Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
  • B60K37/00—Dashboards
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • 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
  • C08K5/10—Esters; Ether-esters
• • 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 laminate and a method for manufacturing the laminate.
• Polyvinyl chloride resin is generally used in a variety of applications due to its excellent properties such as cold resistance, heat resistance, and oil resistance.
• laminates in which polyvinyl chloride resin molded bodies and polyurethane foam molded bodies are laminated adjacent to each other are used to form automobile interior parts such as automobile instrument panels and door trims. Technologies for producing such laminates have been investigated in the past.
• a vinyl chloride resin composition containing vinyl chloride resin, a plasticizer, and additives such as a hydrotalcite-based stabilizer, a zeolite-based stabilizer, and ⁇ -diketones is powder-molded to prepare a vinyl chloride resin molded body, and a polyurethane foam molded body is laminated onto this vinyl chloride resin molded body to produce a laminate.
• the present invention aims to provide a laminate of a polyvinyl chloride resin molded body and a polyurethane foam molded body, in which discoloration of the polyvinyl chloride resin molded body under high temperature conditions is suppressed, and a method for producing said laminate.
• the present inventors have conducted extensive research with the aim of solving the above problems.
• the inventors have discovered that discoloration of vinyl chloride resin molded bodies under high temperature conditions can be suppressed by using a vinyl chloride resin composition containing an aliphatic dicarboxylate salt in addition to vinyl chloride resin and a plasticizer in the production of the vinyl chloride resin molded body that constitutes the laminate, and have completed the present invention.
• the purpose of this invention is to advantageously solve the above problems, and the present invention provides a method for manufacturing the laminates [1] to [6] and the laminates [7] to [12].
• a laminate of a vinyl chloride resin molded article, which is a molded article of a vinyl chloride resin composition containing a vinyl chloride resin, an aliphatic dicarboxylate, and a plasticizer, and a polyurethane foam molded article, is resistant to discoloration of the vinyl chloride resin molded article when exposed to high temperature conditions.
• the plasticizer comprises a polyester containing a structural unit derived from adipic acid and a structural unit derived from a polyhydric alcohol.
• the polyester as a plasticizer, the light resistance and heat shrinkage resistance of the vinyl chloride resin molded article constituting the laminate can be improved.
• the powder flowability of the vinyl chloride resin composition can be improved.
• the meltability of the vinyl chloride resin composition can be increased, while the surface smoothness of the vinyl chloride resin molded article can be improved.
• a method for producing a laminate comprising: a step of molding a vinyl chloride resin composition containing a vinyl chloride resin, an aliphatic dicarboxylate, and a plasticizer to obtain a vinyl chloride resin molded body; and a step of laminating a foamed polyurethane molded body on a surface of the vinyl chloride resin molded body to obtain a laminate in which the vinyl chloride resin molded body and the foamed polyurethane molded body are laminated adjacent to each other.
• a laminate of a vinyl chloride resin molded article obtained by molding a vinyl chloride resin composition containing a vinyl chloride resin, an aliphatic dicarboxylate, and a plasticizer, and a polyurethane foam molded article, is resistant to discoloration of the vinyl chloride resin molded article when exposed to high temperature conditions.
• the plasticizer comprises a polyester containing a structural unit derived from adipic acid and a structural unit derived from a polyhydric alcohol.
• the polyester as a plasticizer, the light resistance and heat shrinkage resistance of the vinyl chloride resin molded article constituting the laminate can be improved.
• the powder flowability of the vinyl chloride resin composition can be improved.
• the meltability of the vinyl chloride resin composition can be increased, while the surface smoothness of the vinyl chloride resin molded article can be improved.
• the present invention provides a laminate of a polyvinyl chloride resin molded body and a polyurethane foam molded body, in which discoloration of the polyvinyl chloride resin molded body under high temperature conditions is suppressed, and a method for producing the laminate.
• the laminate of the present invention can be suitably used as an automobile interior material used in producing automobile interior parts such as an automobile instrument panel and a door trim, etc.
• the method for producing the laminate of the present invention can be used in producing the laminate of the present invention.
• the laminate of the present invention is formed by laminating a vinyl chloride resin molded body and a polyurethane foam molded body adjacent to each other.
• the vinyl chloride resin molded body usually constitutes one surface of the laminate.
• the laminate may have any structure other than the vinyl chloride resin molded body and the polyurethane foam molded body depending on the application.
• the vinyl chloride resin molded body is formed from a vinyl chloride resin composition containing vinyl chloride resin, an aliphatic dicarboxylate, and a plasticizer, so that the vinyl chloride resin molded body is less likely to discolor when exposed to high temperature conditions.
• the reason why molding a vinyl chloride resin molded article using the vinyl chloride resin composition as described above can suppress discoloration of the vinyl chloride resin molded article when the laminate is exposed to high temperature conditions is not clear, but is presumed to be as follows.
• the amine component used as a polymerization catalyst may remain in the polyurethane foam.
• the amine component may migrate from the polyurethane foam molded body to the polyvinyl chloride resin molded body, especially under high temperature conditions.
• the inventor's research has revealed that hydrogen chloride is released from the polyvinyl chloride resin by reaction with the amine component, and this hydrogen chloride causes the polyvinyl chloride resin molded body to discolor.
• the polyvinyl chloride resin molded body contains an aliphatic dicarboxylate derived from the polyvinyl chloride resin composition, and the aliphatic dicarboxylate can deactivate the amine component.
• the aliphatic dicarboxylate since the aliphatic dicarboxylate has two carboxylic acid groups instead of one, the amine component can be strongly captured by the crosslinked structure between the carboxylic acid groups. It is believed that this suppresses the release of hydrogen chloride from the polyvinyl chloride resin caused by the amine component and prevents discoloration of the polyvinyl chloride resin molded body.
• the vinyl chloride resin molded article is an article molded from a vinyl chloride resin composition.
• the vinyl chloride resin composition contains a vinyl chloride resin, an aliphatic dicarboxylate, and a plasticizer, and may optionally contain additives other than the vinyl chloride resin, the aliphatic dicarboxylate, and the plasticizer. Since a vinyl chloride resin molded article is obtained by molding a vinyl chloride resin composition, the mass ratio of each blended component in the vinyl chloride resin molded article is usually the same as the mass ratio of each blended component in the vinyl chloride resin composition.
• the vinyl chloride resin generally, particulate vinyl chloride resin is used.And, as the vinyl chloride resin, for example, one or more kinds of vinyl chloride resin particles can be contained, and optionally, one or more kinds of vinyl chloride resin microparticles can be further contained.
• the vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin microparticles.
• the vinyl chloride resin can be produced by any of the conventionally known production methods, such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization.
• the term "resin particles” refers to particles having a particle diameter of 30 ⁇ m or more
• the term “resin fine particles” refers to particles having a particle diameter of less than 30 ⁇ m.
• Vinyl chloride resins include homopolymers consisting of vinyl chloride monomer units, as well as vinyl chloride copolymers containing preferably 50% by mass or more, more preferably 70% by mass or more, of vinyl chloride monomer units.
• monomers (comonomers) that can be copolymerized with vinyl chloride monomers and that can constitute vinyl chloride copolymers include those described in International Publication No. 2016/098344. These components may be used alone or in combination of two or more types in any ratio.
• the vinyl chloride resin particles In the vinyl chloride resin composition, the vinyl chloride resin particles usually function as a matrix resin (substrate).
• the vinyl chloride resin particles are preferably produced by a suspension polymerization method.
• the average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 800 or more, more preferably 1000 or more, more preferably 5000 or less, more preferably 3000 or less, and even more preferably 2800 or less. If the average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin particles is 800 or more, the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be sufficiently high, while, for example, the tensile properties, particularly the tensile elongation, can be improved.
• a vinyl chloride resin molded body having good tensile elongation can be suitably used as an automobile interior material such as the skin of an automobile instrument panel having excellent ductility, which breaks as designed without scattering fragments when an airbag is inflated and deployed.
• the average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin particles is 5000 or less, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be increased.
• the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles may be 1,400 or more, 1,500 or more, or 1,600 or more, or may be 1,600 or less, 1,500 or less, or 1,400 or less.
• the "average degree of polymerization” can be measured in accordance with JIS K6720-2.
• the average particle size of the 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. If the average particle size of the vinyl chloride resin particles is 30 ⁇ m or more, the powder flowability of the vinyl chloride resin composition can be improved. On the other hand, if the average particle size of the vinyl chloride resin particles is 500 ⁇ m or less, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be increased.
• the "average particle size" can be measured as a volume average particle size by a laser diffraction method in accordance with JIS Z8825.
• the content of the vinyl chloride resin particles in the vinyl chloride resin is preferably 70% by mass or more, more preferably 80% by mass or more, and can be 100% by mass, and is preferably 95% by mass or less, and more preferably 90% by mass or less. If the content of the vinyl chloride resin particles in the vinyl chloride resin is 70% by mass or more, the tensile elongation can be improved while ensuring a sufficiently high physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition. On the other hand, if the content of the vinyl chloride resin particles in the vinyl chloride resin is 95% by mass or less, the powder flowability of the vinyl chloride resin composition can be improved.
• the vinyl chloride resin fine particles usually function as a dusting agent (powder flow improver).
• the vinyl chloride resin fine particles are preferably produced by an emulsion polymerization method.
• the average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin microparticles is preferably 500 or more, more preferably 700 or more, and preferably 2600 or less, more preferably 2400 or less. If the average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin microparticles as a dusting agent is 500 or more, the powder fluidity of the vinyl chloride resin composition can be improved and the tensile elongation of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be improved.
• the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be increased.
• 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 more preferably 1 ⁇ m or more. If the average particle size of the vinyl chloride resin fine particles is 0.1 ⁇ m or more, for example, the powder flowability of the vinyl chloride resin composition can be improved without excessively reducing the size as a dusting agent. On the other hand, if the average particle size of the vinyl chloride resin fine particles is less than 30 ⁇ m, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of the vinyl chloride resin molded body formed can be increased.
• the content of the vinyl chloride resin fine particles in the vinyl chloride resin may be 0% by mass, but is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 30% by mass or less, and more preferably 20% by mass or less. If the content of the vinyl chloride resin fine particles in the vinyl chloride resin is 5% by mass or more, the powder flowability of the vinyl chloride resin composition can be improved. On the other hand, if the content of the vinyl chloride resin fine particles in the vinyl chloride resin is 30% by mass or less, the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be increased.
• the aliphatic dicarboxylate is a component capable of suppressing discoloration of a vinyl chloride resin molded article under high temperature conditions in the laminate of the present invention as described above.
• the aliphatic dicarboxylate is also a component capable of functioning as a powder flow improver for a vinyl chloride resin composition when producing a vinyl chloride resin molded article from the vinyl chloride resin composition.
• the aliphatic dicarboxylate may be used alone or in combination of two or more kinds in any ratio.
• the aliphatic dicarboxylate salt is not particularly limited as long as the aliphatic dicarboxylate is in the form of a salt.
• Preferred examples of the salt include sodium salts, potassium salts, and calcium salts.
• sodium salts are particularly preferred from the viewpoint of further suppressing discoloration of vinyl chloride resin molded articles under high temperature conditions.
• the aliphatic dicarboxylic acid must be used in the form of a salt, i.e., as an aliphatic dicarboxylate. If an aliphatic dicarboxylic acid is used instead of an aliphatic dicarboxylate, discoloration of the vinyl chloride resin molded article constituting the laminate under high temperature conditions cannot be sufficiently suppressed.
• the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylate is not particularly limited as long as it is an aliphatic compound having two carboxylic acid groups, but from the viewpoint of further suppressing discoloration of the vinyl chloride resin molded body under high temperature conditions while increasing the fluidity of the vinyl chloride resin composition, for example, maleic acid, malonic acid, succinic acid, adipic acid, and sebacic acid can be preferably mentioned. Among these, maleic acid is particularly preferable from the viewpoint of further suppressing discoloration of the vinyl chloride resin molded body under high temperature conditions.
• the aliphatic dicarboxylate is preferably a compound represented by the formula NaOOC-R-COONa (wherein R is an aliphatic group having 1 to 8 carbon atoms), and more preferably disodium maleate, disodium malonate, disodium succinate, disodium adipate, and disodium sebacate.
• disodium maleate is particularly preferred from the viewpoint of further suppressing discoloration of vinyl chloride resin molded articles under high temperature conditions.
• the content of the aliphatic dicarboxylate salt in the vinyl chloride resin composition is preferably 0.30 parts by mass or more, more preferably 0.40 parts by mass or more, and even more preferably 2.00 parts by mass or more, and is preferably 8.00 parts by mass or less, and more preferably 7.00 parts by mass or less, per 100 parts by mass of vinyl chloride resin.
• the content of disodium maleate in the vinyl chloride resin composition is, from the viewpoint of further suppressing discoloration of a vinyl chloride resin molded article under high-temperature conditions, preferably 0.30 parts by mass or more, more preferably 0.40 parts by mass or more, even more preferably 1.00 parts by mass or more, even more preferably 2.00 parts by mass or more, preferably 8.00 parts by mass or less, more preferably 7.00 parts by mass or less, even more preferably 5.00 parts by mass or less, even more preferably 4.00 parts by mass or less, and particularly preferably 3.00 parts by mass or less, per 100 parts by mass of vinyl chloride resin.
• the plasticizer is a component capable of imparting flexibility to a vinyl chloride resin molded article formed using the vinyl chloride resin composition.
• a plasticizer in the vinyl chloride resin composition the meltability of the vinyl chloride resin composition is increased, so that molding (particularly powder molding) into a vinyl chloride resin molded article can be easily performed and the surface smoothness of the vinyl chloride resin molded article formed can be increased.
• the plasticizer may be used alone or in combination of two or more kinds in any ratio.
• the content of the plasticizer in the vinyl chloride resin composition is preferably 50 parts by mass or more, more preferably 75 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 85 parts by mass or more, particularly preferably 90 parts by mass or more, preferably 200 parts by mass or less, more preferably 185 parts by mass or less, and even more preferably 150 parts by mass or less, per 100 parts by mass of vinyl chloride resin. If the content of the plasticizer in the vinyl chloride resin composition is 50 parts by mass or more per 100 parts by mass of vinyl chloride resin, the meltability of the vinyl chloride resin composition can be sufficiently increased and sufficient flexibility can be imparted to the vinyl chloride resin molded body formed.
• the content of the plasticizer in the vinyl chloride resin composition is 50 parts by mass or more per 100 parts by mass of vinyl chloride resin, the powder flowability of the vinyl chloride resin composition can be improved.
• the content of the plasticizer in the vinyl chloride resin composition is 200 parts by mass or less per 100 parts by mass of vinyl chloride resin, the light resistance of the vinyl chloride resin molded body formed can be improved.
• the vinyl chloride resin composition preferably contains at least a polyester containing structural units derived from adipic acid and structural units derived from a polyhydric alcohol as a plasticizer, and more preferably contains both the polyester and a plasticizer other than the polyester (hereinafter referred to as "other plasticizers").
• the polyester contains structural units derived from adipic acid and structural units derived from a polyhydric alcohol.
• the vinyl chloride resin composition containing the polyester as a plasticizer can exhibit excellent melting properties.
• the polyester also improves the powder flowability of the vinyl chloride resin composition and can also enhance the light resistance and heat shrinkage resistance of the vinyl chloride resin molded article formed.
• the polyester preferably contains a structural unit derived from 2-methyl-1,3-propanediol as the structural unit derived from the polyhydric alcohol.
• the polyester may contain a structural unit derived from a polyhydric alcohol other than 2-methyl-1,3-propanediol (hereinafter, sometimes referred to as "other polyhydric alcohols") as the structural unit derived from the polyhydric alcohol.
• the content of the structural units derived from 2-methyl-1,3-propanediol in the structural units derived from polyhydric alcohol is preferably more than 70 mol%, more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more, when the total amount of the structural units derived from polyhydric alcohol contained in the polyester is taken as 100 mol%. If the content of the structural units derived from 2-methyl-1,3-propanediol in the total amount of the structural units derived from polyhydric alcohol contained in the polyester is more than 70%, the meltability and powder flowability of the vinyl chloride resin composition can be sufficiently improved, and the light resistance of the vinyl chloride resin molded article formed can be sufficiently increased.
• the content of the structural units derived from 2-methyl-1,3-propanediol in the structural units derived from polyhydric alcohol is 100 mol % when the total amount of the structural units derived from polyhydric alcohol contained in the polyester is taken as 100 mol %. That is, it is particularly preferable that the polyester contains only structural units derived from 2-methyl-1,3-propanediol as structural units derived from polyhydric alcohol.
• polyhydric alcohols other than 2-methyl-1,3-propanediol that can form structural units derived from other polyhydric alcohols in polyesters include 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, and 3-methyl-1,5-pentanediol.
• the content ratio of structural units derived from other polyhydric alcohols in the structural units derived from polyhydric alcohols is preferably less than 30 mol%, more preferably 20 mol% or less, even more preferably 10 mol% or less, and even more preferably 5 mol% or less, when the total amount of structural units derived from polyhydric alcohols contained in the polyester is taken as 100 mol%. If the content ratio of structural units derived from other polyhydric alcohols in the total amount of structural units derived from polyhydric alcohols contained in the polyester is less than 30 mol%, the meltability and powder flowability of the vinyl chloride resin composition can be further improved, and the light resistance of the vinyl chloride resin molded article formed can be further increased.
• the content of structural units derived from other polyhydric alcohols in the structural units derived from polyhydric alcohols is 0 mol % when the total amount of structural units derived from polyhydric alcohols contained in the polyester is 100 mol %. That is, it is particularly preferable that the polyester does not contain structural units derived from polyhydric alcohols other than 2-methyl-1,3-propanediol as structural units derived from polyhydric alcohols.
• the polyester may contain structural units derived from polycarboxylic acids other than adipic acid as structural units derived from polycarboxylic acids, but the content of structural units derived from adipic acid in the total amount of structural units derived from polycarboxylic acids in the polyester is preferably 50 mol % or more, more preferably 80 mol % or more, and particularly preferably 100 mol %. In other words, it is particularly preferable that the polyester contains only structural units derived from adipic acid as structural units derived from polycarboxylic acids.
• the polyester can be obtained by condensation polymerization of adipic acid and a polyhydric alcohol, without any particular limitation.
• the above-mentioned condensation polymerization can be carried out in the presence of a catalyst.
• the above-mentioned condensation polymerization can be carried out using an alcohol and/or a monobasic acid as a terminal termination component.
• the condensation polymerization of adipic acid and a polyhydric alcohol and the termination reaction of the obtained condensation polymer with the above-mentioned terminal termination component may be carried out together or separately.
• the product obtained through the condensation polymerization and termination reaction may be subjected to post-treatment such as distillation.
• the reaction conditions of the condensation polymerization such as the above-mentioned monomers of adipic acid and polyhydric alcohol, and the amounts of the catalyst and terminal termination component, can be known conditions.
• As the polyester commercially available products may be used.
• the catalyst used in the condensation polymerization reaction is not particularly limited, but examples include dibutyltin oxide and tetraalkyl titanate.
• monobasic acids which may be used as end-stopping components include, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, caproic acid, heptanoic acid, caprylic acid, 2-ethylhexyl acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, benzoic acid, and mixtures thereof.
• 2-ethylhexanol is preferred as the end-terminator component.
• the weight average molecular weight of the polyester is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more, and is preferably 10,000 or less, and more preferably 7,000 or less.
• the "weight average molecular weight" of the polyester can be determined as a polystyrene-equivalent value by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
• the acid value of the polyester is preferably 0.5 mgKOH/g or more and 2 mgKOH/g or less. Furthermore, the hydroxyl value of the polyester is preferably 30 mgKOH/g or less, more preferably 10 mgKOH/g or less, and even more preferably 7 mgKOH/g or less.
• the "acid value” and "hydroxyl value” of the polyester can be measured by a method in accordance with JIS K0070.
• the viscosity of the polyester is preferably 500 mPa ⁇ s or more, more preferably 1000 mPa ⁇ s or more, and is preferably 8000 mPa ⁇ s or less, more preferably 5000 mPa ⁇ s or less, and even more preferably 3000 mPa ⁇ s or less.
• the "viscosity" of the polyester can be measured at a temperature of 23°C in accordance with JIS Z8803.
• the content of the polyester in the vinyl chloride resin composition is preferably more than 30 parts by mass per 100 parts by mass of vinyl chloride resin, more preferably 50 parts by mass or more, even more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, particularly preferably 85 parts by mass or more, and preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 140 parts by mass or less. If the content of the polyester in the vinyl chloride resin composition is more than 30 parts by mass per 100 parts by mass of vinyl chloride resin, the meltability and powder flowability of the vinyl chloride resin composition, as well as the light resistance and heat shrinkage resistance of the vinyl chloride resin molded article formed can be improved. On the other hand, if the content of the polyester in the vinyl chloride resin composition is 200 parts by mass or less per 100 parts by mass of vinyl chloride resin, the light resistance of the vinyl chloride resin molded article formed can be improved.
• the content of polyester in the plasticizer is preferably 50% by mass or more, more preferably 65% by mass or more, even more preferably 90% by mass or more, even more preferably 93% by mass or more, particularly preferably 95% by mass or more, and can be 100% by mass or less, preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less, assuming the total mass of the plasticizer to be 100% by mass. If the content of polyester in the plasticizer is 50% by mass or more, the meltability and powder flowability of the vinyl chloride resin composition, as well as the light resistance and heat shrinkage resistance of the vinyl chloride resin molded body formed can be improved. On the other hand, if the content of polyester in the plasticizer is 99% by mass or less, the light resistance of the vinyl chloride resin molded body formed can be improved.
• the content of the other plasticizer in the vinyl chloride resin composition can be 0 parts by mass or more per 100 parts by mass of vinyl chloride resin, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, even more preferably 2 parts by mass or more, preferably 40 parts by mass or less, more preferably 35 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 7 parts by mass or less. If the content of the other plasticizer in the vinyl chloride resin composition is 0.5 parts by mass or more per 100 parts by mass of vinyl chloride resin, the flexibility of the vinyl chloride resin molded body formed can be increased. On the other hand, if the content of the other plasticizer in the vinyl chloride resin composition is 40 parts by mass or less, the powder flowability of the vinyl chloride resin composition can be improved.
• the content of the other plasticizer in the plasticizer can be 0% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, even more preferably 4.2% by mass or more, preferably 50% by mass or less, more preferably 35% by mass or less, even more preferably 10% by mass or less, even more preferably 7% by mass or less, and particularly preferably 5% by mass or less, assuming the total mass of the plasticizer to be 100% by mass. If the content of the other plasticizer in the plasticizer is 1% by mass or more, the flexibility of the vinyl chloride resin molded body formed can be further increased. On the other hand, if the content of the other plasticizer in the plasticizer is 50% by mass or less, the powder flowability of the vinyl chloride resin composition can be improved.
• plasticizers other than the polyesters described above among the plasticizers described in WO 2016/098344. More specifically, as the other plasticizer, trimellitic acid ester and epoxidized vegetable oil can be used, and it is preferable to use epoxidized vegetable oil.
• epoxidized vegetable oil for example, epoxidized soybean oil, epoxidized linseed oil, etc. can be used. Among them, it is preferable to use epoxidized soybean oil as the epoxidized vegetable oil from the viewpoint of improving the tensile properties of the vinyl chloride resin molded article to be formed at low temperatures.
• the content of epoxidized vegetable oil in the vinyl chloride resin composition is preferably 2 parts by mass or more and 7 parts by mass or less per 100 parts by mass of vinyl chloride resin. If the content of epoxidized vegetable oil in the vinyl chloride resin composition is within the above range, the tensile properties of the vinyl chloride resin molded body formed at low temperatures can be improved.
• the content of epoxidized vegetable oil in the plasticizer is preferably 1% by mass or less, more preferably 2% by mass or more, even more preferably 3% by mass or more, even more preferably 3.5% by mass or more, preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less. If the content of epoxidized vegetable oil in the plasticizer is within the above range, the tensile properties of the polyvinyl chloride resin molded body formed at low temperatures can be improved.
• the vinyl chloride resin composition of the present invention may further contain various additives in addition to the above-mentioned components.
• the additives are not particularly limited, and examples thereof include lubricants, stabilizers such as perchloric acid-treated hydrotalcite, zeolite, ⁇ -diketone, fatty acid metal salt, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate (light stabilizer), and 6-amino-1,3-dimethyluracil, release agents, dusting agents other than the above-mentioned vinyl chloride resin fine particles, impact resistance improvers, perchloric acid compounds other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.), antioxidants, antifungal agents, flame retardants, antistatic agents, fillers, foaming agents, pigments, and the like.
• the vinyl chloride resin composition used for producing the vinyl chloride resin molded article can be prepared by mixing the above-mentioned components.
• the method of mixing the vinyl chloride resin, the aliphatic dicarboxylate, the plasticizer, and various additives further blended as necessary is not particularly limited, and for example, the components other than the dusting agent (including the vinyl chloride resin fine particles) are mixed by dry blending, and then the dusting agent is added and mixed.
• the temperature during dry blending is not particularly limited, and is preferably 50°C or higher, more preferably 70°C or higher, and preferably 200°C or lower.
• the foamed polyurethane molded product is not particularly limited, and may be any known foamed polyurethane molded product obtained by reacting isocyanates with polyols or the like to polymerize and foam the polyurethane.
• the isocyanates and polyols are not particularly limited and known ones can be used.
• the polymerization and foaming methods are also not particularly limited and known methods can be used.
• the polymerization catalyst used for the reaction of the isocyanates and polyols is not particularly limited and includes amine components such as triethylenediamine, triethanolamine, and triethylamine.
• the laminate of the present invention described above can be produced by, but is not particularly limited to, a method for producing a laminate of the present invention.
• the method for producing a laminate of the present invention includes a step of forming a vinyl chloride resin composition containing a vinyl chloride resin, an aliphatic dicarboxylate, and a plasticizer to obtain a vinyl chloride resin molded body (molded body forming step), and a step of laminating a foamed polyurethane molded body on the surface of the vinyl chloride resin molded body obtained in the molded body forming step to obtain a laminate in which the vinyl chloride resin molded body and the foamed polyurethane molded body are adjacently laminated (laminate forming step).
• the method for producing a laminate of the present invention may optionally include steps other than the molded body forming step and the laminate forming step. Furthermore, according to the method for producing a laminate of the present invention, a laminate in which discoloration of a vinyl chloride resin molded article under high temperature conditions is suppressed can be efficiently produced.
• a vinyl chloride resin composition containing at least a vinyl chloride resin, an aliphatic dicarboxylate, and a plasticizer, and optionally containing an additive, is molded to obtain a vinyl chloride resin molded body.
• the "vinyl chloride resin,”"aliphaticdicarboxylate,””plasticizer,” and “additive” are the same as those described above in the “Laminate” section, and their preferred examples and preferred contents are also the same as those described above in the "Laminate” section.
• the method for molding the vinyl chloride resin composition into a vinyl chloride resin molded article is not particularly limited, and any known molding method can be used.
• powder slush molding is preferred from the viewpoint of easily obtaining a vinyl chloride resin molded article that can be used well as an automobile interior material, such as the skin for an automobile instrument panel.
• the mold temperature during powder slush molding is not particularly limited, but is preferably 200°C or higher, more preferably 220°C or higher, and is preferably 300°C or lower, and more preferably 280°C or lower.
• the following method can be used, for example, without any particular limitations. That is, the vinyl chloride resin composition of the present invention is sprinkled onto a mold having a temperature in the above range, and the mold is left for 5 to 30 seconds, after which the excess vinyl chloride resin composition is shaken off, and the mold is further left for 30 seconds to 3 minutes at any temperature. The mold is then cooled to 10°C to 60°C, and the obtained vinyl chloride resin molded body is demolded from the mold. Then, a sheet-like molded body having the shape of the mold is obtained.
• a polyurethane foam molded body is laminated (backed) on the surface of the vinyl chloride resin molded body obtained in the molded body formation step to obtain a laminate of the vinyl chloride resin molded body and the polyurethane foam molded body.
• the lamination method of the polyvinyl chloride resin molded body and the polyurethane foam molded body is not particularly limited, and the following methods can be used, for example. That is, (1) a method in which a polyvinyl chloride resin molded body and a polyurethane foam molded body are prepared separately, and then bonded together by heat fusion, heat adhesion, or using a known adhesive; (2) a method in which isocyanates and polyols, which are the raw materials for the polyurethane foam molded body, are reacted on the polyvinyl chloride resin molded body to polymerize and foam the polyurethane, thereby directly forming a polyurethane foam molded body on the polyvinyl chloride resin molded body; and the like.
• the latter method (2) is preferred because of its simple process and the ease of firmly bonding the polyvinyl chloride resin molded body and the polyurethane foam molded body even when laminates of various shapes are obtained.
• ⁇ Powder fluidity> The vinyl chloride resin compositions obtained in the Examples and Comparative Examples were poured from the funnel of a powder property tester (manufactured by Nippon Oil Testing Machinery Co., Ltd., model number "TESTERTYPE 6721") into a 100 cc brass cylinder to fill the cylinder with the vinyl chloride resin composition. Thereafter, the vinyl chloride resin composition was again poured from the cylinder into the funnel and dropped onto a flat plate, and the time (seconds) until all of the vinyl chloride resin composition had finished dropping was measured and recorded as the drop time. The shorter the drop time, the more excellent the powder fluidity of the vinyl chloride resin composition.
• polyester A containing structural units derived from adipic acid and structural units derived from polyhydric alcohol
• Adipic acid as a polyvalent carboxylic acid, 2-methyl-1,3-propanediol as a polyhydric alcohol, and 2-ethylhexanol as a stopper (terminal termination component) were charged into a reaction vessel, tetraisopropyl titanate was added as a catalyst, a solvent was added appropriately, and the temperature was raised while stirring.
• polyester A (viscosity: 2800 mPa ⁇ s, weight average molecular weight: 4200, acid value: 1.0 mgKOH/g, hydroxyl value: 5.5 mgKOH/g) having 2-ethylhexoxy groups at the ends.
• Example 1 Preparation of vinyl chloride resin composition> Of the ingredients shown in Table 1, the ingredients except for the plasticizer (polyester A and epoxidized soybean oil) and the vinyl chloride resin fine particles as a dusting agent were put into a Henschel mixer and mixed. Then, when the temperature of the mixture rose to 80°C, all of the plasticizer was added and the mixture was allowed to dry up (referring to a state in which the plasticizer is absorbed into the vinyl chloride resin particles as the vinyl chloride resin and the mixture becomes smooth). Thereafter, when the dried-up mixture was cooled to a temperature of 70°C or less, the vinyl chloride resin fine particles as a dusting agent were added to prepare a vinyl chloride resin composition.
• the plasticizer polyester A and epoxidized soybean oil
• the vinyl chloride resin fine particles as a dusting agent were put into a Henschel mixer and mixed. Then, when the temperature of the mixture rose to 80°C, all of the plasticizer was added and the mixture was allowed to dry up (referring to
• the powder flowability of the resulting vinyl chloride resin composition was evaluated.
• the results are shown in Table 3.
• the vinyl chloride resin composition obtained above was sprinkled onto a textured mold heated to a temperature of 250° C., and allowed to stand for an arbitrary period of time to melt, after which the excess vinyl chloride resin composition was shaken off.
• the textured mold onto which the vinyl chloride resin composition had been sprinkled was then placed in an oven set at a temperature of 200° C., and 60 seconds after being placed still, the textured mold was cooled with cooling water.
• a vinyl chloride resin molded body (vinyl chloride resin molded sheet) having dimensions of 150 mm ⁇ 200 mm ⁇ 1 mm was demolded from the mold.
• ⁇ Laminate Forming Process> Two of the vinyl chloride resin molded articles obtained above were placed in a mold measuring 200 mm ⁇ 300 mm ⁇ 10 mm with the textured surface facing down so that the two sheets did not overlap each other.
• a mixed liquid was prepared by mixing the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (Polymeric MDI) at a ratio such that the index was 98.
• the prepared mixture was then poured onto two polyvinyl chloride resin molded sheets placed in a metal mold.
• the metal mold was then covered with an aluminum plate measuring 200 mm x 300 mm x 10 mm to seal the metal mold.
• the metal mold was left for 5 minutes after sealing to form a laminate in the metal mold, in which a polyvinyl chloride resin molded body (thickness: 1 mm) as a skin was backed by a polyurethane foam molded body (thickness: 9 mm, density: 0.18 g/cm 3 ).
• the laminate thus formed was removed from the mold, and the laminate was evaluated for its ability to inhibit discoloration of a vinyl chloride resin molded article under high temperature conditions. The results are shown in Table 3.
• Examples 2 to 16, Comparative Example 1 In preparing the vinyl chloride resin composition, a vinyl chloride resin composition, a vinyl chloride resin molded article, and a laminate were prepared in the same manner as in Example 1, except that the types and/or amounts of the blending components used were changed as shown in Tables 1 and 2. Then, evaluations were performed in the same manner as in Example 1. The results are shown in Tables 3 and 4.
• Tables 1 to 4 show that the laminates of Examples 1 to 16 obtained by laminating a vinyl chloride resin molded body made by molding a vinyl chloride resin composition containing vinyl chloride resin, an aliphatic dicarboxylate, and a plasticizer with a polyurethane foam molded body are able to suppress discoloration of the vinyl chloride resin molded body under high temperature conditions compared to Comparative Example 1.
• the present invention provides a laminate of a polyvinyl chloride resin molded body and a polyurethane foam molded body, in which discoloration of the polyvinyl chloride resin molded body under high temperature conditions is suppressed, and a method for producing the laminate.

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