Vinyl chloride-based resin composition, stabilizer composition, modifier, and molded body

Abstract

A vinyl chloride-based resin composition according to the present invention contains a vinyl chloride-based resin (A), a hydrotalcite (B), and one or more stabilizers (C) selected from a group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers, wherein the hydrotalcite (B) has a specific surface area (measured by the BET method) of 5 to 19 m2 / g and is configured to satisfy a prescribed requirement α. Requirement α: Using the vinyl chloride-based resin composition, a resin sheet (thickness 0.7 mm) is prepared using a roll processing machine at 170°C, 30 rpm, and 0.7 mm for 7 minutes, and two of these resin sheets are bonded together to obtain a resin plate under the following conditions. When a b* value in an L*a*b* color system of a resin plate obtained under condition i is taken as a b1 * value, and the b* value in the L*a*b* color system of a resin plate obtained under condition ii is taken as a b2 * value, the b1 * value is 6.0-9.5, and the b2 * value is 15-21. Condition i: Pressed at 190°C for 5 minutes at 80 kg / cm2 and a 1 mm thickness. Condition ii: Pressed at 190°C for 30 minutes at 80 kg / cm2 and a 1 mm thickness.

Description

Vinyl chloride resin composition, stabilizer composition, modifier, and molded article

[0001] The present invention relates to a vinyl chloride resin composition, a stabilizer composition, a modifier, and a molded article.

[0002] By blending with plasticizers and other additives, vinyl chloride resins can have a variety of properties, ranging from hard to semi-hard to soft, and can be used to inexpensively produce molded products with excellent strength and transparency. As a result, they are used in large quantities in pipes, sheets, films, hoses, and other products for civil engineering and building materials, electrical and machinery, daily goods, containers and packaging, agriculture, and more.

[0003] However, it is known that when vinyl chloride resins are heated during or after molding, they undergo thermal decomposition due to a dehydrochlorination reaction, which can lead to deterioration of mechanical properties such as a decrease in strength, discoloration, or molding defects. To prevent these problems, stabilizers for vinyl chloride resins are added.

[0004] Stabilizers for vinyl chloride resins are generally used as stabilizer compositions containing, as a main component, an organic acid salt of zinc, calcium, barium, magnesium, or the like, or an organic tin compound, in combination with a phosphite ester compound, a β-diketone compound, an antioxidant, an epoxy compound, a polyol compound, or the like.

[0005] For example, Patent Document 1 (JP 2017-105929 A) discloses that by combining hydrotalcite, which has a large specific surface area and a small average particle size, with a β-diketone and a metal soap, it is possible to efficiently substitute unstable chlorine in a vinyl chloride resin and efficiently capture hydrogen chloride and released chlorine released during decomposition, thereby obtaining a vinyl chloride resin with excellent thermal stability, coloration resistance, and heat coloration resistance.

[0006] Japanese Patent Application Laid-Open No. 2017-105929

[0007] However, today's vinyl chloride resin compositions are required to have higher performance, and further improvements in durability, transparency, etc. are being sought, and the vinyl chloride resin compositions containing stabilizers that have been proposed so far are no longer sufficient. Furthermore, when vinyl chloride resin compositions are used for a long period of time or exposed to high temperatures, the color and texture of the vinyl chloride resin change, deformation, etc., resulting in a decrease in commercial value, and therefore further improvements are being sought.

[0008] Therefore, the present inventors focused on realizing a vinyl chloride resin composition and a stabilizer composition for vinyl chloride resins that can provide molded articles using the vinyl chloride resin composition that have improved elongation retention while maintaining good appearance.

[0009] As a result of extensive research, the present inventors have unexpectedly discovered a new finding that the use of hydrotalcite having a specific specific surface area can improve the elongation retention of molded articles made from vinyl chloride resin compositions. That is, they have found that good elongation can be maintained even when the molded articles are used for a long period of time or exposed to high temperatures. Furthermore, they have found that molded articles made from vinyl chloride resin compositions become discolored by heat and a portion of the plasticizer escapes from the surface, adding a glittering appearance to the color and significantly deteriorating the appearance. Therefore, they have found that b is used as an index for suppressing such deterioration in appearance. ＊ By focusing on the value, a new index for controlling this was devised, and the present invention was completed.

[0010] That is, according to the present invention, the following techniques relating to vinyl chloride resin compositions and stabilizer compositions for vinyl chloride resins are provided.

[0011] [1] A composition comprising a vinyl chloride resin (A), a hydrotalcite (B), and one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers, wherein the specific surface area (BET method) of the hydrotalcite (B) is 5 to 19 m ２ / g, and satisfying the following requirement α. Requirement α: Using the vinyl chloride resin composition, a resin sheet (thickness 0.7 mm) is prepared by a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes, and two of the resin sheets are laminated together to obtain a resin plate under the following conditions. ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ When the value is １ ＊ The value is 6.0 or more and 9.5 or less, ２ ＊ The value is 15 or more and 21 or less. Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and pressed under the condition of a thickness of 1 mm. [2] The vinyl chloride resin composition according to [1], wherein the hydrotalcite (B) has an average particle size of 0.2 μm or more and 1.0 μm or less. [3] The vinyl chloride resin composition according to [1] or [2], comprising 1 to 20 parts by mass of the hydrotalcite (B) and 0.5 to 10 parts by mass of the stabilizer (C) per 100 parts by mass of the vinyl chloride resin (A). [4] The vinyl chloride resin composition according to any one of [1] to [3], further comprising a plasticizer (D). [5] A stabilizer composition for vinyl chloride resins, comprising hydrotalcite (B) and one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers, wherein the specific surface area (BET method) of the hydrotalcite (B) is 5 to 19 m ２ / g, and satisfies the following requirement β. Requirement β: 10 parts by mass of the stabilizer composition, 100 parts by mass of a vinyl chloride resin (average degree of polymerization 1700), 50 parts by mass of a linear alkyl (C8 and C10) trimellitic triester, and 10 parts by mass of heavy calcium carbonate are mixed at room temperature to prepare a vinyl chloride resin composition. Using the vinyl chloride resin composition, a resin sheet (thickness 0.7 mm) is produced using a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes, and two of the resin sheets are bonded together to obtain a resin plate under the following conditions. The L of the resin plate obtained under condition i ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ When the value is １ ＊ The value is 6.0 or more and 9.5 or less, ２ ＊ The value is 15 or more and 21 or less. Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２, and pressed under the condition of a thickness of 1 mm. [6] The stabilizer composition according to [5], wherein the hydrotalcite (B) has an average particle size of 0.2 μm or more and 1.0 μm or less. [7] The stabilizer composition according to [5] or [6], wherein the content of the hydrotalcite (B) is 70% by mass to 99% by mass based on the total amount of the stabilizer composition. [8] A molded article made of the vinyl chloride resin composition according to any one of [1] to [4]. [9] A modifier for a vinyl chloride resin used in a stabilizer composition containing one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers, wherein the modifier contains hydrotalcite (B), and the specific surface area (BET method) of the hydrotalcite (B) is 5 to 19 m. ２ / g, and the modifier satisfies the following requirement γ. Requirement γ: 8 parts by mass of the modifier, 2 parts by mass of methyltin mercapto, 100 parts by mass of vinyl chloride resin (average degree of polymerization 1700), 50 parts by mass of linear alkyl (C8 and C10) trimellitic triester, and 10 parts by mass of heavy calcium carbonate are mixed at room temperature to prepare a vinyl chloride resin composition. Using the vinyl chloride resin composition, a resin sheet (thickness 0.7 mm) is produced using a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes, and two of the resin sheets are bonded together to obtain a resin plate under the following conditions. The L of the resin plate obtained under condition i ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ When the value is １ ＊ The value is 6.0 or more and 9.5 or less, ２ ＊ The value is 15 or more and 21 or less. Condition i: 190°C, 5 minutes, 80 kg / cm ２, 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and press under the condition of 1 mm thickness.

[0012] According to the present invention, it is possible to provide a vinyl chloride resin composition and a stabilizer composition for vinyl chloride resins that improve the elongation retention of molded articles made from the vinyl chloride resin composition while maintaining a good appearance.

[0013] In this specification, the notation "a to b" in the description of a numerical range means from a to b, unless otherwise specified. For example, "1 to 5 mass%" means "1 mass% to 5 mass%." Furthermore, the lower limit and upper limit of a numerical range can be arbitrarily combined with the lower limit and upper limit of another numerical range.

[0014] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more.

[0015] In this specification, the content of each component in a composition means the total amount of the multiple substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified.

[0016] In this specification, the particle size (μm) is the particle size (D50) corresponding to a cumulative 50% of the volume-based integrated fraction of particles measured by a laser diffraction scattering method.

[0017] The embodiment of this invention will be described below.

[0018] <1. Vinyl chloride resin composition> The vinyl chloride resin composition is a blend based on vinyl chloride resin (PVC) and is in its final form before being processed into a vinyl chloride resin molded article. The vinyl chloride resin composition of this embodiment contains a vinyl chloride resin (A), a hydrotalcite (B), and one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers, and the specific surface area (BET method) of the hydrotalcite (B) is 5 to 19 m ２ / g and is configured to satisfy the following requirement α.

[0019] [Requirement α] Using the vinyl chloride resin composition, a resin sheet (thickness: 0.7 mm) is prepared by a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes, and two of the resin sheets are laminated together to obtain a resin plate under the following conditions. ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ When the value is １ ＊ The value is 6.0 or more and 9.5 or less, ２ ＊ The value is 15 or more and 21 or less. Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and press under the condition of 1 mm thickness.

[0020] According to the vinyl chloride resin composition of this embodiment, a molded article can be obtained that maintains good appearance while improving the elongation retention of the molded article using the vinyl chloride resin composition. That is, conventionally, by simply controlling the YI value, which is known as one of the indicators of thermal stability, there is room for improvement in terms of controlling the deterioration of appearance due to glare and metallic gloss. In contrast, the vinyl chloride resin composition of this embodiment has the advantage that, in addition to the specific surface area of ​​the hydrotalcite (B), the L of the resin plate can be controlled. ＊ a ＊ b ＊ A given b in the color system ＊ By controlling the value, it is possible to obtain a good appearance from a different perspective than before.

[0021] Although the details of the reasons for this are not clear, it is generally known that deterioration of vinyl chloride resins, such as a decrease in elongation and discoloration, occurs when hydrogen chloride released from the vinyl chloride resin promotes further release of hydrogen chloride, leading to a chain reaction. It is believed that hydrotalcite (B) can neutralize this hydrogen chloride by capturing it, thereby suppressing deterioration. It is also believed that the release of plasticizer (D) can be suppressed by, for example, allowing the plasticizer (D) to penetrate between the layers of hydrotalcite (B) or by adsorbing the plasticizer (D) to the surface of hydrotalcite (B). Therefore, it is expected that the larger the specific surface area of ​​hydrotalcite (B), the better the hydrogen chloride capture action and reactivity. However, if the reactivity becomes too high, the reactivity is consumed in a short period of time, and therefore, it is believed that the degradation suppression effect is likely to be reduced when used for a long period of time. Therefore, it is believed that controlling the specific surface area of ​​hydrotalcite (B) is effective. Furthermore, seizure of vinyl chloride resins due to long-term use tends to result in yellow-brown to black coloration. It is assumed that the glare is caused by the addition of the plasticizer that seeps out of the color. ＊ It is believed that by controlling this value as an index, it is possible to effectively suppress deterioration in appearance due to glare.

[0022] The vinyl chloride resin composition of this embodiment uses hydrotalcite (B) having a specific specific surface area and further satisfies the above-mentioned requirement α, which makes it easier to maintain good appearance and elongation of molded articles using the vinyl chloride resin composition. That is, it has been found that by preparing a vinyl chloride resin composition by combining hydrotalcite (B) and stabilizer (C) so as to satisfy requirement α, molded articles using the same can obtain good appearances.

[0023] A vinyl chloride resin composition satisfying the above requirement α can also be achieved by controlling the specific surface area of ​​the hydrotalcite (B), adjusting its particle size, or selecting and adjusting the content of the stabilizer (C). The hydrotalcite (B) specified in this embodiment can be obtained by a known method. For example, a method of wet-pulverizing a slurry to reduce the particle size and increase the specific surface area, a method of increasing the reaction pressure during the synthesis of hydrotalcite to reduce the particle size and increase the specific surface area, or a method of controlling the temperature and pH in the primary reaction, secondary reaction, and hydrothermal reaction using an alkaline aqueous solution, a magnesium salt aqueous solution, or an aluminum salt aqueous solution may be used. Commercially available hydrotalcite may also be used.

[0024] In requirement α, b １ ＊ The value is 6.0 or more and 9.5 or less, preferably 7.0 or more and 9.4 or less, and more preferably 8.3 or more and 9.3 or less. ２ ＊ The value is 15 or more and 21 or less, preferably 17 or more, and more preferably 18.5 or more. １ ＊ value and b ２ ＊ By setting the value to be equal to or greater than the lower limit, good appearance can be improved and good elongation retention can be obtained. １ ＊ value and b ２ ＊ By setting the value to be equal to or less than the above upper limit, it is possible to improve the balance between good elongation retention and appearance.

[0025] Hereinafter, each component contained in the vinyl chloride resin composition will be described in detail.

[0026] [Vinyl chloride resin (A)] The vinyl chloride resin (A) of the present embodiment is not limited by its polymerization method, and any resin obtained by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization can be used without particular limitation.

[0027] As the vinyl chloride resin (A) of this embodiment, for example, a chlorine-containing resin containing chlorine in its structure can be used, and examples thereof include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, and the like. Examples of vinyl chloride resins (A) include pyrene copolymers, vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, and vinyl chloride-various vinyl ether copolymers, as well as blends thereof and other chlorine-free synthetic resins such as acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth)acrylate copolymers, blends with polyesters, block copolymers, graft copolymers, etc. These vinyl chloride resins (A) may be a mixture of two or more types, or may be a mixture with other synthetic resins.

[0028] The average degree of polymerization of the vinyl chloride resin (A) is preferably from 300 to 10,000, more preferably from 500 to 5,000, and even more preferably from 1,000 to 3,000.

[0029] Commercially available vinyl chloride resins (A) can be used, including TH-640, TH-700, and TH-800 manufactured by Taiyo Vinyl Corporation, S-1004, S-1008, and PSH-10 manufactured by Kaneka Corporation, TK-700, TK-800, and TK-1300 manufactured by Shin-Etsu Polymer Co., Ltd., and ZEST1000 and PQHPN manufactured by Shin-Daiichi Vinyl Corporation.

[0030] [Hydrotalcite (B)] The hydrotalcite (B) of this embodiment is used to obtain thermal stability, good elongation, and good appearance.

[0031] The specific surface area (BET method) of hydrotalcite (B) is 5 m ２ / g or more, preferably 7m ２ / g or more, and more preferably 8m ２ / g or more, and more preferably 9m ２ This makes it easier to obtain a good appearance while obtaining good elongation retention. The specific surface area (BET method) of the hydrotalcite (B) is 19 m ２ / g or less, preferably 18m ２ / g or less, more preferably 17m ２ / g or less, more preferably 15m ２ / g or less, more preferably 14m ２ This improves the elongation retention and maintains a good appearance.

[0032] Specifically, a double salt compound composed of magnesium and aluminum, or zinc, magnesium, and aluminum, is preferably used as the hydrotalcite (B). It may also be one in which water of crystallization has been dehydrated. It may also be one that has been treated with perchloric acid. Such hydrotalcite (B) may be a natural product or a synthetic product.

[0033] Specifically, examples of the hydrotalcite (B) of this embodiment include compounds represented by the following formula (I):

[0034] M ２＋ １－ｘ M ３＋ ｘ (OH) ２ A ｎ－ ｘ／ｎ ・mH ２ O (I)

[0035] In formula (I), M ２＋ is a divalent metal ion, such as magnesium, iron, zinc, calcium, lithium, nickel, cobalt, or copper ion; M３＋ is a trivalent metal ion, such as an ion of aluminum, iron, manganese, or chromium; A ｎ－ is an interlayer anion, such as a carbonate ion, a chloride ion, or a nitrate ion, x is in the range of 0<x≦0.33, m is 0 or any positive number, and n is a positive integer.

[0036] Further, specific examples include the following compounds: Mg ０．７５ Mn ０．２５ (OH) ２ (CO ３ ) ０．１２５ ・0.5H ２ O Mg ０．７５ Al ０．２５ (OH) ２ (CO ３ ) ０．１２５ ・0.5H ２ O Mg ０．６９２ Al ０．３０８ (OH) ２ (CO ３ ) ０．１５４ ・0.1H ２ O Mg ０．６８３ Al ０．３１７ (OH) ２ (CO ３ ) ０．１５９ ・0.5H ２ O Mg ０．６６７ Al ０．３３３ (OH) ２ (CO ３ ) ０．１６７ ・0.1H ２ O Mg ０．７５ Al ０．２５ (OH) ２ (ClO ４ ) ０．２５ ・0.5H ２ O Mg ０．６９２ Al ０．３０８ (OH) ２ (ClO ４ ) ０．３０８ ・0.1H ２ O Mg ０．６６７ Al ０．３３３ (OH) ２ (ClO ４ ) ０．３３３ ・0.1H ２ O Mg ０．７５ Fe０．２５ (OH) ２ Cl ０．１２５ ・0.5H ２ O Mg ０．７５ Fe ０．２５ (OH) ２ (CO ３ ) ０．１２５ ・0.5H ２ O Mg ０．７５ Cr ０．２５ (OH) ２ (CO ３ ) ０．１２５ ・0.5H ２ O Ni ０．７５ Al ０．２５ (OH) ２ (CO ３ ) ０．１２５ ・0.5H ２ OZn ０．６６７ Al ０．３３３ (OH) ２ (CO ３ ) ０．１７ ・0.5H ２ O

[0037] Furthermore, the hydrotalcite (B) of this embodiment is more preferably a compound represented by the following formula (II): Mg （１－ｘ） Al ｘ (OH) ２ (CO ３ ) ｘ／２ ・mH ２ O (II)

[0038] Furthermore, the hydrotalcite (B) may be one whose surface is coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal salt of oleic acid, an organic sulfonic acid metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or a wax.

[0039] In the stabilizer composition of the present embodiment, the hydrotalcite (B) may be used alone or in combination of two or more kinds.

[0040] The average particle size (D50) of the hydrotalcite (B) is preferably 0.1 μm or more, preferably 0.2 μm or more, and preferably 0.3 μm or more. On the other hand, the average particle size (D50) of the hydrotalcite (B) is preferably 1.0 μm or less, more preferably 0.9 μm or less, even more preferably 0.8 μm or less, and particularly preferably 0.5 μm or less. By setting the average particle size of the hydrotalcite (B) to the above-mentioned lower limit or more, good physical properties as a vinyl chloride resin composition can be maintained. On the other hand, by setting the average particle size of the hydrotalcite (B) to the above-mentioned upper limit or less, elongation retention can be further improved.

[0041] The average particle size (D50) of the hydrotalcite (B) is a particle size corresponding to a cumulative 50% of the volume-based integrated fraction determined by a laser diffraction scattering method, and can be measured using a "Microtrac particle size analyzer (MT3300EX)" or the like.

[0042] The content of the hydrotalcite (B) is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, even more preferably 5 to 12 parts by mass, and particularly preferably 8 to 10 parts by mass, relative to 100 parts by mass of the vinyl chloride resin (A). By setting the content of the hydrotalcite (B) to the above-mentioned lower limit or more, it is possible to obtain a good appearance while improving elongation retention. On the other hand, by setting the content of the hydrotalcite (B) to the above-mentioned upper limit or less, it is possible to maintain good processability while maintaining a moderate elongation.

[0043] [Stabilizer (C)] The stabilizer (C) of the present embodiment is preferably one or more selected from the group consisting of complex metal soap-based stabilizers, organotin-based stabilizers, and lead-based stabilizers. Among these, the stabilizer (C) is more preferably a complex metal soap-based stabilizer or an organotin-based stabilizer, and even more preferably an organotin-based stabilizer.

[0044] (Complex Metal Soap-Based Stabilizer) The complex metal soap-based stabilizer is a stabilizer that uses a complex metal salt obtained by combining a complex metal salt with an organic acid. The complex metal is not particularly limited as long as it is a so-called non-toxic metal other than lead and cadmium, and examples thereof include barium (Ba) / zinc (Zn)-based, calcium (Ca) / Zn-based, Ca / magnesium (Mg)-based, Ba / Ca / Zn-based, and Ca / Mg / Zn-based complex metals. Examples of organic acids include organic carboxylic acids, phenols, and organic phosphoric acids, with organic carboxylic acids being preferred. Specifically, the organic carboxylic acid is a long-chain fatty acid having 10 to 22 carbon atoms, preferably a saturated or unsaturated fatty acid having 14 to 18 carbon atoms. Specific examples include saturated fatty acids such as 2-ethylhexanoic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, hydroxystearic acid, behenic acid, and arachidic acid; and unsaturated fatty acids such as linderic acid, tsuzuic acid, petroselinic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and arachidonic acid.

[0045] (Organotin stabilizer) The organotin stabilizer may be any known stabilizer that has been widely used as a stabilizer for vinyl chloride resins.As the organotin stabilizer, for example, octyltin mercaptide-based stabilizers such as methyltin mercapto, dimethyltin mercapto, dibutyltin mercapto, and dioctyltin mercapto; octyltin maleate-based stabilizers such as dibutyltin maleate, dibutyltin maleate polymer, dioctyltin maleate, and dioctyltin maleate polymer;

[0046] (Lead-Based Stabilizer) The lead-based stabilizer may also be any known stabilizer that has been widely used as a stabilizer for vinyl chloride resins. Examples of the lead-based stabilizer include inorganic lead stabilizers such as white lead, basic lead sulfite, dibasic lead sulfite, tribasic lead sulfate, dibasic lead phosphite, and silica gel coprecipitated lead silicate; lead stearate, lead laurate, lead benzoate, dibasic lead stearate, and lead naphthenate.

[0047] The content of the stabilizer (C) is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the vinyl chloride resin (A). By setting the content of the stabilizer (C) to the above-mentioned lower limit or more, good thermal stability can be obtained. On the other hand, by setting the content of the stabilizer (C) to the above-mentioned upper limit or less, the appearance of the molded article can be improved and good mechanical strength can be maintained.

[0048] Furthermore, the mass ratio of the stabilizer (C) to the hydrotalcite (B) (stabilizer (C) / hydrotalcite (B)) is preferably 0.10 to 0.50, more preferably 0.11 to 0.40, even more preferably 0.12 to 0.30, and still more preferably 0.13 to 0.20, from the viewpoint of obtaining good elongation retention and appearance.

[0049] [Others] In addition to the hydrotalcite (B) and stabilizer (C), the vinyl chloride resin composition of the present embodiment may contain known additives such as a plasticizer (D), an antioxidant, a β-diketone compound, an ultraviolet absorber, a lubricant, a processing aid, a hindered amine light stabilizer, perchlorates, inorganic aids, fillers, colorants, crosslinking agents, antistatic agents, plate-out inhibitors, surface treatment agents, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, release agents, pigments, and foaming agents. It is preferable that the vinyl chloride resin composition of the present embodiment does not contain a calcium hydroxide solid solution.

[0050] (Plasticizer (D)) The plasticizer (D) is used to impart flexibility and facilitate processing. Examples of the plasticizer (D) include phthalate-based plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; adipate-based plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, and di(butyldiglycol) adipate; phosphate-based plasticizers such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(isopropylphenyl)phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri(butoxyethyl)phosphate, and octyldiphenyl phosphate; ethylene glycol, diethylene glycol, and the like. Examples of suitable plasticizers include polyester-based plasticizers that use a polyhydric alcohol such as ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, or neopentyl glycol, and a dibasic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, or terephthalic acid, and optionally a monohydric alcohol or a monocarboxylic acid as a stopper; tetrahydrophthalic acid-based plasticizers, azelaic acid-based plasticizers, sebacic acid-based plasticizers, stearic acid-based plasticizers, citric acid-based plasticizers, trimellitic acid-based plasticizers, pyromellitic acid-based plasticizers, and biphenylene polycarboxylic acid-based plasticizers. These plasticizers may be used alone or in combination of two or more. Of these, trimellitic acid-based plasticizers are preferred.

[0051] Specific examples of trimellitic acid plasticizers include linear alkyl trimellitic acid triesters such as trioctyl trimellitate (particularly n-octyl), tridecyl (n-decyl) trimellitate, trinonyl (n-nonyl) trimellitate, and tripentyl (n-pentyl) trimellitate; and branched alkyl trimellitic acid triesters such as tris(2-ethylhexyl) trimellitate, triisononyl trimellitate, and triisodecyl trimellitate. Furthermore, trimellitic acid plasticizers may contain a mixture of linear or branched alkyl groups with different carbon numbers (C6 to C12) in one molecule. For example, they may be linear alkyl trimellitic acid triesters (linear alkyl (C8 and C10) trimellitic acid triesters) containing a mixture of linear alkyl groups with 8 and 10 carbon atoms in one molecule.

[0052] The content of the plasticizer (D) is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, per 100 parts by mass of the vinyl chloride resin (A). By setting the content of the plasticizer (D) to the above-mentioned lower limit or more, good thermal stability can be obtained. On the other hand, by setting the content of the plasticizer (D) to the above-mentioned upper limit or less, the appearance of the molded article can be improved and good mechanical strength can be maintained.

[0053] (Antioxidant) The antioxidant is not particularly limited as long as it is a conventionally known antioxidant, and examples thereof include phenolic antioxidants and sulfur-based antioxidants. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and the like. nate)], 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butylic acid]glycol ester, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylenebis(4-ethyl-6-tert-butylphenol), Ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc.

[0054] The content of the phenolic antioxidant is 0.01 to 1 part by mass, preferably 0.01 to 0.8 parts by mass, more preferably 0.01 to 0.7 parts by mass, and even more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the vinyl chloride resin (A).

[0055] Examples of sulfur-based antioxidants include dialkyl thiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and β-alkyl mercaptopropionates of polyols such as pentaerythritol tetra(β-dodecylmercaptopropionate). These sulfur-based antioxidants may be used alone or in combination of two or more.

[0056] (β-diketone compounds) Examples of β-diketone compounds include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, distearoylmethane, stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, bis(acetylacetonyl) ... Examples of suitable metal salts include (4-octylbenzoyl)methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis(4-carboxymethylbenzoyl)methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, ethyl acetoacetate, cyclohexane-1,3-dione, methyl 3,6-dimethyl-2,4-dioxycyclohexane-1-carboxylate, 2-acetylcyclohexanone, dimedone, and 2-benzoylcyclohexane. Metal salts of these salts can also be used. Examples of suitable metal salts include lithium salts, sodium salts, potassium salts, calcium salts, zinc salts, magnesium salts, and aluminum salts. Preferred examples of suitable metal salts include calcium acetylacetone and zinc acetylacetone.

[0057] (ultraviolet absorber) Examples of ultraviolet absorbers include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol, and polyethylene glycol esters of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole; phenyl salicylate, benzoates such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; methyl-α-cyano-β,β-diphenylacrylate, methyl- cyanoacrylates such as 2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine. These ultraviolet absorbers may be used alone or in combination of two or more.

[0058] (Lubricant) The lubricant is used to improve the processability of the vinyl chloride resin (A). Examples of lubricants include hydrocarbon-based lubricants such as low molecular weight wax, paraffin wax, polyethylene wax, chlorinated hydrocarbons, and fluorocarbons; natural wax-based lubricants such as carnauba wax and candelilla wax; fatty acid-based lubricants such as higher fatty acids such as lauric acid, stearic acid, and behenic acid, or hydroxy fatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide, and oleylamide, or alkylene bisaliphatic amides such as methylene bisstearylamide and ethylene bisstearylamide; fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, and distearyl phthalate. or fatty acid alcohol ester-based lubricants such as fatty acid polyhydric alcohol ester compounds such as glycerin tristearate, sorbitan tristearate, pentaerythritol tetrastearate, dipentaerythritol hexastearate, polyglycerin polyricinoleate, and hydrogenated castor oil, or complex ester compounds of monobasic fatty acids and polybasic organic acids with polyhydric alcohols, such as dipentaerythritol adipic acid-stearic acid ester; aliphatic alcohol-based lubricants such as stearyl alcohol, lauryl alcohol, and palmityl alcohol; metal soaps; montanic acid-based lubricants such as partially saponified montanic acid ester; acrylic lubricants; silicone oil, etc. These lubricants may be used alone or in combination of two or more.

[0059] When a lubricant is contained, the content of the lubricant is preferably 0.01 to 5.0 parts by mass, more preferably 0.05 to 4.0 parts by mass, and even more preferably 0.1 to 3.0 parts by mass, relative to 100 parts by mass of the vinyl chloride resin (A) from the viewpoint of processability.

[0060] (Processing Aid) The processing aid can be appropriately selected from known processing aids. Examples of processing aids include homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; copolymers of the above alkyl methacrylates with alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; copolymers of the above alkyl methacrylates with aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; and copolymers of the above alkyl methacrylates with vinyl cyan compounds such as acrylonitrile and methacrylonitrile. These processing aids may be used alone or in combination of two or more.

[0061] When a processing aid is contained, the content of the processing aid is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the vinyl chloride resin (A).

[0062] (Perchlorates) Examples of perchlorates include metal perchlorates, ammonium perchlorate, and perchlorate-treated silicates. Examples of metals constituting these metal salts include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and aluminum. The metal perchlorates may be anhydrous or hydrated, or may be dissolved in an alcohol-based or ester-based solvent such as butyl diglycol or butyl diglycol adipate, or a dehydrate thereof. These perchlorates may be used alone or in combination of two or more.

[0063] (Hindered Amine Light Stabilizer) Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, and tetrakis(2,2,6,6-tetramethyl-4-piperidyl). tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5 -di-tert-butyl-4-hydroxybenzyl)malonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], 1,2,3,4-butanecarboxylic acid / 2,2-bis(hydroxymethyl)-1,3-propanediol / 3-hydroxy-2,2-dimethylpropanal / 1,2,2,6,6-pentamethyl-4-piperidinyl ester polycondensate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate / methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate mixture, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / dibromoethane polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine azin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-ylamino]undecane , 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-ylamino]undecane, 3,9-bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[1,1-dimethyl-2-{ tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 2,2,6,6-tetramethyl-4-piperidylhexadecanoate, 2,2,6,6-tetramethyl-4-piperidyloctadecanoate, etc. The hindered amine light stabilizer may be used alone or in combination of two or more types.

[0064] (Inorganic Auxiliary Agent) Examples of inorganic auxiliary agents include hydrotalcite compounds other than the hydrotalcite (B) and zeolite compounds.

[0065] As the hydrotalcite compound other than the hydrotalcite (B), a double salt compound composed of magnesium and aluminum, or zinc, magnesium, and aluminum is preferably used. It may also be one in which the water of crystallization has been dehydrated. Such a hydrotalcite compound may be a natural product or a synthetic product. There are no limitations on the crystal structure, crystal particle size, etc. of the hydrotalcite compound. Furthermore, hydrotalcite compounds whose surfaces are coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal salt of oleic acid, an organic sulfonic acid metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or a wax may also be used.

[0066] Zeolite compounds are aluminosilicates of alkali or alkaline earth metals having a unique three-dimensional zeolite crystal structure, and representative examples thereof include A-type, X-type, Y-type, and P-type zeolites, monodenite, analcite, sodalite-group aluminosilicates, clinobutyrolite, erionite, and chabazite. These zeolite compounds may be either hydrous compounds containing water of crystallization (so-called zeolite water) or anhydrous compounds from which the water of crystallization has been removed. Zeolite compounds having a particle size of 0.1 to 50 μm can be used, with 0.5 to 10 μm being preferred. The inorganic auxiliary may be used alone or in combination of two or more types.

[0067] In this embodiment, when an inorganic auxiliary is contained, the content of the hydrotalcite (B) is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 99% by mass or more, relative to the total amount of the inorganic auxiliary, and may be 100% by mass.

[0068] [Method for Producing Vinyl Chloride Resin Composition] The vinyl chloride resin composition of the present embodiment can be molded by a known molding method, such as roll processing, extrusion molding, melt casting, pressure molding, injection molding, or calendar molding.

[0069] 2. Stabilizer Composition The stabilizer composition of the present embodiment is for use in vinyl chloride resins, and is an additive (mixture) used as one component of the vinyl chloride resin composition described above.

[0070] The stabilizer composition of the present embodiment is a stabilizer composition for vinyl chloride resins, comprising hydrotalcite (B) and one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers, wherein the specific surface area (BET method) of the hydrotalcite (B) is 5 to 19 m ２ / g and is configured to satisfy the following requirement β.

[0071] Requirement β: 10 parts by mass of the stabilizer composition, 100 parts by mass of a vinyl chloride resin (average degree of polymerization 1700), 50 parts by mass of a linear alkyl (C8 and C10) trimellitic triester, and 10 parts by mass of heavy calcium carbonate are mixed at room temperature to prepare a vinyl chloride resin composition. Using the vinyl chloride resin composition, a resin sheet (thickness 0.7 mm) is produced using a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes, and two of the resin sheets are bonded together to obtain a resin plate under the following conditions. The L of the resin plate obtained under condition i ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ When the value is １ ＊ The value is 6.0 or more and 9.5 or less, ２ ＊ The value is 15 or more and 21 or less. Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and press under the condition of 1 mm thickness.

[0072] The stabilizer composition of this embodiment uses hydrotalcite (B) having a specific specific surface area, thereby improving the elongation retention of a molded article made from a vinyl chloride resin composition containing the stabilizer composition of this embodiment while maintaining a good appearance. That is, conventionally, by simply controlling the YI value, which is known as one of the indicators of thermal stability, there was room for improvement in terms of controlling the deterioration of appearance due to glare and metallic gloss. In contrast, the stabilizer composition of this embodiment uses the L of the resin plate in addition to the specific surface area of ​​the hydrotalcite (B). ＊ a ＊ b ＊ A given b in the color system ＊ By controlling the value, it is possible to obtain a good appearance from a different perspective than before.

[0073] A stabilizer composition that satisfies the above requirement β can be realized by adjusting the specific surface area or particle size of the hydrotalcite (B), or by adjusting the selection and content of the stabilizer (C).

[0074] Each component contained in the stabilizer composition will be described in detail below.

[0075] The hydrotalcite (B) and stabilizer (C) contained in the stabilizer composition of this embodiment may be the same as those described for the vinyl chloride resin composition. The stabilizer composition may comprise hydrotalcite (B) and one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers.

[0076] Furthermore, the content of the hydrotalcite (B) in the stabilizer composition of the present embodiment is not particularly limited, and can be adjusted depending on the content of the vinyl chloride resin (A) in the vinyl chloride resin composition to which the stabilizer composition is applied.

[0077] In addition, in the stabilizer composition of the present embodiment, the mass ratio of the stabilizer (C) to the hydrotalcite (B) (stabilizer (C) / hydrotalcite (B)) is preferably 0.10 to 0.50, more preferably 0.15 to 0.40, and even more preferably 0.20 to 0.30, from the viewpoint of obtaining good elongation retention and appearance.

[0078] [Solvent] The stabilizer composition of the present embodiment may contain a solvent from the viewpoint of solubility of the stabilizer component. The solvent is preferably an organic solvent, more preferably an organic solvent having a boiling point of 100°C or higher, even more preferably an organic solvent having a boiling point of 120°C or higher, and particularly preferably an organic solvent having a boiling point of 150°C or higher. Examples of preferred organic solvents include alcohol-based organic solvents such as 3-methoxy-n-butanol, 2-ethylhexanol, undecanol, and tridecanol; glycol-based organic solvents such as methyl diglycol, butyl diglycol, and methyl propylene glycol; and hydrocarbon solvents such as liquid paraffin, naphthenic solvents, normal paraffinic solvents, isoparaffinic solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and mineral oil. Only one solvent may be used, or two or more solvents may be used in combination.

[0079] [Others] In addition to the hydrotalcite (B), stabilizer (C), and solvent, the stabilizer composition of the present embodiment can use the same additives as those described for the vinyl chloride resin composition, and may also use known additives such as plasticizer (D), antioxidant, UV absorber, lubricant, processing aid, filler, colorant, crosslinking agent, antistatic agent, plate-out inhibitor, surface treatment agent, flame retardant, fluorescent agent, antifungal agent, bactericide, metal deactivator, mold release agent, pigment, and foaming agent. These known additives may be contained in either the vinyl chloride resin composition or the stabilizer composition, or may be contained in both.

[0080] [Method for Producing Stabilizer Composition] The method for producing the stabilizer composition of this embodiment is not particularly limited, and may involve mixing hydrotalcite (B), one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers, as well as optional components and, if necessary, a solvent. Various mixers can be used for mixing. Heating may also be applied during mixing. Examples of mixers include a tumbler mixer, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a Super Mixer, and a Nauta mixer. Alternatively, the above components may be directly blended with the vinyl chloride resin (A) individually or in combination to prepare a vinyl chloride resin composition.

[0081] [Method of Using the Stabilizer Composition] The stabilizer composition of this embodiment is used by adding it to a vinyl chloride resin (A) or a vinyl chloride resin composition containing a vinyl chloride resin. The amount of the stabilizer composition of this embodiment used is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 7.0 parts by mass, and even more preferably 1.0 to 4.0 parts by mass, per 100 parts by mass of the vinyl chloride resin (A). By using an amount of the stabilizer composition that is equal to or greater than the above-mentioned lower limit, stability is easily improved, and by using an amount that is equal to or less than the above-mentioned upper limit, the properties of the vinyl chloride resin (A) are easily maintained while maintaining stability.

[0082] <3. Modifier> The modifier is intended to be a modifier used in a stabilizer composition for vinyl chloride resins, which contains one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers. When used in a stabilizer composition, the modifier has the function of imparting elongation and the like to a molded article made of a vinyl chloride resin composition using the same. The modifier of this embodiment contains hydrotalcite (B), and the hydrotalcite (B) has a specific surface area (BET method) of 5 to 19 m. ２ / g and preferably satisfies the following requirement γ: This allows for the production of molded articles using the vinyl chloride resin composition that have improved elongation retention while maintaining good appearance.

[0083] Requirement γ: 8 parts by mass of the modifier, 2 parts by mass of methyltin mercapto, 100 parts by mass of vinyl chloride resin (average degree of polymerization 1700), 50 parts by mass of linear alkyl (C8 and C10) trimellitic triester, and 10 parts by mass of heavy calcium carbonate are mixed at room temperature to prepare a vinyl chloride resin composition. Using the vinyl chloride resin composition, a resin sheet (thickness 0.7 mm) is produced using a roll processing machine at 170 ° C, 30 rpm, 0.7 mm, and 7 minutes, and two of the resin sheets are bonded together to obtain a resin plate under the following conditions. The L of the resin plate obtained under condition i ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ When the value is １ ＊ The value is 6.0 or more and 9.5 or less, ２ ＊ The value is 15 or more and 21 or less. Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and press under the condition of 1 mm thickness.

[0084] A modifier that satisfies the above requirement γ can be realized by adjusting the specific surface area or particle size of the hydrotalcite (B).

[0085] Specifically, the modifier may be hydrotalcite (B).

[0086] <4. Molded Article> The molded article of this embodiment is obtained from the vinyl chloride resin composition of this embodiment. Examples of the molded article of this embodiment include piping materials such as pipes, joints, and piping components; building and structural materials such as wall materials, flooring materials, window frames, corrugated sheets, and gutters; automotive interior and exterior materials; electric wire coating materials; agricultural materials; food packaging materials; miscellaneous goods such as packing, gaskets, hoses, sheets, trays, bottles, and toys, daily necessities, stationery, decorative panels, industrial panels, and IC cases. Among these, the molded article is suitable for use in rigid or semi-rigid transparent molded articles, and specifically can be used for containers, industrial panels, decorative panels, trays, films, shrink films, sheets, building materials, water supply and drainage pipes, plates, joints, automotive materials, hoses, IC cases, and bottles, which require glass-like transparency.

[0087] Although the embodiments of this embodiment have been described above, these are merely examples of this embodiment, and various other configurations can also be adopted.

[0088] Next, the present invention will be described in detail with reference to examples, but the contents of the present embodiment are not limited to the examples.

[0089] Examples and Comparative Examples (1) Raw Materials [Vinyl chloride resin (A)] PVC "TK-1700E" manufactured by Shin-Etsu Chemical Co., Ltd., average degree of polymerization 1700 [Hydrotalcite (B)] Hydrotalcites 1 to 10: Water, basic magnesium carbonate, aluminum hydroxide, and sodium hydroxide were mixed and reacted at a certain temperature for a certain time, and then subjected to the steps of cooling, solid-liquid separation, washing, dehydration, drying, and pulverization to give hydrotalcites having a specific surface area (g / m) shown in Tables 1 and 2. ２Hydrotalcites 1 to 10 with different particle sizes (μm) were prepared. [Stabilizer (C)] Ca / Zn stabilizer (composition: zinc stearate 1.0 part by mass, calcium stearate 0.3 part by mass) Organotin stabilizer: methyltin mercapto [Plasticizer (D)] Trimellitic acid plasticizer: linear alkyl (C8 and C10) trimellitic acid triester containing a mixture of linear alkyls having 8 and 10 carbon atoms, "ADEKACIZER C-810L" (manufactured by ADEKA Corporation) [Additives] Phenol antioxidant: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], "ADEKASTAB AO-60" (manufactured by ADEKA Corporation) β-diketone compound: stearoylbenzoylmethane

[0090] (2) Preparation of stabilizer composition and modifier In this example, a mixture of stabilizer (C) and hydrotalcite (B) was used as the stabilizer composition, and hydrotalcite (B) was used as the modifier. The stabilizer composition and modifier were prepared according to the formulations (parts by mass) shown in Tables 1 and 2.

[0091] (3) Preparation of Vinyl Chloride Resin Compositions Vinyl chloride resin (A) and the stabilizer composition obtained above were blended in a Henschel mixer according to the formulations (parts by mass) shown in Tables 1 and 2 to obtain each vinyl chloride resin composition.

[0092] (4) Physical Properties The following tests were conducted for requirement α. The results are shown in Tables 1 and 2. Using each vinyl chloride resin composition obtained in (3) above, a resin sheet (thickness 0.7 mm) was prepared using a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes. Two of the resin sheets were bonded together to obtain a resin plate under the following conditions. The L of the resin plate obtained under condition i ＊ a ＊ b ＊ L in color system ＊ Value, a ＊ value, b ＊ The values ​​were measured and １ ＊ Value, a １ ＊ value, b １ ＊value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ L in color system ＊ Value, a ＊ value, b ＊ The values ​​were measured and ２ ＊ Value, a ２ ＊ value, b ２ ＊ Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and press under the condition of 1 mm thickness.

[0093] The following test was conducted regarding requirement β. As a result, the results for Examples 12 to 17 and Comparative Examples 6 to 9 were the same as those for requirement α. Requirement β: A vinyl chloride resin composition was prepared by mixing 10 parts by mass of the stabilizer composition obtained in (2) above, 100 parts by mass of a vinyl chloride resin (average degree of polymerization 1700), 50 parts by mass of a linear alkyl (C8 and C10) trimellitic triester, and 10 parts by mass of heavy calcium carbonate at room temperature. Using the vinyl chloride resin composition, a resin sheet (thickness 0.7 mm) was produced using a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes, and two of the resin sheets were bonded together to obtain a resin plate under the following conditions. The L of the resin plate obtained under condition i ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and press under the condition of 1 mm thickness.

[0094] The following test was conducted regarding requirement γ. As a result, the results for Examples 12 to 17 and Comparative Examples 6 to 9 were the same as those for requirement α. Requirement γ: A vinyl chloride resin composition was prepared by mixing 8 parts by mass of the modifier (hydrotalcite) prepared in (2) above, 2 parts by mass of methyltin mercapto, 100 parts by mass of a vinyl chloride resin (average degree of polymerization 1700), 50 parts by mass of a linear alkyl (C8 and C10) trimellitic triester, and 10 parts by mass of heavy calcium carbonate at room temperature. Using the vinyl chloride resin composition, a resin sheet (thickness 0.7 mm) was produced using a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes. Two of the resin sheets were bonded together to obtain a resin plate under the following conditions. The L of the resin plate obtained under condition i ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and press under the condition of 1 mm thickness.

[0095] (5) Evaluation The vinyl chloride resin compositions thus obtained were subjected to the following heat aging property tests. The evaluation results are shown in Tables 1 and 2.

[0096] <Test> Using each of the obtained vinyl chloride resin compositions, vinyl chloride sheets were produced using a roll processing machine under the following conditions: Conditions: 170°C, 20 rpm, 0.3 mm, 11 minutes (the sheet was adjusted to a thickness of 0.3 mm to 1.2 mm just before lifting). Next, the obtained vinyl chloride sheets were pressed using a press (conditions: 180°C, compressed to 1 mm, 5 minutes, 50 kg / cm). ２) was performed to prepare a plate. Test pieces for tensile testing were prepared from the prepared plate using a JIS K71132 dumbbell. The test pieces were placed in an oven at 158°C and removed after 168 hours, 504 hours, 600 hours, and 840 hours, and the following evaluations were performed on each test piece.

[0097] [Measurement of Elongation Percentage] A tensile test was performed at a tensile speed of 200 mm / min using the following tensile tester on the test specimens before they were placed in the oven and on the test specimens after they were removed from the oven and cooled to room temperature, and the elongation percentage (%) of each test specimen was measured. The elongation percentage (%) was calculated by [gage line movement distance (mm)] ÷ [initial gage line distance (2.5 mm)] × 100. Testing equipment name: Autograph AGS-X (Shimadzu Corporation)

[0098] [Appearance] The test piece before being placed in the oven (control) and the test piece after being removed from the oven and cooled to room temperature were observed, and the appearance of the test piece after being removed from the oven and cooled to room temperature was evaluated according to the following criteria. (Criteria) A: The test piece discolored to yellow or brown, but there was no glare or stickiness on the surface, and no shrinkage. B: The test piece discolored to brown or black, there was some glare and stickiness on the surface, and there was some shrinkage. C: The test piece discolored to black, there was some glare and stickiness on the surface, and there was significant shrinkage.

[0099]

[0100]

[0101] This application claims priority based on Japanese Patent Application No. 2024-105989, filed July 1, 2024, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A composition comprising a vinyl chloride resin (A), a hydrotalcite (B), and one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers, wherein the specific surface area (BET method) of the hydrotalcite (B) is 5 to 19 m ２ / g, and satisfying the following requirement α. Requirement α: Using the vinyl chloride resin composition, a resin sheet (thickness 0.7 mm) is prepared by a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes, and two of the resin sheets are laminated together to obtain a resin plate under the following conditions. ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ When the value is １ ＊ The value is 6.0 or more and 9.5 or less, ２ ＊ The value is 15 or more and 21 or less. Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and press under the condition of 1 mm thickness.

2. The vinyl chloride resin composition according to claim 1, wherein the hydrotalcite (B) has an average particle size of 0.2 μm or more and 1.0 μm or less.

3. The vinyl chloride resin composition according to claim 1 or 2, comprising 1 to 20 parts by mass of the hydrotalcite (B) and 0.5 to 10 parts by mass of the stabilizer (C) per 100 parts by mass of the vinyl chloride resin (A).

4. The vinyl chloride resin composition according to any one of claims 1 to 3, further comprising a plasticizer (D).

5. A stabilizer composition for vinyl chloride resins, comprising hydrotalcite (B) and one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers, wherein the specific surface area (BET method) of the hydrotalcite (B) is 5 to 19 m ２ / g, and satisfies the following requirement β. Requirement β: 10 parts by mass of the stabilizer composition, 100 parts by mass of a vinyl chloride resin (average degree of polymerization 1700), 50 parts by mass of a linear alkyl (C8 and C10) trimellitic triester, and 10 parts by mass of heavy calcium carbonate are mixed at room temperature to prepare a vinyl chloride resin composition. Using the vinyl chloride resin composition, a resin sheet (thickness 0.7 mm) is produced using a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes, and two of the resin sheets are bonded together to obtain a resin plate under the following conditions. The L of the resin plate obtained under condition i ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ When the value is １ ＊ The value is 6.0 or more and 9.5 or less, ２ ＊ The value is 15 or more and 21 or less. Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and press under the condition of 1 mm thickness.

6. The stabilizer composition according to claim 5, wherein the hydrotalcite (B) has an average particle size of 0.2 μm or more and 1.0 μm or less.

7. The stabilizer composition according to claim 5 or 6, wherein the content of the hydrotalcite (B) is 70% by mass to 99% by mass based on the total amount of the stabilizer composition.

8. A molded article made from the vinyl chloride resin composition according to any one of claims 1 to 4.

9. A modifier for use in a stabilizer composition for vinyl chloride resins, which contains one or more stabilizers (C) selected from the group consisting of complex metal soap-based, organotin-based, and lead-based stabilizers, the modifier containing hydrotalcite (B), and the specific surface area (BET method) of the hydrotalcite (B) is 5 to 19 m ２ / g and satisfying the following requirement γ: Requirement γ: A vinyl chloride resin composition is prepared by mixing 8 parts by mass of the modifier, 2 parts by mass of methyltin mercapto, 100 parts by mass of a vinyl chloride resin (average degree of polymerization 1700), 50 parts by mass of a linear alkyl (C8 and C10) trimellitic triester, and 10 parts by mass of heavy calcium carbonate at room temperature. Using the vinyl chloride resin composition, a resin sheet (thickness: 0.7 mm) was prepared by a roll processing machine at 170°C, 30 rpm, 0.7 mm, and 7 minutes, and two of the resin sheets were laminated together to obtain a resin plate under the following conditions. ＊ a ＊ b ＊ b in the color system ＊ The value is b １ ＊ value, and the L of the resin plate obtained under condition ii ＊ a ＊ b ＊ b in the color system ＊ The value is b ２ ＊ When the value is １ ＊ The value is 6.0 or more and 9.5 or less, ２ ＊ The value is 15 or more and 21 or less. Condition i: 190°C, 5 minutes, 80 kg / cm ２ , 1 mm thickness. Condition ii: 190 ° C, 30 minutes, 80 kg / cm ２ , and press under the condition of 1 mm thickness.

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