CN118900887A - Vinyl chloride resin composition, vinyl chloride resin molded article, and laminate - Google Patents
Vinyl chloride resin composition, vinyl chloride resin molded article, and laminate Download PDFInfo
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- CN118900887A CN118900887A CN202380022986.XA CN202380022986A CN118900887A CN 118900887 A CN118900887 A CN 118900887A CN 202380022986 A CN202380022986 A CN 202380022986A CN 118900887 A CN118900887 A CN 118900887A
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- Prior art keywords
- vinyl chloride
- chloride resin
- resin composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/18—Slush casting, i.e. pouring moulding material into a hollow mould with excess material being poured off
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/36—Feeding the material on to the mould, core or other substrate
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- 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
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a vinyl chloride resin composition, which can form a vinyl chloride resin molded body with suppressed odor generation. The vinyl chloride resin composition of the present invention comprises a vinyl chloride resin, a plasticizer, and a lactone compound represented by the following formula (I) [ formula (I), wherein R 1～R4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or a hydrocarbon group which may have a substituent ], and the content of the lactone compound is 0.005 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin.
Description
Technical Field
The present invention relates to a vinyl chloride resin composition, a vinyl chloride resin molded body, and a laminate.
Background
Vinyl chloride resins are generally excellent in cold resistance, heat resistance, oil resistance, and other properties, and therefore are used in various applications.
Specifically, for example, for forming automotive interior parts such as automobile instrument panels and door trims, automotive interior materials such as a skin formed of a vinyl chloride resin molded body and a laminate formed by lining a skin formed of a vinyl chloride resin molded body with a foam such as foamed polyurethane are used.
Further, a vinyl chloride resin molded article constituting the skin of an automotive interior part such as an automobile instrument panel can be produced by powder molding a vinyl chloride resin composition containing a vinyl chloride resin, a plasticizer, a pigment and other additives by a known molding method such as powder slush molding (for example, refer to patent document 1).
Specifically, for example, in patent document 1, a skin formed from a vinyl chloride resin molded body is produced by powder slush molding a vinyl chloride resin composition containing vinyl chloride resin particles, a trimellitate plasticizer, and an additive such as a pigment formed from a mixture of phthalocyanine blue, titanium oxide, and carbon.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 8-291243.
Disclosure of Invention
Problems to be solved by the invention
Here, when a vinyl chloride resin molded article is used as an automotive interior material such as a skin of an automobile instrument panel, there is a problem that odor is generated from the vinyl chloride resin molded article and passengers of an automobile are not fast enough. Therefore, it is required to suppress the generation of odor from the vinyl chloride resin molded article.
Accordingly, an object of the present invention is to provide a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article in which generation of odor is suppressed.
The present invention also provides a vinyl chloride resin molded article in which the generation of odor is suppressed.
Further, the present invention aims to provide a laminate which has the vinyl chloride resin molded article and which is suppressed in odor generation.
Solution for solving the problem
The present inventors have conducted intensive studies with a view to solving the above-mentioned problems. Then, the present inventors have found that when a vinyl chloride resin composition containing a lactone compound having a cis-form content of at least a predetermined value is molded so as to have a predetermined content with respect to a vinyl chloride resin, a molded vinyl chloride resin product having suppressed odor generation can be obtained, and completed the present invention.
That is, the present invention aims to advantageously solve the above problems, and [1] the vinyl chloride resin composition of the present invention is characterized by comprising a vinyl chloride resin, a plasticizer and a lactone compound represented by the following formula (I),
[ Chemical formula 1]
In the formula (I), R 1～R4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or a hydrocarbon group which may have a substituent, and the content of the lactone compound is 0.005 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin. When a vinyl chloride resin composition comprising a vinyl chloride resin, a plasticizer and a lactone compound having the above-described predetermined structure is used, and the content of the lactone compound is within a predetermined range, a vinyl chloride resin molded article having suppressed odor generation can be formed.
In the vinyl chloride resin composition according to [2] above, R 1 preferably represents a hydrocarbon group. When a lactone compound having a hydrocarbon group as R 1 in the above formula (I) is used, the generation of odor from the formed vinyl chloride resin molded article can be further suppressed.
Further, the vinyl chloride resin composition according to the above [2] is preferably one wherein the hydrocarbon group constituting R 1 has 1 to 20 carbon atoms. If the number of carbon atoms of the hydrocarbon group constituting R 1 in the above formula (I) is 1 or more and 20 or less, the generation of odor from the formed vinyl chloride resin molded body can be further suppressed.
Further, the vinyl chloride resin composition according to [4] or [3] is preferably a chain hydrocarbon group as the hydrocarbon group constituting R 1. If the hydrocarbon group constituting R 1 in the above formula (I) is a chain hydrocarbon group, the generation of odor from the formed vinyl chloride resin molded body can be further suppressed.
Further, the vinyl chloride resin composition according to any one of [2] to [4] above, wherein the hydrocarbon group constituting R 1 is preferably an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. If the hydrocarbon group constituting R 1 in the above formula (I) is the above-mentioned predetermined alkyl group or alkenyl group, the generation of odor from the formed vinyl chloride resin molded body can be further suppressed.
The vinyl chloride resin composition according to any one of [2] to [5], wherein the hydrocarbon group constituting R 1 is preferably an alkenyl group having 2 to 10 carbon atoms. If the hydrocarbon group constituting R 1 in the above formula (I) is the above-mentioned predetermined alkenyl group, the generation of odor from the formed vinyl chloride resin molded body can be further suppressed.
Further, in the vinyl chloride resin composition according to any one of [1] to [6], R 2～R4 is preferably a hydrogen atom. If R 2～R4 in the above formula (I) is a hydrogen atom, the generation of odor from the formed vinyl chloride resin molded article can be further suppressed.
The vinyl chloride resin composition according to any one of [1] to [7], wherein the lactone compound preferably contains jasmine lactone. When jasmine lactone is used as the lactone compound, the generation of odor from the formed vinyl chloride resin molded body can be further suppressed.
Further, the vinyl chloride resin composition according to any one of [1] to [8] is preferably such that the plasticizer is contained in an amount of 50 to 200 parts by mass based on 100 parts by mass of the vinyl chloride resin. If the content of the plasticizer relative to the vinyl chloride resin is within the above-described predetermined range, the generation of odor from the formed vinyl chloride resin molded body can be further suppressed and the tensile elongation at low temperature (hereinafter, sometimes referred to as "low-temperature tensile elongation") of the vinyl chloride resin molded body can be ensured sufficiently high.
The vinyl chloride resin composition according to any one of [1] to [9] above, wherein [10] is preferably used for powder molding. When the vinyl chloride resin composition is used for powder molding, a vinyl chloride resin molded article which can be suitably used as an automotive interior material such as a skin for an automotive instrument panel can be easily obtained.
The vinyl chloride resin composition according to any one of [1] to [10] above is preferably used for powder slush molding. When the vinyl chloride resin composition is used for powder slush molding, a vinyl chloride resin molded article which can be used favorably as an automotive interior material such as a skin for an automotive instrument panel can be more easily obtained.
Further, the present invention is directed to solving the above problems, and the vinyl chloride resin molded article of the present invention of [12] is characterized by being molded from the vinyl chloride resin composition of any one of the above items [1] to [11 ]. The vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition in this manner suppresses the generation of odor.
The vinyl chloride resin molded article of [13] above [12] is preferably used for automobile instrument panel skins. The vinyl chloride resin molded article of the present invention can be preferably used as a skin of an automobile instrument panel in which the generation of odor is suppressed.
Further, the present invention is directed to a laminate of the present invention characterized in that it comprises a foamed polyurethane molded body and the vinyl chloride resin molded body of the above [12] or [13], which advantageously solves the above-mentioned problems. The laminate comprising the foamed polyurethane molded body and the vinyl chloride resin molded body suppresses the generation of odor.
The laminate of [15] above [14] is preferably for an automobile instrument panel. When the laminate of the present invention is used for an automobile instrument panel in this way, an automobile instrument panel in which odor generation from the skin is suppressed can be produced.
Effects of the invention
According to the present invention, a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article having suppressed generation of odor can be provided.
Further, according to the present invention, a vinyl chloride resin molded article having suppressed generation of odor can be provided.
Further, according to the present invention, a laminate having the vinyl chloride resin molded article and having suppressed odor generation can be provided.
Detailed Description
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, in forming the vinyl chloride resin molded article of the present invention. The vinyl chloride resin molded article formed using the vinyl chloride resin composition of the present invention can be preferably used as an automotive interior material such as a skin of an automotive interior part such as an automobile instrument panel or door trim.
The vinyl chloride resin molded article of the present invention can be used, for example, in forming the laminate of the present invention. The laminate formed using the vinyl chloride resin molded body of the present invention can be preferably used as an automotive interior material used for manufacturing automotive interior parts such as an automobile instrument panel and a door trim.
(Vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention is characterized by comprising (a) a vinyl chloride resin, (b) a plasticizer, and (c) a lactone compound having a predetermined structure (hereinafter, sometimes simply referred to as "(c) lactone compound"), (c) the content of the lactone compound being within a predetermined range.
The vinyl chloride resin composition of the present invention may optionally contain additives other than the above (a) vinyl chloride resin, (b) plasticizer and (c) lactone compound.
The vinyl chloride resin composition of the present invention contains at least the above (a) vinyl chloride resin, (b) plasticizer and (c) lactone compound, and the content of the (c) lactone compound is within a predetermined range, so that a vinyl chloride resin molded article having suppressed odor generation can be formed.
Therefore, when the vinyl chloride resin composition of the present invention is used, a vinyl chloride resin molded article suitable as an automotive interior material such as an automobile instrument panel skin or door trim skin, which is suppressed in the occurrence of odor, can be obtained.
Further, the vinyl chloride resin molded article formed using the vinyl chloride resin composition of the present invention is also excellent in low-temperature tensile elongation.
In addition, for example, from the viewpoint that a vinyl chloride resin molded article which can be suitably used as an automotive interior material can be easily obtained by using the vinyl chloride resin composition of the present invention, the vinyl chloride resin composition of the present invention is preferably used for powder molding, more preferably for powder slush molding.
Vinyl chloride resin (a)
As the vinyl chloride resin (a), a granular vinyl chloride resin is generally used. Further, as the vinyl chloride resin (a), for example, one or two or more types of vinyl chloride resin particles may be contained, and one or two or more types of vinyl chloride resin fine particles may be optionally further contained. (a) The vinyl chloride resin particularly preferably contains at least vinyl chloride resin particles, more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.
The vinyl chloride resin (a) can be produced by any conventionally known production method such as suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization.
In the present specification, "resin particles" means particles having a particle diameter of 30 μm or more, and "resin fine particles" means particles having a particle diameter of less than 30 μm.
The vinyl chloride resin (a) may be a vinyl chloride copolymer containing preferably 50% by mass or more, more preferably 70% by mass or more of a vinyl chloride monomer unit, in addition to a homopolymer formed of a vinyl chloride monomer unit. Further, as a specific example of a monomer (comonomer) capable of copolymerizing with a vinyl chloride monomer, which can constitute a vinyl chloride copolymer, a monomer described in, for example, international publication No. 2016/098344 can be used. These components may be used singly or in combination of two or more kinds in any ratio.
Vinyl chloride resin particles
In the vinyl chloride resin composition, the vinyl chloride resin particles generally function as a matrix resin (base material). In addition, the vinyl chloride resin particles are preferably produced by a suspension polymerization method.
[ Average polymerization degree ]
The average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 800 or more, more preferably 900 or more, preferably 5000 or less, more preferably 3000 or less, and further preferably 2800 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is not less than the above lower limit, it is possible to sufficiently secure the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition and to improve, for example, the tensile characteristics, particularly the tensile elongation. Further, the vinyl chloride resin molded article having a good tensile elongation can be preferably used as an automobile interior material such as a skin of an automobile instrument panel, which is excellent in ductility, and which is designed to be split without scattering fragments when an airbag is inflated and deployed. On the other hand, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is not more than the upper limit, the meltability of the vinyl chloride resin composition can be improved.
In the present invention, the "average polymerization degree" can be measured in accordance with JIS K6720-2.
[ Average particle diameter ]
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, preferably 500 μm or less, more preferably 200 μm or less. If the average particle diameter of the vinyl chloride resin particles is not less than the lower limit, the powder flowability 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 not more than the upper limit, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of a vinyl chloride resin molded article formed using the vinyl chloride resin composition can be improved.
In the present invention, the "average particle diameter" can be measured as a volume average particle diameter by a laser diffraction method in accordance with JIS Z8825.
[ Content ratio ]
The content of the vinyl chloride resin particles in the (a) vinyl chloride resin is preferably 70 mass% or more, more preferably 80 mass% or more, and can be 100 mass%, preferably 95 mass% or less, more preferably 90 mass% or less. If the content ratio of the vinyl chloride resin particles in the vinyl chloride resin (a) is not less than the lower limit, the physical strength of the vinyl chloride resin molded article formed using the vinyl chloride resin composition can be sufficiently ensured and the tensile elongation can be improved. Further, if the content ratio of the vinyl chloride resin particles in the vinyl chloride resin (a) is not more than the upper limit, the powder flowability of the vinyl chloride resin composition can be improved.
Vinyl chloride resin particles
In the vinyl chloride resin composition, the vinyl chloride resin fine particles generally function as a release agent (powder flowability improver). The vinyl chloride resin fine particles are preferably produced by emulsion polymerization.
[ 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 2600 or less, and still more preferably 2400 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles as the release agent is not less than the lower limit, the powder flowability of the vinyl chloride resin composition can be improved and the tensile elongation of the vinyl chloride resin molded article formed using the vinyl chloride resin composition 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 not more than the upper limit, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of the vinyl chloride resin molded article formed using the vinyl chloride resin composition can be improved.
[ Average particle diameter ]
The average particle diameter of the vinyl chloride resin fine particles is usually less than 30. Mu.m, preferably 10. Mu.m, more preferably 5. Mu.m, still more preferably 0.1. Mu.m, and still more preferably 1. Mu.m. If the average particle diameter of the vinyl chloride resin fine particles is not less than the lower limit, for example, the powder flowability of the vinyl chloride resin composition can be improved without making the size of the separator too small. On the other hand, if the average particle diameter of the vinyl chloride resin fine particles is not more than the upper limit, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of a vinyl chloride resin molded article formed using the vinyl chloride resin composition can be improved.
[ Content ratio ]
The content of the vinyl chloride resin fine particles in the (a) vinyl chloride resin may be 0% by mass, preferably 5% by mass or more, more preferably 10% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less. If the content of the vinyl chloride resin fine particles in the vinyl chloride resin (a) is not less than the lower limit, the powder flowability of the vinyl chloride resin composition can be improved. On the other hand, if the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin (a) is not more than the upper limit, the physical strength of the vinyl chloride resin molded article formed using the vinyl chloride resin composition can be improved.
Plasticizer < (b)
(B) The plasticizer is a component capable of imparting sufficient flexibility to a vinyl chloride resin molded body formed using the vinyl chloride resin composition. For example, by using the plasticizer (b) in the vinyl chloride resin composition, the formed vinyl chloride resin molded article can exhibit excellent low-temperature tensile elongation.
Further, it is presumed that (b) a plasticizer may cause odor generation from a vinyl chloride resin molded article, but it is considered that the use of (b) a plasticizer and (c) a lactone compound described later in combination in a vinyl chloride resin composition can give a vinyl chloride resin molded article excellent low-temperature tensile elongation and also suppress odor generation.
Content
The content of the plasticizer (b) in the vinyl chloride resin composition is more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, still more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, preferably 200 parts by mass or less, still more preferably 180 parts by mass or less, still more preferably 150 parts by mass or less, still more preferably 120 parts by mass or less, and still more preferably 100 parts by mass or less, relative to 100 parts by mass of the vinyl chloride resin (a).
If the content of the plasticizer (b) in the vinyl chloride resin composition is not less than the lower limit, the occurrence of odor from the formed vinyl chloride resin molded article can be sufficiently suppressed and the low-temperature tensile elongation of the vinyl chloride resin molded article can be further improved. On the other hand, if the content of the plasticizer (b) in the vinyl chloride resin composition is not more than the upper limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded article can be sufficiently ensured and the generation of odor from the vinyl chloride resin molded article can be further suppressed.
Species < >
As the plasticizer (b), for example, a primary plasticizer, a secondary plasticizer, and the like described in international publication No. 2016/098344 can be used. These components may be used singly or in combination of two or more kinds in any ratio.
Among the above plasticizers, from the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded article, it is preferable to use at least a primary plasticizer as the (b) plasticizer, and it is more preferable to use a primary plasticizer and a secondary plasticizer in combination. Specifically, as the plasticizer (b), at least trimellitate is preferably used, and more preferably, trimellitate and epoxidized vegetable oil are used in combination.
< (B 1) a partial benzene Tri-acid ester >
(B) The trimellitate (b 1) that can be contained in the plasticizer is preferably an ester compound of trimellitic acid and a monohydric alcohol.
Specific examples of the monohydric alcohol include, but are not particularly limited to, aliphatic alcohols such as 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol. As the monohydric alcohol, an aliphatic alcohol having 6 to 18 carbon atoms is particularly preferable.
As the trimellitate (b 1), a triester in which the carboxyl groups of trimellitic acid are substantially completely esterified with the monohydric alcohol is particularly preferable. The alcohol residue moiety in the triester may be derived from the same alcohol or may be derived from different alcohols.
The trimellitate (b 1) may be formed of a single compound or may be a mixture of different compounds.
Specific examples of the preferred (b 1) trimellitates are tri-n-hexyl trimellitate, tri-n-heptyl trimellitate, tri-n-octyl trimellitate, tri (2-ethylhexyl) trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, triisodecyl trimellitate, tri-n-undecyl trimellitate, tri-n-dodecyl trimellitate, trialkyl trimellitate (having two or more alkyl groups having different carbon atoms in the molecule [ wherein the carbon atoms are 6 to 18], tri-n-alkyl trimellitate (having two or more alkyl groups having different carbon atoms in the molecule [ wherein the carbon atoms are 6 to 18 ]), and mixtures thereof, and the like.
(B) The content of (b 1) trimellitate in the plasticizer is not particularly limited, but is preferably 75% by mass or more, more preferably 88% by mass or more, further preferably 94% by mass or more, preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 97% by mass or less. If the content of (b 1) trimellitate in the plasticizer (b) is within the above-specified range, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved.
The content of (b 1) trimellitate in the vinyl chloride resin composition is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 65 parts by mass or more, still more preferably 75 parts by mass or more, preferably 199 parts by mass or less, still more preferably 179 parts by mass or less, still more preferably 148 parts by mass or less, still more preferably 118 parts by mass or less, and still more preferably 98 parts by mass or less, relative to 100 parts by mass of the (a) vinyl chloride resin. If the content of (b 1) trimellitate in the vinyl chloride resin composition is within the above-specified range, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved. Further, if the content of (b 1) trimellitate in the vinyl chloride resin composition is not more than the upper limit, generation of odor from the vinyl chloride resin molded body can be further suppressed.
Epoxy resin (b 2) chemical vegetable oil >)
Examples of the epoxidized vegetable oil (b 2) which can be contained in the plasticizer (b) include epoxidized soybean oil, epoxidized linseed oil and the like. In particular, epoxidized soybean oil is preferably used from the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded article.
(B) The content ratio of the epoxidized vegetable oil (b 2) in the plasticizer is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, preferably 25% by mass or less, more preferably 12% by mass or less, further preferably 6% by mass or less. If the content ratio of (b 2) the epoxidized vegetable oil in (b) the plasticizer is within the above-specified range, the low-temperature tensile elongation of the formed vinyl chloride resin molded article can be further improved.
The content of the epoxidized vegetable oil (b 2) in the vinyl chloride resin composition is not particularly limited, but is preferably 1 part by mass or more, more preferably 2 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the vinyl chloride resin (a). If the content of the epoxidized vegetable oil (b 2) in the vinyl chloride resin composition is within the above-specified range, the low-temperature tensile elongation of the formed vinyl chloride resin molded article can be further improved.
< Lactone-based Compounds >)
The lactone compound (c) in the vinyl chloride resin composition is a component capable of suppressing the generation of odor from the formed vinyl chloride resin molded article. The cause of the odor is presumed to be components (for example, (a) a vinyl chloride resin, (b) a plasticizer, and additives described later) included in the vinyl chloride resin composition for forming the vinyl chloride resin molded article.
The lactone compound (c) is a compound represented by the following formula (I).
[ Chemical formula 2]
In the formula (I), R 1～R4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or a hydrocarbon group which may have a substituent.
Examples of the halogen atom constituting R 1～R4 include a fluorine atom and a chlorine atom.
The (unsubstituted) hydrocarbon group constituting R 1～R4 may be a cyclic hydrocarbon group such as an aromatic hydrocarbon group or a chain hydrocarbon group, and from the viewpoint of further suppressing the generation of odor from the formed vinyl chloride resin molded article, the chain hydrocarbon group is preferable. The chain hydrocarbon group may be linear or branched, and is preferably linear from the viewpoint of further suppressing the generation of odor from the formed vinyl chloride resin molded article.
The hydrocarbon group may be an unsaturated hydrocarbon group having an unsaturated bond (carbon-carbon double bond, carbon-carbon triple bond), or may be a saturated hydrocarbon group having no unsaturated bond, and is preferably an unsaturated hydrocarbon group from the viewpoint of further suppressing the generation of odor from the formed vinyl chloride resin molded article.
The number of carbon atoms of the hydrocarbon group may be 1 or more, and is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, more preferably 5 or more, preferably 20 or less, more preferably 10 or less, more preferably 8 or less, more preferably 6 or less, and particularly preferably 5, from the viewpoint of further suppressing the generation of odor from the formed vinyl chloride resin molded article.
In the case where the hydrocarbon group which can constitute R 1～R4 has a substituent, the substituent is not particularly limited, and examples thereof include a halogen atom (chlorine atom, fluorine atom, etc.), a hydroxyl group, an amino group, a thiol group, and the like. The above-mentioned hydrocarbon group may have only one kind of these substituents, or may have two or more kinds of these substituents. In addition, R 1 may have one substituent or two or more substituents.
Further, the hydrocarbon group capable of constituting R 1～R4 is preferably a hydrocarbon group having no substituent from the viewpoint of further suppressing the generation of odor from the formed vinyl chloride resin molded body.
Further, the hydrocarbon group capable of constituting R 1～R4 is preferably an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms from the viewpoint of further suppressing the generation of odor from the formed vinyl chloride resin molded body.
More preferable specific examples of the hydrocarbon group capable of constituting R 1～R4 include, from the viewpoint of further suppressing the generation of odor from the formed vinyl chloride resin molded body: alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, n-heptyl, isoheptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl and the like; alkenyl groups having 2 to 10 carbon atoms such as vinyl, 1-propenyl, 2-propenyl (allyl), 2-butenyl, 3-butenyl, isobutenyl, 4-pentenyl, 3-pentenyl, trans-2-pentenyl, cis-2-pentenyl, 1-pentenyl, 3-methyl-2-pentenyl, 5-hexenyl, 3-hexenyl, 2-hexenyl, heptenyl, octenyl, nonenyl and decenyl groups.
Further, from the viewpoint of suppressing the generation of odor from the formed vinyl chloride resin molded article, the hydrocarbon group capable of constituting R 1～R4 is particularly preferably an alkenyl group having 2 to 10 carbon atoms. The number of carbon atoms of the alkenyl group is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, preferably 8 or less, more preferably 6 or less, and particularly preferably 5. Specifically, the alkenyl group which can form the hydrocarbon group of R 1～R4 is particularly preferably a pentenyl group such as 4-pentenyl group, 3-pentenyl group, trans-2-pentenyl group, cis-2-pentenyl group, or 1-pentenyl group.
In the above formula (I), R 1～R4 is not particularly limited as long as each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a thiol group, or a hydrocarbon group which may have a substituent.
Further, from the viewpoint of further suppressing the generation of odor from the formed vinyl chloride resin molded body, it is preferable that R 1 represents at least a hydrocarbon group, and at least one of R 2～R4 represents a hydrogen atom, more preferably at least two of R 2～R4 represent a hydrogen atom, and still more preferably R 2～R4 each represent a hydrogen atom.
Further, as the lactone-based compound represented by the above formula (I), a lactone-based compound represented by the following formula (Ia), in which R 1 represents cis-2-pentenyl group and R 2～R4 each represents a hydrogen atom, is particularly preferably used.
[ Chemical formula 3]
The content of the lactone compound (c) in the vinyl chloride resin composition is preferably 0.005 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.06 parts by mass or more, still more preferably 0.07 parts by mass or more, still more preferably 0.08 parts by mass or more, and is preferably 15 parts by mass or less, preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 0.8 parts by mass or less, still more preferably 0.5 parts by mass or less, and particularly preferably 0.1 part by mass or less, relative to 100 parts by mass of the vinyl chloride resin (a). If the content of the lactone compound (c) in the vinyl chloride resin composition is within the above-described predetermined range, the generation of odor from the formed vinyl chloride resin molded article can be sufficiently suppressed. Further, if the content of the lactone compound (c) in the vinyl chloride resin composition is within the above-described predetermined range, the low-temperature tensile elongation of the formed vinyl chloride resin molded article can be sufficiently ensured.
The content of the lactone compound (c) in the vinyl chloride resin composition is preferably 0.005 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.06 parts by mass or more, still more preferably 0.07 parts by mass or more, still more preferably 0.08 parts by mass or more, preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 0.8 parts by mass or less, still more preferably 0.5 parts by mass or less, and particularly preferably 0.1 part by mass or less, relative to 100 parts by mass of the plasticizer (b). If the content of the lactone compound (c) in the vinyl chloride resin composition is within the above-described predetermined range, the generation of odor from the formed vinyl chloride resin molded article can be further suppressed and the low-temperature tensile elongation of the vinyl chloride resin molded article can be sufficiently ensured.
< Additive >)
The vinyl chloride resin composition of the present invention may contain various additives in addition to the above-mentioned components. The additive is not particularly limited, and examples thereof include: a lubricant; perchloric acid treatment stabilizers such as hydrotalcite, zeolite, beta-diketone, fatty acid metal salt, and the like; a release agent; a release agent other than the above vinyl chloride resin fine particles; an impact modifier; perchloric acid compounds other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.); an antioxidant; a mildew inhibitor; a flame retardant; an antistatic agent; a filler; a light stabilizer; a foaming agent; pigments, and the like.
The additives that can be contained in the vinyl chloride resin composition of the present invention may be, for example, additives described in International publication No. 2016/098344, and the preferable content thereof may be the same as that described in International publication No. 2016/098344.
Process for producing vinyl chloride resin composition
The vinyl chloride resin composition of the present invention can be prepared by mixing the above-mentioned components.
The method for mixing the vinyl chloride resin (a), the plasticizer (b), the lactone compound (c) and, if necessary, various additives is not particularly limited, and examples thereof include the following methods: a method in which the components other than the release agent (including vinyl chloride resin fine particles) are mixed by dry blending, and then the release agent is added to the mixture. The dry blending is preferably carried out using a Henschel mixer. The temperature at the time of dry blending is not particularly limited, but is preferably 50℃or higher, more preferably 70℃or higher, and still more preferably 200℃or lower.
Use of vinyl chloride resin composition
The obtained vinyl chloride resin composition is not particularly limited, and can be preferably used for powder molding, and can be more preferably used for powder slush molding.
(Vinyl chloride resin molded article)
The vinyl chloride resin molded article of the present invention is characterized by being obtained by molding the vinyl chloride resin composition by any method. Further, since the vinyl chloride resin molded article of the present invention is formed using the above-described vinyl chloride resin composition, it is usually composed of at least (a) a vinyl chloride resin, (b) a plasticizer and a predetermined amount of (c) a lactone compound, and thus the occurrence of odor can be suppressed. Further, since the vinyl chloride resin molded article of the present invention is formed using the above-mentioned vinyl chloride resin composition, the low-temperature tensile elongation is also excellent.
Therefore, the laminate formed by lining the foamed polyurethane molded article with the vinyl chloride resin molded article of the present invention is preferably used as an automotive interior material such as a skin of an automotive instrument panel because the occurrence of odor is suppressed.
Method for Forming vinyl chloride resin molded article
Here, in the case of forming a vinyl chloride resin molded article by powder slush molding, the mold temperature at the time of powder slush molding is not particularly limited, but is preferably 200 ℃ or higher, more preferably 220 ℃ or higher, preferably 300 ℃ or lower, more preferably 280 ℃ or lower.
In addition, the vinyl chloride resin molded article is not particularly limited, and for example, the following method can be used. That is, the vinyl chloride resin composition of the present invention is poured into a mold having the above temperature range, left for a period of 5 seconds to 30 seconds, and then the remaining vinyl chloride resin composition is shaken off, and further left for a period of 30 seconds to 3 minutes at an arbitrary temperature. Thereafter, the mold is cooled to a temperature of 10 ℃ or higher and 60 ℃ or lower, and the obtained vinyl chloride resin molded article of the present invention is released from the mold. Then, a sheet-like molded body shaped like a metal mold was obtained.
(Laminate)
The laminate of the present invention comprises a foamed polyurethane molded body and the above vinyl chloride resin molded body. In addition, the vinyl chloride resin molded body generally constitutes a surface on one side of the laminate.
Further, the laminate of the present invention has a vinyl chloride resin molded article formed using the vinyl chloride resin composition of the present invention, for example, and thus can suppress the generation of odor. Therefore, the laminate of the present invention can be preferably used as an automotive interior material for forming automotive interior parts, particularly automotive instrument panels.
The method for laminating the foamed polyurethane molded article and the vinyl chloride resin molded article is not particularly limited, and the following method can be used, for example. Namely, there can be mentioned: (1) A method of preparing a foamed polyurethane molded article and a vinyl chloride resin molded article, respectively, and then bonding the two by using a heat-sealing, a heat-bonding, a known adhesive, or the like; (2) And a method in which an isocyanate as a raw material of a foamed polyurethane molded article is reacted with a polyol or the like on a vinyl chloride resin molded article to polymerize the resultant, and polyurethane is foamed by a known method, whereby a foamed polyurethane molded article is directly formed on the vinyl chloride resin molded article. The latter method (2) is particularly preferable from the viewpoint of simplification of the process and the easiness of firmly adhering the vinyl chloride resin molded body and the foamed urethane molded body in the case of obtaining a laminate of various shapes.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "%" and "parts" indicating amounts are based on mass.
Further, the low-temperature tensile elongation and odor strength of the vinyl chloride resin molded sheet were measured and evaluated by the following methods.
< Low temperature tensile elongation >)
The molded sheet of vinyl chloride resin obtained by punching with the use of a dumbbell No. 1 cutter described in JIS K6251 was measured for tensile elongation at break (%) at a low temperature of-35℃at a tensile rate of 200 mm/min in accordance with JIS K7113. The greater the value of the tensile elongation at break, the more excellent the tensile elongation at low temperature (low-temperature tensile elongation) of the vinyl chloride resin molded sheet.
< Odor Strength >)
The obtained vinyl chloride resin molded sheet was placed in a 1L glass bottle, closed with a cap, and left to stand in an oven at 80℃for 2 hours to heat.
After heating, the glass bottle was taken out, the cap was opened, and the odor of the air in the bottle was smelled by 7 panelists, and the higher the odor, the higher the level, the reference from level 0 to level 5 was displayed, and the judgment was made at 0.5 level intervals, as described below.
Level 0: odorless
Stage 1: barely perceptible odor
2 Stages: weak odor distinguishable as a certain odor
3 Stages: easily perceivable malodour
4 Stages: strong odor
5 Stages: intense odor
In the number of steps of the 7-person determination result, the maximum value and the minimum value were removed, and the average value was taken as the odor intensity.
Example 1
< Preparation of vinyl chloride resin composition >
The components other than the plasticizer and the vinyl chloride resin fine particles as the release agent among the compounding ingredients shown in table 1 were mixed by adding them to a henschel mixer. Then, all of the plasticizer was added at the time when the temperature of the mixture was raised to 80 ℃, thereby drying out the mixture (meaning that the plasticizer was absorbed by vinyl chloride resin particles as vinyl chloride resin, and the mixture was in a dry state). Then, vinyl chloride resin fine particles as a release agent were added at a time when the temperature of the dried mixture was cooled to 70 ℃ or lower to prepare a vinyl chloride resin composition.
< Formation of vinyl chloride resin molded body >
A vinyl chloride resin molded sheet having dimensions of 150 mm. Times.200 mm. Times.1 mm was prepared as follows.
Specifically, the vinyl chloride resin composition obtained above was sprinkled into a metal mold with a bite heated to 250 ℃ and allowed to stand for an arbitrary period of time to melt, after which the remaining vinyl chloride resin composition was shaken off. Then, the metal mold with the bite into which the vinyl chloride resin composition was spread was left to stand in an oven set to a temperature of 200 ℃, and the metal mold with the bite was cooled with cooling water at a time of 60 seconds from the standing. The vinyl chloride resin molded sheet as the vinyl chloride resin molded body was released from the mold at a timing when the mold temperature was cooled to 40 ℃.
Then, the odor intensity and the low-temperature tensile elongation of the obtained vinyl chloride resin molded sheet (size: 150 mm. Times.200 mm. Times.1 mm) were measured and evaluated in the above-described manner. The results are shown in Table 1.
Examples 2 to 5 and comparative examples 1 to 3
A vinyl chloride resin composition and a vinyl chloride resin molded article were produced in the same manner as in example 1, except that the amount of the lactone compound used in jasmine lactone was changed as shown in table 1. Then, measurement and evaluation were performed in the same manner as in example 1. The results are shown in Table 1.
TABLE 1
1) New first vinyl chloride Co., ltd., product name "ZEST 1700ZI" (vinyl chloride resin particles obtained by suspension polymerization, average degree of polymerization 1700, average particle diameter 130 μm)
2) New first vinyl chloride Co., ltd., product name "ZEST PQLTX" (prepared by emulsion polymerization method, average polymerization degree: 800. average particle diameter: 1.8 μm)
3) "Trimex T-08" manufactured by Kagaku corporation and its product name (trimellitic acid tri-2-ethylhexyl ester)
4) Product name "ADK CIZER O-130S" manufactured by Kagaku Ai Dike "
5) Product name "ALCAMAIZER (registered trademark) 5" manufactured by Kagaku chemical industry Co., ltd "
6) Product name "MIZUKALIZER DS" manufactured by water chemical industry Co., ltd "
7) Karenz DK-1, product name of Zhaoyao electric Co., ltd "
8) Sakai chemical industry Co., ltd., product name "SAKAI SZ2000"
9) ADK STAB LS-12 manufactured by Kagaku Ai Dike, product name "
10 Jasmonate, product name "jasmine lactone" manufactured by japan rui Weng Zhushi co "
11 DAP 4720BLACK, product name of Dai-Ji Industrial Co Ltd "
As is clear from Table 1, the vinyl chloride resin molded sheets formed from the vinyl chloride resin compositions of examples 1 to 5, which contained a vinyl chloride resin, a plasticizer, and a lactone compound having a predetermined structure, and the content of the lactone compound was within a predetermined range, suppressed the generation of odor.
On the other hand, it was found that the vinyl chloride resin molded sheet formed using the vinyl chloride resin composition of comparative example 1 containing no lactone compound having a predetermined structure could not suppress the generation of odor.
Further, it was found that the vinyl chloride resin molded sheet formed using the vinyl chloride resin composition of comparative example 2 in which the content of the lactone compound having a predetermined structure did not satisfy the predetermined range was also insufficient in suppressing the generation of odor.
Further, it was found that the vinyl chloride resin molded sheet formed using the vinyl chloride resin composition of comparative example 3 in which the content of the lactone compound having a predetermined structure exceeded the predetermined range was also insufficient in suppressing the generation of odor.
Industrial applicability
According to the present invention, a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article having suppressed generation of odor can be provided.
Further, according to the present invention, a vinyl chloride resin molded article having suppressed generation of odor can be provided.
Further, according to the present invention, a laminate having the vinyl chloride resin molded article and having suppressed odor generation can be provided.
Claims (15)
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| JP2022050604 | 2022-03-25 | ||
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| PCT/JP2023/009722 WO2023182060A1 (en) | 2022-03-25 | 2023-03-13 | Vinyl chloride resin composition, vinyl chloride resin molded article, and laminate |
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| JPH07103303B2 (en) * | 1987-03-13 | 1995-11-08 | 株式会社クラレ | Β-Methyl-δ-valerolactone polymer composition having improved thermal stability |
| JP2001342310A (en) * | 2000-05-30 | 2001-12-14 | Mitsui Chemicals Inc | Sustained-releasable 4-methyl-1-pentene copolymer composition and its use |
| CN1788059A (en) * | 2003-06-26 | 2006-06-14 | 中国涂料株式会社 | Low-odor solvent-based coating composition |
| BRPI0823206A2 (en) * | 2008-10-03 | 2014-10-14 | Sca Hygiene Prod Ab | CLEANING ELEMENT WITH ODOR CONTROLLING SUBSTANCE |
| US20110028625A1 (en) * | 2009-08-03 | 2011-02-03 | International Automotive Components Group North America, Inc. | Low voc and fog, low temperature pvc for seamless air bag doors |
| FR3007766B1 (en) * | 2013-07-01 | 2017-11-03 | Arkema France | PHENOLIC POLYSULFIDES WITH IMPROVED ODOR |
| JP2017218472A (en) * | 2016-06-03 | 2017-12-14 | 株式会社タカマテリアルアンドシステムズ研究所 | Oily ink composition |
| US11643541B2 (en) * | 2017-11-02 | 2023-05-09 | Kaneka Corporation | Vinyl chloride-based resin composition for powder molding, and vinyl chloride-based resin-molded body and laminate |
| CN111655785A (en) * | 2018-03-29 | 2020-09-11 | 日本瑞翁株式会社 | Vinyl chloride resin composition, method for producing vinyl chloride resin composition, vinyl chloride resin molded body, and laminate |
| WO2021166722A1 (en) * | 2020-02-17 | 2021-08-26 | 日本ゼオン株式会社 | Vinyl chloride resin composition for powder molding, vinyl chloride resin molded article and laminate |
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| JP7785274B2 (en) * | 2020-05-20 | 2025-12-15 | 大洋塩ビ株式会社 | Vinyl chloride polymer composition, its production method and uses |
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