WO2021261162A1 - 塩化ビニル樹脂組成物、粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体の製造方法 - Google Patents

塩化ビニル樹脂組成物、粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体の製造方法 Download PDF

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WO2021261162A1
WO2021261162A1 PCT/JP2021/020167 JP2021020167W WO2021261162A1 WO 2021261162 A1 WO2021261162 A1 WO 2021261162A1 JP 2021020167 W JP2021020167 W JP 2021020167W WO 2021261162 A1 WO2021261162 A1 WO 2021261162A1
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Prior art keywords
vinyl chloride
chloride resin
resin composition
fine particles
molded body
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Ceased
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PCT/JP2021/020167
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English (en)
French (fr)
Japanese (ja)
Inventor
翔太 西村
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Zeon Corp
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Zeon Corp
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Priority to JP2022532445A priority Critical patent/JPWO2021261162A1/ja
Publication of WO2021261162A1 publication Critical patent/WO2021261162A1/ja
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Ceased legal-status Critical Current

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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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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 method for producing a vinyl chloride resin composition, a method for producing a vinyl chloride resin composition for powder molding, a method for producing a vinyl chloride resin molded body, and a method for producing a laminated body.
  • Vinyl chloride resin is generally used for various purposes because it has excellent properties such as cold resistance, heat resistance, and oil resistance.
  • a foam made of a vinyl chloride resin molded body or a skin made of a vinyl chloride resin molded body is lined with a foam such as polyurethane foam.
  • Automotive interior materials such as laminated bodies made of plastic are used.
  • the vinyl chloride resin molded body constituting the outer skin of the automobile interior parts such as the automobile instrument panel is, for example, vinyl chloride resin particles as a matrix resin (base material), a thermoplastic agent, and a dusting agent (powder).
  • a vinyl chloride resin composition for powder molding containing vinyl chloride resin fine particles as a fluidity improver containing vinyl chloride resin fine particles as a fluidity improver
  • additives such as pigments
  • a known molding method such as powder slush molding.
  • the vinyl chloride resin composition for powder molding is usually prepared by mixing components excluding a dusting agent (for example, vinyl chloride resin fine particles, etc.) under heating, and then adding and mixing the dusting agent.
  • a dusting agent for example, vinyl chloride resin fine particles, etc.
  • the vinyl chloride resin composition for powder molding is, for example, mixed while heating the components excluding the plasticizer and the dusting agent, and then the plasticizer is added to the obtained mixture to dry up (for example).
  • the plasticizer is absorbed by the vinyl chloride resin particles as the matrix resin to make the mixture smoother.
  • the dusting agent is added to and mixed with the cooled dried-up mixture. ing.
  • the vinyl chloride resin molded body and the foamed polyurethane molded body are satisfactorily adhered to the laminate formed by lining the foamed polyurethane molded body with the vinyl chloride resin molded body used as the skin of automobile interior parts. It is required that it is difficult to peel off.
  • the vinyl chloride resin molded product obtained by molding the conventional vinyl chloride resin composition for powder molding has room for improvement in adhesiveness to the foamed polyurethane molded product.
  • an object of the present invention is to provide a vinyl chloride resin composition for powder molding capable of forming a vinyl chloride resin molded body having excellent adhesion to a foamed polyurethane molded body.
  • Another object of the present invention is to provide a vinyl chloride resin molded product having excellent adhesiveness to a foamed polyurethane molded product.
  • the present inventor has made diligent studies for the purpose of solving the above problems. Then, the present inventor obtained vinyl chloride obtained by mixing a component for hot mixing containing vinyl chloride resin particles, a plasticizer, and vinyl chloride resin fine particles, and optionally further containing an additive such as a pigment, under heating. If a vinyl chloride resin composition for powder molding obtained by adding vinyl chloride resin fine particles as a dusting agent to the resin composition is used, a vinyl chloride resin molded body having excellent adhesion to a foamed polyurethane molded body can be obtained. We found that it could be obtained and completed the present invention.
  • the "resin particles” refer to particles having a particle diameter of 30 ⁇ m or more, and the “resin fine particles” refer to particles having a particle diameter of less than 30 ⁇ m.
  • the present invention aims to advantageously solve the above problems, and the method for producing a vinyl chloride resin composition of the present invention comprises (a) vinyl chloride resin particles and (b) a plasticizer. , (C) It is characterized by including a step of mixing components for hot mixing including vinyl chloride resin fine particles under heating.
  • the vinyl chloride resin composition obtained by mixing the components for hot mixing including (a) vinyl chloride resin particles, (b) plasticizer, and (c) vinyl chloride resin fine particles under heating is used.
  • the premixed components containing the (a) vinyl chloride resin particles and the (c) vinyl chloride resin fine particles are mixed while being heated, and then mixed.
  • the vinyl chloride resin composition can be prepared by adding the plasticizer (b) to the obtained mixture and drying it up.
  • the component for hot mixing is 0.5 parts by mass or more of the (c) vinyl chloride resin fine particles per 100 parts by mass of the (a) vinyl chloride resin particles. It is preferably contained in a proportion of parts by mass or less.
  • the ratio of the vinyl chloride resin fine particles is within the above range, the meltability of the vinyl chloride resin composition for powder molding obtained by using the vinyl chloride resin composition is enhanced, and the vinyl chloride for powder molding is enhanced.
  • the stickiness of the surface can be further reduced while further improving the adhesiveness to the foamed polyurethane molded body.
  • the average degree of polymerization of the vinyl chloride resin constituting the (c) vinyl chloride resin fine particles is preferably 500 or more and 5000 or less.
  • the "average degree of polymerization" can be measured according to JIS K6720-2.
  • the present invention is intended to advantageously solve the above problems, and the method for producing a vinyl chloride resin composition for powder molding of the present invention is the method for producing a vinyl chloride resin composition described above. It is characterized by including a step of mixing the vinyl chloride resin composition produced by using any of the above and (d) the vinyl chloride resin fine particles. As described above, if the vinyl chloride resin composition produced by the above-mentioned method for producing the vinyl chloride resin composition and (d) the vinyl chloride resin fine particles are mixed, the adhesiveness to the foamed polyurethane molded body is only excellent. Further, a vinyl chloride resin composition for powder molding capable of forming a vinyl chloride resin molded body in which the surface stickiness is suppressed can be obtained.
  • the present invention is intended to advantageously solve the above problems, and the method for producing a vinyl chloride resin molded product of the present invention is the above-mentioned method for producing a vinyl chloride resin composition for powder molding. It is characterized by including a step of powder forming a vinyl chloride resin composition for powder forming produced using the above.
  • the vinyl chloride resin composition for powder molding produced by the above-mentioned method for producing the vinyl chloride resin composition for powder molding is powder-molded, the adhesiveness to the foamed polyurethane molded body is excellent and the adhesiveness to the foamed polyurethane molded body is excellent. It is possible to obtain a vinyl chloride resin molded product in which the stickiness of the surface is suppressed.
  • the powder molding is powder slush molding.
  • powder slash molding it is easier to obtain a vinyl chloride resin molded product that can be satisfactorily used as an automobile interior material such as a skin for an automobile instrument panel.
  • the present invention is intended to advantageously solve the above problems, and the method for producing a laminate of the present invention uses a foamed polyurethane molded product and the above-mentioned method for producing a vinyl chloride resin molded product. It is characterized by including a step of laminating the vinyl chloride resin molded product produced in the above process. As described above, by using the vinyl chloride resin molded product manufactured by the above-mentioned manufacturing method of the vinyl chloride resin molded product, a laminate in which the vinyl chloride resin molded product and the foamed polyurethane molded product are well adhered can be obtained. Can be done.
  • the present invention aims to advantageously solve the above problems, and the vinyl chloride resin composition of the present invention has (a) vinyl chloride resin fine particles on the surface of (a) vinyl chloride resin particles. It is characterized by containing composite particles which are fused and contain (b) a plasticizer. As described above, a vinyl chloride resin composition containing (a) composite particles obtained by fusing (c) vinyl chloride resin fine particles to the surface of vinyl chloride resin particles and (b) composite particles containing a plasticizer can be obtained.
  • a vinyl chloride resin composition for powder molding which not only has excellent adhesion to a foamed polyurethane molded body but also can form a vinyl chloride resin molded body in which the surface stickiness is suppressed. can.
  • the vinyl chloride resin composition for powder molding of the present invention is the above-mentioned vinyl chloride resin composition and (d) vinyl chloride. It is characterized by containing resin fine particles. As described above, if the vinyl chloride resin composition for powder molding containing the above-mentioned vinyl chloride resin composition and (d) vinyl chloride resin fine particles is used, the adhesiveness to the foamed polyurethane molded body is excellent and the surface surface is excellent. It is possible to form a vinyl chloride resin molded product in which stickiness is also suppressed.
  • a vinyl chloride resin composition for powder molding capable of forming a vinyl chloride resin molded body having excellent adhesion to a foamed polyurethane molded body. Further, according to the present invention, it is possible to provide a vinyl chloride resin molded product having excellent adhesiveness to the foamed polyurethane molded product. Further, according to the present invention, it is possible to provide a laminated body in which a vinyl chloride resin molded body and a foamed polyurethane molded body are well bonded.
  • the vinyl chloride resin composition produced according to the production method of the present invention may be used as it is as a molding material for a vinyl chloride resin molded body, but usually, a vinyl chloride resin composition for powder molding is used according to the production method of the present invention. Used when manufacturing. Further, the vinyl chloride resin composition for powder molding produced according to the production method of the present invention can be used when producing a vinyl chloride resin molded body according to the production method of the present invention.
  • the vinyl chloride resin molded product can be suitably used as an automobile interior material such as a skin provided for an automobile interior part such as an automobile instrument panel and a door trim.
  • the vinyl chloride resin molded product produced according to the production method of the present invention can be used, for example, when producing a laminate according to the production method of the present invention. Then, the laminate formed by using the vinyl chloride resin molded body can be suitably used as an automobile interior material used when manufacturing an automobile interior part such as an automobile instrument panel and a door trim.
  • a component for hot mixing is mixed under heating to obtain a vinyl chloride resin composition.
  • the vinyl chloride resin composition produced according to the method for producing the vinyl chloride resin composition of the present invention has adhesiveness to the foamed polyurethane molded body by being mixed with (d) vinyl chloride resin fine particles as a dusting agent. It can be used as a vinyl chloride resin composition for powder molding capable of forming a vinyl chloride resin molded body having not only excellent properties but also suppressed surface stickiness.
  • the components for hot mixing include (a) vinyl chloride resin particles, (b) a plasticizer, and (c) vinyl chloride resin fine particles, and optionally further (e) an additive.
  • (A) Vinyl chloride resin particles for example, one kind or two or more kinds of vinyl chloride resin particles can be contained.
  • the vinyl chloride resin constituting the (a) vinyl chloride resin particles in addition to the copolymer composed of the vinyl chloride monomer unit, the vinyl chloride monomer unit is preferably 50% by mass or more, more preferably 70. Examples thereof include vinyl chloride-based copolymers containing a mass% or more.
  • a monomer (comonomer) copolymerizable with a vinyl chloride monomer that can constitute a vinyl chloride-based copolymer for example, it is described in International Publication No. 2016/098344. Can be mentioned.
  • one of these components may be used alone, or two or more of these components may be used in combination at any ratio.
  • the vinyl chloride resin particles (a) are not particularly limited, and 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, preferably 5000 or less, and 3000 or less. It is more preferably present, and further preferably 2800 or less.
  • the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is equal to or higher than the above lower limit, for example, tensile properties, particularly tensile elongation, can be obtained while sufficiently ensuring the physical strength of the vinyl chloride resin molded product. Because it can be done better.
  • a vinyl chloride resin molded body having good tensile elongation can be used, for example, as a skin of an automobile instrument panel having excellent ductility, which breaks as designed without scattering debris when the airbag expands and expands. It can be suitably used as an automobile interior material. Further, (a) if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition for powder molding prepared by using the vinyl chloride resin composition is determined. This is because it can be improved.
  • the average particle size of (a) vinyl chloride resin particles is usually 30 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, preferably 500 ⁇ m or less, and more preferably 200 ⁇ m or less.
  • the "average particle size" is based on JIS Z8825 and can be measured as a volume average particle size by a laser diffraction method.
  • the plasticizer is not particularly limited, and any plasticizer can be used.
  • the plasticizer includes, for example, the plasticizer described in International Publication No. 2016/098344, the dodecanedioic acid diester described in International Publication No. 2015/141181, and International Publication No. 2020 /.
  • the polyester or the like described in No. 090556 can be used.
  • one type may be used alone, or two or more types may be mixed and used at an arbitrary ratio.
  • the plasticizer is a polyester containing a structural unit derived from adipic acid (adipic acid-based polyester), a polyester containing a structural unit derived from sebacic acid (sevacinic acid-based polyester), and a structure derived from phthalic acid. It is preferable to contain a polyester such as a polyester containing a unit (phthalic acid-based polyester).
  • the (b) plasticizer contains polyester containing a structural unit derived from adipic acid, and adipic acid. It is particularly preferable to include a polyester containing a structural unit derived from an acid and a structural unit derived from 3-methyl-1,5-pentanediol. Further, from the viewpoint of improving the flexibility and tensile properties of the vinyl chloride resin molded product at low temperature, it is preferable that the (b) plasticizer contains a dodecane diacid diester such as dodecane diacid di (2-ethylhexyl). .. Further, from the viewpoint of improving the tensile properties of the vinyl chloride resin molded product, the (b) plasticizer preferably contains epoxidized soybean oil.
  • the content of the (b) plasticizer in the components for hot mixing is preferably 80 parts by mass or more, preferably 90 parts by mass or more, with respect to 100 parts by mass of the (a) vinyl chloride resin particles. Is more preferably 100 parts by mass or more, more preferably 200 parts by mass or less, further preferably 180 parts by mass or less, still more preferably 150 parts by mass or less.
  • the content of (b) the plasticizer in the components for hot mixing is within the above-mentioned predetermined range, the tensile properties of the vinyl chloride resin molded product can be satisfactorily improved.
  • the content ratio of polyester in the plasticizer is preferably 80% by mass or more, more preferably 85% by mass or more, and 100% by mass. It can be as follows, preferably 95% by mass or less, and more preferably 90% by mass or less.
  • the content ratio of polyester in the plasticizer is at least the above lower limit, the tensile properties of the vinyl chloride resin molded product can be further improved, and the heat-resistant shrinkage of the laminated body can be further improved.
  • vinyl chloride resin fine particles for example, one kind or two or more kinds of vinyl chloride resin fine particles can be contained.
  • the vinyl chloride resin constituting the vinyl chloride resin fine particles (c) the same vinyl chloride resin as described above can be mentioned as the vinyl chloride resin constituting the vinyl chloride resin particles (a).
  • the vinyl chloride resin fine particles (c) are not particularly limited, and are preferably produced by an emulsion polymerization method.
  • the average degree of polymerization of the vinyl chloride resin constituting the (c) vinyl chloride resin fine particles is preferably 500 or more, more preferably 700 or more, further preferably 1500 or more, further preferably 5000 or less, and even more preferably 2400 or less.
  • (C) When the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is at least the above lower limit, the stickiness of the surface of the vinyl chloride resin molded product can be further suppressed. Further, if (c) the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition for powder molding prepared by using the vinyl chloride resin composition is determined. Can be improved.
  • the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles may be different from the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles (a) without particular limitation.
  • 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 preferable.
  • the average particle diameter of the vinyl chloride resin fine particles is at least the above lower limit, it is possible to obtain a vinyl chloride resin molded body having excellent adhesiveness to the foamed polyurethane molded body without excessively reducing the size.
  • the content of the (c) vinyl chloride resin fine particles in the hot mix component is preferably 0.5 part by mass or more per 100 parts by mass of the (a) vinyl chloride resin particles, and is preferably 2 parts by mass or more. It is more preferably 2.5 parts by mass or more, further preferably 10 parts by mass or less, further preferably 5 parts by mass or less, still more preferably 3 parts by mass or less. ..
  • the content of (c) vinyl chloride resin fine particles in the components for hot mixing is equal to or higher than the above lower limit, the adhesiveness of the vinyl chloride resin molded product to the foamed polyurethane molded product is further improved, and the vinyl chloride resin molded product is further improved. The stickiness of the surface of the surface can be further suppressed. Further, if the content of the (c) vinyl chloride resin fine particles in the hot mix component is not more than the above upper limit value, the meltability of the vinyl chloride resin composition for powder molding prepared by using the vinyl chloride resin composition is increased. Can be improved.
  • the additive is not particularly limited, and is a lubricant (surface modifier) such as fatty acid amide; a stabilizer such as perchlorate-treated hydrotalcite, zeolite, ⁇ -diketone, fatty acid metal salt; Molding agent; Impact resistance improving agent; Perchlorate compound other than perchlorate-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.); Antioxidant; Antifungal agent; Flame retardant; Antistatic agent; Fillers; light stabilizers; foaming agents; pigments; and the like.
  • additives that can be contained in the hot mix component for example, those described in International Publication No. 2016/098344 and International Publication No. 2016/07592 can be used, and the suitable content thereof is also international. It can be the same as the description of Publication No. 2016/098344 and International Publication No. 2016/075902.
  • the mixing of the components for hot mixing under heating can be performed by mixing the above-mentioned components all at once or in any order while heating them.
  • the mixing of the components for hot mixing under heating contains (a) vinyl chloride resin particles and (c) vinyl chloride resin fine particles, and optionally (b) a part of the plasticizer and / or (e) addition.
  • the obtained mixture is (b) the rest of the plasticizer (when the premixed component contains a part of (b) the plasticizer).
  • the components for hot mixing are preferably mixed by dry blending, and more preferably by using a Henschel mixer.
  • the temperature at the time of mixing is not particularly limited, and is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, preferably 200 ° C. or lower, and more preferably 100 ° C. or lower.
  • the vinyl chloride resin composition prepared by mixing the components for hot mixing under heating is said to be (c) mixed with a plasticizer in the presence of vinyl chloride resin fine particles and dried up.
  • a dry-up mixed mixture according to the prior art a mixture obtained by mixing components other than a plasticizer and a dusting agent while heating and then adding a plasticizer to the obtained mixture to dry up? It's different.
  • the vinyl chloride resin fine particles are not particularly limited, and (a) the surface of the vinyl chloride resin particles is not particularly limited. Can be fused.
  • (a) vinyl chloride resin fine particles are fused to the surface of (a) vinyl chloride resin particles, as shown in the scanning electron microscope (SEM) photograph in FIG. It is a composite particle made of (b) and may contain a composite particle in which a plasticizer is absorbed.
  • the composite particles include, for example, (a) a central portion containing a vinyl chloride resin derived from vinyl chloride resin particles, (c) a vinyl chloride resin derived from vinyl chloride resin fine particles, and optionally (e) an additive. It may have a structure including a surface layer portion further containing.
  • the vinyl chloride resin composition produced by using the method for producing a vinyl chloride resin composition of the present invention and (d) vinyl chloride resin fine particles are mixed.
  • a vinyl chloride resin composition for powder molding is obtained. Since the vinyl chloride resin composition for powder molding produced according to the method for producing the vinyl chloride resin composition for powder molding of the present invention contains the above-mentioned vinyl chloride resin composition, it can be used as a foamed polyurethane molded body. It is possible to form a vinyl chloride resin molded product that not only has excellent adhesiveness but also suppresses stickiness on the surface.
  • a vinyl chloride resin composition for powder molding of the present invention in addition to the vinyl chloride resin composition and (d) vinyl chloride resin fine particles, (d) other dusting agents other than the vinyl chloride resin fine particles, etc. May be mixed to prepare a vinyl chloride resin composition for powder molding.
  • the other dusting agent for example, those described in International Publication No. 2016/098344 can be used.
  • ⁇ Vinyl chloride resin composition As the vinyl chloride resin composition, a vinyl chloride resin composition produced by using the method for producing a vinyl chloride resin composition of the present invention is used.
  • vinyl chloride resin fine particles In the vinyl chloride resin composition for powder molding, (d) the vinyl chloride resin fine particles usually function as a dusting agent (powder fluidity improving agent).
  • the (d) vinyl chloride resin fine particles for example, one kind or two or more kinds of vinyl chloride resin fine particles can be contained.
  • the vinyl chloride resin constituting the (d) vinyl chloride resin fine particles include (a) vinyl chloride resin particles and (c) the same vinyl chloride resin as the vinyl chloride resin constituting the vinyl chloride resin fine particles. be able to.
  • the vinyl chloride resin fine particles (d) are not particularly limited, and are preferably produced by an emulsion polymerization method. Further, as the (d) vinyl chloride resin fine particles, the same fine particles as the (c) vinyl chloride resin fine particles used in preparing the vinyl chloride resin composition may be used, or the (c) vinyl chloride resin fine particles may be used. May use different fine particles.
  • the average degree of polymerization of the vinyl chloride resin constituting the (d) vinyl chloride resin fine particles is preferably 500 or more, more preferably 700 or more, further preferably 1500 or more, preferably 2600 or less, and more preferably 2400 or less.
  • the average degree of polymerization of the vinyl chloride resin constituting the (d) vinyl chloride resin fine particles as the dusting agent is at least the above lower limit, the powder fluidity of the vinyl chloride resin composition for powder molding becomes better. This is because the tensile elongation of the molded product obtained by using the composition becomes better.
  • 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 preferable.
  • the average particle size of the vinyl chloride resin fine particles is equal to or larger than the above lower limit, the powder fluidity of the vinyl chloride resin composition for powder molding can be further improved without, for example, reducing the size of the dusting agent excessively. Because it can be made good.
  • the average particle size of the vinyl chloride resin fine particles is equal to or less than the above upper limit, the meltability of the vinyl chloride resin composition for powder molding is further enhanced, and the surface smoothness of the formed vinyl chloride resin molded body is improved. This is because it can be further improved.
  • the amount of (d) vinyl chloride resin fine particles to be mixed with the vinyl chloride resin composition shall be 5 parts by mass or more per 100 parts by mass of (a) vinyl chloride resin particles used for preparing the vinyl chloride resin composition. Is more preferable, 8 parts by mass or more is more preferable, 30 parts by mass or less is preferable, and 15 parts by mass or less is more preferable.
  • (D) When the amount of the vinyl chloride resin fine particles is not less than the above lower limit, the powder fluidity of the vinyl chloride resin composition for powder molding is further improved. Further, (d) when the amount of the vinyl chloride resin fine particles is not more than the above upper limit, the physical strength of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition for powder molding can be further increased. be.
  • the vinyl chloride resin composition and (d) the vinyl chloride resin fine particles are not particularly limited, and are preferably mixed by a dry blend, and more preferably by using a mixer. Further, (d) the vinyl chloride resin fine particles are obtained after preparing a vinyl chloride resin composition by mixing the components for hot mixing under heating according to the method for producing a vinyl chloride resin composition of the present invention. It is preferable to cool the composition before mixing.
  • the vinyl chloride resin composition for powder molding prepared by mixing the vinyl chloride resin composition and (d) vinyl chloride resin fine particles is not particularly limited, but is not particularly limited, but for example, the scanning type shown in FIG. As shown in the electron microscope (SEM) photograph, (a) vinyl chloride resin fine particles may adhere to the surface of the composite particles formed by fusion of (c) vinyl chloride resin fine particles to the surface of (a) vinyl chloride resin particles. ..
  • a vinyl chloride resin composition for powder molding produced by using the method for producing a vinyl chloride resin composition for powder molding of the present invention is powder-molded and vinyl chloride. Form a resin molded body. Since the vinyl chloride resin molded product produced according to the method for producing the vinyl chloride resin molded product of the present invention is formed by using the above-mentioned vinyl chloride resin composition for powder molding, it can be applied to a foamed polyurethane molded product. It has excellent adhesiveness and suppresses stickiness on the surface.
  • the vinyl chloride resin molded body and the foamed polyurethane molded body adhere well and are difficult to peel off, so that the automobile instrument It can be suitably used as an automobile interior material such as a panel skin.
  • the mold temperature at the time of powder slash molding is not particularly limited, and is preferably 200 ° C. or higher, more preferably 220 ° C. or higher.
  • the temperature is preferably 300 ° C. or lower, more preferably 280 ° C. or lower.
  • the vinyl chloride resin molded product is produced by powder slash molding, for example, the following method can be used without particular limitation.
  • the excess vinyl chloride resin composition for powder molding is shaken off, and further. , Leave it for 30 seconds or more and 3 minutes or less under any temperature. Then, the mold is cooled to 10 ° C. or higher and 60 ° C. or lower, and the obtained vinyl chloride resin molded product is removed from the mold. Then, a sheet-shaped molded body in the shape of a mold is obtained.
  • a vinyl chloride resin molded body manufactured by using the method for producing a vinyl chloride resin molded body of the present invention and a foamed polyurethane molded body are laminated to obtain a laminated body.
  • the vinyl chloride resin molded body usually constitutes one surface of the laminated body. Since the laminate manufactured according to the method for producing a laminate of the present invention is formed by using the above-mentioned vinyl chloride resin molded body, the vinyl chloride resin molded body and the foamed polyurethane molded body adhere well to each other. ing. Therefore, the laminate is suitably used as an automobile interior part, particularly as an automobile interior material for forming an automobile instrument panel.
  • the method of laminating the foamed polyurethane molded body and the vinyl chloride resin molded body is not particularly limited, and for example, the following method can be used. That is, (1) a method in which a foamed polyurethane molded body and a vinyl chloride resin molded body are separately prepared and then bonded by heat fusion, heat bonding, or using a known adhesive or the like; (2) vinyl chloride. Polyurethane foamed on a resin molded body Polyurethane foamed on a vinyl chloride resin molded body by reacting isocyanates, which are the raw materials of the molded body, with polyols to polymerize, and foaming polyurethane by a known method.
  • the latter method (2) is preferable because the process is simple and the vinyl chloride resin molded body and the foamed polyurethane molded body can be easily firmly adhered even when a laminated body having various shapes is obtained. Is.
  • the melting temperature of the vinyl chloride resin composition for powder molding was measured using a heated mold. Specifically, the mold was placed on a hot plate that was heated stepwise at equal intervals in the range of 170 ° C. to 270 ° C. to obtain a mold that was heated stepwise. Then, the vinyl chloride resin composition for powder molding was sprinkled on the stepwise heated mold and left to stand for a predetermined time (30 seconds) to melt it. Next, the excess vinyl chloride resin composition for powder molding is shaken off, the mold is cooled with water, and the vinyl chloride resin molding sheet in which the vinyl chloride resin composition for powder molding is molded into a belt shape is formed into gold. Demolded from the mold.
  • the surface of the demolded vinyl chloride resin molded sheet was visually observed, and the temperature at the point where the vinyl chloride resin composition for powder molding was melted was defined as the melting temperature.
  • the melted portion was determined to be a portion of the molded vinyl chloride resin molded sheet having a smooth surface without leaving a particle shape. The lower the melting temperature, the better the melting property of the vinyl chloride resin composition for powder molding. ⁇ Low temperature tensile elongation and low temperature tensile strength> The obtained vinyl chloride resin molded sheet was punched out with a No.
  • the vinyl chloride resin molded sheet was peeled off from the foamed polyurethane molded body of the laminate formed by lining the vinyl chloride resin molded sheet with the foamed polyurethane molded body.
  • the surface on the side where the foamed polyurethane molded body was lined was visually confirmed, and the polyurethane adhesiveness was evaluated according to the following criteria. The more the foam is confirmed to be broken, the higher the adhesiveness of the vinyl chloride resin molded sheet to the foamed polyurethane molded body is shown.
  • polyesters used in the examples and comparative examples were prepared as follows.
  • ⁇ Polyester A> Adipic acid as a polyvalent carboxylic acid, 3-methyl-1,5-pentanediol as a polyhydric alcohol, and 2-ethylhexanol as a stopper (terminal stop component) are charged in a reaction vessel, and tetraisopropyl titanate is used as a catalyst.
  • a solvent was appropriately added, and the temperature was raised while stirring.
  • the by-product water was removed under normal pressure and reduced pressure, and finally the temperature was raised to 220 to 230 ° C. to complete the dehydration condensation reaction.
  • the obtained product was subjected to thin film distillation under the conditions of a pressure of 4 to 80 Pa and a mantle temperature of 250 ° C., and the polyester A having a 2-ethylhexoxy group at the end (viscosity: 3600 mPa ⁇ s, number average molecular weight: 5300, Acid value: 0.32, hydroxyl value: 12.7) were obtained.
  • Example 1 ⁇ Preparation of vinyl chloride resin composition> Among the components for hot mixing shown in Table 1, the components excluding the plasticizer (polyester A, di-dodecaneate (2-ethylhexyl) and epoxidized soybean oil) were placed in a Henshell mixer and mixed. Then, when the temperature of the mixture rises to 80 ° C., all the above-mentioned plasticizers are added to dry up (meaning that the plasticizer is absorbed by the particles of the vinyl chloride resin and the above-mentioned mixture becomes smoother). To prepare a vinyl chloride resin composition.
  • the plasticizer polyester A, di-dodecaneate (2-ethylhexyl) and epoxidized soybean oil
  • the vinyl chloride resin composition for powder molding obtained above is sprinkled on a textured mold heated to a temperature of 250 ° C., left to stand for an arbitrary time to melt, and then excess powder molding.
  • the vinyl chloride resin composition for use was shaken off.
  • the textured mold sprinkled with the vinyl chloride resin composition for powder molding is allowed to stand in an oven set at a temperature of 200 ° C., and the textured mold is cooled 60 seconds after the standing. Cooled with water.
  • the vinyl chloride resin molded sheet as the vinyl chloride resin molded body was removed from the mold.
  • a mixed solution was prepared in which the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) were mixed at a ratio of an index of 98. Then, the prepared mixed liquid was poured onto the vinyl chloride resin molded sheet laid in the mold as described above. Then, the mold was covered with an aluminum plate having a size of 348 mm ⁇ 255 mm ⁇ 10 mm, and the mold was sealed. By leaving the mold closed for 5 minutes, the vinyl chloride resin molded sheet (thickness: 1 mm) as the outer skin is lined with a foamed polyurethane molded body (thickness: 9 mm, density: 0.2 g / cm 3). The laminated body was formed. Then, the formed laminate was taken out from the mold, and the adhesiveness was evaluated according to the above-mentioned method. The results are shown in Table 1.
  • Example 2 (Examples 2 to 8) (C) A vinyl chloride resin composition, a vinyl chloride resin composition for powder molding, and vinyl chloride in the same manner as in Example 1 except that the types and addition amounts of the vinyl chloride resin fine particles were changed as shown in Table 1. A resin molded body and a laminated body were produced. Then, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. In Example 7, the obtained vinyl chloride resin composition and the vinyl chloride resin composition for powder molding were observed and photographed with a scanning electron microscope (SEM). The obtained SEM photographs are shown in FIGS. 1 and 2.
  • SEM scanning electron microscope
  • a vinyl chloride resin composition for powder molding capable of forming a vinyl chloride resin molded body having excellent adhesion to a foamed polyurethane molded body. Further, according to the present invention, it is possible to provide a vinyl chloride resin molded product having excellent adhesiveness to the foamed polyurethane molded product. Further, according to the present invention, it is possible to provide a laminated body in which a vinyl chloride resin molded body and a foamed polyurethane molded body are well bonded.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
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