WO2019189268A1 - Vinyl chloride resin composition, production method for vinyl chloride resin composition, vinyl chloride resin molded body, and laminate - Google Patents

Vinyl chloride resin composition, production method for vinyl chloride resin composition, vinyl chloride resin molded body, and laminate Download PDF

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Publication number
WO2019189268A1
WO2019189268A1 PCT/JP2019/013023 JP2019013023W WO2019189268A1 WO 2019189268 A1 WO2019189268 A1 WO 2019189268A1 JP 2019013023 W JP2019013023 W JP 2019013023W WO 2019189268 A1 WO2019189268 A1 WO 2019189268A1
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WO
WIPO (PCT)
Prior art keywords
vinyl chloride
chloride resin
resin composition
chemisorption
deodorant
Prior art date
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PCT/JP2019/013023
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French (fr)
Japanese (ja)
Inventor
高橋　和也
Original Assignee
日本ゼオン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to JP2020510968A priority Critical patent/JPWO2019189268A1/en
Priority to CN201980010342.2A priority patent/CN111655785A/en
Publication of WO2019189268A1 publication Critical patent/WO2019189268A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a vinyl chloride resin composition, a method for producing a vinyl chloride resin composition, a vinyl chloride resin molded article, and a laminate.
  • Vinyl chloride resins are generally used in various applications because they are excellent in properties such as cold resistance, heat resistance, and oil resistance.
  • a skin made of a vinyl chloride resin molded body or a foam body such as a polyurethane foam molded body is lined on the skin made of a vinyl chloride resin molded body.
  • Automotive interior materials such as laminates are used.
  • the vinyl chloride resin molded body used as the skin is produced by molding a vinyl chloride resin composition containing a vinyl chloride resin and a plasticizer using a known molding method such as powder slush molding. (For example, refer to Patent Document 1).
  • the vinyl chloride resin molded article is used as an automobile interior material such as a skin of an automobile interior part, an odor component such as an aldehyde-based gas is generated from the vinyl chloride resin molded article, and the passenger of the automobile The problem is that it can be uncomfortable. Therefore, it is required to reduce the amount of odorous components generated from the vinyl chloride resin molded body.
  • an object of this invention is to provide the vinyl chloride resin molded object with which the generation amount of the odor component was reduced.
  • Another object of the present invention is to provide a vinyl chloride resin composition capable of forming a vinyl chloride resin molded body with reduced generation of odor components, and a laminate having the vinyl chloride resin molded body. .
  • the present inventor has intensively studied for the purpose of solving the above problems. And if this inventor uses the vinyl chloride resin composition which contains a vinyl chloride resin and the chemisorption type deodorant whose heat-resistant temperature and volume average particle diameter are in the predetermined range, the amount of generation
  • the vinyl chloride resin composition of this invention contains (a) vinyl chloride resin and (b) chemisorption type deodorant.
  • a heat-resistant temperature of the (b) chemisorption deodorant is 150 ° C. or higher, and a volume average particle diameter of the (b) chemisorption deodorant is 0.5 ⁇ m. It is 10 ⁇ m or less.
  • the “volume average particle diameter of the chemisorption deodorant” means a particle diameter at which the cumulative volume calculated from the small diameter side is 50% in the particle size distribution (volume basis) measured by the laser diffraction method. (D50).
  • the “heat-resistant temperature of the chemisorption deodorant” is the maximum temperature within the range of the heating temperature that can maintain the deodorization performance even after the chemisorption deodorant is heated. is there.
  • the (b) chemisorption deodorant is an oxide of at least one element selected from the group consisting of magnesium, aluminum, silicon, and zirconium, and / or It is preferable to contain a hydroxide. If the (b) chemisorption deodorant contains an oxide and / or hydroxide of the predetermined element, the odor component from the vinyl chloride resin molded article formed using the vinyl chloride resin composition The amount of generation can be further reduced.
  • the (b) chemisorption deodorant preferably contains a hydrazide compound and / or an amine compound, and more preferably contains zirconium oxide. If the (b) chemisorption deodorant includes a hydrazide compound and / or an amine compound, the amount of odorous components generated from the vinyl chloride resin molded body formed using the vinyl chloride resin composition is further reduced. If zirconium oxide is further included, the amount of odorous components generated from the vinyl chloride resin molded product can be further reduced.
  • the content of the (b) chemisorption deodorant is 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the (a) vinyl chloride resin. It is preferable.
  • the content of the (b) chemisorption deodorant is 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the (a) vinyl chloride resin, it is formed using a vinyl chloride resin composition. The amount of odorous components generated from the vinyl chloride resin molded product can be further reduced, and the tensile elongation of the resulting vinyl chloride resin molded product can be sufficiently ensured.
  • the vinyl chloride resin composition of the present invention is preferably used for powder molding. If the vinyl chloride resin composition is used for powder molding, for example, a vinyl chloride resin molded body that can be used favorably as the skin of automobile interior parts can be easily obtained.
  • the vinyl chloride resin composition of the present invention is preferably used for powder slush molding. If the vinyl chloride resin composition is used for powder slush molding, for example, a vinyl chloride resin molded body that can be used favorably as the skin of automobile interior parts can be obtained more easily.
  • the manufacturing method of the vinyl chloride resin composition of the present invention is a method of manufacturing a vinyl chloride resin composition containing a vinyl chloride resin and a chemisorption deodorant, and the heat resistance temperature of the chemisorption deodorant is
  • the chemical adsorption deodorant has a volume average particle size of 0.5 ⁇ m or more and 10 ⁇ m or less
  • the vinyl chloride resin composition contains a dusting agent
  • the vinyl chloride resin composition Step A of preparing a composition (X) containing components other than the chemisorption deodorant and dusting agent, and Step B of adding the dusting agent to the composition (X)
  • the vinyl chloride resin composition is obtained by adding a chemisorption deodorant simultaneously with the addition of the dusting agent or after the dusting agent is added, the amount of odorous components generated is reduced.
  • a resin molded body can be formed.
  • the vinyl chloride resin molded object of this invention shape
  • the vinyl chloride resin molded product of the present invention can be used for the skin of automobile interior parts.
  • the laminated body of this invention has a foaming polyurethane molding and one of the vinyl chloride resin moldings mentioned above.
  • the laminate can include a vinyl chloride resin molded product portion in which the amount of odorous components generated is reduced.
  • this invention it is possible to provide a vinyl chloride resin molded body in which the amount of odorous components generated is reduced. Moreover, this invention can provide the laminated body which has the vinyl chloride resin composition which can form the said vinyl chloride resin molded object, and the said vinyl chloride resin molded object.
  • the vinyl chloride resin composition of the present invention can be used, for example, when forming the vinyl chloride resin molded article of the present invention.
  • the vinyl chloride resin molded object formed using the vinyl chloride resin composition of this invention can be used for manufacture of the laminated body of this invention which has the said vinyl chloride resin molded object, for example.
  • the vinyl chloride resin molded body of the present invention can be suitably used for automobile interior materials, for example, for the skin of automobile interior parts such as automobile instrument panels.
  • the vinyl chloride resin composition of this invention can be prepared with the manufacturing method of the vinyl chloride resin composition of this invention, for example.
  • the vinyl chloride resin composition of the present invention comprises (a) a vinyl chloride resin, and (b) a chemisorption deodorant whose heat-resistant temperature and volume average particle diameter are within a predetermined range, and optionally other An additive may be further included.
  • the vinyl chloride resin composition of the present invention described above includes at least (a) the vinyl chloride resin and (b) a chemisorption deodorant having a heat resistant temperature and a volume average particle size within a predetermined range. Therefore, if the vinyl chloride resin composition is used, a vinyl chloride resin molded body in which the generation amount of odor components is reduced can be formed.
  • the (a) vinyl chloride resin for example, one kind or two or more kinds of vinyl chloride resin particles can be contained, and optionally one kind or two or more kinds of vinyl chloride resin particles are further contained. be able to.
  • the vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.
  • the (a) vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method or bulk polymerization method.
  • “resin particles” refers to particles having a particle size of 30 ⁇ m or more, and “resin particles” refers to particles having a particle size of less than 30 ⁇ m.
  • the vinyl chloride resin (a) is preferably a vinyl chloride containing a vinyl chloride monomer unit in addition to a homopolymer composed of vinyl chloride monomer units, preferably 50% by mass or more, more preferably 70% by mass or more.
  • examples thereof include a system copolymer.
  • a monomer (comonomer) copolymerizable with a vinyl chloride monomer that can constitute a vinyl chloride copolymer for example, as described in International Publication No. 2016/098344 Things can be used.
  • these components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • Vinyl chloride resin particles In the vinyl chloride resin composition, the vinyl chloride resin particles usually function as a matrix resin (base material). The vinyl chloride resin particles are preferably produced by a suspension polymerization method.
  • the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 800 or more, more preferably 1000 or more, and preferably 5000 or less, more preferably 3000 or less. Preferably, it is 2800 or less, more preferably 1300 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is 800 or more, the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition is sufficiently secured, for example, tensile elongation Can be improved.
  • the vinyl chloride resin molded product having a low peak top temperature of the loss elastic modulus E ′′ after the heat aging test and good tensile elongation can be obtained without, for example, debris scattering when the airbag is expanded and deployed. It can be suitably used as an automobile interior material such as a skin of an automotive instrument panel having a good ductility, which can break as designed, while the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is 5000 or less. If it exists, the meltability of a vinyl chloride resin composition can be improved and the surface smoothness of the vinyl chloride resin molded object formed using the said composition can be improved. In the present invention, the “average degree of polymerization” can be measured according to JIS K6720-2.
  • the average particle diameter of the vinyl chloride resin particles is usually 30 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, further preferably 136 ⁇ m or more, particularly preferably 145 ⁇ m or more, and 500 ⁇ m or less. Preferably, 200 ⁇ m or less is more preferable. If the average particle diameter of the vinyl chloride resin particles is 30 ⁇ m or more, the powder fluidity of the vinyl chloride resin composition can be improved. On the other hand, if the average particle diameter of the vinyl chloride resin particles is 500 ⁇ m or less, the meltability of the vinyl chloride resin composition is improved and the surface smoothness of the vinyl chloride resin molded body formed using the composition is improved. Can do.
  • the “average particle diameter of vinyl chloride resin particles” can be measured as a volume average particle diameter by a laser diffraction method in accordance with JIS Z8825.
  • the content ratio of the vinyl chloride resin particles in the vinyl chloride resin is preferably 70% by mass or more, more preferably 80% by mass or more, and can be 100% by mass. It is preferable that it is mass% or less, and it is more preferable that it is 90 mass% or less.
  • Vinyl chloride resin fine particles In the vinyl chloride resin composition, the vinyl chloride resin fine particles usually function as a dusting agent (powder fluidity improver).
  • the vinyl chloride resin fine particles are preferably produced by an emulsion polymerization method.
  • the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is preferably 500 or more, more preferably 700 or more, still more preferably 800 or more, preferably 3000 or less, and more preferably 2500 or less. If the average degree of polymerization of the vinyl chloride resin constituting the fine particle of the vinyl chloride resin as a dusting agent is 500 or more, the powder flowability of the vinyl chloride resin composition is improved and molding obtained using the composition The tensile elongation of the body can be improved.
  • the meltability of the vinyl chloride resin composition increases, and the surface smoothness of the vinyl chloride resin molded body formed using the composition increases. Can be improved.
  • the average particle size of the vinyl chloride resin fine particles is usually less than 30 ⁇ m, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, preferably 0.1 ⁇ m or more, and 1 ⁇ m or more. Is more preferably 1.8 ⁇ m or more. If the average particle diameter of the vinyl chloride resin fine particles is 0.1 ⁇ m or more, for example, the powder fluidity of the vinyl chloride resin composition can be improved without excessively reducing the size as a dusting agent.
  • average particle diameter of the vinyl chloride resin fine particles is less than 30 ⁇ m, the meltability of the vinyl chloride resin composition is increased, and the surface smoothness of the vinyl chloride resin molded body formed using the composition can be improved. it can.
  • “average particle diameter of vinyl chloride resin fine particles” can be measured as a volume average particle diameter by a laser diffraction method in accordance with JIS Z8825.
  • the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 30% by mass or less, More preferably, it is 20 mass% or less.
  • the content rate of the vinyl chloride resin fine particles in the vinyl chloride resin is 5% by mass or more, the powder flowability of the vinyl chloride resin composition can be improved.
  • the content of the vinyl chloride resin fine particles in the vinyl chloride resin is 30% by mass or less, the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be increased. .
  • the chemisorption type deodorant is a material that can adsorb or decompose the odor component by forming a chemical bond with the odor component, and exhibit a deodorizing effect. From the vinyl chloride resin composition, It is a component that can reduce the amount of odorous components generated from the vinyl chloride resin molded body when or after the vinyl chloride resin molded body is formed. However, (b) the chemisorption deodorant may contain a material that can physically adsorb the odor component and exert a deodorizing effect.
  • the odor component which (b) chemisorption type deodorant makes object is not specifically limited, For example, basic gas, such as ammonia and an amine; Acid gas, such as an acetic acid and isovaleric acid; Formaldehyde, acetaldehyde, octanal Aldehyde-based gas such as nonenal; sulfur-based gas such as hydrogen sulfide and methyl mercaptan;
  • the (b) chemisorption deodorant is preferably capable of deodorizing at least an aldehyde gas.
  • a chemisorption type deodorant can deodorize the aldehyde type gas as an odor component, the generation amount of the odor component from the obtained vinyl chloride resin molding can be further reduced.
  • the heat resistant temperature of the (b) chemisorption deodorant needs to be 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 300 ° C. or higher, and 1000 ° C. or lower. It is preferable that it is 500 degreeC or less.
  • the heat-resistant temperature of a chemisorption type deodorant is 150 degreeC or more, the generation amount of the odor component from the obtained vinyl chloride resin molding can be reduced favorably.
  • the heat-resistant temperature of the (b) chemisorption type deodorant is 1000 ° C. or less, the handleability of the (b) chemisorption type deodorant, the obtained vinyl chloride resin molded article, and (b) the chemisorption type Disposal of deodorant becomes easy.
  • the volume average particle size of the (b) chemisorption deodorant needs to be 0.5 ⁇ m or more, preferably 0.8 ⁇ m or more, and more preferably 1.2 ⁇ m or more. , 1.5 ⁇ m or more is more preferable, 2.0 ⁇ m or more is particularly preferable, 10 ⁇ m or less is required, 9 ⁇ m or less is preferable, and 8 ⁇ m or less is more preferable. More preferably, it is 7 micrometers or less, and it is especially preferable that it is 6.0 micrometers or less.
  • the volume average particle diameter of the chemisorption deodorant is not less than the above lower limit, the amount of odorous components generated from the resulting vinyl chloride resin molded article can be reduced favorably. On the other hand, if the volume average particle diameter of the (b) chemisorption deodorant is not more than the above upper limit, the tensile elongation of the obtained vinyl chloride resin molded article can be sufficiently ensured.
  • the (b) chemisorption deodorant described above is not particularly limited, and any known chemisorption deodorant can be used.
  • any known chemisorption deodorant can be used.
  • various oxides, hydroxides, hydrazide compounds, amino Guanidine salts, amine compounds, and the like can be used.
  • chemisorption type deodorant 1 type may be used independently and multiple types may be mixed and used by arbitrary ratios.
  • oxide and / or hydroxide examples include an oxide of at least one element selected from the group consisting of magnesium, aluminum, silicon, zirconium, silver, copper, zinc, and manganese, and / or A hydroxide is mentioned.
  • an oxide and / or hydroxide of at least one element selected from the group consisting of magnesium, aluminum, silicon, and zirconium is preferable.
  • the oxide and / or hydroxide may be a hydrate.
  • hydrazide compound examples include dihydrazide compounds such as adipic acid dihydrazide, sebacic acid dihydrazide, carbonyl dihydrazide, succinic acid dihydrazide, and oxalic acid dihydrazide.
  • aminoguanidine salts include aminoguanidine hydrochloride, aminoguanidine sulfate, aminoguanidine bicarbonate and the like.
  • a polyamine compound etc. are mentioned as a specific example of an amine compound.
  • polyamine compound examples include aliphatic polyamines such as diethylenetriamine and tetraethylenepentamine; aromatic polyamines; alicyclic polyamines; In addition, it is preferable to use what was carry
  • the (b) chemisorption deodorant it is preferable to use an oxide and / or hydroxide of at least one element selected from the group consisting of magnesium, aluminum, silicon and zirconium. (B) If the oxide and / or hydroxide of the predetermined element is used as the chemisorption deodorant, the amount of odorous components generated from the resulting vinyl chloride resin molded product can be further reduced.
  • a hydrazide compound and / or an amine compound as the (b) chemisorption deodorant.
  • B Even when a hydrazide compound and / or an amine compound is used as the chemisorption deodorant, the amount of odorous components generated from the resulting vinyl chloride resin molded product can be further reduced. Further, when a hydrazide compound and / or an amine compound is used as the (b) chemisorption deodorant, it is more preferable to use zirconium oxide in combination.
  • the chemisorption deodorant in the vinyl chloride resin composition contains a hydrazide compound and / or an amine compound and further contains zirconium oxide, the amount of odorous components generated from the resulting vinyl chloride resin molded product is further reduced. can do.
  • a chemisorption type deodorant a hydrazide compound and / or an amine compound and zirconium oxide are used in combination to further reduce the amount of odorous components generated from the resulting vinyl chloride resin molded article.
  • the reason why the odor can be produced is not clear, but it is presumed that the odor components of different types such as basic gas, acid gas, aldehyde gas, and sulfur gas can be deodorized by the above configuration.
  • (b) as a chemisorption type deodorant silicon dioxide-zirconium oxide mixture, zeolite-sebacate dihydrazide mixture, magnesium oxide-aluminum oxide hydrate mixture, zirconium oxide hydrate, and amine compound supported hydroxide
  • silicon dioxide-zirconium oxide mixture and a zeolite-sebacate dihydrazide mixture are used in combination, or a magnesium oxide-aluminum oxide hydrate mixture, zirconium oxide hydrate, and an amine compound-supported aluminum hydroxide.
  • a magnesium oxide-aluminum oxide hydrate mixture, a zirconium oxide hydrate, and an amine compound-supported aluminum hydroxide are more preferable, and it is more preferable to use a magnesium oxide-aluminum oxide hydrate mixture, a zirconium oxide hydrate, and an amine compound-supported aluminum hydroxide in combination.
  • the predetermined chemisorption type deodorant is used as the chemisorption type deodorant, the amount of odorous components generated from the resulting vinyl chloride resin molded product can be further reduced, and (b) chemisorption When the chemisorption deodorant is used as a mold deodorant in the predetermined combination, the amount of odorous components generated from the obtained vinyl chloride resin molded product can be further reduced.
  • (b) chemisorption deodorant commercially available products can be used.
  • the content of the (b) chemisorption deodorant is preferably 0.5 parts by mass or more and more preferably 0.8 parts by mass or more per 100 parts by mass of the (a) vinyl chloride resin. Preferably, it is 1.0 part by mass or more, more preferably 10 parts by mass or less, more preferably 6 parts by mass or less, and further preferably 4 parts by mass or less.
  • content of a chemisorption type deodorant is more than the said minimum, the generation amount of the odor component from the obtained vinyl chloride resin molding can be reduced further.
  • the content of the (b) chemisorption deodorant is not more than the above upper limit, the tensile elongation of the obtained vinyl chloride resin molded article can be sufficiently ensured.
  • the vinyl chloride resin composition of the present invention may further contain various additives in addition to the components described above.
  • Additives are not particularly limited, and include, for example, plasticizers such as trimellitic acid esters; stabilizers such as perchloric acid-treated hydrotalcite, zeolite, ⁇ -diketone, and fatty acid metal salts; mold release agents; Other dusting agents other than vinyl chloride resin fine particles; Impact resistance improvers; Perchloric acid compounds other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.); Antioxidants; Flame retardants; antistatic agents; fillers; light stabilizers; foaming agents; molding processability modifiers (silicone oil, etc.); Examples of such additives include, but are not limited to, those described in International Publication No.
  • the vinyl chloride resin composition of the present invention preferably contains a plasticizer. If the vinyl chloride resin composition includes a plasticizer, the resulting vinyl chloride resin molded article can have good tensile elongation at low temperatures.
  • a plasticizer containing trimellitic acid ester is preferable, a plasticizer containing trimellitic acid trialkyl ester is more preferable, and a plasticizer containing trimellitic acid tri-n-octyl is more preferable.
  • the vinyl chloride resin composition contains the above-mentioned preferred plasticizer, it is possible to further improve the tensile elongation of the resulting vinyl chloride resin molded article at a low temperature.
  • content of the plasticizer in a vinyl chloride resin composition is 50 to 200 mass parts per 100 mass parts of (a) vinyl chloride resin.
  • vinyl chloride resin composition can be used suitably for powder molding, and can be used suitably by powder slush molding.
  • the method for producing a vinyl chloride resin composition of the present invention is a method for producing a vinyl chloride resin composition containing a vinyl chloride resin and a chemisorption deodorant, and the heat resistance temperature of the chemisorption deodorant is 150.
  • Step A for preparing a composition (X) containing components other than the chemisorption deodorant and dusting agent Step B for adding the dusting agent to the composition (X)
  • Step B for adding the dusting agent to the composition (X) At the same time as step B, a chemisorption deodorant is added to the composition (X), or after obtaining the composition (Y) by the step B, the chemisorption type quenching is added to the composition (Y).
  • step C2 of adding an odorant It is characterized by that.
  • the vinyl chloride resin composition which can form the vinyl chloride resin molded object with which the generation amount of the odor component was reduced can be manufactured.
  • a vinyl chloride resin a chemisorption type deodorant, and a dusting agent, what was mentioned above in the item of "vinyl chloride resin composition" can be used.
  • Step A a composition (X) containing components other than the chemisorption deodorant and dusting agent among the components of the vinyl chloride resin composition is prepared.
  • a step of mixing components other than the chemisorption deodorant and dusting agent (including vinyl chloride resin fine particles) by dry blending it is preferable to use a Henschel mixer for the dry blending.
  • the temperature during dry blending is not particularly limited and is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and preferably 200 ° C. or lower.
  • a plasticizer is included in the components of the vinyl chloride resin composition, among the components of the vinyl chloride resin composition, a plasticizer, a chemisorption deodorant, and a dusting agent (including vinyl chloride resin fine particles)
  • the components other than are mixed by dry blending, and when the resulting mixture is heated and heated to a predetermined temperature, a plasticizer is added to the mixture, and the mixture is further heated to dry up ( The plasticizer is absorbed by the vinyl chloride resin particles, which are vinyl chloride resins, and the mixture is further improved.).
  • step B a dusting agent is added to the composition (X).
  • the step B is not particularly limited.
  • the dusting agent (vinyl chloride resin fine particles described above in the section of “vinyl chloride resin composition” is added to the composition (X) obtained in the above step A.
  • the manufacturing method of the vinyl chloride resin composition of this invention is the process C1 which adds a chemisorption type deodorizer to the said composition (X) simultaneously with the said process B in addition to the process A and the process B which were mentioned above, Alternatively, the method further includes a step C2 of adding the chemisorption deodorant to the composition (Y) after obtaining the composition (Y) by the step B.
  • the manufacturing method of the vinyl chloride resin composition of this invention WHEREIN: It is hard to lose the deodorizing performance of a chemisorption type deodorant in the process of including the said process C2 rather than the said process C1, and the obtained vinyl chloride resin This is preferable because the amount of odorous components generated from the vinyl chloride resin molded article formed using the composition can be further reduced.
  • the temperature of the composition (X) or the composition (Y) when adding the chemisorption deodorant is preferably 10 ° C or higher, more preferably 20 ° C or higher, and 50 ° C or lower. It is preferable that it is 35 degrees C or less.
  • the chemisorption deodorant is the composition (X) or composition (Y ) It becomes easier to disperse uniformly.
  • the temperature of the composition (X) or composition (Y) when adding the chemisorption deodorant is not more than the above upper limit, the deodorization performance of the chemisorption deodorant is prevented from being lowered. It becomes easy to do.
  • the vinyl chloride resin molded article of the present invention is obtained by molding the above-described vinyl chloride resin composition by an arbitrary method.
  • the vinyl chloride resin molded article of the present invention is formed using any of the vinyl chloride resin compositions described above, and at least (a) the vinyl chloride resin, (b) the heat resistant temperature and the volume average particle diameter are the above. Therefore, the amount of odorous components generated is reduced. Therefore, the vinyl chloride resin molded article of the present invention can be suitably used as an automobile interior material, in particular, as a skin of an automobile interior part such as an automobile instrument panel.
  • the mold temperature at the time of powder slush molding is not particularly limited and is preferably 200 ° C. or higher, and preferably 220 ° C. or higher. More preferably, it is preferably 300 ° C. or less, and more preferably 280 ° C. or less.
  • the vinyl chloride resin composition of the present invention is sprinkled on a mold in the above temperature range, left for 5 seconds to 30 seconds, and then the excess vinyl chloride resin composition is shaken off, and further at an arbitrary temperature. Leave for 30 seconds to 3 minutes. Thereafter, the mold is cooled to 10 ° C. or more and 60 ° C. or less, and the obtained vinyl chloride resin molded article of the present invention is removed from the mold. Then, a sheet-like molded body having a shape of a mold is obtained.
  • the laminated body of this invention has a foaming polyurethane molded object and either of the vinyl chloride resin molded object mentioned above.
  • the vinyl chloride resin molded body usually constitutes one surface of the laminate.
  • the laminate of the present invention has, for example, a vinyl chloride resin molded body that is formed using the vinyl chloride resin composition of the present invention and has a reduced generation amount of odor components, an automobile interior material, In particular, it can be suitably used as the skin of automobile interior parts such as automobile instrument panels.
  • the lamination method of the foamed polyurethane molded product and the vinyl chloride resin molded product is not particularly limited, and for example, the following method can be used. That is, (1) A method in which a foamed polyurethane molded product and a vinyl chloride resin molded product are separately prepared and then bonded together by heat fusion, thermal bonding, or using a known adhesive; (2) Vinyl chloride Polymerization is performed by reacting isocyanates, which are raw materials of the polyurethane foam molded body, and polyols on the resin molded body, and polyurethane is foamed by a known method to form polyurethane foam on the vinyl chloride resin molded body. And a method of directly forming a molded body. Among these, the latter method (2) is preferable because the process is simple and the vinyl chloride resin molded body and the polyurethane foam molded body can be firmly bonded to each other even in the case of obtaining laminated bodies having various shapes. It is.
  • Example 1 Preparation of vinyl chloride resin composition> Among the blending components shown in Table 1, components other than the plasticizer (trimellitic acid ester) and the vinyl chloride resin fine particles as the dusting agent were placed in a Henschel mixer and mixed. Then, when the temperature of the mixture rises to 80 ° C., all of the plasticizer is added, and the temperature is further raised to dry up (the plasticizer is absorbed by the vinyl chloride resin particles, which are vinyl chloride resins, The mixture was further improved.) To obtain a composition (X). Thereafter, when the composition (X) was cooled to a temperature of 70 ° C. or less, vinyl chloride resin fine particles as a dusting agent were added and mixed to obtain a composition (Y).
  • the embossed mold sprinkled with the vinyl chloride resin composition was allowed to stand in an oven set at a temperature of 200 ° C., and the embossed mold was cooled with cooling water when 60 seconds had elapsed after standing. .
  • the mold temperature was cooled to 40 ° C.
  • a 145 mm ⁇ 175 mm ⁇ 1 mm vinyl chloride resin molded sheet as a vinyl chloride resin molded body was removed from the mold.
  • the amount of octanal generated (A1) and the amount of total aldehyde generated (TA1) were measured according to the method described above.
  • Example 1 A vinyl chloride resin composition and a vinyl chloride resin molded sheet were produced in the same manner as in Example 1 except that no chemisorption deodorant was used when preparing the vinyl chloride resin composition. 1, the amount of octanal generated (B1) and the total amount of aldehyde generated (TB1) were measured.
  • Example in the case of comparing Example 1 using a chemisorption type deodorant and Comparative Example 1 having the same conditions as Example 1 except that no chemisorption type deodorant was used The reduction rate (C1) of the amount of octanal generation in 1 and the reduction rate (TC1) of the generation amount of all aldehydes were calculated by the methods described above. The results are shown in Table 1.
  • Example 2 A vinyl chloride resin composition and a vinyl chloride resin molded sheet were produced in the same manner as in Example 1 except that the compounding components of the vinyl chloride resin composition were changed as shown in Table 1. The same method as in Example 1 was used to measure the amount of octanal generated (A2) and the amount of total aldehyde generated (TA2).
  • Example 2 A vinyl chloride resin composition and a vinyl chloride resin molded sheet were produced in the same manner as in Example 2 except that no chemisorption deodorant was used when preparing the vinyl chloride resin composition.
  • the amount of octanal generated (B2) and the amount of total aldehyde generated (TB2) were measured by the same method.
  • Example 2 in the case of comparing Example 2 using a chemisorption type deodorant and Comparative Example 2 having the same conditions as Example 2 except that no chemisorption type deodorant was used
  • the reduction rate (C2) of the generation amount of octanal and the reduction rate (TC2) of the generation amount of all aldehydes were calculated by the above-described methods. The results are shown in Table 1.
  • Example 1 using a vinyl chloride resin composition containing (a) a vinyl chloride resin and (b) a chemisorption deodorant having a heat resistant temperature and a volume average particle size within a predetermined range and
  • the vinyl chloride resin molded article 2 includes (a) a vinyl chloride resin, but (b) a vinyl chloride resin composition that does not contain a chemisorption deodorant having a heat resistant temperature and a volume average particle diameter within a predetermined range. It can be seen that the amount of odorous components (aldehyde) generated is reduced as compared with the vinyl chloride resin molded articles of Comparative Examples 1 and 2 using the above.
  • this invention it is possible to provide a vinyl chloride resin molded body in which the amount of odorous components generated is reduced. Moreover, this invention can provide the laminated body which has the vinyl chloride resin composition which can form the said vinyl chloride resin molded object, and the said vinyl chloride resin molded object.

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Abstract

The purpose of the present invention is to provide a vinyl chloride resin composition that makes it possible to form a vinyl chloride resin molded body that generates fewer odorous components. This vinyl chloride resin composition includes a vinyl chloride resin (a) and a chemical-adsorption-type deodorizer (b). The vinyl chloride resin composition is characterized in that the heat-resistance temperature of the chemical-adsorption-type deodorizer (b) is at least 150°C and in that the volume average particle diameter of the chemical-adsorption-type deodorizer (b) is 0.5–10 μm. The chemical-adsorption-type deodorizer (b) ideally includes an oxide and/or a hydroxide of at least one element selected from the group that consists of magnesium, aluminum, silicon, and zirconium.

Description

塩化ビニル樹脂組成物、塩化ビニル樹脂組成物の製造方法、塩化ビニル樹脂成形体および積層体Vinyl chloride resin composition, method for producing vinyl chloride resin composition, vinyl chloride resin molded article and laminate
　本発明は、塩化ビニル樹脂組成物、塩化ビニル樹脂組成物の製造方法、塩化ビニル樹脂成形体および積層体に関するものである。 The present invention relates to a vinyl chloride resin composition, a method for producing a vinyl chloride resin composition, a vinyl chloride resin molded article, and a laminate.
　塩化ビニル樹脂は、一般に、耐寒性、耐熱性、耐油性などの特性に優れているため、種々の用途に用いられている。
　具体的には、例えば、自動車インスツルメントパネル等の自動車内装部品の形成には、塩化ビニル樹脂成形体からなる表皮や塩化ビニル樹脂成形体からなる表皮に発泡ポリウレタン成形体等の発泡体を裏打ちしてなる積層体などの自動車内装材が用いられている。 Vinyl chloride resins are generally used in various applications because they are excellent in properties such as cold resistance, heat resistance, and oil resistance.
Specifically, for example, for the formation of automobile interior parts such as an automobile instrument panel, a skin made of a vinyl chloride resin molded body or a foam body such as a polyurethane foam molded body is lined on the skin made of a vinyl chloride resin molded body. Automotive interior materials such as laminates are used.
　そして、表皮として用いられる塩化ビニル樹脂成形体は、例えば、塩化ビニル樹脂と、可塑剤とを含む塩化ビニル樹脂組成物をパウダースラッシュ成形などの既知の成形方法を用いて成形することにより製造されている（例えば、特許文献１参照）。 The vinyl chloride resin molded body used as the skin is produced by molding a vinyl chloride resin composition containing a vinyl chloride resin and a plasticizer using a known molding method such as powder slush molding. (For example, refer to Patent Document 1).
国際公開第２０１４／０９１８６７号International Publication No. 2014/091867
　ここで、塩化ビニル樹脂成形体を自動車内装部品の表皮などの自動車内装材として使用した場合、当該塩化ビニル樹脂成形体から、例えば、アルデヒド系ガス等の臭気成分が発生し、自動車の搭乗員に不快感を与え得ることが問題となっている。そのため、塩化ビニル樹脂成形体からの臭気成分の発生量を低減することが求められる。 Here, when the vinyl chloride resin molded article is used as an automobile interior material such as a skin of an automobile interior part, an odor component such as an aldehyde-based gas is generated from the vinyl chloride resin molded article, and the passenger of the automobile The problem is that it can be uncomfortable. Therefore, it is required to reduce the amount of odorous components generated from the vinyl chloride resin molded body.
　そこで、本発明は、臭気成分の発生量が低減された塩化ビニル樹脂成形体を提供することを目的とする。
　また、本発明は、臭気成分の発生量が低減された塩化ビニル樹脂成形体を形成可能な塩化ビニル樹脂組成物、および、当該塩化ビニル樹脂成形体を有する積層体を提供することを目的とする。 Then, an object of this invention is to provide the vinyl chloride resin molded object with which the generation amount of the odor component was reduced.
Another object of the present invention is to provide a vinyl chloride resin composition capable of forming a vinyl chloride resin molded body with reduced generation of odor components, and a laminate having the vinyl chloride resin molded body. .
　本発明者は、上記課題を解決することを目的として鋭意検討を行った。そして、本発明者は、塩化ビニル樹脂と、耐熱温度および体積平均粒子径が所定の範囲内である化学吸着型消臭剤とを含む塩化ビニル樹脂組成物を用いれば、臭気成分の発生量が低減された塩化ビニル樹脂成形体が形成可能であることを見出し、本発明を完成させた。 The present inventor has intensively studied for the purpose of solving the above problems. And if this inventor uses the vinyl chloride resin composition which contains a vinyl chloride resin and the chemisorption type deodorant whose heat-resistant temperature and volume average particle diameter are in the predetermined range, the amount of generation | occurrence | production of an odor component will be carried out. The present inventors have found that a reduced vinyl chloride resin molded body can be formed and completed the present invention.
　即ち、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の塩化ビニル樹脂組成物は、（ａ）塩化ビニル樹脂、および（ｂ）化学吸着型消臭剤を含む塩化ビニル樹脂組成物であり、前記（ｂ）化学吸着型消臭剤の耐熱温度が、１５０℃以上であり、前記（ｂ）化学吸着型消臭剤の体積平均粒子径が、０．５μｍ以上１０μｍ以下であることを特徴とする。このように、（ａ）塩化ビニル樹脂と、（ｂ）耐熱温度および体積平均粒子径が所定の範囲内である化学吸着型消臭剤とを含む塩化ビニル樹脂組成物を用いれば、臭気成分の発生量が低減された塩化ビニル樹脂成形体を形成することができる。
　なお、本発明において、「化学吸着型消臭剤の体積平均粒子径」とは、レーザー回折法で測定された粒度分布（体積基準）において小径側から計算した累積体積が５０％となる粒子径（Ｄ５０）を指す。
　また、本発明において、「化学吸着型消臭剤の耐熱温度」とは、当該化学吸着型消臭剤が加熱された後も消臭性能を維持し得る加熱温度の範囲内での最高温度である。 That is, this invention aims at solving the said subject advantageously, The vinyl chloride resin composition of this invention contains (a) vinyl chloride resin and (b) chemisorption type deodorant. A heat-resistant temperature of the (b) chemisorption deodorant is 150 ° C. or higher, and a volume average particle diameter of the (b) chemisorption deodorant is 0.5 μm. It is 10 μm or less. Thus, if a vinyl chloride resin composition containing (a) a vinyl chloride resin and (b) a chemisorption deodorant having a heat resistant temperature and a volume average particle size within a predetermined range is used, A vinyl chloride resin molded body with a reduced generation amount can be formed.
In the present invention, the “volume average particle diameter of the chemisorption deodorant” means a particle diameter at which the cumulative volume calculated from the small diameter side is 50% in the particle size distribution (volume basis) measured by the laser diffraction method. (D50).
In the present invention, the “heat-resistant temperature of the chemisorption deodorant” is the maximum temperature within the range of the heating temperature that can maintain the deodorization performance even after the chemisorption deodorant is heated. is there.
　ここで、本発明の塩化ビニル樹脂組成物は、前記（ｂ）化学吸着型消臭剤が、マグネシウム、アルミニウム、ケイ素、およびジルコニウムからなる群より選ばれる少なくとも１種の元素の酸化物および／または水酸化物を含むことが好ましい。前記（ｂ）化学吸着型消臭剤が、上記所定の元素の酸化物および／または水酸化物を含めば、塩化ビニル樹脂組成物を用いて形成される塩化ビニル樹脂成形体からの臭気成分の発生量を更に低減することができる。 Here, in the vinyl chloride resin composition of the present invention, the (b) chemisorption deodorant is an oxide of at least one element selected from the group consisting of magnesium, aluminum, silicon, and zirconium, and / or It is preferable to contain a hydroxide. If the (b) chemisorption deodorant contains an oxide and / or hydroxide of the predetermined element, the odor component from the vinyl chloride resin molded article formed using the vinyl chloride resin composition The amount of generation can be further reduced.
　また、本発明の塩化ビニル樹脂組成物は、前記（ｂ）化学吸着型消臭剤が、ヒドラジド化合物および／またはアミン化合物を含むことが好ましく、更に酸化ジルコニウムを含むことがより好ましい。前記（ｂ）化学吸着型消臭剤が、ヒドラジド化合物および／またはアミン化合物を含めば、塩化ビニル樹脂組成物を用いて形成される塩化ビニル樹脂成形体からの臭気成分の発生量を更に低減することができ、更に酸化ジルコニウムを含めば、上記塩化ビニル樹脂成形体からの臭気成分の発生量を一層低減することができる。 In the vinyl chloride resin composition of the present invention, the (b) chemisorption deodorant preferably contains a hydrazide compound and / or an amine compound, and more preferably contains zirconium oxide. If the (b) chemisorption deodorant includes a hydrazide compound and / or an amine compound, the amount of odorous components generated from the vinyl chloride resin molded body formed using the vinyl chloride resin composition is further reduced. If zirconium oxide is further included, the amount of odorous components generated from the vinyl chloride resin molded product can be further reduced.
　さらに、本発明の塩化ビニル樹脂組成物は、前記（ｂ）化学吸着型消臭剤の含有量が、前記（ａ）塩化ビニル樹脂１００質量部当たり０．５質量部以上１０質量部以下であることが好ましい。前記（ｂ）化学吸着型消臭剤の含有量が、前記（ａ）塩化ビニル樹脂１００質量部当たり０．５質量部以上１０質量部以下であれば、塩化ビニル樹脂組成物を用いて形成される塩化ビニル樹脂成形体からの臭気成分の発生量を更に低減し得ると共に、得られる塩化ビニル樹脂成形体の引張伸びを十分に確保することができる。 Furthermore, in the vinyl chloride resin composition of the present invention, the content of the (b) chemisorption deodorant is 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the (a) vinyl chloride resin. It is preferable. When the content of the (b) chemisorption deodorant is 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the (a) vinyl chloride resin, it is formed using a vinyl chloride resin composition. The amount of odorous components generated from the vinyl chloride resin molded product can be further reduced, and the tensile elongation of the resulting vinyl chloride resin molded product can be sufficiently ensured.
　また、本発明の塩化ビニル樹脂組成物は、粉体成形に用いられることが好ましい。塩化ビニル樹脂組成物を粉体成形に用いれば、例えば、自動車内装部品の表皮として良好に使用し得る塩化ビニル樹脂成形体が容易に得られる。 The vinyl chloride resin composition of the present invention is preferably used for powder molding. If the vinyl chloride resin composition is used for powder molding, for example, a vinyl chloride resin molded body that can be used favorably as the skin of automobile interior parts can be easily obtained.
　さらに、本発明の塩化ビニル樹脂組成物は、パウダースラッシュ成形に用いられることが好ましい。塩化ビニル樹脂組成物をパウダースラッシュ成形に用いれば、例えば、自動車内装部品の表皮として良好に使用し得る塩化ビニル樹脂成形体が一層容易に得られる。 Furthermore, the vinyl chloride resin composition of the present invention is preferably used for powder slush molding. If the vinyl chloride resin composition is used for powder slush molding, for example, a vinyl chloride resin molded body that can be used favorably as the skin of automobile interior parts can be obtained more easily.
　そして、本発明の塩化ビニル樹脂組成物の製造方法は、塩化ビニル樹脂および化学吸着型消臭剤を含む塩化ビニル樹脂組成物を製造する方法であり、前記化学吸着型消臭剤の耐熱温度が、１５０℃以上であり、前記化学吸着型消臭剤の体積平均粒子径が、０．５μｍ以上１０μｍ以下であり、前記塩化ビニル樹脂組成物は、ダスティング剤を含み、前記塩化ビニル樹脂組成物の成分のうち、前記化学吸着型消臭剤およびダスティング剤以外の成分を含む組成物（Ｘ）を調製する工程Ａと、前記組成物（Ｘ）に前記ダスティング剤を添加する工程Ｂと、前記工程Ｂと同時に前記組成物（Ｘ）に化学吸着型消臭剤を添加する工程Ｃ１、または、前記工程Ｂにより組成物（Ｙ）を得た後に前記組成物（Ｙ）に前記化学吸着型消臭剤を添加する工程Ｃ２と、を含むことを特徴とする。このように、塩化ビニル樹脂組成物の成分のうち、耐熱温度および体積平均粒子径が所定の範囲内である化学吸着型消臭剤とダスティング剤とを除く成分を含む組成物を調製した後、ダスティング剤の添加と同時に、または、ダスティング剤を添加した後に化学吸着型消臭剤を添加して得られる塩化ビニル樹脂組成物であれば、臭気成分の発生量が低減された塩化ビニル樹脂成形体を形成可能である。 And the manufacturing method of the vinyl chloride resin composition of the present invention is a method of manufacturing a vinyl chloride resin composition containing a vinyl chloride resin and a chemisorption deodorant, and the heat resistance temperature of the chemisorption deodorant is The chemical adsorption deodorant has a volume average particle size of 0.5 μm or more and 10 μm or less, the vinyl chloride resin composition contains a dusting agent, and the vinyl chloride resin composition Step A of preparing a composition (X) containing components other than the chemisorption deodorant and dusting agent, and Step B of adding the dusting agent to the composition (X) The step C1 of adding a chemisorption deodorant to the composition (X) simultaneously with the step B, or the step (B) after obtaining the composition (Y) by the step B Process C to add mold deodorant 2 and. Thus, after preparing the composition containing the components except the chemical adsorption type deodorant and the dusting agent whose heat-resistant temperature and volume average particle diameter are within the predetermined ranges among the components of the vinyl chloride resin composition If the vinyl chloride resin composition is obtained by adding a chemisorption deodorant simultaneously with the addition of the dusting agent or after the dusting agent is added, the amount of odorous components generated is reduced. A resin molded body can be formed.
　また、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の塩化ビニル樹脂成形体は、上述した塩化ビニル樹脂組成物のいずれかを成形してなることを特徴とする。上記塩化ビニル樹脂組成物を用いて得られる塩化ビニル樹脂成形体は、臭気成分の発生量が低減されている。 Moreover, this invention aims at solving the said subject advantageously, The vinyl chloride resin molded object of this invention shape | molds one of the vinyl chloride resin compositions mentioned above, It is characterized by the above-mentioned. And In the vinyl chloride resin molded body obtained using the vinyl chloride resin composition, the amount of odorous components generated is reduced.
　更に、本発明の塩化ビニル樹脂成形体は、自動車内装部品の表皮用として用いることができる。 Furthermore, the vinyl chloride resin molded product of the present invention can be used for the skin of automobile interior parts.
　また、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の積層体は、発泡ポリウレタン成形体と、上述したいずれかの塩化ビニル樹脂成形体とを有することを特徴とする。発泡ポリウレタン成形体および上述の塩化ビニル樹脂成形体を用いて積層体とすれば、当該積層体は、臭気成分の発生量が低減された塩化ビニル樹脂成形体部分を備えることができる。 Moreover, this invention aims at solving the said subject advantageously, and the laminated body of this invention has a foaming polyurethane molding and one of the vinyl chloride resin moldings mentioned above. Features. If a foamed polyurethane molded product and the above-described vinyl chloride resin molded product are used to form a laminate, the laminate can include a vinyl chloride resin molded product portion in which the amount of odorous components generated is reduced.
　本発明によれば、臭気成分の発生量が低減された塩化ビニル樹脂成形体を提供することができる。また、本発明は、当該塩化ビニル樹脂成形体を形成可能な塩化ビニル樹脂組成物、および、当該塩化ビニル樹脂成形体を有する積層体を提供することができる。 According to the present invention, it is possible to provide a vinyl chloride resin molded body in which the amount of odorous components generated is reduced. Moreover, this invention can provide the laminated body which has the vinyl chloride resin composition which can form the said vinyl chloride resin molded object, and the said vinyl chloride resin molded object.
　以下、本発明の実施形態について詳細に説明する。
　本発明の塩化ビニル樹脂組成物は、例えば、本発明の塩化ビニル樹脂成形体を形成する際に用いることができる。また、本発明の塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体は、例えば、当該塩化ビニル樹脂成形体を有する本発明の積層体の製造に用いることができる。そして、本発明の塩化ビニル樹脂成形体は、例えば、自動車インスツルメントパネル等の自動車内装部品の表皮用など、自動車内装材用として好適に用いることができる。なお、本発明の塩化ビニル樹脂組成物は、例えば、本発明の塩化ビニル樹脂組成物の製造方法により、調製することができる。 Hereinafter, embodiments of the present invention will be described in detail.
The vinyl chloride resin composition of the present invention can be used, for example, when forming the vinyl chloride resin molded article of the present invention. Moreover, the vinyl chloride resin molded object formed using the vinyl chloride resin composition of this invention can be used for manufacture of the laminated body of this invention which has the said vinyl chloride resin molded object, for example. The vinyl chloride resin molded body of the present invention can be suitably used for automobile interior materials, for example, for the skin of automobile interior parts such as automobile instrument panels. In addition, the vinyl chloride resin composition of this invention can be prepared with the manufacturing method of the vinyl chloride resin composition of this invention, for example.
（塩化ビニル樹脂組成物）
　本発明の塩化ビニル樹脂組成物は、（ａ）塩化ビニル樹脂と、（ｂ）耐熱温度および体積平均粒子径が所定の範囲内である化学吸着型消臭剤とを含み、任意に、その他の添加剤を更に含んでもよい。
　そして、上述した本発明の塩化ビニル樹脂組成物は、少なくとも、上記（ａ）塩化ビニル樹脂と、（ｂ）耐熱温度および体積平均粒子径が所定の範囲内である化学吸着型消臭剤とを含んでいるため、当該塩化ビニル樹脂組成物を使用すれば、臭気成分の発生量が低減された塩化ビニル樹脂成形体を形成することができる。 (Vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention comprises (a) a vinyl chloride resin, and (b) a chemisorption deodorant whose heat-resistant temperature and volume average particle diameter are within a predetermined range, and optionally other An additive may be further included.
The vinyl chloride resin composition of the present invention described above includes at least (a) the vinyl chloride resin and (b) a chemisorption deodorant having a heat resistant temperature and a volume average particle size within a predetermined range. Therefore, if the vinyl chloride resin composition is used, a vinyl chloride resin molded body in which the generation amount of odor components is reduced can be formed.
＜（ａ）塩化ビニル樹脂＞
　ここで、（ａ）塩化ビニル樹脂としては、例えば、１種類または２種類以上の塩化ビニル樹脂粒子を含有することができ、任意に、１種類または２種類以上の塩化ビニル樹脂微粒子を更に含有することができる。中でも、（ａ）塩化ビニル樹脂は、少なくとも塩化ビニル樹脂粒子を含有することが好ましく、塩化ビニル樹脂粒子および塩化ビニル樹脂微粒子を含有することがより好ましい。
　そして、（ａ）塩化ビニル樹脂は、懸濁重合法、乳化重合法、溶液重合法、塊状重合法など、従来から知られているいずれの製造法によっても製造し得る。
　なお、本明細書において、「樹脂粒子」とは、粒子径が３０μｍ以上の粒子を指し、「樹脂微粒子」とは、粒子径が３０μｍ未満の粒子を指す。 <(A) Vinyl chloride resin>
Here, as the (a) vinyl chloride resin, for example, one kind or two or more kinds of vinyl chloride resin particles can be contained, and optionally one kind or two or more kinds of vinyl chloride resin particles are further contained. be able to. Among these, (a) the vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.
The (a) vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method or bulk polymerization method.
In the present specification, “resin particles” refers to particles having a particle size of 30 μm or more, and “resin particles” refers to particles having a particle size of less than 30 μm.
　また、（ａ）塩化ビニル樹脂としては、塩化ビニル単量体単位からなる単独重合体の他、塩化ビニル単量体単位を好ましくは５０質量％以上、より好ましくは７０質量％以上含有する塩化ビニル系共重合体が挙げられる。そして、塩化ビニル系共重合体を構成し得る、塩化ビニル単量体と共重合可能な単量体（共単量体）の具体例としては、例えば、国際公開第２０１６／０９８３４４号に記載のものを使用することができる。また、これらの成分は、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。 The vinyl chloride resin (a) is preferably a vinyl chloride containing a vinyl chloride monomer unit in addition to a homopolymer composed of vinyl chloride monomer units, preferably 50% by mass or more, more preferably 70% by mass or more. Examples thereof include a system copolymer. And as a specific example of a monomer (comonomer) copolymerizable with a vinyl chloride monomer that can constitute a vinyl chloride copolymer, for example, as described in International Publication No. 2016/098344 Things can be used. Moreover, these components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
＜＜塩化ビニル樹脂粒子＞＞
　塩化ビニル樹脂組成物において、塩化ビニル樹脂粒子は、通常、マトリックス樹脂（基材）として機能する。なお、塩化ビニル樹脂粒子は、懸濁重合法により製造することが好ましい。 << Vinyl chloride resin particles >>
In the vinyl chloride resin composition, the vinyl chloride resin particles usually function as a matrix resin (base material). The vinyl chloride resin particles are preferably produced by a suspension polymerization method.
［平均重合度］
　そして、塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度は、８００以上であることが好ましく、１０００以上であることがより好ましく、５０００以下であることが好ましく、３０００以下であることがより好ましく、２８００以下であることが更に好ましく、１３００以下であることが一層好ましい。塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度が８００以上であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の物理的強度を十分確保しつつ、例えば、引張伸びを良好にできる。そして、熱老化試験後における損失弾性率Ｅ”のピークトップ温度が低く、且つ引張伸びが良好な塩化ビニル樹脂成形体は、例えば、エアバッグが膨張、展開した際に、破片が飛散することなく設計通りに割れる、良好な延性を有する自動車インスツルメントパネルの表皮などの自動車内装材として好適に用いることができる。一方、塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度が５０００以下であれば、塩化ビニル樹脂組成物の溶融性を向上させ、当該組成物を用いて形成した塩化ビニル樹脂成形体の表面平滑性を向上できる。
　なお、本発明において「平均重合度」は、ＪＩＳ Ｋ６７２０－２に準拠して測定することができる。 [Average polymerization degree]
The average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 800 or more, more preferably 1000 or more, and preferably 5000 or less, more preferably 3000 or less. Preferably, it is 2800 or less, more preferably 1300 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is 800 or more, the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition is sufficiently secured, for example, tensile elongation Can be improved. And the vinyl chloride resin molded product having a low peak top temperature of the loss elastic modulus E ″ after the heat aging test and good tensile elongation can be obtained without, for example, debris scattering when the airbag is expanded and deployed. It can be suitably used as an automobile interior material such as a skin of an automotive instrument panel having a good ductility, which can break as designed, while the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is 5000 or less. If it exists, the meltability of a vinyl chloride resin composition can be improved and the surface smoothness of the vinyl chloride resin molded object formed using the said composition can be improved.
In the present invention, the “average degree of polymerization” can be measured according to JIS K6720-2.
［平均粒子径］
　また、塩化ビニル樹脂粒子の平均粒子径は、通常３０μｍ以上であり、５０μｍ以上が好ましく、１００μｍ以上がより好ましく、１３６μｍ以上であることが更に好ましく、１４５μｍ以上であることが特に好ましく、５００μｍ以下が好ましく、２００μｍ以下がより好ましい。塩化ビニル樹脂粒子の平均粒子径が３０μｍ以上であれば、塩化ビニル樹脂組成物の粉体流動性を向上させることができる。一方、塩化ビニル樹脂粒子の平均粒子径が５００μｍ以下であれば、塩化ビニル樹脂組成物の溶融性を高めると共に、当該組成物を用いて形成した塩化ビニル樹脂成形体の表面平滑性を向上させることができる。
　なお、本発明において、「塩化ビニル樹脂粒子の平均粒子径」は、ＪＩＳ Ｚ８８２５に準拠し、レーザー回折法により体積平均粒子径として測定することができる。 [Average particle size]
The average particle diameter of the vinyl chloride resin particles is usually 30 μm or more, preferably 50 μm or more, more preferably 100 μm or more, further preferably 136 μm or more, particularly preferably 145 μm or more, and 500 μm or less. Preferably, 200 μm or less is more preferable. If the average particle diameter of the vinyl chloride resin particles is 30 μm or more, the powder fluidity of the vinyl chloride resin composition can be improved. On the other hand, if the average particle diameter of the vinyl chloride resin particles is 500 μm or less, the meltability of the vinyl chloride resin composition is improved and the surface smoothness of the vinyl chloride resin molded body formed using the composition is improved. Can do.
In the present invention, the “average particle diameter of vinyl chloride resin particles” can be measured as a volume average particle diameter by a laser diffraction method in accordance with JIS Z8825.
［含有割合］
　そして、（ａ）塩化ビニル樹脂中の塩化ビニル樹脂粒子の含有割合は、７０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、１００質量％とすることができ、９５質量％以下であることが好ましく、９０質量％以下であることがより好ましい。（ａ）塩化ビニル樹脂中の塩化ビニル樹脂粒子の含有割合が７０質量％以上であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の物理的強度を十分確保しつつ、引張伸びを良好にできる。一方、（ａ）塩化ビニル樹脂中の塩化ビニル樹脂粒子の含有割合が９５質量％以下であれば、塩化ビニル樹脂組成物の粉体流動性を向上させることができる。 [Content ratio]
The content ratio of the vinyl chloride resin particles in the vinyl chloride resin is preferably 70% by mass or more, more preferably 80% by mass or more, and can be 100% by mass. It is preferable that it is mass% or less, and it is more preferable that it is 90 mass% or less. (A) If the content ratio of the vinyl chloride resin particles in the vinyl chloride resin is 70% by mass or more, the tensile strength is ensured while sufficiently securing the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition. Elongation can be improved. On the other hand, if the content ratio of the vinyl chloride resin particles in the vinyl chloride resin is 95% by mass or less, the powder flowability of the vinyl chloride resin composition can be improved.
＜＜塩化ビニル樹脂微粒子＞＞
　塩化ビニル樹脂組成物において、塩化ビニル樹脂微粒子は、通常、ダスティング剤（粉体流動性改良剤）として機能する。なお、塩化ビニル樹脂微粒子は、乳化重合法により製造することが好ましい。 << Vinyl chloride resin fine particles >>
In the vinyl chloride resin composition, the vinyl chloride resin fine particles usually function as a dusting agent (powder fluidity improver). The vinyl chloride resin fine particles are preferably produced by an emulsion polymerization method.
［平均重合度］
　そして、塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の平均重合度は、５００以上が好ましく、７００以上がより好ましく、８００以上が更に好ましく、３０００以下が好ましく、２５００以下がより好ましい。ダスティング剤としての塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の平均重合度が５００以上であれば、塩化ビニル樹脂組成物の粉体流動性が向上すると共に、当該組成物を用いて得られる成形体の引張伸びを良好にすることができる。一方、塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の平均重合度が３０００以下であれば、塩化ビニル樹脂組成物の溶融性が高まり、当該組成物を用いて形成した塩化ビニル樹脂成形体の表面平滑性を向上させることができる。 [Average polymerization degree]
The average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is preferably 500 or more, more preferably 700 or more, still more preferably 800 or more, preferably 3000 or less, and more preferably 2500 or less. If the average degree of polymerization of the vinyl chloride resin constituting the fine particle of the vinyl chloride resin as a dusting agent is 500 or more, the powder flowability of the vinyl chloride resin composition is improved and molding obtained using the composition The tensile elongation of the body can be improved. On the other hand, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is 3000 or less, the meltability of the vinyl chloride resin composition increases, and the surface smoothness of the vinyl chloride resin molded body formed using the composition increases. Can be improved.
［平均粒子径］
　また、塩化ビニル樹脂微粒子の平均粒子径は、通常３０μｍ未満であり、１０μｍ以下であることが好ましく、５μｍ以下であることがより好ましく、０．１μｍ以上であることが好ましく、１μｍ以上であることがより好ましく、１．８μｍ以上であることが更に好ましい。塩化ビニル樹脂微粒子の平均粒子径が０．１μｍ以上であれば、例えばダスティング剤としてのサイズを過度に小さくすることなく、塩化ビニル樹脂組成物の粉体流動性を向上させることができる。一方、塩化ビニル樹脂微粒子の平均粒子径が３０μｍ未満であれば、塩化ビニル樹脂組成物の溶融性が高まり、当該組成物を用いて形成した塩化ビニル樹脂成形体の表面平滑性を向上させることができる。
　なお、本発明において、「塩化ビニル樹脂微粒子の平均粒子径」は、ＪＩＳ Ｚ８８２５に準拠し、レーザー回折法により体積平均粒子径として測定することができる。 [Average particle size]
The average particle size of the vinyl chloride resin fine particles is usually less than 30 μm, preferably 10 μm or less, more preferably 5 μm or less, preferably 0.1 μm or more, and 1 μm or more. Is more preferably 1.8 μm or more. If the average particle diameter of the vinyl chloride resin fine particles is 0.1 μm or more, for example, the powder fluidity of the vinyl chloride resin composition can be improved without excessively reducing the size as a dusting agent. On the other hand, if the average particle diameter of the vinyl chloride resin fine particles is less than 30 μm, the meltability of the vinyl chloride resin composition is increased, and the surface smoothness of the vinyl chloride resin molded body formed using the composition can be improved. it can.
In the present invention, “average particle diameter of vinyl chloride resin fine particles” can be measured as a volume average particle diameter by a laser diffraction method in accordance with JIS Z8825.
［含有割合］
　そして、（ａ）塩化ビニル樹脂中の塩化ビニル樹脂微粒子の含有割合は、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、３０質量％以下であることが好ましく、２０質量％以下であることがより好ましい。（ａ）塩化ビニル樹脂中の塩化ビニル樹脂微粒子の含有割合が５質量％以上であれば、塩化ビニル樹脂組成物の粉体流動性を向上させることができる。一方、（ａ）塩化ビニル樹脂中の塩化ビニル樹脂微粒子の含有割合が３０質量％以下であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の物理的強度を高めることができる。 [Content ratio]
And (a) the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 30% by mass or less, More preferably, it is 20 mass% or less. (A) If the content rate of the vinyl chloride resin fine particles in the vinyl chloride resin is 5% by mass or more, the powder flowability of the vinyl chloride resin composition can be improved. On the other hand, if the content of the vinyl chloride resin fine particles in the vinyl chloride resin is 30% by mass or less, the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be increased. .
＜（ｂ）化学吸着型消臭剤＞
　（ｂ）化学吸着型消臭剤は、臭気成分と化学結合を形成することにより、臭気成分を吸着または分解して、消臭効果を発揮することができる材料であり、塩化ビニル樹脂組成物から塩化ビニル樹脂成形体を形成したとき、あるいは形成した後に、当該塩化ビニル樹脂成形体からの臭気成分の発生量を低減し得る成分である。ただし、（ｂ）化学吸着型消臭剤には、臭気成分と物理的に吸着して消臭効果を発揮し得る材料が含まれていてもよいものとする。 <(B) Chemisorption type deodorant>
(B) The chemisorption type deodorant is a material that can adsorb or decompose the odor component by forming a chemical bond with the odor component, and exhibit a deodorizing effect. From the vinyl chloride resin composition, It is a component that can reduce the amount of odorous components generated from the vinyl chloride resin molded body when or after the vinyl chloride resin molded body is formed. However, (b) the chemisorption deodorant may contain a material that can physically adsorb the odor component and exert a deodorizing effect.
　なお、（ｂ）化学吸着型消臭剤が対象とする臭気成分は、特に限定されず、例えば、アンモニア、アミン等の塩基性ガス；酢酸、イソ吉草酸等の酸性ガス；ホルムアルデヒド、アセトアルデヒド、オクタナール、ノネナール等のアルデヒド系ガス；硫化水素、メチルメルカプタン等の硫黄系ガス；などである。特に、（ｂ）化学吸着型消臭剤は、少なくともアルデヒド系ガスを消臭可能であることが好ましい。（ｂ）化学吸着型消臭剤が臭気成分としてのアルデヒド系ガスを消臭可能であれば、得られる塩化ビニル樹脂成形体からの臭気成分の発生量を更に低減することができる。 In addition, the odor component which (b) chemisorption type deodorant makes object is not specifically limited, For example, basic gas, such as ammonia and an amine; Acid gas, such as an acetic acid and isovaleric acid; Formaldehyde, acetaldehyde, octanal Aldehyde-based gas such as nonenal; sulfur-based gas such as hydrogen sulfide and methyl mercaptan; In particular, the (b) chemisorption deodorant is preferably capable of deodorizing at least an aldehyde gas. (B) If a chemisorption type deodorant can deodorize the aldehyde type gas as an odor component, the generation amount of the odor component from the obtained vinyl chloride resin molding can be further reduced.
　ここで、（ｂ）化学吸着型消臭剤の耐熱温度は、１５０℃以上であることが必要であり、１６０℃以上であることが好ましく、３００℃以上であることがより好ましく、１０００℃以下であることが好ましく、５００℃以下であることがより好ましい。（ｂ）化学吸着型消臭剤の耐熱温度が１５０℃以上であれば、得られる塩化ビニル樹脂成形体からの臭気成分の発生量を良好に低減することができる。一方、（ｂ）化学吸着型消臭剤の耐熱温度が１０００℃以下であれば、（ｂ）化学吸着型消臭剤の取り扱い性や、得られる塩化ビニル樹脂成形体及び（ｂ）化学吸着型消臭剤の廃棄時の処理が容易になる。 Here, the heat resistant temperature of the (b) chemisorption deodorant needs to be 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 300 ° C. or higher, and 1000 ° C. or lower. It is preferable that it is 500 degreeC or less. (B) If the heat-resistant temperature of a chemisorption type deodorant is 150 degreeC or more, the generation amount of the odor component from the obtained vinyl chloride resin molding can be reduced favorably. On the other hand, if the heat-resistant temperature of the (b) chemisorption type deodorant is 1000 ° C. or less, the handleability of the (b) chemisorption type deodorant, the obtained vinyl chloride resin molded article, and (b) the chemisorption type Disposal of deodorant becomes easy.
　また、（ｂ）化学吸着型消臭剤の体積平均粒子径は、０．５μｍ以上であることが必要であり、０．８μｍ以上であることが好ましく、１．２μｍ以上であることがより好ましく、１．５μｍ以上であることが更に好ましく、２．０μｍ以上であることが特に好ましく、１０μｍ以下であることが必要であり、９μｍ以下であることが好ましく、８μｍ以下であることがより好ましく、７μｍ以下であることが更に好ましく、６．０μｍ以下であることが特に好ましい。（ｂ）化学吸着型消臭剤の体積平均粒子径が上記下限以上であれば、得られる塩化ビニル樹脂成形体からの臭気成分の発生量を良好に低減することができる。一方、（ｂ）化学吸着型消臭剤の体積平均粒子径が上記上限以下であれば、得られる塩化ビニル樹脂成形体の引張伸びを十分に確保することができる。 In addition, the volume average particle size of the (b) chemisorption deodorant needs to be 0.5 μm or more, preferably 0.8 μm or more, and more preferably 1.2 μm or more. , 1.5 μm or more is more preferable, 2.0 μm or more is particularly preferable, 10 μm or less is required, 9 μm or less is preferable, and 8 μm or less is more preferable. More preferably, it is 7 micrometers or less, and it is especially preferable that it is 6.0 micrometers or less. (B) If the volume average particle diameter of the chemisorption deodorant is not less than the above lower limit, the amount of odorous components generated from the resulting vinyl chloride resin molded article can be reduced favorably. On the other hand, if the volume average particle diameter of the (b) chemisorption deodorant is not more than the above upper limit, the tensile elongation of the obtained vinyl chloride resin molded article can be sufficiently ensured.
　上述した（ｂ）化学吸着型消臭剤としては、特に限定されることなく、既知の化学吸着型消臭剤を用いることができ、例えば、各種の酸化物、水酸化物、ヒドラジド化合物、アミノグアニジン塩、およびアミン化合物等を用いることができる。なお、（ｂ）化学吸着型消臭剤としては、１種類を単独で使用してもよいし、複数種類を任意の比率で混合して使用してもよい。 The (b) chemisorption deodorant described above is not particularly limited, and any known chemisorption deodorant can be used. For example, various oxides, hydroxides, hydrazide compounds, amino Guanidine salts, amine compounds, and the like can be used. In addition, as (b) chemisorption type deodorant, 1 type may be used independently and multiple types may be mixed and used by arbitrary ratios.
　ここで、酸化物および／または水酸化物の具体例としては、マグネシウム、アルミニウム、ケイ素、ジルコニウム、銀、銅、亜鉛、およびマンガンからなる群より選ばれる少なくとも１種の元素の酸化物および／または水酸化物が挙げられる。その中でも、マグネシウム、アルミニウム、ケイ素、およびジルコニウムからなる群より選ばれる少なくとも１種の元素の酸化物および／または水酸化物が好ましい。なお、上記酸化物および／または水酸化物は、水和物であってもよい。 Here, specific examples of the oxide and / or hydroxide include an oxide of at least one element selected from the group consisting of magnesium, aluminum, silicon, zirconium, silver, copper, zinc, and manganese, and / or A hydroxide is mentioned. Among these, an oxide and / or hydroxide of at least one element selected from the group consisting of magnesium, aluminum, silicon, and zirconium is preferable. The oxide and / or hydroxide may be a hydrate.
　また、ヒドラジド化合物の具体例としては、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド、カルボニルジヒドラジド、コハク酸ジヒドラジド、シュウ酸ジヒドラジドなどのジヒドラジド化合物が挙げられる。
　さらに、アミノグアニジン塩としては、アミノグアニジン塩酸塩やアミノグアニジン硫酸塩、アミノグアニジン重炭酸塩などが挙げられる。
　さらに、アミン化合物の具体例としては、ポリアミン化合物等が挙げられる。そして、ポリアミン化合物としては、例えば、ジエチレントリアミン、テトラエチレンペンタミン等の脂肪族ポリアミン；芳香族ポリアミン；脂環式ポリアミン；などが挙げられる。
　なお、上述したヒドラジド化合物、アミノグアニジン塩およびアミン化合物は、ゼオライト、シリカゲル、上述した酸化物および／または水酸化物、等に担持および／または混合されたものを使用することが好ましい。 Specific examples of the hydrazide compound include dihydrazide compounds such as adipic acid dihydrazide, sebacic acid dihydrazide, carbonyl dihydrazide, succinic acid dihydrazide, and oxalic acid dihydrazide.
Further, aminoguanidine salts include aminoguanidine hydrochloride, aminoguanidine sulfate, aminoguanidine bicarbonate and the like.
Furthermore, a polyamine compound etc. are mentioned as a specific example of an amine compound. Examples of the polyamine compound include aliphatic polyamines such as diethylenetriamine and tetraethylenepentamine; aromatic polyamines; alicyclic polyamines;
In addition, it is preferable to use what was carry | supported and / or mixed with the hydrazide compound, aminoguanidine salt, and amine compound which were mentioned above to a zeolite, a silica gel, the oxide mentioned above and / or a hydroxide.
　そして、（ｂ）化学吸着型消臭剤としては、マグネシウム、アルミニウム、ケイ素、ジルコニウムからなる群より選ばれる少なくとも１種の元素の酸化物および／または水酸化物を用いることが好ましい。（ｂ）化学吸着型消臭剤として、上記所定の元素の酸化物および／また水酸化物を用いれば、得られる塩化ビニル樹脂成形体からの臭気成分の発生量を更に低減することができる。 And, as the (b) chemisorption deodorant, it is preferable to use an oxide and / or hydroxide of at least one element selected from the group consisting of magnesium, aluminum, silicon and zirconium. (B) If the oxide and / or hydroxide of the predetermined element is used as the chemisorption deodorant, the amount of odorous components generated from the resulting vinyl chloride resin molded product can be further reduced.
　また、（ｂ）化学吸着型消臭剤として、ヒドラジド化合物および／またはアミン化合物を用いることも好ましい。（ｂ）化学吸着型消臭剤として、ヒドラジド化合物および／またはアミン化合物を用いても、得られる塩化ビニル樹脂成形体からの臭気成分の発生量を更に低減することができる。さらに、（ｂ）化学吸着型消臭剤として、ヒドラジド化合物および／またはアミン化合物を用いる場合、酸化ジルコニウムを併用することがより好ましい。塩化ビニル樹脂組成物中の化学吸着型消臭剤がヒドラジド化合物および／またはアミン化合物を含み、且つ、酸化ジルコニウムを更に含めば、得られる塩化ビニル樹脂成形体からの臭気成分の発生量を一層低減することができる。ここで、（ｂ）化学吸着型消臭剤として、ヒドラジド化合物および／またはアミン化合物と酸化ジルコニウムとを併用することにより、得られる塩化ビニル樹脂成形体からの臭気成分の発生量を一層低減することができる理由は、明らかではないが、上記のような構成とすることにより、塩基性ガス、酸性ガス、アルデヒド系ガス、および硫黄系ガス等の種類の異なる臭気成分を消臭できるためと推察される。 It is also preferable to use a hydrazide compound and / or an amine compound as the (b) chemisorption deodorant. (B) Even when a hydrazide compound and / or an amine compound is used as the chemisorption deodorant, the amount of odorous components generated from the resulting vinyl chloride resin molded product can be further reduced. Further, when a hydrazide compound and / or an amine compound is used as the (b) chemisorption deodorant, it is more preferable to use zirconium oxide in combination. If the chemisorption deodorant in the vinyl chloride resin composition contains a hydrazide compound and / or an amine compound and further contains zirconium oxide, the amount of odorous components generated from the resulting vinyl chloride resin molded product is further reduced. can do. Here, as (b) a chemisorption type deodorant, a hydrazide compound and / or an amine compound and zirconium oxide are used in combination to further reduce the amount of odorous components generated from the resulting vinyl chloride resin molded article. The reason why the odor can be produced is not clear, but it is presumed that the odor components of different types such as basic gas, acid gas, aldehyde gas, and sulfur gas can be deodorized by the above configuration. The
　さらに、（ｂ）化学吸着型消臭剤としては、二酸化ケイ素－酸化ジルコニウム混合物、ゼオライト－セバシン酸ジヒドラジド混合物、酸化マグネシウム－酸化アルミニウム水和物混合物、酸化ジルコニウム水和物、およびアミン化合物担持水酸化アルミニウムを用いることが好ましく、二酸化ケイ素－酸化ジルコニウム混合物とゼオライト－セバシン酸ジヒドラジド混合物とを併用、または、酸化マグネシウム－酸化アルミニウム水和物混合物と、酸化ジルコニウム水和物と、アミン化合物担持水酸化アルミニウムとを併用することがより好ましく、酸化マグネシウム－酸化アルミニウム水和物混合物と、酸化ジルコニウム水和物と、アミン化合物担持水酸化アルミニウムとを併用することが更に好ましい。（ｂ）化学吸着型消臭剤として上記所定の化学吸着型消臭剤を用いれば、得られる塩化ビニル樹脂成形体からの臭気成分の発生量を更に低減することができ、（ｂ）化学吸着型消臭剤として当該化学吸着型消臭剤を上記所定の組み合わせで併用すれば、得られる塩化ビニル樹脂成形体からの臭気成分の発生量を一層低減することができる。 Further, (b) as a chemisorption type deodorant, silicon dioxide-zirconium oxide mixture, zeolite-sebacate dihydrazide mixture, magnesium oxide-aluminum oxide hydrate mixture, zirconium oxide hydrate, and amine compound supported hydroxide Aluminum is preferably used, and a silicon dioxide-zirconium oxide mixture and a zeolite-sebacate dihydrazide mixture are used in combination, or a magnesium oxide-aluminum oxide hydrate mixture, zirconium oxide hydrate, and an amine compound-supported aluminum hydroxide. Are more preferable, and it is more preferable to use a magnesium oxide-aluminum oxide hydrate mixture, a zirconium oxide hydrate, and an amine compound-supported aluminum hydroxide in combination. (B) If the predetermined chemisorption type deodorant is used as the chemisorption type deodorant, the amount of odorous components generated from the resulting vinyl chloride resin molded product can be further reduced, and (b) chemisorption When the chemisorption deodorant is used as a mold deodorant in the predetermined combination, the amount of odorous components generated from the obtained vinyl chloride resin molded product can be further reduced.
　また、（ｂ）化学吸着型消臭剤としては、市販品を用いることもでき、例えば、ラサ工業社製「ＫＤ－５１１」、シナネンゼオミック社製「ダッシュライトＳ」、東亞合成社製「ケスモン ＮＳ－７０」、東亞合成社製「ケスモン ＮＳ－８０Ｅ」、東亞合成社製「ケスモン ＮＳ－２３１」などを用いることができる。 In addition, as the (b) chemisorption deodorant, commercially available products can be used. For example, “KD-511” manufactured by Lhasa Kogyo Co., “Dashlight S” manufactured by Sinanen Zeomic Co., “Kesmon manufactured by Toagosei Co., Ltd. NS-70 ”,“ Kesmon NS-80E ”manufactured by Toagosei Co., Ltd., and“ Kesmon NS-231 ”manufactured by Toagosei Co., Ltd. can be used.
　ここで、（ｂ）化学吸着型消臭剤の含有量は、（ａ）塩化ビニル樹脂１００質量部当たり０．５質量部以上であることが好ましく、０．８質量部以上であることがより好ましく、１．０質量部以上であることが更に好ましく、１０質量部以下であることが好ましく、６質量部以下であることがより好ましく、４質量部以下であることが更に好ましい。（ｂ）化学吸着型消臭剤の含有量が上記下限以上であれば、得られる塩化ビニル樹脂成形体からの臭気成分の発生量を一層低減することができる。一方、（ｂ）化学吸着型消臭剤の含有量が上記上限以下であれば、得られる塩化ビニル樹脂成形体の引張伸びを十分に確保することができる。 Here, the content of the (b) chemisorption deodorant is preferably 0.5 parts by mass or more and more preferably 0.8 parts by mass or more per 100 parts by mass of the (a) vinyl chloride resin. Preferably, it is 1.0 part by mass or more, more preferably 10 parts by mass or less, more preferably 6 parts by mass or less, and further preferably 4 parts by mass or less. (B) If content of a chemisorption type deodorant is more than the said minimum, the generation amount of the odor component from the obtained vinyl chloride resin molding can be reduced further. On the other hand, if the content of the (b) chemisorption deodorant is not more than the above upper limit, the tensile elongation of the obtained vinyl chloride resin molded article can be sufficiently ensured.
＜添加剤＞
　本発明の塩化ビニル樹脂組成物は、上述した成分以外に、各種添加剤を更に含有してもよい。添加剤としては、特に限定されることなく、例えば、トリメリット酸エステルなどの可塑剤；過塩素酸処理ハイドロタルサイト、ゼオライト、β－ジケトン、脂肪酸金属塩などの安定剤；離型剤；上記塩化ビニル樹脂微粒子以外のその他のダスティング剤；耐衝撃性改良剤；過塩素酸処理ハイドロタルサイト以外の過塩素酸化合物（過塩素酸ナトリウム、過塩素酸カリウム等）；酸化防止剤；防カビ剤；難燃剤；帯電防止剤；充填剤；光安定剤；発泡剤；成形加工性調節剤（シリコーンオイル等）；着色剤が挙げられる。
　このような添加剤としては、特に限定されることなく、例えば、国際公開第２０１６／０９８３４４号に記載のもの（ただし、上述した化学吸着型消臭剤として機能し得る水酸化物、ヒドラジド化合物およびアミン化合物を除く。）を使用することができる。
　上記したように、添加剤は特に限定されることなく使用することができるが、その中でも、本発明の塩化ビニル樹脂組成物は、可塑剤を含有していることが好ましい。塩化ビニル樹脂組成物が可塑剤を含めば、得られる塩化ビニル樹脂成形体の低温下における引っ張り伸びを良好にすることができる。
　そして、可塑剤の中でも、トリメリット酸エステルを含有する可塑剤が好ましく、トリメリット酸トリアルキルエステルを含有する可塑剤がより好ましく、トリメリット酸トリｎ－オクチルを含有する可塑剤が更に好ましい。塩化ビニル樹脂組成物が上記の好ましい可塑剤を含むことで、得られる塩化ビニル樹脂成形体の低温下における引っ張り伸びを更に良好にすることができる。
　なお、塩化ビニル樹脂組成物中の可塑剤の含有量は、（ａ）塩化ビニル樹脂１００質量部当たり５０質量部以上２００質量部以下であることが好ましい。塩化ビニル樹脂組成物中の可塑剤の含有量が上記下限以上であれば、得られる塩化ビニル樹脂成形体の低温下における引っ張り伸びを更に良好にすることができる。一方、塩化ビニル樹脂組成物中の可塑剤の含有量が上記上限以下であれば、得られる塩化ビニル樹脂成形体の表面のべた付きをより抑制し、表面滑り性をより高めることができる。 <Additives>
The vinyl chloride resin composition of the present invention may further contain various additives in addition to the components described above. Additives are not particularly limited, and include, for example, plasticizers such as trimellitic acid esters; stabilizers such as perchloric acid-treated hydrotalcite, zeolite, β-diketone, and fatty acid metal salts; mold release agents; Other dusting agents other than vinyl chloride resin fine particles; Impact resistance improvers; Perchloric acid compounds other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.); Antioxidants; Flame retardants; antistatic agents; fillers; light stabilizers; foaming agents; molding processability modifiers (silicone oil, etc.);
Examples of such additives include, but are not limited to, those described in International Publication No. 2016/098344 (however, the above-described hydroxide, hydrazide compound, and hydrazide compound that can function as a chemisorption deodorant) Except amine compounds) can be used.
As described above, the additive can be used without any particular limitation. Among them, the vinyl chloride resin composition of the present invention preferably contains a plasticizer. If the vinyl chloride resin composition includes a plasticizer, the resulting vinyl chloride resin molded article can have good tensile elongation at low temperatures.
Among the plasticizers, a plasticizer containing trimellitic acid ester is preferable, a plasticizer containing trimellitic acid trialkyl ester is more preferable, and a plasticizer containing trimellitic acid tri-n-octyl is more preferable. When the vinyl chloride resin composition contains the above-mentioned preferred plasticizer, it is possible to further improve the tensile elongation of the resulting vinyl chloride resin molded article at a low temperature.
In addition, it is preferable that content of the plasticizer in a vinyl chloride resin composition is 50 to 200 mass parts per 100 mass parts of (a) vinyl chloride resin. If content of the plasticizer in a vinyl chloride resin composition is more than the said minimum, the tensile elongation in the low temperature of the obtained vinyl chloride resin molded object can be made still more favorable. On the other hand, if content of the plasticizer in a vinyl chloride resin composition is below the said upper limit, the stickiness of the surface of the obtained vinyl chloride resin molding can be suppressed more and surface slipperiness can be improved more.
＜塩化ビニル樹脂組成物の用途＞
　そして、得られた塩化ビニル樹脂組成物は、粉体成形に好適に用いることができ、パウダースラッシュ成形により好適に用いることができる。 <Uses of vinyl chloride resin composition>
And the obtained vinyl chloride resin composition can be used suitably for powder molding, and can be used suitably by powder slush molding.
（塩化ビニル樹脂組成物の製造方法）
　本発明の塩化ビニル樹脂組成物の製造方法は、塩化ビニル樹脂および化学吸着型消臭剤を含む塩化ビニル樹脂組成物を製造する方法であり、前記化学吸着型消臭剤の耐熱温度が、１５０℃以上であり、前記化学吸着型消臭剤の体積平均粒子径が、０．５μｍ以上１０μｍ以下であり、前記塩化ビニル樹脂組成物は、ダスティング剤を含み、前記塩化ビニル樹脂組成物の成分のうち、前記化学吸着型消臭剤およびダスティング剤以外の成分を含む組成物（Ｘ）を調製する工程Ａと、前記組成物（Ｘ）に前記ダスティング剤を添加する工程Ｂと、前記工程Ｂと同時に前記組成物（Ｘ）に化学吸着型消臭剤を添加する工程Ｃ１、または、前記工程Ｂにより組成物（Ｙ）を得た後に前記組成物（Ｙ）に前記化学吸着型消臭剤を添加する工程Ｃ２と、を含むことを特徴とする。そして、本発明の塩化ビニル樹脂組成物の製造方法によれば、臭気成分の発生量が低減された塩化ビニル樹脂成形体を形成可能な塩化ビニル樹脂組成物を製造することができる。
　なお、塩化ビニル樹脂、化学吸着型消臭剤、およびダスティング剤としては、「塩化ビニル樹脂組成物」の項で上述したものを用いることができる。 (Method for producing vinyl chloride resin composition)
The method for producing a vinyl chloride resin composition of the present invention is a method for producing a vinyl chloride resin composition containing a vinyl chloride resin and a chemisorption deodorant, and the heat resistance temperature of the chemisorption deodorant is 150. And the volume average particle size of the chemisorption deodorant is not less than 0.5 μm and not more than 10 μm, and the vinyl chloride resin composition contains a dusting agent, and is a component of the vinyl chloride resin composition Among them, Step A for preparing a composition (X) containing components other than the chemisorption deodorant and dusting agent, Step B for adding the dusting agent to the composition (X), At the same time as step B, a chemisorption deodorant is added to the composition (X), or after obtaining the composition (Y) by the step B, the chemisorption type quenching is added to the composition (Y). Including step C2 of adding an odorant. It is characterized by that. And according to the manufacturing method of the vinyl chloride resin composition of this invention, the vinyl chloride resin composition which can form the vinyl chloride resin molded object with which the generation amount of the odor component was reduced can be manufactured.
In addition, as a vinyl chloride resin, a chemisorption type deodorant, and a dusting agent, what was mentioned above in the item of "vinyl chloride resin composition" can be used.
＜工程Ａ＞
　工程Ａでは、塩化ビニル樹脂組成物の成分のうち、前記化学吸着型消臭剤およびダスティング剤以外の成分を含む組成物（Ｘ）を調製する。例えば、「塩化ビニル樹脂組成物」の項で上述した成分のうち、化学吸着型消臭剤およびダスティング剤（塩化ビニル樹脂微粒子を含む）以外の成分をドライブレンドにより混合する工程が挙げられる。ここで、ドライブレンドには、ヘンシェルミキサーを使用することが好ましい。なお、ドライブレンド時の温度は、特に制限されることなく、５０℃以上が好ましく、７０℃以上がより好ましく、２００℃以下が好ましい。
　また、塩化ビニル樹脂組成物の成分に可塑剤が含まれる場合、当該塩化ビニル樹脂組成物の成分のうち、可塑剤と化学吸着型消臭剤とダスティング剤（塩化ビニル樹脂微粒子を含む）とを除く成分をドライブレンドにより混合し、得られた混合物を加温して所定の温度まで昇温させた時点で、可塑剤を当該混合物に添加し、混合物を更に昇温させることでドライアップ（可塑剤が、塩化ビニル樹脂である塩化ビニル樹脂粒子に吸収されて、上記混合物がさらさらになった状態をいう。）させることもできる。 <Process A>
In Step A, a composition (X) containing components other than the chemisorption deodorant and dusting agent among the components of the vinyl chloride resin composition is prepared. For example, among the components described above in the section “Vinyl chloride resin composition”, there may be mentioned a step of mixing components other than the chemisorption deodorant and dusting agent (including vinyl chloride resin fine particles) by dry blending. Here, it is preferable to use a Henschel mixer for the dry blending. The temperature during dry blending is not particularly limited and is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and preferably 200 ° C. or lower.
Further, when a plasticizer is included in the components of the vinyl chloride resin composition, among the components of the vinyl chloride resin composition, a plasticizer, a chemisorption deodorant, and a dusting agent (including vinyl chloride resin fine particles) The components other than are mixed by dry blending, and when the resulting mixture is heated and heated to a predetermined temperature, a plasticizer is added to the mixture, and the mixture is further heated to dry up ( The plasticizer is absorbed by the vinyl chloride resin particles, which are vinyl chloride resins, and the mixture is further improved.).
＜工程Ｂ＞
　次いで、工程Ｂでは、組成物（Ｘ）にダスティング剤を添加する。工程Ｂとしては、特に限定されることはなく、例えば、上記工程Ａで得られた組成物（Ｘ）に、「塩化ビニル樹脂組成物」の項で上述したダスティング剤（塩化ビニル樹脂微粒子を含む）を更に添加して混合する工程が挙げられる。 <Process B>
Next, in step B, a dusting agent is added to the composition (X). The step B is not particularly limited. For example, the dusting agent (vinyl chloride resin fine particles described above in the section of “vinyl chloride resin composition” is added to the composition (X) obtained in the above step A. A step of further adding and mixing.
＜工程Ｃ１またはＣ２＞
　そして、本発明の塩化ビニル樹脂組成物の製造方法は、上述した工程Ａおよび工程Ｂに加えて、当該工程Ｂと同時に前記組成物（Ｘ）に化学吸着型消臭剤を添加する工程Ｃ１、または、当該工程Ｂにより組成物（Ｙ）を得た後に前記組成物（Ｙ）に前記化学吸着型消臭剤を添加する工程Ｃ２をさらに含む。そして、本発明の塩化ビニル樹脂組成物の製造方法は、上記工程Ｃ１よりも上記工程Ｃ２を含むほうが、化学吸着型消臭剤の消臭性能が工程中に失われにくく、得られる塩化ビニル樹脂組成物を用いて形成される塩化ビニル樹脂成形体からの臭気成分の発生量を更に低減し得るため、好ましい。
　なお、化学吸着型消臭剤を添加する時の組成物（Ｘ）または組成物（Ｙ）の温度は、１０℃以上であることが好ましく、２０℃以上であることがより好ましく、５０℃以下であることが好ましく、３５℃以下であることがより好ましい。化学吸着型消臭剤を添加する時の組成物（Ｘ）または組成物（Ｙ）の温度が、上記下限以上であれば、化学吸着型消臭剤が組成物（Ｘ）または組成物（Ｙ）中により均一に分散しやすくなる。一方、化学吸着型消臭剤を添加する時の組成物（Ｘ）または組成物（Ｙ）の温度が上記上限以下であれば、化学吸着型消臭剤の消臭性能が低下することを防止しやすくなる。 <Process C1 or C2>
And the manufacturing method of the vinyl chloride resin composition of this invention is the process C1 which adds a chemisorption type deodorizer to the said composition (X) simultaneously with the said process B in addition to the process A and the process B which were mentioned above, Alternatively, the method further includes a step C2 of adding the chemisorption deodorant to the composition (Y) after obtaining the composition (Y) by the step B. And the manufacturing method of the vinyl chloride resin composition of this invention WHEREIN: It is hard to lose the deodorizing performance of a chemisorption type deodorant in the process of including the said process C2 rather than the said process C1, and the obtained vinyl chloride resin This is preferable because the amount of odorous components generated from the vinyl chloride resin molded article formed using the composition can be further reduced.
The temperature of the composition (X) or the composition (Y) when adding the chemisorption deodorant is preferably 10 ° C or higher, more preferably 20 ° C or higher, and 50 ° C or lower. It is preferable that it is 35 degrees C or less. If the temperature of the composition (X) or the composition (Y) when adding the chemisorption deodorant is equal to or higher than the above lower limit, the chemisorption deodorant is the composition (X) or composition (Y ) It becomes easier to disperse uniformly. On the other hand, if the temperature of the composition (X) or composition (Y) when adding the chemisorption deodorant is not more than the above upper limit, the deodorization performance of the chemisorption deodorant is prevented from being lowered. It becomes easy to do.
（塩化ビニル樹脂成形体）
　本発明の塩化ビニル樹脂成形体は、上述した塩化ビニル樹脂組成物を、任意の方法で成形することにより得られることを特徴とする。そして、本発明の塩化ビニル樹脂成形体は、上述した塩化ビニル樹脂組成物の何れかを用いて形成され、少なくとも、（ａ）塩化ビニル樹脂と、（ｂ）耐熱温度および体積平均粒子径が上述の所定の範囲内である化学吸着型消臭剤とを含んでいるため、臭気成分の発生量が低減されている。従って、本発明の塩化ビニル樹脂成形体は、自動車内装材、特に、自動車インスツルメントパネル等の自動車内装部品の表皮として好適に用いることができる。 (Vinyl chloride resin molding)
The vinyl chloride resin molded article of the present invention is obtained by molding the above-described vinyl chloride resin composition by an arbitrary method. The vinyl chloride resin molded article of the present invention is formed using any of the vinyl chloride resin compositions described above, and at least (a) the vinyl chloride resin, (b) the heat resistant temperature and the volume average particle diameter are the above. Therefore, the amount of odorous components generated is reduced. Therefore, the vinyl chloride resin molded article of the present invention can be suitably used as an automobile interior material, in particular, as a skin of an automobile interior part such as an automobile instrument panel.
＜塩化ビニル樹脂成形体の形成方法＞
　ここで、パウダースラッシュ成形により塩化ビニル樹脂成形体を形成する場合、パウダースラッシュ成形時の金型温度は、特に制限されることなく、２００℃以上とすることが好ましく、２２０℃以上とすることがより好ましく、３００℃以下とすることが好ましく、２８０℃以下とすることがより好ましい。 <Method for forming vinyl chloride resin molding>
Here, in the case of forming a vinyl chloride resin molded body by powder slush molding, the mold temperature at the time of powder slush molding is not particularly limited and is preferably 200 ° C. or higher, and preferably 220 ° C. or higher. More preferably, it is preferably 300 ° C. or less, and more preferably 280 ° C. or less.
　そして、塩化ビニル樹脂成形体を製造する際には、特に限定されることなく、例えば、以下の方法を用いることができる。即ち、上記温度範囲の金型に本発明の塩化ビニル樹脂組成物を振りかけて、５秒以上３０秒以下の間放置した後、余剰の塩化ビニル樹脂組成物を振り落とし、更に、任意の温度下、３０秒以上３分以下の間放置する。その後、金型を１０℃以上６０℃以下に冷却し、得られた本発明の塩化ビニル樹脂成形体を金型から脱型する。そして、金型の形状をかたどったシート状の成形体を得る。 And when manufacturing a vinyl chloride resin molding, it is not specifically limited, For example, the following methods can be used. That is, the vinyl chloride resin composition of the present invention is sprinkled on a mold in the above temperature range, left for 5 seconds to 30 seconds, and then the excess vinyl chloride resin composition is shaken off, and further at an arbitrary temperature. Leave for 30 seconds to 3 minutes. Thereafter, the mold is cooled to 10 ° C. or more and 60 ° C. or less, and the obtained vinyl chloride resin molded article of the present invention is removed from the mold. Then, a sheet-like molded body having a shape of a mold is obtained.
（積層体）
　本発明の積層体は、発泡ポリウレタン成形体と、上述した塩化ビニル樹脂成形体のいずれかとを有する。なお、塩化ビニル樹脂成形体は、通常、積層体の一方の表面を構成する。
　そして、本発明の積層体は、例えば、本発明の塩化ビニル樹脂組成物を用いて形成され、臭気成分の発生量が低減された塩化ビニル樹脂成形体を有しているため、自動車内装材、特に、自動車インスツルメントパネル等の自動車内装部品の表皮として好適に用いることができる。 (Laminate)
The laminated body of this invention has a foaming polyurethane molded object and either of the vinyl chloride resin molded object mentioned above. The vinyl chloride resin molded body usually constitutes one surface of the laminate.
And since the laminate of the present invention has, for example, a vinyl chloride resin molded body that is formed using the vinyl chloride resin composition of the present invention and has a reduced generation amount of odor components, an automobile interior material, In particular, it can be suitably used as the skin of automobile interior parts such as automobile instrument panels.
　ここで、発泡ポリウレタン成形体と塩化ビニル樹脂成形体との積層方法は、特に限定されることなく、例えば、以下の方法を用いることができる。即ち、（１）発泡ポリウレタン成形体と、塩化ビニル樹脂成形体とを別途準備した後に、熱融着、熱接着、または、公知の接着剤などを用いることにより貼り合わせる方法；（２）塩化ビニル樹脂成形体上で発泡ポリウレタン成形体の原料となるイソシアネート類とポリオール類などとを反応させて重合を行うと共に、公知の方法によりポリウレタンの発泡を行うことにより、塩化ビニル樹脂成形体上に発泡ポリウレタン成形体を直接形成する方法；などが挙げられる。中でも、工程が簡素である点、および、種々の形状の積層体を得る場合においても塩化ビニル樹脂成形体と発泡ポリウレタン成形体とを強固に接着し易い点から、後者の方法（２）が好適である。 Here, the lamination method of the foamed polyurethane molded product and the vinyl chloride resin molded product is not particularly limited, and for example, the following method can be used. That is, (1) A method in which a foamed polyurethane molded product and a vinyl chloride resin molded product are separately prepared and then bonded together by heat fusion, thermal bonding, or using a known adhesive; (2) Vinyl chloride Polymerization is performed by reacting isocyanates, which are raw materials of the polyurethane foam molded body, and polyols on the resin molded body, and polyurethane is foamed by a known method to form polyurethane foam on the vinyl chloride resin molded body. And a method of directly forming a molded body. Among these, the latter method (2) is preferable because the process is simple and the vinyl chloride resin molded body and the polyurethane foam molded body can be firmly bonded to each other even in the case of obtaining laminated bodies having various shapes. It is.
　以下、本発明について実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、以下の説明において、量を表す「％」および「部」は、特に断らない限り、質量基準である。
　そして、塩化ビニル樹脂成形体からのオクタナールおよび全アルデヒドの発生量と、当該成分の発生量の削減率とは下記の方法で測定および算出した。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%” and “part” representing amounts are based on mass unless otherwise specified.
And the generation amount of octanal and total aldehyde from the vinyl chloride resin molded body and the reduction rate of the generation amount of the component were measured and calculated by the following method.
＜オクタナールおよび全アルデヒドの発生量＞
　各実施例および比較例で得られた塩化ビニル樹脂成形体から約１０ｇの試験片を採取し、臭気用サンプリングバック（容量２Ｌ）に入れ、窒素ガス(純度９９．９９９９％以上)１．６Ｌを充填した。その後、乾燥機で加熱し（８０℃／１ｈ）、当該臭気用サンプリングバック内のヘッドスペースガスを捕集管（ＴｅｎａｘＴＡ）に捕集し、加熱脱着法にてガスクロマトグラフ質量分析計による揮発成分の定性および定量分析を行い、塩化ビニル樹脂成形体からのオクタナールおよび全アルデヒドの発生量を測定した。なお、装置および測定条件は下記の通りである。
［装置］
　加熱脱着装置：島津製作所社製「ＴＤ－２０」
　ガスクロマトグラフ質量分析計：島津製作社製「ＧＣＭＳ－ＱＰ２０１０ Ｐｌｕｓ」
［加熱脱着装置条件］
　ディソープション温度：２５０℃
　ガス流量：６０ｍＬ／ｍｉｎ
　トラップ冷却温度：－２２℃
［ガスクロマトグラフ条件］
　キャリヤーガス：ヘリウム
　カラム圧力：１００ｋＰａ
　カラム：ＤＢ－５ｍｓ（内径０．２５ｍｍ、長さ３０ｍ、膜厚０．２５μｍ)
　スプリット比：定量２０：１、定性５０：１
　カラム槽温度：初期温度４０℃５分保持、昇温速度４℃／ｍｉｎ、最終温度２５０℃１０分保持
［質量分析条件］
　イオン化法：電子イオン化法
　インターフェース温度：２００℃
　イオン源温度：２００℃
　スキャン範囲：ｍ／ｚ１０－５００ <Amounts of octanal and total aldehyde generated>
About 10 g of a test piece was collected from the vinyl chloride resin molded bodies obtained in each of the examples and comparative examples, put into an odor sampling bag (capacity 2 L), and 1.6 L of nitrogen gas (purity 99.9999% or more) was added. Filled. Then, it heats with a dryer (80 degreeC / 1h), the head space gas in the sampling bag for the said odor is collected in a collection tube (TenaxTA), and the volatile component of a volatile component by a gas chromatograph mass spectrometer by a heat desorption method Qualitative and quantitative analysis was performed, and the amount of octanal and total aldehyde generated from the vinyl chloride resin molded product was measured. The apparatus and measurement conditions are as follows.
[apparatus]
Thermal desorption device: “TD-20” manufactured by Shimadzu Corporation
Gas chromatograph mass spectrometer: “GCMS-QP2010 Plus” manufactured by Shimadzu Corporation
[Heat desorption equipment conditions]
Desorption temperature: 250 ° C
Gas flow rate: 60 mL / min
Trap cooling temperature: -22 ° C
[Gas chromatographic conditions]
Carrier gas: helium Column pressure: 100 kPa
Column: DB-5ms (inner diameter 0.25mm, length 30m, film thickness 0.25μm)
Split ratio: quantitative 20: 1, qualitative 50: 1
Column bath temperature: initial temperature 40 ° C. held for 5 minutes, heating rate 4 ° C./min, final temperature 250 ° C. held for 10 minutes [mass analysis conditions]
Ionization method: Electron ionization method Interface temperature: 200 ° C
Ion source temperature: 200 ° C
Scan range: m / z 10-500
　そして、化学吸着型消臭剤を使用した実施例ｎ（ｎは１以上の整数）におけるオクタナールの発生量（Ａｎ）および全アルデヒドの発生量（ＴＡｎ）と、化学吸着型消臭剤を使用しなかったこと以外は実施例ｎと同じ条件である比較例ｎにおけるオクタナールの発生量（Ｂｎ）および全アルデヒドの発生量（ＴＢｎ）とを比較した場合の、実施例ｎにおけるオクタナールの発生量の削減率（Ｃｎ）および全アルデヒドの発生量の削減率（ＴＣｎ）を、それぞれ下記の式により算出した。
　オクタナールの削減率Ｃｎ（％）＝（Ｂｎ－Ａｎ）×１００／Ｂｎ
　全アルデヒドの削減率ＴＣｎ（％）＝（ＴＢｎ－ＴＡｎ）×１００／ＴＢｎ Then, the amount of octanal generated (An) and the amount of total aldehyde (TAn) in Example n (n is an integer of 1 or more) using a chemisorption deodorant, and a chemisorption deodorant were used. Reduction of the amount of octanal generated in Example n in comparison with the amount of generated octanal (Bn) and total amount of aldehyde (TBn) in Comparative Example n, which are the same conditions as Example n except that there was no The rate (Cn) and the reduction rate (TCn) of the total amount of aldehydes were calculated by the following equations, respectively.
Octanal reduction rate Cn (%) = (Bn−An) × 100 / Bn
Reduction rate of total aldehydes TCn (%) = (TBn−TAn) × 100 / TBn
（実施例１）
＜塩化ビニル樹脂組成物の調製＞
　表１に示す配合成分のうち、可塑剤（トリメリット酸エステル）と、ダスティング剤である塩化ビニル樹脂微粒子とを除く成分をヘンシェルミキサーに入れて混合した。そして、混合物の温度が８０℃に上昇した時点で上記可塑剤を全て添加し、更に昇温することにより、ドライアップ（可塑剤が、塩化ビニル樹脂である塩化ビニル樹脂粒子に吸収されて、上記混合物がさらさらになった状態をいう。）させて、組成物（Ｘ）を得た。その後、当該組成物（Ｘ）が温度７０℃以下に冷却された時点で、ダスティング剤である塩化ビニル樹脂微粒子を入れて混合し、組成物（Ｙ）を得た。さらにその後、当該組成物（Ｙ）が温度３５℃以下に冷却された時点で、化学吸着型消臭剤としての酸化マグネシウム－酸化アルミニウム水和物混合物、酸化ジルコニウム水和物、およびアミン化合物担持水酸化アルミニウムを入れて混合し、塩化ビニル樹脂組成物を調製した。
＜塩化ビニル樹脂成形体の形成＞
　上述で得られた塩化ビニル樹脂組成物を、温度２５０℃に加熱したシボ付き金型に振りかけ、８秒～２０秒程度の任意の時間放置して溶融させた後、余剰の塩化ビニル樹脂組成物を振り落とした。その後、当該塩化ビニル樹脂組成物を振りかけたシボ付き金型を、温度２００℃に設定したオーブン内に静置し、静置から６０秒経過した時点で当該シボ付き金型を冷却水で冷却した。金型温度が４０℃まで冷却された時点で、塩化ビニル樹脂成形体としての、１４５ｍｍ×１７５ｍｍ×１ｍｍの塩化ビニル樹脂成形シートを金型から脱型した。
　そして、得られた塩化ビニル樹脂成形シートについて、上述の方法に従って、オクタナールの発生量（Ａ１）および全アルデヒドの発生量（ＴＡ１）の測定を行なった。 Example 1
<Preparation of vinyl chloride resin composition>
Among the blending components shown in Table 1, components other than the plasticizer (trimellitic acid ester) and the vinyl chloride resin fine particles as the dusting agent were placed in a Henschel mixer and mixed. Then, when the temperature of the mixture rises to 80 ° C., all of the plasticizer is added, and the temperature is further raised to dry up (the plasticizer is absorbed by the vinyl chloride resin particles, which are vinyl chloride resins, The mixture was further improved.) To obtain a composition (X). Thereafter, when the composition (X) was cooled to a temperature of 70 ° C. or less, vinyl chloride resin fine particles as a dusting agent were added and mixed to obtain a composition (Y). Thereafter, when the composition (Y) is cooled to a temperature of 35 ° C. or lower, a magnesium oxide-aluminum oxide hydrate mixture, zirconium oxide hydrate, and amine compound-supported water as a chemisorption deodorant Aluminum oxide was added and mixed to prepare a vinyl chloride resin composition.
<Formation of vinyl chloride resin molding>
The vinyl chloride resin composition obtained above is sprinkled on a mold with a texture heated to a temperature of 250 ° C., left to melt for an arbitrary time of about 8 to 20 seconds, and then an excess vinyl chloride resin composition. Shaken off. Thereafter, the embossed mold sprinkled with the vinyl chloride resin composition was allowed to stand in an oven set at a temperature of 200 ° C., and the embossed mold was cooled with cooling water when 60 seconds had elapsed after standing. . When the mold temperature was cooled to 40 ° C., a 145 mm × 175 mm × 1 mm vinyl chloride resin molded sheet as a vinyl chloride resin molded body was removed from the mold.
Then, for the obtained vinyl chloride resin molded sheet, the amount of octanal generated (A1) and the amount of total aldehyde generated (TA1) were measured according to the method described above.
（比較例１）
　塩化ビニル樹脂組成物の調製時に、化学吸着型消臭剤を使用しなかったこと以外は、実施例１と同様にして、塩化ビニル樹脂組成物、および塩化ビニル樹脂成形シートを製造し、実施例１と同様の方法により、オクタナールの発生量（Ｂ１）および全アルデヒドの発生量（ＴＢ１）の測定を行なった。 (Comparative Example 1)
A vinyl chloride resin composition and a vinyl chloride resin molded sheet were produced in the same manner as in Example 1 except that no chemisorption deodorant was used when preparing the vinyl chloride resin composition. 1, the amount of octanal generated (B1) and the total amount of aldehyde generated (TB1) were measured.
　そして、化学吸着型消臭剤を使用した実施例１と、化学吸着型消臭剤を使用しなかったこと以外は実施例１と同じ条件である比較例１とを比較した場合の、実施例１におけるオクタナールの発生量の削減率（Ｃ１）および全アルデヒドの発生量の削減率（ＴＣ１）を、それぞれ上述の方法により算出した。結果を表１に示す。 And Example in the case of comparing Example 1 using a chemisorption type deodorant and Comparative Example 1 having the same conditions as Example 1 except that no chemisorption type deodorant was used The reduction rate (C1) of the amount of octanal generation in 1 and the reduction rate (TC1) of the generation amount of all aldehydes were calculated by the methods described above. The results are shown in Table 1.
（実施例２）
　塩化ビニル樹脂組成物の配合成分を表１のように変更した以外は、実施例１と同様にして、塩化ビニル樹脂組成物、および塩化ビニル樹脂成形シートを製造し、実施例１と同様の方法により、オクタナールの発生量（Ａ２）および全アルデヒドの発生量（ＴＡ２）の測定を行なった。 (Example 2)
A vinyl chloride resin composition and a vinyl chloride resin molded sheet were produced in the same manner as in Example 1 except that the compounding components of the vinyl chloride resin composition were changed as shown in Table 1. The same method as in Example 1 Was used to measure the amount of octanal generated (A2) and the amount of total aldehyde generated (TA2).
（比較例２）
　塩化ビニル樹脂組成物の調製時に、化学吸着型消臭剤を使用しなかったこと以外は、実施例２と同様にして、塩化ビニル樹脂組成物、塩化ビニル樹脂成形シートを製造し、実施例１と同様の方法により、オクタナールの発生量（Ｂ２）および全アルデヒドの発生量（ＴＢ２）の測定を行なった。 (Comparative Example 2)
A vinyl chloride resin composition and a vinyl chloride resin molded sheet were produced in the same manner as in Example 2 except that no chemisorption deodorant was used when preparing the vinyl chloride resin composition. The amount of octanal generated (B2) and the amount of total aldehyde generated (TB2) were measured by the same method.
　そして、化学吸着型消臭剤を使用した実施例２と、化学吸着型消臭剤を使用しなかったこと以外は実施例２と同じ条件である比較例２とを比較した場合の、実施例２におけるオクタナールの発生量の削減率（Ｃ２）および全アルデヒドの発生量の削減率（ＴＣ２）を、それぞれ上述の方法により算出した。結果を表１に示す。 And Example in the case of comparing Example 2 using a chemisorption type deodorant and Comparative Example 2 having the same conditions as Example 2 except that no chemisorption type deodorant was used The reduction rate (C2) of the generation amount of octanal and the reduction rate (TC2) of the generation amount of all aldehydes were calculated by the above-described methods. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
１）新第一塩ビ（株）製、製品名「ＺＥＳＴ　１０００Ｚ」（懸濁重合で得られた塩化ビニル樹脂粒子、平均重合度１０００、平均粒子径１４５μｍ）
２）寧波台塑社製、製品名「Ｓ－７０」（懸濁重合で得られた塩化ビニル樹脂粒子、平均重合度１３００、平均粒子径１３６μｍ）
３）新第一塩ビ社製、製品名「ＺＥＳＴ ＰＱＬＴＸ」(乳化重合法で得られた塩化ビニル樹脂微粒子、平均重合度８００、平均粒子径１．８μｍ)
４）花王社製、製品名「トリメックスＮ－０８」
５）協和化学工業社製、製品名「アルカマイザー（登録商標）５」
６）水澤化学工業社製、製品名「ＭＩＺＵＫＡＬＩＺＥＲ　ＤＳ」
７）昭和電工社製、製品名「カレンズＤＫ－１」
８）堺化学工業社、製品名「ＳＡＫＡＩ　ＳＺ２０００」
９）ＡＤＥＫＡ社製、製品名「アデカスタブ　ＬＡ－６３Ｐ」
１０）ＡＤＥＫＡ社製、製品名「アデカスタブ　１５００」
１１）ＡＤＥＫＡ社製、製品名「アデカスタブ　ＬＳ－１２」
１２）大日精化社製、製品名「ＤＡ　ＰＸ　１７２０（Ａ）ブラック」
１３）ラサ工業社製、製品名「ＫＤ－５１１」（二酸化ケイ素－酸化ジルコニウム混合物、耐熱温度：５００℃、体積平均粒子径：２．５μｍ）
１４）シナネンゼオミック社製、製品名「ダッシュライトＳ」（ゼオライト－セバシン酸ジヒドラジド混合物、耐熱温度：３００℃、体積平均粒子径：２．０μｍ）
１５）東亞合成社製、製品名「ケスモン　ＮＳ－７０」（酸化マグネシウム－酸化アルミニウム水和物混合物、耐熱温度：３５０℃、体積平均粒子径：６．０μｍ）
１６）東亞合成社製、製品名「ケスモン　ＮＳ－８０Ｅ」（酸化ジルコニウム水和物、耐熱温度：３５０℃、体積平均粒子径：２．０μｍ）
１７）東亞合成社製、製品名「ケスモン　ＮＳ－２３１」（アミン化合物担持水酸化アルミニウム、耐熱温度：１６０℃、体積平均粒子径：５．０μｍ） 1) Product name “ZEST 1000Z” manufactured by Shin Daiichi PVC Co., Ltd. (vinyl chloride resin particles obtained by suspension polymerization, average polymerization degree 1000, average particle diameter 145 μm)
2) Product name “S-70” manufactured by Ningbodai Plastic Co., Ltd. (vinyl chloride resin particles obtained by suspension polymerization, average polymerization degree 1300, average particle diameter 136 μm)
3) Product name “ZEST PQLTX” (manufactured by Shin-Daiichi PVC Co., Ltd.) (vinyl chloride resin fine particles obtained by emulsion polymerization method, average polymerization degree 800, average particle diameter 1.8 μm)
4) Product name “Trimex N-08” manufactured by Kao Corporation
5) Product name “Alkamizer (registered trademark) 5” manufactured by Kyowa Chemical Industry Co., Ltd.
6) Product name “MIZUKALIZER DS” manufactured by Mizusawa Chemical Industry Co., Ltd.
7) Product name “Karenz DK-1” manufactured by Showa Denko KK
8) Sakai Chemical Industry Co., Ltd., product name “SAKAI SZ2000”
9) Product name "ADEKA STAB LA-63P" manufactured by ADEKA
10) Product name “Adeka Stub 1500” manufactured by ADEKA
11) Product name “ADEKA STAB LS-12” manufactured by ADEKA
12) Product name “DA PX 1720 (A) Black” manufactured by Dainichi Seika Co., Ltd.
13) Product name “KD-511” manufactured by Lhasa Kogyo Co., Ltd. (silicon dioxide-zirconium oxide mixture, heat-resistant temperature: 500 ° C., volume average particle size: 2.5 μm)
14) Product name “Dashlite S” (manufactured by Sinanen Zeomic Co., Ltd. (Zeolite-sebacate dihydrazide mixture, heat-resistant temperature: 300 ° C., volume average particle size: 2.0 μm))
15) Product name “Kesmon NS-70” manufactured by Toagosei Co., Ltd. (magnesium oxide-aluminum oxide hydrate mixture, heat-resistant temperature: 350 ° C., volume average particle size: 6.0 μm)
16) Product name “Kesmon NS-80E” manufactured by Toagosei Co., Ltd. (zirconium oxide hydrate, heat-resistant temperature: 350 ° C., volume average particle diameter: 2.0 μm)
17) Product name “Kesmon NS-231” manufactured by Toagosei Co., Ltd. (amine compound-supported aluminum hydroxide, heat-resistant temperature: 160 ° C., volume average particle size: 5.0 μm)
　表１より、（ａ）塩化ビニル樹脂と、（ｂ）耐熱温度および体積平均粒子径が所定の範囲内である化学吸着型消臭剤とを含む塩化ビニル樹脂組成物を用いた実施例１および２の塩化ビニル樹脂成形体は、（ａ）塩化ビニル樹脂を含むが、（ｂ）耐熱温度および体積平均粒子径が所定の範囲内である化学吸着型消臭剤を含まない塩化ビニル樹脂組成物を用いた比較例１および２の塩化ビニル樹脂成形体に比して、臭気成分（アルデヒド）の発生量が低減されていることがわかる。 From Table 1, Example 1 using a vinyl chloride resin composition containing (a) a vinyl chloride resin and (b) a chemisorption deodorant having a heat resistant temperature and a volume average particle size within a predetermined range and The vinyl chloride resin molded article 2 includes (a) a vinyl chloride resin, but (b) a vinyl chloride resin composition that does not contain a chemisorption deodorant having a heat resistant temperature and a volume average particle diameter within a predetermined range. It can be seen that the amount of odorous components (aldehyde) generated is reduced as compared with the vinyl chloride resin molded articles of Comparative Examples 1 and 2 using the above.
　本発明によれば、臭気成分の発生量が低減された塩化ビニル樹脂成形体を提供することができる。また、本発明は、当該塩化ビニル樹脂成形体を形成可能な塩化ビニル樹脂組成物、および、当該塩化ビニル樹脂成形体を有する積層体を提供することができる。 According to the present invention, it is possible to provide a vinyl chloride resin molded body in which the amount of odorous components generated is reduced. Moreover, this invention can provide the laminated body which has the vinyl chloride resin composition which can form the said vinyl chloride resin molded object, and the said vinyl chloride resin molded object.

Claims (11)

  1. 　（ａ）塩化ビニル樹脂、および（ｂ）化学吸着型消臭剤を含む塩化ビニル樹脂組成物であり、
    　前記（ｂ）化学吸着型消臭剤の耐熱温度が、１５０℃以上であり、
    　前記（ｂ）化学吸着型消臭剤の体積平均粒子径が、０．５μｍ以上１０μｍ以下である、塩化ビニル樹脂組成物。     A vinyl chloride resin composition comprising (a) a vinyl chloride resin, and (b) a chemisorption deodorant;
    The heat resistant temperature of the (b) chemisorption deodorant is 150 ° C. or higher,
    The vinyl chloride resin composition in which the volume average particle size of the (b) chemisorption deodorant is 0.5 μm or more and 10 μm or less.
  2. 　前記（ｂ）化学吸着型消臭剤が、マグネシウム、アルミニウム、ケイ素、およびジルコニウムからなる群より選ばれる少なくとも１種の元素の酸化物および／または水酸化物を含む、請求項１に記載の塩化ビニル樹脂組成物。 The chlorination according to claim 1, wherein the (b) chemisorption deodorant contains an oxide and / or hydroxide of at least one element selected from the group consisting of magnesium, aluminum, silicon, and zirconium. Vinyl resin composition.
  3. 　前記（ｂ）化学吸着型消臭剤が、ヒドラジド化合物および／またはアミン化合物を含む、請求項１または２に記載の塩化ビニル樹脂組成物。 The vinyl chloride resin composition according to claim 1 or 2, wherein the (b) chemisorption deodorant includes a hydrazide compound and / or an amine compound.
  4. 　前記（ｂ）化学吸着型消臭剤が、更に酸化ジルコニウムを含む、請求項３に記載の塩化ビニル樹脂組成物。 The vinyl chloride resin composition according to claim 3, wherein the (b) chemisorption deodorant further contains zirconium oxide.
  5. 　前記（ｂ）化学吸着型消臭剤の含有量が、前記（ａ）塩化ビニル樹脂１００質量部当たり０．５質量部以上１０質量部以下である、請求項１～４のいずれかに記載の塩化ビニル樹脂組成物。 The content of the (b) chemisorption deodorant is 0.5 to 10 parts by mass per 100 parts by mass of the (a) vinyl chloride resin. Vinyl chloride resin composition.
  6. 　粉体成形に用いられる、請求項１～５のいずれかに記載の塩化ビニル樹脂組成物。 The vinyl chloride resin composition according to any one of claims 1 to 5, which is used for powder molding.
  7. 　パウダースラッシュ成形に用いられる、請求項６に記載の塩化ビニル樹脂組成物。 The vinyl chloride resin composition according to claim 6, which is used for powder slush molding.
  8. 　塩化ビニル樹脂および化学吸着型消臭剤を含む塩化ビニル樹脂組成物を製造する方法であり、
    　前記化学吸着型消臭剤の耐熱温度が、１５０℃以上であり、
    　前記化学吸着型消臭剤の体積平均粒子径が、０．５μｍ以上１０μｍ以下であり、
    　前記塩化ビニル樹脂組成物は、ダスティング剤を含み、
    　前記塩化ビニル樹脂組成物の成分のうち、前記化学吸着型消臭剤およびダスティング剤以外の成分を含む組成物（Ｘ）を調製する工程Ａと、
    　前記組成物（Ｘ）に前記ダスティング剤を添加する工程Ｂと、
    　前記工程Ｂと同時に前記組成物（Ｘ）に化学吸着型消臭剤を添加する工程Ｃ１、または、前記工程Ｂにより組成物（Ｙ）を得た後に前記組成物（Ｙ）に前記化学吸着型消臭剤を添加する工程Ｃ２と、
    を含む、塩化ビニル樹脂組成物の製造方法。     A method for producing a vinyl chloride resin composition comprising a vinyl chloride resin and a chemisorption deodorant,
    The heat resistance temperature of the chemisorption deodorant is 150 ° C. or higher,
    The volume average particle size of the chemisorption deodorant is 0.5 μm or more and 10 μm or less,
    The vinyl chloride resin composition includes a dusting agent,
    Step A of preparing a composition (X) containing components other than the chemisorption deodorant and dusting agent among the components of the vinyl chloride resin composition;
    Step B of adding the dusting agent to the composition (X);
    Step C1 of adding a chemisorption deodorant to the composition (X) simultaneously with the step B, or obtaining the composition (Y) by the step B and then adding the chemisorption type to the composition (Y) Step C2 for adding a deodorant,
    A method for producing a vinyl chloride resin composition, comprising:
  9. 　請求項１～７のいずれかに記載の塩化ビニル樹脂組成物を成形してなる、塩化ビニル樹脂成形体。 A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to any one of claims 1 to 7.
  10. 　自動車内装部品の表皮用である、請求項９に記載の塩化ビニル樹脂成形体。 The vinyl chloride resin molded article according to claim 9, which is used for the skin of automobile interior parts.
  11. 　発泡ポリウレタン成形体と、請求項９または１０に記載の塩化ビニル樹脂成形体とを有する、積層体。 A laminate having a foamed polyurethane molded product and the vinyl chloride resin molded product according to claim 9 or 10.
PCT/JP2019/013023 2018-03-29 2019-03-26 Vinyl chloride resin composition, production method for vinyl chloride resin composition, vinyl chloride resin molded body, and laminate WO2019189268A1 (en)

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