JP2017105929A - Vinyl chloride-based resin composition for calender molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride-based resin composition excellent in thermal stability and heat resistant colorability that can withstand calender molding without using a heavy metal-based stabilizer such as lead, tin and barium, and to provide a molded article formed by calender molding a vinyl chloride-based resin composition excellent in thermal stability and heat resistant colorability.SOLUTION: A vinyl chloride-based resin composition for calender molding contains: (A) at least one of hydrotalcite having a specific surface area of 10-60 m/g and an average particle size of 0.1-0.59 μm of 0.01-10 pts.mass; (B) at least one of β-diketone compounds of 0.01-5.0 pts.mass.; and (C) at least one of metallic soap of 0.01-5.0 pts.mass, with respect to a vinyl chloride-based resin of 100 pts.mass.SELECTED DRAWING: None

Description

  The present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition that is excellent in thermal stability, color resistance, and heat resistance coloration and is suitable for calendar molding.

  Vinyl chloride resin is excellent in flame retardancy, chemical resistance, mechanical stability, transparency, adhesiveness, printability, etc. Also, by adding a plasticizer, the hardness can be easily changed from hard to soft. Therefore, it is used for various purposes. In particular, a hard vinyl chloride resin composition containing no plasticizer or a semi-rigid vinyl chloride resin composition containing a small amount of plasticizer is widely used for building materials and the like because of its excellent rigidity. Therefore, they are required to have higher performance not only during processing exposed to high temperature and pressure but also in heat stability and weather resistance as a molded product.

  In the case of hard transparent molded products, it is also used for containers that require transparency for glass, industrial boards, decorative boards, films and sheets, etc., making it a very versatile resin. On the other hand, as mentioned above, in addition to insufficient stability to light and heat, vinyl chloride resin has the disadvantage that it is liable to be decomposed mainly due to dehydrohalogenation during heat molding and product use. It is known that there is. In particular, molding by calendering requires good heat stability because excessive heat is applied to the thin film for a long time.

  In order to improve such drawbacks, various stabilizers such as metal salts of organic acids, organic tin compounds, organic phosphite compounds, epoxy compounds, β-diketone compounds, antioxidants, ultraviolet absorbers and the like have been conventionally used. Attempts have been made to improve the stability of vinyl chloride resins by blending.

  Conventionally, heavy metal stabilizers such as lead and cadmium have been used as the stabilizer from the viewpoint of cost advantage, etc. Recently, interest in environmental problems has increased, and toxicity and environment of heavy metals etc. As a result, barium-zinc composite stabilizers tend to be used. However, recently, since the environmental impact of barium has begun to be a concern, it is desired to replace it with a low-toxicity calcium-zinc, magnesium-zinc or calcium-magnesium-zinc composite stabilizer. Yes.

  From such a viewpoint, a method of adding an organic acid calcium salt, an organic acid zinc salt, a basic phosphite and a hydrotalcite compound (Patent Document 1), an organic acid alkaline earth metal salt, an organic acid zinc salt, A method of adding a basic zinc phosphate and a hydrotalcite compound (Patent Document 2) has been proposed, but performance such as heat resistance in calender molding was insufficient even when used in combination.

  In addition, a method of adding an organic acid zinc salt, zinc-modified hydrotalcite and sugar alcohol has been proposed (Patent Document 3). However, when the performance is insufficient depending on the selected components, expensive components are used. There was a problem that had to be done.

JP-A-9-67489 JP 2003-160707 A WO2011 / 024399

  Accordingly, an object of the present invention is to provide a vinyl chloride resin composition excellent in thermal stability and heat resistant colorability that can withstand calendar molding without using heavy metal stabilizers such as lead, tin, and barium. Another object of the present invention is to provide a molded article obtained by calender molding a vinyl chloride resin composition having excellent thermal stability and heat-resistant coloring property.

Accordingly, as a result of intensive studies to solve the above-mentioned problems, the present inventors have combined a hydrotalcite having a large specific surface area and a small average particle diameter with β-diketone and metal soap, so that unstable chlorine of the vinyl chloride resin can be obtained. And found that a vinyl chloride resin with excellent thermal stability, color resistance and heat resistance can be obtained by efficiently replacing hydrogen chloride and desorbed chlorine released during decomposition. The present invention has been reached.
That is, the present invention is based on 100 parts by weight of vinyl chloride resin.
(A) 0.01 to 10 parts by mass of at least one hydrotalcite compound having a specific surface area of 10 to 60 m ² / g and an average particle size of 0.1 to 0.59 μm;
(B) 0.01 to 5.0 parts by weight of at least one β-diketone compound,
(C) The present invention relates to a vinyl chloride resin composition characterized in that it contains 0.01 to 5.0 parts by mass of at least one metal soap.

The present invention also relates to a molded article comprising the vinyl chloride resin composition.
The present invention also relates to a method for producing a molded product, characterized in that the vinyl chloride resin composition is calendered.

ADVANTAGE OF THE INVENTION According to this invention, the vinyl chloride resin composition excellent in the thermal stability and heat-resistant coloring property which can endure calendar shaping | molding can be provided. The vinyl chloride resin composition of the present invention has high transparency and is suitable for obtaining a molded product excellent in heat stability, color resistance and heat resistance coloration.
In applications where transparency is required, the molded product of the present invention is excellent in transparency and coloring resistance.

Hereinafter, the vinyl chloride resin composition of the present invention will be described in detail.
The present invention is a vinyl chloride resin composition for calendar molding.
First, the vinyl chloride resin used in the present invention is not particularly limited to the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, for example, 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, chloride Vinyl-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, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride- Rinic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers and other vinyl chloride resins, and their blends or other chlorines Synthetic resins not containing acrylonitrile, such as acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blended product with polyester, etc. A block copolymer, a graph and a copolymer, etc. can be mentioned.

Next, the zinc-modified hydrotalcite compound (A) used in the vinyl chloride resin composition of the present invention will be described.
The hydrotalcite compound used as the component (A) in the present invention is represented by the following general formula (I).
M ²⁺ _1-x M ³⁺ _x (OH) ₂ A ^n- _{x / n} · mH ₂ O (I)
However, M ²⁺ in the formula (I) is a divalent metal ion, and represents ions of magnesium, iron, zinc, calcium, lithium, nickel, cobalt, copper, etc., and M ³⁺ is a trivalent metal ion. , and the stands aluminum, iron, manganese, ions such as chromium, a ^n-is the interlayer anion, represents a carbonate ion, chloride ion, nitrate ion and the like. x is in the range of 0 <x ≦ 0.33, and m represents 0 or any positive number.

Specific examples of the hydrotalcite compound used in the present invention 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 Fe _0.25 (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 O
Zn _0.667 Al _0.333 (OH) ₂ (CO ₃ ) _0.17 · 0.5H ₂ O

As the hydrotalcite of the component (A) in the present invention, a hydrotalcite compound represented by the following general formula (II) is preferably used.
Mg _(1-x) Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (II)

Furthermore, the hydrotalcite-based compound used as the component (A) of the present invention is a zinc-modified hydrotalcite represented by the following general formula (III) from the viewpoint of processability, thermal stability, and colorability. More preferably.
M _y1 Zn _y2 Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (III)
However, M in the formula (III) represents magnesium or magnesium and calcium. x
, Y1 and y2 are numbers that satisfy the conditions represented by the following relational expressions, respectively, and m is 0 or an arbitrary positive number.
0 <x ≦ 0.5, y1 + y2 = 1−x, y1 ≧ y2, 0.3 ≦ y1 <1, 0 <y2 <0.5

  The zinc-modified hydrotalcite compound is a double salt compound containing magnesium, zinc and aluminum as metal components, or a double salt compound containing magnesium, calcium, zinc and aluminum as metal components. In the present invention, it is even more preferable to use a double salt compound containing magnesium, zinc and aluminum as metal components from the viewpoint of colorability.

  These double salt compounds are obtained by treating a hydrotalcite compound with a zinc compound in a usual manner, and are treated or post-treated with a zinc compound during the synthesis of the hydrotalcite compound. The zinc-modified hydrotalcite compound obtained by Naturally, a commercial item can also be used in this invention.

Specific examples of the zinc-modified hydrotalcite compound used in the present invention include the following compounds.
Mg _0.38 Zn _0.3 Al _0.32 (OH) ₂ (CO ₃ ) _0.16 · 0.2H ₂ O
Mg _0.45 Zn _0.23 Al _0.32 (OH) ₂ (CO ₃ ) _0.16
Mg _0.48 Zn _0.18 Al _0.34 (OH) ₂ (CO ₃ ) _0.17
Mg _0.48 Zn _0.2 Al _0.32 (OH) ₂ (CO ₃ ) _0.16
Mg _0.5 Zn _0.17 Al _0.33 (OH) ₂ (CO ₃ ) _0.165 · 0.45H ₂ O
Mg _0.5 Zn _0.18 Al _0.32 (OH) ₂ (CO ₃ ) _0.16
Mg _0.5 Zn _0.2 Al _0.3 (OH) ₂ (CO ₃ ) _0.16
Mg _0.5 Zn _0.2 Al _0.3 (OH) ₂ (CO ₃ ) _0.15 · 0.52H ₂ O
Mg _0.5 Zn _0.25 Al _0.25 (OH) ₂ (CO ₃ ) _0.125
Mg _0.51 Zn _0.17 Al _0.32 (OH) ₂ (CO ₃ ) _0.16
Mg _0.52 Zn _0.16 Al _0.32 (OH) ₂ (CO ₃ ) _0.16 · 0.5H ₂ O
Mg _0.55 Zn _0.15 Al _0.32 (OH) ₂ (CO ₃ ) _0.15
Mg _0.6 Zn _0.14 Al _0.26 (OH) ₂ (CO ₃ ) _0.13
Mg _0.6 Zn _0.16 Al _0.24 (OH) ₂ (CO ₃ ) _0.12
Mg _0.6 Zn _0.2 Al _0.2 (OH) ₂ (CO ₃ ) _0.1
Mg _0.4 Ca _0.1 Zn _0.18 Al _0.32 (OH) ₂ (CO ₃ ) _0.16
Mg _0.3 Ca _0.2 Zn _0.2 Al _0.3 (OH) ₂ (CO ₃ ) _0.15
Mg _0.5 Zn _0.17 Al _0.33 (OH) ₂ (CO ₃ ) _0.17 · 0.5H ₂ O
Mg _0.5 Zn _0.17 Al _0.33 (OH) ₂ (CO ₃ ) _0.17 · 0.42H ₂ O
Mg _0.6 Zn _0.16 Al _0.24 (OH) ₂ (CO ₃ ) _0.12 · 0.45H ₂ O
Mg _0.5 Zn _0.25 Al _0.25 (OH) ₂ (CO ₃ ) _0.13 · 0.39H ₂ O
Mg _0.5 Zn _0.17 Al _0.33 (OH) ₂ (CO ₃ ) _0.17
Mg _0.5 Zn _0.25 Al _0.25 (OH) ₂ (CO ₃ ) _0.13
Mg _3/6 Zn _1/6 Al _2/6 (OH) ₂ (CO ₃ ) _1/6 · 0.5H ₂ O
Mg _3/6 Zn _1/6 Al _2/6 (OH) ₂ (CO ₃ ) _1/6

  In the present invention, only one type of these zinc-modified hydrotalcite compounds may be used, but two or more types may be used in combination.

  In the present invention, the surface of the zinc-modified hydrotalcite compound is coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, or an organic sulfonic acid metal such as an alkali metal dodecylbenzenesulfonate. Those coated with salts, higher fatty acid amides, higher fatty acid esters, wax or the like can also be used. In addition, water obtained by dehydrating crystal water can be used.

  The content of the zinc-modified hydrotalcite compound which is the component (A) in the present invention is 0.01 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and is transparent, heat stable, and resistant to coloring. From the viewpoint of heat resistance and heat-resistant colorability, it is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 5 parts by mass. When the content is less than 0.01 part by mass, the thermal stability of the resin composition is insufficient, and when the content exceeds 10 parts by mass, performance deterioration such as reduction in coloring resistance of the resin composition occurs.

The specific surface area of the zinc-modified hydrotalcite compound as the component (A) in the present invention is 10 to 60 m ² / g as the value measured by a BET method, is preferably 15 to 50 m ² / g, 20 to 50 m ² / G is more preferable. If the specific surface area is less than 10 m ² / g, the thermal stability and heat resistant colorability of the resin composition are insufficient, and it is difficult to produce hydrotalcite itself for hydrotalcite exceeding 60 m ² / g.

  Moreover, the average particle diameter (% 50) of the zinc-modified hydrotalcite compound which is the component (A) in the present invention is 0.1 to 0.59 μm, preferably 0.1 to 0.5 μm, -0.45 micrometer is more preferable, 0.1-0.25 micrometer is still more preferable. For hydrotalcite having an average particle size (% 50) of less than 0.1 μm, it is difficult to produce hydrotalcite itself, and with hydrotalcite of 0.59 μm or more, the dispersibility deteriorates and the heat of the resin composition Stability and heat resistant colorability are insufficient.

Next, the (B) component β-diketone compound used in the vinyl chloride resin composition for calendar molding of the present invention will be described.
Examples of the β-diketone compound used as the component (B) in the present invention include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylacetylmethane. , Phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, stearoylbenzoylmethane, bis (4-octylbenzoyl) methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, Bis (4-carboxymethylbenzoyl) methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, Rohekisan-1,3-dione, 3,6-dimethyl-2,4-dioxy cyclohexane -1-carboxylate, 2-acetyl cyclohexanone, dimedone, 2-benzoyl-cyclohexane, and the like.

  Moreover, as a β-diketone compound, metal salts of these β-diketone compounds can also be used. Examples of the metal species that can provide the β-diketone metal salt include alkali metals such as lithium, sodium, and potassium; magnesium, calcium, strontium, zinc, aluminum, and the like. The β-diketone compound is preferably dibenzoylmethane or stearoylbenzoylmethane from the viewpoint of color resistance and transparency.

  The content of the β-diketone compound as the component (B) in the present invention is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and is resistant to coloring and heat. To 0.05 to 2.0 parts by mass, and more preferably 0.1 to 1.0 part by mass. When the content of the β-diketone compound is less than 0.01 parts by mass, the heat-resistant coloring may be insufficient, and when it exceeds 5.0 parts by mass, there is a decrease in performance such as a decrease in thermal stability.

Next, the metal soap as the component (C) used in the vinyl chloride resin composition of the present invention will be described.
The metal soap used as the component (C) in the present invention is a metal salt of carboxylic acid. Examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, neodecanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid P-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p- Tertiary octylsalicylic acid, elaidic acid, oleic acid, linoleic acid, lino Monovalent carboxylic acids such as inic acid, thioglycolic acid, mercaptopropionic acid, octyl mercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthal Divalent carboxylic acids such as acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, or the like Monoester or monoamide compounds; di- or triester compounds of trivalent or tetravalent carboxylic acids such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, merophanic acid, pyromellitic acid and the like.
Examples of the metal used for the metal soap of component (C) of the present invention include sodium, potassium, calcium, barium, aluminum, zinc, magnesium and the like.

  Among these metal soaps, from the viewpoint of heat resistance and color resistance, the carboxylic acid is preferably octylic acid, lauric acid, stearic acid, oleic acid, versatic acid, benzoic acid, and the metals forming the salt are zinc, calcium, Barium is preferred. The component (C) metal soap of the present invention may be used alone or in combination of two or more.

  The content of the component (C) metal soap in the present invention is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and has transparency, thermal stability, color resistance, and heat resistance. From the viewpoint of colorability, it is preferably 0.01 to 4.0 parts by mass, more preferably 0.05 to 3.0 parts by mass, and most preferably 0.1 to 2.0 parts by mass. If the content is less than 0.01 parts by mass, the heat-resistant colorability is insufficient, and if it exceeds 5.0 parts by mass, the thermal stability is lowered.

  From the viewpoint of processability, the vinyl chloride resin composition of the present invention preferably further contains a lubricant. Examples of the lubricant used include hydrocarbon lubricants such as low molecular wax, paraffin wax, polyethylene wax, chlorinated hydrocarbon, and fluorocarbon; natural wax lubricants such as carnauba wax and candelilla wax; lauric acid, stearic acid, Fatty acid lubricants such as higher fatty acids such as behenic acid or oxyfatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide, oleylamide or alkylene such as methylenebisstearylamide, ethylenebisstearylamide Aliphatic amide type lubricants such as bisaliphatic amides; fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, distearyl phthalate, glycerin tristearate, sorbitan tristearate Monovalent compounds such as fatty acid polyhydric alcohol ester compounds such as rate, pentaerythritol tetrastearate, dipentaerythritol hexastearate, polyglycerin polyricinoleate, hydrogenated castor oil, or adipic acid / stearic acid ester of dipentaerythritol Fatty alcohol ester lubricants such as fatty acid and polybasic organic acid and polyhydric alcohol compound ester compounds; aliphatic alcohol lubricants such as stearyl alcohol, lauryl alcohol, palmityl alcohol; metal soaps; partially saponified montanic acid esters Montanic acid type lubricants such as; acrylic type lubricants; silicone oils and the like. These lubricants may be used alone or in combination of two or more.

  In the case of using the lubricant in the present invention, the content is preferably 0.01 to 5.0 parts by mass, particularly 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin from the viewpoint of processability. It is preferably 3.0 parts by mass. If the content of the lubricant is less than 0.01 parts by mass, the processability may be insufficient, and if it exceeds 5.0 parts by mass, the performance may be deteriorated, such as decreasing the transparency.

  Moreover, it is preferable that the vinyl chloride resin composition of the present invention further contains a processing aid from the viewpoint of processability. The processing aid can be appropriately selected from known processing aids, but acrylic acid processing aids are preferred. Examples of processing aids include, for example, homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; the above alkyl methacrylates and alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate. Copolymer; Copolymer of the above alkyl methacrylate with an aromatic vinyl compound such as styrene, α-methylstyrene, vinyl toluene; Copolymerization of the above alkyl methacrylate with a vinyl cyan compound such as acrylonitrile, methacrylonitrile, etc. A coalescence etc. can be mentioned. These processing aids may be used alone or in combination of two or more.

  When a processing aid is used in the composition of the present invention, the content thereof is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Part. If the content of the processing aid is less than 0.01 parts by mass, the processability may be insufficient, and if it exceeds 10 parts by mass, the performance may be lowered, for example, the transparency may be reduced.

  The vinyl chloride resin composition of the present invention preferably further contains a phenolic antioxidant from the viewpoints of heat resistance and heat resistance colorability. Examples of the phenolic antioxidant used in the present invention include 2,6-ditertiarybutyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditertiary). Butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate] 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) Propionic acid amide], 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-me Til-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] Glycol ester, 4,4′-butylidenebis (6-tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4- Dibutyl-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) isocyanate 1,3,5-tris (3,5-ditert-butyl-4-hydroxylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) ) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′ , 5′-ditert-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-tetraoxa Pyro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

  The content in the case of using a phenolic antioxidant in the present invention is 0.01 to 5.0 with respect to 100 parts by mass of the vinyl chloride resin from the viewpoints of thermal stability, color resistance, and heat resistance coloration. It is preferable that it is a mass part, It is preferable that it is especially 0.05-3.0 mass part, and 0.05-1.0 mass part is more preferable. When the content is less than 0.01 parts by mass, the coloration resistance may be insufficient. When the content exceeds 5.0 parts by mass, the performance may deteriorate, for example, the transparency may be reduced.

  In addition, the vinyl chloride resin composition of the present invention includes other additives usually used in vinyl chloride resin compositions, such as plasticizers, polyethers, organic acid metal salts other than the above metal soaps, zeolite compounds, excessive additives. Effects of the present invention include chlorates, epoxy compounds, phosphorus-based, phenol-based and sulfur-based antioxidants, ultraviolet absorbers, hindered amine light stabilizers, reinforcing agents, fillers, flame retardants, flame retardant aids, etc. It can also be blended within a range that does not impair.

  Examples of the plasticizer include dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate and the like; dioctyl adipate, diisononyl adipate , Diisodecyl adipate, di (butyl diglycol) adipate and other adipate plasticizers; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri Phosphate such as (butoxyethyl) phosphate, octyl diphenyl phosphate Plasticizers; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, Polyhydric alcohols such as 1,6-hexanediol and neopentyl glycol, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, Polyester plasticizer using dibasic acid such as terephthalic acid and using monohydric alcohol and monocarboxylic acid as a stopper if necessary; tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, Stearic acid plasticizer, citric acid plasticizer, Trimerit System plasticizers, pyromellitic acid plasticizers include biphenylene polycarboxylic acid plasticizers. These plasticizers may be used alone or in combination of two or more.

The present invention is particularly preferably used as a hard vinyl chloride resin composition containing no plasticizer or a hard or semi-rigid plasticizer containing a small amount of plasticizer.
The content of the plasticizer in the case of being hard is preferably less than 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, and the content of the plasticizer in the case of being semi-hard is 100 parts by weight of the vinyl chloride resin. The amount is preferably 5 to 30 parts by mass.

  Examples of the polyether include pentaerythritol, dipentaerythritol, polypentaerythritol, sorbitol, mannitol, maltitol, lactitol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose, lactose, trimethylolpropane, ditritol. Examples include methylolpropane, pentaerythritol or stearic acid partial ester of dipentaerythritol, bis (dipentaerythritol) adipate, glycerin, diglycerin, tris (2-hydroxyethyl) isocyanurate, and the like. Two or more kinds may be used as a mixture.

  Examples of the organic acid metal salt other than the metal soap include metal (sodium, potassium, calcium, barium, aluminum, magnesium, zinc) salts of phenols and organic phosphoric acids.

  Examples of the phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexyl. Phenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisoxylphenol, methyl tertiary octylphenol and the like.

  Examples of the organic phosphoric acids include mono or dioctyl phosphoric acid, mono or didodecyl phosphoric acid, mono or dioctadecyl phosphoric acid, mono or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, and phosphonic acid stearyl ester. Etc.

  The metal salts of the above phenols and organic phosphoric acids may be acidic salts, neutral salts, basic salts, or overbased complexes obtained by neutralizing part or all of the bases of the basic salts with carbonic acid. Good.

  The above-mentioned zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure, and representative examples thereof include A-type, X-type, Y-type and P-type zeolite, monodenite, anal Sites, sodalite group aluminosilicates, clinobutyrolite, erionite, chabazite, and the like, and water-containing substances having crystal water (so-called zeolite water) of these zeolitic compounds or anhydrous water from which crystal water has been removed Any of those may be used, and those having a particle size of 0.1 to 50 μm can be used, and those having a particle size of 0.5 to 10 μm are particularly preferable.

Examples of the perchlorates include perchloric acid metal salts, ammonium perchlorate, perchloric acid-treated hydrotalcite, and perchloric acid-treated silicates.
Examples of the metal constituting the perchloric acid metal salt include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and aluminum. The perchloric acid metal salt may be an anhydride or a hydrated salt, or may be a solution dissolved in an alcohol or ester solvent such as butyl diglycol or butyl diglycol adipate or a dehydrate thereof.

  Examples of the epoxy compound include bisphenol type and novolak type epoxy resins, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, Epoxidized tall oil fatty acid octyl, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, -butyl, -2-ethylhexyl or stearyl, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,2-epoxy Propane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, biphenyl (3,4-epoxycyclohexyl) adipate and the like.

  Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono-, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylene bis (4,6-di-tert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, bird Lauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl) -4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4 , 6-Diamylphenyl)]-isopropylidene diphenyl phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5- Methylphenol) diphosphite, hexa (tri Decyl) .1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- Examples include 10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, and the like.

  The content of the phosphorus-based antioxidant used in the present invention is preferably 0.01 to 5 parts by mass, particularly 0.1 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Preferably there is.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl, and β-alkyl mercapto of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include propionic acid esters.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 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-th 2- (2-hydroxyphenyl) benzotriazoles such as octyl-6-benzotriazolyl) phenol, polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; phenyl Benzoates such as salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; Substituted oxanilides such as 2-ethyl-2′-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3- Shea such as methyl-3- (p-methoxyphenyl) acrylate Acrylate, and the like.

  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-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis ( , 2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2, 2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetraethyl-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- -(2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-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 And hindered amine compounds such as undecane.

As the reinforcing material, fibrous, plate-like, granular, and powdery materials that are usually used for reinforcing synthetic resins can be used. Specifically, asbestos fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite, elastadite, gypsum fiber, silica fiber, silica・ Inorganic fiber reinforcements such as alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton, jute, hemp , Sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper scrap, waste paper, wool and other organic fibrous reinforcements, glass flakes, non-swelling mica, graphite, metal foil, ceramic beads, clay, mica, seri Site, zeo Ito, bentonite, dolomite, kaolin, finely divided silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, titanium dioxide, aluminum silicate, gypsum, Novacurite And plate-like and granular reinforcing materials such as dosonite and white clay. These reinforcing materials may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or with a coupling agent such as aminosilane or epoxysilane. It may be processed.
The content of these reinforcing agents is preferably 0.1 to 30 parts by mass, and preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  Specific examples of the filler include calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium aluminate silicate. , Hydrocalumite, aluminum silicate, magnesium silicate, calcium silicate, silicate metal salts such as zeolite, activated clay, talc, clay, bengara, asbestos, antimony trioxide, silica, glass beads, mica, sericite, Glass flakes, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonolite, MOS, phosphate fiber, glass fiber, carbon fiber, aramid fiber and the like can be mentioned.

  Examples of the flame retardants and flame retardant aids include triazine ring-containing compounds, metal hydroxides, other inorganic phosphorus, halogen flame retardants, silicon flame retardants, phosphate ester flame retardants, and condensed phosphate ester flame retardants. Examples include flame retardants, intomesent flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant aids, and organic flame retardant aids.

  Examples of the triazine ring-containing compound include melamine, ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene Dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimeramine and the like can be mentioned.

  Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, and zinc hydroxide.

  Examples of the phosphate ester flame retardant include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl Phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t -Butylphenyl) phosphate, isopropylphenyldiphenylphosphate, bis- (isopropylphosphate) Le) diphenyl phosphate, tris - (isopropylphenyl) phosphate, and the like.

  Examples of the condensed phosphate ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Examples of messentic flame retardants include ammonium salts and amine salts of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, piperazine pyrophosphate, and the like.

  Examples of the other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof, and various commercially available products can be used.

  To the vinyl chloride resin composition for transparent products of the present invention, a stabilizing aid usually used for vinyl chloride resins can be added within a range that does not impair the effects of the present invention. Examples of such stabilizing aids include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid and the like.

  In addition, in the vinyl chloride resin composition for transparent products of the present invention, additives that are usually used in vinyl chloride resins as necessary, for example, crosslinking agents, antistatic agents, antifogging agents, plate-out preventing agents , Surface treatment agents, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, pigments, antioxidants, light stabilizers, and the like, as long as the effects of the present invention are not impaired. be able to.

  The vinyl chloride resin composition of the present invention can be used regardless of the preparation method, mixing method and processing method. Examples of the preparation method include vinyl chloride resin, the above component (A), ( B) component, (C) component, and other additive components as needed, or a method of charging separately, and mixing methods include V-type blender, ribbon blender, Henschel mixer, Examples of the mixing method include a rocking mixer, a tumbler mixer, a planetary mixer, a Banbury mixer, a mill mixer, a mixing roll, a kneader, and a mixing method using a kneader.

As long as the molded article of the present invention includes the vinyl chloride resin composition of the present invention, the content of the vinyl chloride resin composition in the molded article is not particularly limited, but the effects of the present invention are sufficiently exhibited. In view of the above, the content of the vinyl chloride resin composition is preferably at least 30% by mass or more.
Moreover, although a shaping | molding method is not restrict | limited, From the point of the effect of this invention, what was calendered is preferable.

Next, calendar molding which is one of the preferable molding methods will be described.
Calender molding is a molding method in which a resin is melted while being kneaded between heated rolls, and is stretched to a predetermined thickness through a number of rolls, and is used in the production of films, sheets, leathers, plates and the like.

  Since calendar molding is a thin resin processing, compared to other molding methods such as extrusion molding, melt casting, pressure molding, etc., the resin is significantly more susceptible to heat during processing, and the resin deteriorates. It has become a big problem. However, the vinyl chloride resin composition of the present invention is characterized in that it hardly undergoes thermal deterioration even in calendar molding where the heat conditions are very severe.

  As a calendar molding device, for example, conventional two-calendar calendar, three-series calendar, four-series calendar, S-type calendar, reverse L-type calendar, Z-type calendar, oblique Z-type calendar, etc. A known apparatus used for the above can be used without particular limitation.

  As molding conditions, the resin temperature is preferably 140 to 240 ° C, more preferably 150 to 230 ° C. The surface temperature of the roll is preferably from 130 ° C to 230 ° C, more preferably from 140 ° C to 220 ° C. When the surface temperature of the roll is lower than the above range, calender molding may be difficult, which is not preferable. When the roll temperature is higher than the above range, the mold release property from the roll may be deteriorated, which is not preferable. The linear velocity of the roll is preferably 5 m / min, more preferably 7 m / min, particularly 8 m / min to 60 m / min, further 50 m / min, particularly 40 m / min.

  Further, since the vinyl chloride resin composition of the present invention can be used regardless of the processing method of the vinyl chloride resin, it can be used for the above-described extrusion molding, melt casting, pressure molding and the like. .

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited by the following examples. In the following examples and the like,% is based on mass unless otherwise specified.

[Examples 1-4 and Comparative Examples 1-4]
Using the hydrotalcite shown in Table 1 below, the blends shown in Table 2 below were blended with a Henschel mixer, and then a sheet was prepared by calendering. Specifically, a sheet was prepared by roll kneading under conditions of 180 ° C. × 30 rpm × 0.6 mm. Various tests were performed by the following test methods using the obtained sheets. The results are shown in Table 2.

<Decomposition test>
At the time of roll kneading, the time when the phenomenon that the sheet does not peel from the roll due to thermal decomposition of the sheet appeared was measured. A longer measurement time is better, and if it is 20 minutes or less, it cannot withstand actual use.

<Dynamic thermal stability test>
A sheet sample is taken every 3 minutes during roll kneading and the time when the sheet is black is displayed. The longer the time, the better. If it is 15 minutes or less, it cannot withstand actual use.

<Static thermal stability test>
A sheet sample was collected 3 minutes after roll kneading, and the obtained sheet was put into two kinds of gear ovens of 190 ° C. and 200 ° C., respectively, and the time until the sheet was blackened was measured. The longer the time, the better. In the 190 ° C. test, those that are 40 minutes or less are unacceptable, and in the 200 ° C. test, those that are 20 minutes or less are unacceptable.

Claims (5)

For 100 parts by mass of vinyl chloride resin,
(A) 0.01-10 parts by mass of at least one hydrotalcite having a specific surface area of 10-60 m ² / g and an average particle size of 0.1-0.59 μm,
(B) 0.01 to 5.0 parts by weight of at least one β-diketone compound,
(C) A vinyl chloride-based resin composition for calendering, which contains 0.01 to 5.0 parts by mass of at least one metal soap.   The vinyl chloride resin composition for calender molding according to claim 1, wherein the hydrotalcite of the component (A) is zinc-modified hydrotalcite.   The vinyl chloride resin composition for calender molding according to claim 1 or 2, wherein the metal soap as the component (C) is at least one selected from calcium salts, zinc salts, and magnesium salts.   A molded article comprising the vinyl chloride resin composition according to any one of claims 1 to 3.   The manufacturing method of the molded article characterized by carrying out the calendar molding of the vinyl chloride-type resin composition of any one of Claims 1-3.