minutes after the start. In the double-layer tube, the surface temperature became constant earlier than in the single-layer tube, but it was also measured 60 minutes after the start.

[Pipe deformation test]
Room temperature 23 ° C ± 2 ° C in a constant temperature room, light irradiation for 6 hours, followed by room temperature standing for 6 hours, 1 cycle of heating cycle accumulated 10 times, 20 times, 50 times and the degree of pipe deformation after heating cycle Was measured by the following method.
Mark the position and angle of the pipe used for the pipe deformation test, take out the pipe after the heating cycle, stretch a cotton thread as a water thread between the two ends, and connect the water thread and the pipe surface The gap was measured with a vernier caliper, and the gap around the entire length of the pipe where the gap was widest was recorded as the maximum bending amount (cm) of the pipe. When continuing the heating cycle, the heating cycle was continued by setting the position and angle of the pipe to be exactly the same as before.

[Color change test]
The pipes were exposed side by side and exposed, the chromaticity b ^* before and after the start of the exposure test was measured, and the CIE color difference Δb ^* of the pipe surface was calculated. For measurement of chromaticity, using a color difference meter 8080 manufactured by Nippon Denshi Kogyo Co., Ltd., the chromaticity b ^* of the tube top before the exposure test is b ₀ and the chromaticity b ₁ of the same position after exposure is b The difference Δb ^* (= b ₁ −b ₀ ) was determined.

From the above results, it can be seen that in Examples 1 to 10, the rise in surface temperature is suppressed and the deformation and color change of the pipe are also suppressed as compared with Comparative Examples 1 to 4.
From the comparison of Examples 3 to 5, it can be seen that there is no substantial difference in the effect even if the particle diameter is different in the organic pigment, and the effect by the adjustment of the particle diameter is unique to the composite oxide inorganic pigment .

The hard polyvinyl chloride resin molded product of the present invention can be suitably used as a water pipe, drainage pipe, joint, material for fluid transportation such as mass, rain gutter etc., material for outdoor building materials such as window frame, roof material etc.

Claims (5)

  A hard vinyl chloride resin molded article comprising a vinyl chloride resin and 0.05 to 5 parts by mass of a complex oxide inorganic pigment with respect to 100 parts by mass of the vinyl chloride resin, wherein the complex oxide based inorganic material is A hard vinyl chloride resin molded article, wherein the median diameter of pigment based on area is 1.0 to 100 μm.   Furthermore, the rigid polyvinyl chloride resin molded object of Claim 1 containing the inorganic pigment which contains 1 type of metallic elements.   The rigid vinyl chloride resin molded article according to claim 1, further comprising an organic pigment.   The rigid vinyl chloride resin molded article according to any one of claims 1 to 3, which is a pipe, a joint, or a mass.   A hard vinyl chloride resin molded article having a multilayer structure having a layer consisting of the hard vinyl chloride resin molded article according to any one of claims 1 to 4 on the outer surface side.