Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • 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
  • B60K37/20—Dashboard panels
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
  • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
  • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
  • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

• the present invention relates to a composition for forming a resin layer, a vinyl chloride resin laminated sheet and a method for producing the same, and 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 vinyl chloride resin molded body obtained by molding a vinyl chloride resin composition into a sheet (hereinafter, "vinyl chloride resin molded sheet").
• An automobile interior material such as a laminate made of a foam material such as polyurethane foam is used for a skin material made of (may be referred to as) or a skin material made of the vinyl chloride resin molded sheet.
• a vinyl chloride resin composition containing a vinyl chloride resin and a plasticizer is used (see, for example, Patent Documents 1 and 2).
• the present inventor has arranged a vinyl chloride resin laminate having a resin layer containing a resin having an SP value in a predetermined range as a main component on at least one side of a vinyl chloride resin molded sheet containing a plasticizer in the thickness direction.
• the present inventors lined a foamed polyurethane molded body on the surface of the vinyl chloride resin laminated sheet on the side where the resin layer is arranged (that is, the vinyl chloride resin molded sheet via the resin layer). It was found that the transfer of the plastic agent from the vinyl chloride resin molded sheet can be satisfactorily suppressed when the laminated body is produced (so that the foamed polyurethane molded body adheres to the molded body).
• the resin layer having the above-mentioned resin whose SP value is in a predetermined range as a main component has high humidity. It was found that there is room for improvement in durability (that is, moisture heat resistance) under high temperature (for example, humidity 80% RH or more, temperature 80 ° C. or more) conditions.
• an object of the present invention is to provide a resin layer forming composition capable of satisfactorily suppressing the migration of a plasticizer from a vinyl chloride resin molded sheet and forming a resin layer having excellent moisture and heat resistance.
• Another object of the present invention is to provide a vinyl chloride resin laminated sheet which can satisfactorily suppress the migration of a plasticizer from a vinyl chloride resin molded sheet and has excellent moisture and heat resistance of the resin layer, and a method for producing the same.
• an object of the present invention is to provide a laminate which can satisfactorily suppress the migration of a plasticizer from a vinyl chloride resin molded sheet and has excellent moisture and heat resistance.
• the present inventor has conducted diligent studies for the purpose of solving the above problems. Then, the present inventor can transfer the plasticizer from the vinyl chloride resin molded sheet by using a resin layer forming composition containing a resin having an SP value and a degree of polymerization of each of predetermined values or more and an organometallic compound.
• the present invention has been completed by finding that it is possible to form a resin layer which can be suppressed well and has excellent moisture and heat resistance.
• the present invention is intended to advantageously solve the above problems, and the resin layer forming composition of the present invention is a resin layer forming composition containing resin A and an organic metal compound.
• the SP value of the resin A is 14 (cal / cm 3 ) 1/2 or more, and the degree of polymerization of the resin A is 300 or more.
• the resin layer forming composition containing the resin having the SP value and the degree of polymerization of each of the predetermined values or more and the organometallic compound the migration of the plasticizer from the vinyl chloride resin molded sheet is satisfactorily suppressed. At the same time, it is possible to form a resin layer having excellent moisture and heat resistance.
• the SP value means a solubility parameter.
• the SP value can be calculated by using the method introduced in Hansen Solubility Parameter A User's Handbook, 2ndEd (CRCPress).
• the SP value of the organic compound can also be estimated from the molecular structure of the organic compound. Specifically, it can be calculated using simulation software (for example, "HSPiP" (http://www.hansen-solubility.com)) that can calculate the SP value from the SMILE equation.
• HSPiP "http://www.hansen-solubility.com)
• Hansen SOLUBILITY PARAMETERS A User's Handbook Second Edition, Charles M.I.
• the SP value is determined based on the theory described in Hansen.
• the degree of polymerization refers to the number of monomer units (monomer units) contained in the polymer (polymer) constituting the resin.
• the degree of polymerization of polyvinyl alcohol as the resin A can be determined as the average degree of polymerization measured according to the method described in JIS K6726.
• the content of the organometallic compound is preferably 3.00 parts by mass or more and 10.00 parts by mass or less with respect to 100 parts by mass of the resin A.
• the content of the organometallic compound is within the above-mentioned predetermined range, the moisture and heat resistance of the formed resin layer can be further enhanced, and the storage stability of the resin layer forming composition can be enhanced.
• the organometallic compound contains an organic titanium compound.
• the organometallic compound contains the organotitanium compound, the moisture and heat resistance of the formed resin layer can be further enhanced.
• the present invention aims to advantageously solve the above problems, and the vinyl chloride resin laminated sheet of the present invention includes a vinyl chloride resin molded sheet containing a vinyl chloride resin and a plasticizer, and the vinyl chloride.
• a vinyl chloride resin laminated sheet having a resin layer L arranged on at least one side in the thickness direction of the resin molded sheet, wherein the resin layer L uses any of the above-mentioned resin layer forming compositions. It is characterized by being formed.
• the resin laminated sheet can satisfactorily suppress the migration of the plastic agent from the vinyl chloride resin molded sheet, and is excellent in the moisture and heat resistance of the resin layer.
• the vinyl chloride resin laminated sheet of the present invention is preferably used for the skin of an automobile instrument panel.
• the vinyl chloride resin laminated sheet of the present invention is used as the skin of an automobile instrument panel, the migration of the plasticizer from the vinyl chloride resin molded sheet can be satisfactorily suppressed, and the deterioration of the skin can be prevented.
• any of the above-mentioned resin layer forming compositions is applied to at least one side of the vinyl chloride resin molded sheet containing the vinyl chloride resin and the plasticizing agent in the thickness direction. It is characterized by including a coating step of forming a resin layer L by drying the coated composition for forming a resin layer.
• the applied resin layer forming composition after applying any of the above-mentioned resin layer forming compositions to at least one side in the thickness direction of the vinyl chloride resin molded sheet containing the vinyl chloride resin and the plasticizer, the applied resin layer forming composition.
• the vinyl chloride resin laminated sheet produced by drying an object to form the resin layer L can satisfactorily suppress the migration of the plasticizer from the vinyl chloride resin molded sheet, and is excellent in the moisture and heat resistance of the resin layer.
• the present invention aims to advantageously solve the above problems, and the laminate of the present invention is a laminate having a foamed polyurethane molded article and any of the above-mentioned vinyl chloride resin laminate sheets.
• the resin layer L is arranged between the foamed polyurethane molded product and the vinyl chloride resin molded sheet.
• a laminate having the foamed polyurethane molded body and any of the above-mentioned vinyl chloride resin laminated sheets, and the resin layer L is arranged between the foamed polyurethane molded body and the vinyl chloride resin molded sheet.
• the transfer of the plasticizer from the vinyl chloride resin molded sheet can be satisfactorily suppressed, and the moisture and heat resistance is excellent.
• a resin layer forming composition capable of satisfactorily suppressing the migration of a plasticizer from a vinyl chloride resin molded sheet and forming a resin layer having excellent moisture and heat resistance.
• a vinyl chloride resin laminated sheet and a method for producing the same which can satisfactorily suppress the migration of the plasticizer from the vinyl chloride resin molded sheet and have excellent moisture and heat resistance of the resin layer.
• the resin layer forming composition of the present invention can be used, for example, in the production of the vinyl chloride resin laminated sheet of the present invention.
• the vinyl chloride resin laminated sheet of the present invention includes a resin layer L formed by using the composition for forming a resin layer of the present invention.
• the vinyl chloride resin laminated sheet of the present invention can be used, for example, for producing the laminated body of the present invention.
• the vinyl chloride resin laminated sheet of the present invention can be suitably used as an automobile interior material, for example, the skin of an automobile interior part such as an automobile instrument panel.
• the vinyl chloride resin laminated sheet of the present invention can be produced by the method for producing the vinyl chloride resin laminated sheet of the present invention.
• composition for forming a resin layer of the present invention is characterized by containing a resin A having an SP value and a degree of polymerization of each of predetermined values or more, and an organometallic compound.
• the resin layer forming composition of the present invention may optionally contain other components other than the resin A and the organometallic compound.
• the composition for forming a resin layer of the present invention is usually obtained by dispersing or dissolving the resin A, an organometallic compound, and other components in a known solvent.
• the resin A is a component that functions as a matrix resin (base material) in the resin layer L formed by using the resin layer forming composition and can satisfactorily suppress the migration of the plasticizer from the vinyl chloride resin molded sheet. ..
• the content ratio of the resin A in the composition for forming the resin layer can be arbitrarily adjusted within the range in which the desired effect of the present invention can be obtained.
• the SP value of the resin A needs to be 14 (cal / cm 3 ) 1/2 or more, preferably 15 (cal / cm 3 ) 1/2 or more, and 16 (cal / cm) or more. 3 ) More preferably, it is 1/2 or more.
• the SP value of the resin A is preferably 30 (cal / cm 3 ) 1/2 or less, more preferably 25 (cal / cm 3 ) 1/2 or less, and 22 (cal / cm 3 ). still more preferably 1/2 or less, and particularly preferably 20 (cal / cm 3) 1/2 or less.
• the SP value of the resin A is 30 (cal / cm 3 ) 1/2 or less, the flexibility of the resin layer L can be increased.
• the degree of polymerization of the resin A needs to be 300 or more, preferably 320 or more, more preferably 350 or more, further preferably 380 or more, and 400 or more. Is more preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less.
• the degree of polymerization of the resin A is at least the above lower limit, the moisture and heat resistance of the formed resin layer can be enhanced.
• the degree of polymerization of the resin A is not more than the above upper limit, the obtained composition for forming a resin layer is excellent in handleability at the time of coating.
• the molecular weight of the resin A is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using THF as a solvent is 21,000 or more. Is more preferable, 22,000 or more is more preferable, 24,000 or more is further preferable, 70,000 or less is preferable, 56,000 or less is more preferable, and 42,000 or less is further preferable.
• Mw polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography
• GPC gel permeation chromatography
• the resin A described above includes, for example, polyvinyl alcohol (also referred to as a completely saponified product from polyvinyl acetate or a partially saponified product from polyvinyl acetate.
• the resin A it is preferable to use a resin having a hydroxyl group ( ⁇ OH group), and it is particularly preferable to use polyvinyl alcohol.
• a resin having a hydroxyl group (-OH group) is used as the resin A, the polymers constituting the resin A can be satisfactorily crosslinked with an organometallic compound described later, and the moisture and heat resistance of the formed resin layer can be further enhanced. it can. Further, when polyvinyl alcohol is used as the resin A, the formed resin layer can further better suppress the migration of the plasticizer from the vinyl chloride resin molded sheet.
• the "hydroxyl group (-OH group)" in the above does not include the structure of -OH in the carboxyl group (-COOH) of acrylic resins such as polyacrylic acid and polymethacrylic acid. To do.
• the degree of saponification from polyvinyl acetate in polyvinyl alcohol can be 60% or more, preferably 61% or more, more preferably 62% or more, and preferably 63% or more. More preferably, it is more preferably 65% or more, it can be 100%, it is preferably less than 100%, it is preferably 90% or less, and it is more preferably 80% or less, 70. It is more preferably% or less.
• the degree of saponification from polyvinyl acetate in polyvinyl alcohol is at least the above lower limit, the formed resin layer can further better suppress the migration of the plastic agent from the vinyl chloride resin molded sheet.
• the degree of saponification from polyvinyl acetate in polyvinyl alcohol is not more than the above upper limit, the flexibility of the formed resin layer can be increased.
• the degree of saponification from polyvinyl acetate in polyvinyl alcohol can be measured in accordance with JIS K6726 (polyvinyl alcohol test method).
• the degree of saponification from polyvinyl acetate is 65%. It is preferable to use one.
• the organometallic compound is a component that functions as a cross-linking agent for cross-linking the polymers constituting the resin A described above and can enhance the moisture and heat resistance of the formed resin layer.
• the organometallic compound is not particularly limited as long as it can satisfactorily crosslink the polymers constituting the resin A, and for example, an organotitanium compound, an organozirconium compound, or the like can be used. Above all, it is preferable to use an organic titanium compound from the viewpoint of further enhancing the moisture and heat resistance of the formed resin layer.
• the organic titanium compound for example, it is preferable to use a titanium chelate compound.
• the titanium chelate compound contains a chelating agent having an ability to coordinate with a titanium atom.
• the titanium chelating compound include titanium containing hydroxycarboxylic acid such as lactic acid and / or a salt thereof; trialcohol amine such as triethanolamine; 2- (2-aminoethylamino) ethanol; and the like as a chelating agent. Chelated compounds can be used.
• a titanium chelate compound containing hydroxycarboxylic acid and / or a salt thereof as a chelating agent, and lactic acid and / or a salt thereof is contained as a chelating agent. It is more preferable to use a titanium chelate compound containing lactic acid, further preferably a titanium chelate compound containing a salt of lactic acid as a chelating agent, and particularly preferably to use a titanium chelate compound containing an ammonium salt of lactic acid as a chelating agent.
• titanium chelate compound containing hydroxycarboxylic acid and / or a salt thereof as a chelating agent examples include titanium lactate (specific formula: Ti (OH) 2 [OCH (CH 3 ) COOH] 2 ; dihydroxybis (lactate)). also referred to as titanium), titanium lactate ammonium salt. (rational formula: Ti (OH) 2 [OCH (CH 3) COO -] 2 (NH 4 +) 2; dihydroxy bis (ammonium lactate) may be referred to as titanium There is also.) Etc.
• titanium chelate compound containing trialcohol amine as a chelating agent examples include titanium triethanolamineate (specification formula: Ti (Oi-C 3 H 7 ) 2 (C 6 H 14 O 3 N) 2 ). ; Titanium diisopropoxybis (sometimes referred to as triethanolamineate)) and the like.
• titanium chelate compound containing 2- (2-aminoethylamino) ethanol as a chelating agent a titanium-aminoethylamino ethanolate (rational formula: (i-C 3 H 7 O) Ti (OC 2 H 4 NHC 2 H 4 NH 2 ) 3 ) and the like.
• the titanium chelate compounds include the above-mentioned titanium lactate (specification formula: Ti (OH) 2 [OCH (CH 3 ) COOH] 2 ) and titanium lactate ammonium. salt (rational formula: Ti (OH) 2 [OCH (CH 3) COO -] 2 (NH 4 +) 2) etc., it is preferable to use a titanium chelate compound having a hydroxyl group directly bonded to the titanium atom.
• the organometallic compound a commercially available product can also be used.
• the organic titanium compound "TC-300" (titanium lactate ammonium salt), "TC-310” (titanium lactate), “TC-315" (titanium lactate), “TC-335" manufactured by Matsumoto Fine Chemicals Co., Ltd. (Titanium Lactate), “TC-400” (Titanium Triethanol Aminate), “TC-510” (Titanium Amino Ethyl Amino Ethanolate) and the like can be used.
• the organic zirconium compound "ZC-126” (zirconium chloride compound) manufactured by Matsumoto Fine Chemicals Co., Ltd. or the like can also be used.
• the content of the organometallic compound in the resin layer forming composition is preferably 3.00 parts by mass or more, more preferably 3.50 parts by mass or more, with respect to 100 parts by mass of the resin A. It is more preferably .00 parts by mass or more, preferably 10.00 parts by mass or less, more preferably 8.00 parts by mass or less, and further preferably 6.00 parts by mass or less.
• the content of the organometallic compound in the resin layer forming composition is at least the above lower limit, the moisture and heat resistance of the formed resin layer can be further enhanced.
• the content of the organometallic compound in the resin layer forming composition is not more than the above upper limit, the components in the resin layer forming composition are precipitated without excessively increasing the pH of the resin layer forming composition. This can be suppressed and the storage stability of the resin layer forming composition can be enhanced.
• composition for forming a resin layer of the present invention may optionally contain other components other than the resin A and the organometallic compound described above.
• other components for example, a binder, a plasticizer for a resin layer, a dispersant and the like can be used.
• the composition for forming a resin layer of the present invention may optionally contain a binder.
• the adhesiveness of the formed resin layer to the vinyl chloride resin molded sheet can be enhanced. It is assumed that the binder has a component different from that of the resin A described above.
• a urethane-based binder and an acrylic ester-based binder it is preferable to use a urethane-based binder and an acrylic ester-based binder, and it is more preferable to use a urethane-based binder. If at least one of a urethane-based binder and an acrylic ester-based binder is used as the binder, the adhesiveness of the formed resin layer to the vinyl chloride resin molded sheet can be further enhanced.
• the urethane-based binder is a polyurethane obtained by reacting isocyanates with polyols or the like.
• the urethane binder is a polyester polyurethane obtained by using a polyester polyol as the polyol; a polycarbonate polyurethane obtained by using a polycarbonate polyol as the polyol; a polyether polyol obtained by using a polyether polyol as the polyol.
• Polycarbonate; Polycarbonate polyester-based polyurethane obtained by using a mixture of polycarbonate polyol and polyester polyol as polyols; polyester polyether-based polyurethane obtained by using a mixture of polyester polyol and polyether polyol as polyols; and the like can be used.
• polyester-based polyurethane From the viewpoint of further enhancing the adhesiveness of the formed resin layer to the vinyl chloride resin molded sheet, it is preferable to use polyester-based polyurethane, polycarbonate-based polyurethane, and polycarbonate-based polyurethane as the urethane-based binder, and polyester-based polyurethane. And it is more preferable to use polycarbonate-based polyurethane, and it is further preferable to use polyester-based polyurethane.
• the polyurethane that can be used as the urethane binder is either a yellowing polyurethane obtained by using an aromatic polyisocyanate as an isocyanate or a non-yellowing polyurethane obtained by using an aliphatic polyisocyanate as an isocyanate.
• a yellowish polyurethane obtained by using an aromatic polyisocyanate as an isocyanate is more preferable.
• a commercially available product can also be used as the urethane binder.
• Commercially available urethane binders include Toupe's "Toatan S” (polycarbonate polyester polyurethane), Daiichi Kogyo Seiyaku Co., Ltd. "Superflex (registered trademark) 460” (non-yellowing polycarbonate polyurethane), and Daiichi Kogyo. "Superflex (registered trademark) 740" (yellowing polyester-based polyurethane) manufactured by Pharmaceutical Co., Ltd. can be preferably used.
• the acrylic ester-based binder a known acrylic ester-based polymer that can function as a binder can be used.
• the acrylic ester-based polymer is a polymer containing a structural unit derived from a (meth) acrylic acid ester monomer.
• the acrylic ester-based polymer is a monomer containing a (meth) acrylic acid ester monomer, optionally an acidic group-containing monomer, an ⁇ , ⁇ -unsaturated nitrile monomer, and other monomers. It is obtained by polymerizing the composition.
• a known monomer can be used as each of the above-mentioned monomers.
• the content of the binder in the composition for forming the resin layer is preferably 2.5 parts by mass or more, and more preferably 3.3 parts by mass or more, based on 100 parts by mass of the resin A in terms of dry mass. Preferably, it is more preferably 4.0 parts by mass or more, further preferably 5.0 parts by mass or more, preferably 25.0 parts by mass or less, and preferably 20.0 parts by mass or less. It is more preferably 15.0 parts by mass or less, particularly preferably 10.0 parts by mass or less, and most preferably 7.5 parts by mass or less.
• the content of the binder in the resin layer forming composition is at least the above lower limit, the adhesiveness of the formed resin layer to the vinyl chloride resin molded sheet can be further enhanced.
• the content of the binder in the composition for forming the resin layer is not more than the above upper limit, the formed resin layer can further better suppress the migration of the plasticizer from the vinyl chloride resin molded sheet.
• the composition for forming a resin layer of the present invention may optionally contain a plasticizer for a resin layer.
• the composition for forming the resin layer contains a plasticizer for the resin layer, the formed resin layer can exhibit excellent flexibility. Therefore, the flexibility of the vinyl chloride resin laminated sheet provided with the resin layer can be increased.
• the plasticizer for the resin layer can be imparted to the resin layer in which particularly excellent flexibility is formed when polyvinyl alcohol is used as the resin A.
• plasticizer for the resin layer examples include diol compounds having 1 to 4 carbon atoms such as methylene glycol, ethylene glycol, n-propylene glycol and n-butylene glycol; terminal alkyl-modified polyalkylenes such as methyl polyglycol and ethyl polyglycol. Oxide; is preferred, and terminal alkyl-modified polyalkylene oxides are more preferred. If the above-mentioned compound is used as a plasticizer for a resin layer, the flexibility of the formed resin layer can be further increased.
• the terminal alkyl group in the terminal alkyl-modified polyalkylene oxide is preferably an alkyl group having 1 to 4 carbon atoms, and may be a methyl group and / or an ethyl group. More preferably, it is more preferably a methyl group.
• the terminal alkyl-modified polyalkylene oxide may be either double-terminal alkyl-modified or one-terminal alkyl-modified, but is preferably one-terminal alkyl-modified.
• the polyalkylene oxide used for preparing the terminal alkyl-modified polyalkylene oxide is preferably polyethylene oxide and / or polypropylene oxide, and is preferably polyethylene oxide. More preferred.
• the number average degree of polymerization of the polyalkylene oxide is preferably 2 or more, preferably 20 or less, and more preferably 10 or less.
• methyl polyglycol also referred to as "polyethylene glycol monomethyl ether” which is a one-terminal methyl-modified polyethylene oxide.
• the content of the plasticizing agent for the resin layer in the composition for forming the resin layer is preferably 2.5 parts by mass or more, and more preferably 3.3 parts by mass or more with respect to 100 parts by mass of the resin A. , 3.5 parts by mass or more, more preferably 4.0 parts by mass or more, further preferably 5.0 parts by mass or more, and 20.0 parts by mass or less. It is more preferably 15.0 parts by mass or less, further preferably 10.0 parts by mass or less, further preferably 8.0 parts by mass or less, and 7.0 parts by mass or less. Is even more preferable.
• the content of the resin layer plasticizer in the resin layer forming composition is at least the above lower limit, the flexibility of the formed resin layer can be further increased.
• the content of the plasticizer for the resin layer in the composition for forming the resin layer is not more than the above upper limit, the formed resin layer further suppresses the migration of the plasticizer from the vinyl chloride resin molded sheet. Can be done.
• the composition for forming a resin layer of the present invention may optionally contain a dispersant. Since the resin layer forming composition contains a dispersant, components such as an arbitrary binder can be satisfactorily dispersed in the resin layer forming composition. Therefore, the storage stability of the resin layer forming composition can be enhanced.
• the dispersant is not particularly limited, and a known dispersant can be used, but a surfactant can be particularly preferably used as the dispersant.
• the surfactant include a nonionic surfactant such as polyoxyalkylene alkyl ether; an anionic surfactant such as sodium dodecylbenzene sulfonate; and a cationic surfactant such as dodecyl ammonium chloride. Of these, nonionic surfactants are more preferable.
• the content of the dispersant in the composition for forming the resin layer can be arbitrarily adjusted within the range in which the desired effect of the present invention can be obtained.
• the composition for forming a resin layer is usually obtained by dissolving or dispersing the above-mentioned resin A, an organometallic compound, and other components in a known solvent.
• a known solvent such as water, formic acid, acetic acid, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, diacetone alcohol, dimethyl ether and diethyl ether are used depending on the characteristics of the resin A and the organic metal compound. Can be used. It should be noted that one of these solvents may be used alone, or a plurality of types may be mixed and used.
• the content of the solvent in the composition for forming the resin layer can be appropriately adjusted within the range in which the desired effect of the present invention can be obtained.
• the method for preparing the composition for forming a resin layer of the present invention is not particularly limited as long as the composition containing the resin A and the organometallic compound described above can be obtained.
• a resin layer forming composition can be prepared by adding resin A, an organometallic compound, and any other component to the above-mentioned solvent and mixing them by a method such as stirring.
• the solvent may be appropriately heated or cooled according to the properties of each component to adjust the temperature so that each component can be satisfactorily dissolved or dispersed.
• resin A and, if necessary, a plasticizer and a dispersant for a resin layer are added to the solvent, and the temperature is preferably 40 ° C. or higher and 50 ° C. until the components such as resin A are dissolved or dispersed in the solvent.
• the mixture is stirred and mixed while being heated at the following temperature, and then cooled to preferably 35 ° C. or lower, more preferably room temperature (23 ° C.), and then an organic metal compound and, if necessary, a binder (for example, a urethane-based binder). ) Can be further added and mixed to prepare a composition for forming a resin layer.
• the vinyl chloride resin laminated sheet of the present invention has a vinyl chloride resin molded sheet containing a vinyl chloride resin and a plasticizing agent, and a resin layer L arranged on at least one side of the vinyl chloride resin molded sheet in the thickness direction.
• the layer L is formed by using the above-mentioned composition for forming a resin layer.
• the resin layer L formed by using the above-mentioned resin layer forming composition is arranged on at least one side of the vinyl chloride resin molded sheet in the thickness direction.
• the migration of the plasticizer from the vinyl chloride resin molded sheet can be satisfactorily suppressed, and the resin layer has excellent moisture and heat resistance.
• the vinyl chloride resin laminated sheet of the present invention is suitably used as an automobile interior member, specifically, as a skin of automobile interior parts such as an automobile instrument panel and a door trim, and in particular, an automobile instrument. It is preferably used for the skin of a panel.
• the vinyl chloride resin molded sheet containing the vinyl chloride resin and the plasticizer is obtained by molding the vinyl chloride resin composition containing the vinyl chloride resin and the plasticizer into a sheet shape.
• the vinyl chloride resin composition contains a vinyl chloride resin and a plasticizer, and may further contain various additives and the like.
• vinyl chloride resin contained in the vinyl chloride resin composition
• one kind or two or more kinds of vinyl chloride resin particles can be contained, and optionally one kind or two or more kinds of vinyl chloride resin fine particles.
• the vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.
• the “resin particles” refer to particles having a particle diameter of 30 ⁇ m or more
• the “resin fine particles” refer to particles having a particle diameter of less than 30 ⁇ m.
• the vinyl chloride resin particles usually function as a matrix resin (base material), and the vinyl chloride resin fine particles usually function as a dusting agent (powder fluidity improving agent).
• the vinyl chloride resin particles are preferably produced by a suspension polymerization method, and the vinyl chloride resin fine particles are preferably produced by an emulsion polymerization method.
• the vinyl chloride resin can be produced by any conventionally known production method such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and a bulk polymerization method.
• a vinyl chloride-based copolymer containing a vinyl chloride monomer unit in an amount of preferably 50% by mass or more, more preferably 70% by mass or more is used.
• a monomer (comonomer) copolymerizable with a vinyl chloride monomer that can constitute a vinyl chloride-based copolymer include olefins such as ethylene and propylene; allyl chloride, vinylidene chloride, and the like.
• Halogenized olefins such as vinyl fluoride and ethylene trifluoride; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; allyl-3-chloro-2-oxypropyl Allyl ethers such as ethers and allylglycidyl ethers; unsaturated carboxylic acids such as acrylic acid, maleic acid, itaconic acid, -2-hydroxyethyl acrylate, methyl methacrylate, monomethyl maleate, diethyl maleate, maleic anhydride, etc.
• carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate
• vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether
• allyl-3-chloro-2-oxypropyl Allyl ethers such as ethers and allylglycidyl ethers
• unsaturated carboxylic acids
• ester or its acid anhydrides unsaturated nitriles such as acrylonitrile, methacrylonitrile; acrylamides such as acrylamide, N-methylol acrylamide, acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropyltrimethylammonium chloride; Allylamines such as allylamine benzoate and diallyldimethylammonium chloride and derivatives thereof; and the like.
• the monomers exemplified above are only a part of the co-monomono, and the co-monomono is "Polyvinyl Chloride" edited by the Vinyl Subcommittee of the Kinki Chemical Association, Nikkan Kogyo Shimbun (1988) No. 75- Various monomers exemplified on page 104 can be used. Only one kind of these comonomers may be used, or two or more kinds may be used.
• the vinyl chloride resin includes resins such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, and chlorinated polyethylene, and (1) vinyl chloride or (1) vinyl chloride. 2) A resin obtained by graft-polymerizing vinyl chloride and the co-monomer is also included.
• (meth) acrylic means acrylic and / or methacrylic.
• the SP value of the polymer used as the vinyl chloride resin is preferably 8 (cal / cm 3 ) 1/2 or more, more preferably 9 (cal / cm 3 ) 1/2 or more, and 11 preferably (cal / cm 3) is 1/2 or less, more preferably 10 (cal / cm 3) 1/2 or less.
• the SP value of the polymer used as the vinyl chloride resin is within the above-mentioned predetermined range, the migration of the plasticizer from the vinyl chloride resin molded sheet can be further suppressed.
• the vinyl chloride resin composition further contains a plasticizer. If the vinyl chloride resin composition does not contain a plasticizer, a vinyl chloride resin molded sheet cannot be satisfactorily obtained using the vinyl chloride resin composition.
• the "plasticizer” used in the vinyl chloride resin composition is different from the “plasticizer for resin layer” that can be used in the above-mentioned composition for forming a resin layer (that is, can be contained in the resin layer L described later). It is an ingredient.
• plasticizer does not mean “plasticizer for resin layer” that can be contained in the resin layer L, but “plasticizer” used for the vinyl chloride resin composition. It shall refer to the “agent”, that is, the "plasticizer” contained in the vinyl chloride resin molded sheet.
• the content of the plasticizer is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and further preferably 92 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. It is more preferably 97 parts by mass or more, more preferably 200 parts by mass or less, further preferably 150 parts by mass or less, and further preferably 100 parts by mass or less.
• the content of the plasticizer is equal to or higher than the above lower limit, excellent flexibility can be imparted to the vinyl chloride resin composition, for example, it can be easily processed into a vinyl chloride resin molded sheet, and the obtained vinyl chloride resin molded sheet has a low temperature. This is because good tensile elongation underneath can be imparted.
• the content of the plasticizer is not more than the above upper limit, the stickiness of the surface of the obtained vinyl chloride resin molded sheet can be further suppressed and the surface slipperiness can be further enhanced.
• plasticizer examples include the following primary plasticizers and secondary plasticizers.
• primary plasticizers trimethyl trimellitic acid, triethyl trimellitic acid, tri-n-propyl trimellitic acid, tri-n-butyl trimellitic acid, tri-n-pentyl trimellitic acid, tri-n trimellitic acid -Hexyl, tri-n-heptyl trimellitic acid, tri-n-octyl trimellitic acid, di-n-octyl-mono-n-decyl trimellitic acid, mono-n-octyl-di-n-decyl trimellitic acid , Trimellitic acid tri-n-nonyl, trimellitic acid tri-n-decyl, trimellitic acid tri-n-undecyl, trimellitic acid tri-n-dodecyl, trimellitic acid tri-n-tridecyl, trimellitic acid tri -N
• Trimellitic acid ester [Note that these trimellitic acid esters may consist of a single compound or may be a mixture. ]; Trimellitic acid tri-i-propyl, trimellitic acid tri-i-butyl, trimellitic acid tri-i-pentyl, trimellitic acid tri-i-hexyl, trimellitic acid tri-i-heptyl, trimellitic acid tri- i-octyl, trimellitic acid tri- (2-ethylhexyl), trimellitic acid tri-i-nonyl, trimellitic acid tri-i-decyl, trimellitic acid tri-i-undecyl, trimellitic acid tri-i-dodecyl , Trimellitic acid tri-i-tridecyl, trimellitic acid tri-i-tetradecyl, trimellitic acid tri-i-pentadecyl, trimellitic acid tri-i-hexadecyl, trimellitic acid tri-i-
• trimellitic acid esters may be composed of a single compound or may be a mixture.
• Tetramethyl pyromellitic acid Tetramethyl pyromellitic acid, tetraethyl pyromellitic acid, tetra-n-propyl pyromellitic acid, tetra-n-butyl pyromellitic acid, tetra-n-pentyl pyromellitic acid, tetra-n-hexyl pyromellitic acid, pyromellitic acid Tetra-n-heptyl, tetra-n-octyl pyromellitic acid, tetra-n-nonyl pyromellitic acid, tetra-n-decyl pyromellitic acid, tetra-n-undecyl pyromellitic acid, tetra-n-dodecyl pyromellitic acid, tetra
• a linear pyromellitic acid ester in which the alkyl group constituting the ester is linear may be composed of a single compound or a mixture.
• Branched pyromellitic acid ester [Note that these pyromellitic acid esters may be composed of a single compound or may be a mixture. ]; Didimethylphthalate, diethylphthalate, dibutylphthalate, di- (2-ethylhexyl) phthalate, di-n-octylphthalate, diisobutylphthalate, diheptylphthalate, diphenylphthalate, diisodecylphthalate, ditridecylphthalate, diundecylphthalate, dibenzylphthalate, Phtalic acid derivatives such as butylbenzylphthalate, dinonylphthalate, dicyclohexylphthalate; Isophthalic acid derivatives such as dimethylisophthalate, di- (2-ethylhexyl) isophthalate, diisooctylisophthalate; Tetrahydrophthalic acid derivatives such as di- (2-ethylhe
• Glycol derivative such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate; Epoxy derivatives such as diisodecyl epoxyhexahydrophthalate, epoxytriglyceride, octyl oxylated oleate, decyl epoxidized oleate; Polyester-based plasticizers such as adipic acid-based polyester, sebacic acid-based polyester, and phthalic acid-based polyester; And so on.
• examples of the so-called secondary plasticizer include fatty acid esters of glycols such as chlorinated paraffin and triethylene glycol dicaprelate, butyl epoxy stearate, phenyloleate, and methyl dihydroabietic acid.
• plasticizers only one type of these plasticizers may be used, and for example, two or more types such as a primary plasticizer and a secondary plasticizer may be used in combination.
• a secondary plasticizer it is preferable to use the secondary plasticizer in combination with a primary plasticizer having an equal mass or more.
• the trimellitic acid ester and / or the trimellitic acid ester from the viewpoint of improving the moldability of the vinyl chloride resin composition, it is preferable to use the trimellitic acid ester and / or the trimellitic acid ester, and the trimellitic acid ester is used. It is more preferable to use a linear trimellitic acid ester, and it is further preferable to use a linear trimellitic acid ester having two or more alkyl groups having different carbon atoms in the molecule. Further, the alkyl group preferably has 8 to 10 carbon atoms, and more preferably the alkyl group is an n-octyl group or an n-decyl group. Then, it is preferable to further use epoxidized soybean oil together with the above-mentioned trimellitic acid ester.
• the SP value of the plasticizer used in the vinyl chloride resin composition is preferably 7 (cal / cm 3 ) 1/2 or more, and more preferably 8 (cal / cm 3 ) 1/2 or more. , 12 (cal / cm 3 ) 1/2 or less, and more preferably 10 (cal / cm 3 ) 1/2 or less.
• the SP value of the plasticizer used as the vinyl chloride resin is within the above-mentioned predetermined range, the migration of the plasticizer from the vinyl chloride resin molded sheet can be further suppressed.
• the vinyl chloride resin composition may further contain various additives in addition to the above-mentioned components.
• the additive is not particularly limited, and is a lubricant such as silicone oil; a stabilizer such as perchloric acid-treated hydrotalcite, zeolite, ⁇ -diketone, fatty acid metal salt; a mold release agent; other than the above-mentioned vinyl chloride resin fine particles. Dusting agents; and other additives; etc.
• silicone oil examples include ether-modified silicone oil, fatty acid amide-modified silicone oil, and unmodified silicone oil.
• the content of the silicone oil is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and 0.15 part by mass with respect to 100 parts by mass of the vinyl chloride resin. It is more preferably 1.5 parts by mass or less, more preferably 1.0 part by mass or less, further preferably 0.5 part by mass or less, and 0.4 mass by mass. It is more preferable that the amount is less than or equal to a part. This is because when the content of the silicone oil is at least the above lower limit, the stickiness of the surface of the vinyl chloride resin molded sheet can be sufficiently reduced and the surface slipperiness can be improved.
• the content of the silicone oil is not more than the above upper limit, for example, even when the vinyl chloride resin molding sheet is continuously molded, the surface of the molding die or the like may be formed due to the excessive amount of the silicone oil. This is because it can be suppressed from being contaminated.
• Perchloric acid-treated hydrotalcite- Perchloric acid-treated hydrotalcites which can be contained in vinyl chloride resin compositions, are, for example, added hydrotalcite in a dilute aqueous solution of perchloric acid, stirred, and then filtered, dehydrated or dried as needed. by at least partially perchlorate anions of carbonic acid anion in hydrotalcite (CO 3 2-) - by (perchlorate anion 2 moles per carbonate anion 1 mole substituted) substituted by (ClO 4) , Can be easily produced as a perchloric acid-introduced hydrotalcite.
• the molar ratio of the hydrotalcite to the perchloric acid can be arbitrarily set, but in general, 0.1 mol or more and 2 mol or less of perchloric acid is preferable with respect to 1 mol of hydrotalcite.
• the substitution rate of the carbonate anion with the perchlorate anion in the untreated (unsubstituted without introducing the perchlorate anion) hydrotalcite is preferably 50 mol% or more, more preferably 70 mol%. Above, more preferably 85 mol% or more.
• the substitution rate of the carbonate anion with the perchlorate anion in the untreated (unsubstituted hydrotalcite without introducing the perchlorate anion) is preferably 95 mol% or less.
• the vinyl chloride resin molded sheet is easier because the substitution rate of the carbonate anion in the untreated (unsubstituted hydrotalcite without perchlorate anion) with the perchlorate anion is within the above range. This is because it can be manufactured in.
• Hydrotalsite is a non - stoichiometric compound represented by the general formula: [Mg 1-x Al x (OH) 2 ] x + [(CO 3 ) x / 2 ⁇ mH 2 O] x- , and is positively charged.
• x is a number in the range greater than 0 and 0.33 or less.
• Natural hydrotalcite is a Mg 6 Al 2 (OH) 16 CO 3 ⁇ 4H 2 O.
• the synthetic hydrotalcite Mg 4.5 Al 2 (OH) 13 CO 3 ⁇ 3.5H 2 O are commercially available.
• a method for synthesizing synthetic hydrotalcite is described in, for example, Japanese Patent Application Laid-Open No. 61-174270.
• the content of the perchloric acid-treated hydrotalcite is not particularly limited, and is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the vinyl chloride resin. 7 parts by mass or less is preferable, and 6 parts by mass or less is more preferable.
• the content of the perchloric acid-treated hydrotalcite is within the above range, the vinyl chloride resin molded sheet obtained by molding the vinyl chloride resin composition can maintain better tensile elongation at low temperature. Is.
• the vinyl chloride resin composition may contain zeolite as a stabilizer.
• Zeolites have the general formula: M x / n ⁇ [(AlO 2 ) x ⁇ (SiO 2 ) y ] ⁇ zH 2 O (in the general formula, M is a metal ion having a valence of n, and x + y is a tetrahedral per lattice. It is a compound represented by the number of bodies, z is the number of moles of water).
• Examples of the type of M in the general formula include monovalent or divalent metals such as Na, Li, Ca, Mg, and Zn, and mixed types thereof.
• the content of zeolite is not particularly limited, and is preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin.
• ⁇ -diketone is used to more effectively suppress fluctuations in the initial color tone of the vinyl chloride resin molded sheet obtained by molding the vinyl chloride resin composition.
• Specific examples of the ⁇ -diketone include dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane and the like.
• One of these ⁇ -diketones may be used alone, or two or more thereof may be used in combination.
• the content of ⁇ -diketone is not particularly limited, and is preferably 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin.
• the fatty acid metal salt that can be contained in the vinyl chloride resin composition is not particularly limited, and may be any fatty acid metal salt. Among them, a monovalent fatty acid metal salt is preferable, a monovalent fatty acid metal salt having 12 to 24 carbon atoms is more preferable, and a monovalent fatty acid metal salt having 15 to 21 carbon atoms is further preferable. Specific examples of fatty acid metal salts include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, 2-ethyl.
• a metal capable of generating a polyvalent cation is preferable, a metal capable of generating a divalent cation is more preferable, and a divalent cation in the third to sixth cycles of the periodic table is preferable.
• a metal capable of producing a divalent cation is particularly preferable, and a metal capable of producing a divalent cation in the fourth cycle of the periodic table is particularly preferable.
• the most preferred fatty acid metal salt is zinc stearate.
• the content of the fatty acid metal salt is not particularly limited, and is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, and 5 part by mass with respect to 100 parts by mass of the vinyl chloride resin. It is preferably parts or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less. This is because when the content of the fatty acid metal salt is within the above range, the value of the color difference of the vinyl chloride resin molded sheet obtained by molding the vinyl chloride resin composition can be reduced.
• the release agent is not particularly limited, and examples thereof include 12-hydroxystearic acid-based lubricants such as 12-hydroxystearic acid, 12-hydroxystearic acid ester, and 12-hydroxystearic acid oligomer.
• the content of the release agent is not particularly limited, and may be 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin.
• dusting agents other than the vinyl chloride resin fine particles that can be contained in the vinyl chloride resin composition include inorganic fine particles such as calcium carbonate, talc, and aluminum oxide; polyacrylonitrile resin fine particles, poly (meth) acrylate resin fine particles. , Polystyrene resin fine particles, polyethylene resin fine particles, polypropylene resin fine particles, polyester resin fine particles, polyamide resin fine particles and other organic fine particles; Of these, inorganic fine particles having an average particle size of 10 nm or more and 100 nm or less are preferable.
• the content of the other dusting agent is not particularly limited, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, based on 100 parts by mass of the vinyl chloride resin.
• Other dusting agents may be used alone or in combination of two or more, or may be used in combination with the above-mentioned vinyl chloride resin fine particles.
• additives that can be contained in the vinyl chloride resin composition are not particularly limited, and are, for example, perchloric acid compounds other than colorants (pigments), impact resistance improvers, and perchloric acid-treated hydrotalcites.
• Epoxy vegetable oil-based heat stabilizers such as (sodium perchlorate, potassium perchlorate, etc.), epoxy soybean oil, epoxy linseed oil, etc .; antioxidants, antifungal agents, flame retardants, antistatic agents, fillers , Light stabilizer, foaming agent and the like.
• the colorant examples are quinacridone pigment, perylene pigment, polyazo condensation pigment, isoindolinone pigment, copper phthalocyanine pigment, titanium white, and carbon black.
• One or more pigments are used.
• Quinacridone pigments are obtained by treating p-phenylenedianthranilic acids with concentrated sulfuric acid and exhibit a yellowish red to reddish purple hue.
• quinacridone pigments are quinacridone red, quinacridone magenta, and quinacridone violet.
• the perylene-based pigment is obtained by a condensation reaction of perylene-3,4,9,10-tetracarboxylic dianhydride and an aromatic primary amine, and exhibits hues of red to purplish red and brown.
• perylene-based pigments are perylene red, perylene orange, perylene maroon, perylene vermilion, and perylene bordeaux.
• the polyazo condensed pigment is obtained by condensing the azo dye in a solvent to increase the molecular weight, and exhibits the hues of yellow and red pigments.
• Specific examples of the polyazo condensed pigment are polyazo red, polyazo yellow, chromoftal orange, chromoftal red, and chromophthal scarlet.
• the isoindolinone pigment is obtained by a condensation reaction of 4,5,6,7-tetrachloroisoindolinone and an aromatic primary diamine, and exhibits a greenish yellow to red and brown hues.
• isoindolinone pigment is isoindolinone yellow.
• Copper phthalocyanine pigments are pigments in which copper is coordinated with phthalocyanines, and exhibit a hue from yellowish green to bright blue.
• Specific examples of copper phthalocyanine pigments are phthalocyanine green and phthalocyanine blue.
• Titanium white is a white pigment made of titanium dioxide, which has a large hiding power and is available in anatas type and rutile type.
• Carbon black is a black pigment containing carbon as a main component and containing oxygen, hydrogen, and nitrogen. Specific examples of carbon black are thermal black, acetylene black, channel black, furnace black, lamp black, and bone black.
• the impact resistance improving agent examples include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, and chlorosulfonated polyethylene.
• the vinyl chloride resin composition one kind or two or more kinds of impact resistance improving agents can be used.
• the impact resistance improver is dispersed as a non-uniform phase of fine elastic particles in the vinyl chloride resin composition.
• the chains and polar groups graft-polymerized on the elastic particles are compatible with the vinyl chloride resin, and the impact resistance of the vinyl chloride resin molded sheet obtained by molding the vinyl chloride resin composition is improved.
• antioxidants are phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants such as phosphite, and the like.
• antifungal agent examples include an aliphatic ester antifungal agent, a hydrocarbon antifungal agent, an organic nitrogen antifungal agent, an organic nitrogen sulfur antifungal agent, and the like.
• flame retardants are halogen-based flame retardants; phosphorus-based flame retardants such as phosphoric acid esters; inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide; and the like.
• antistatic agents include anionic antistatic agents such as fatty acid salts, higher alcohol sulfate esters, and sulfonates; cationic antistatic agents such as aliphatic amine salts and quaternary ammonium salts; polyoxyethylene alkyl.
• anionic antistatic agents such as fatty acid salts, higher alcohol sulfate esters, and sulfonates
• cationic antistatic agents such as aliphatic amine salts and quaternary ammonium salts
• polyoxyethylene alkyl Nonionic antistatic agents such as ethers and polyoxyethylene alkylphenol ethers; etc.
• fillers are silica, talc, mica, calcium carbonate, clay and the like.
• light stabilizers are ultraviolet absorbers such as benzotriazole-based, benzophenone-based, and nickel-chelate-based light stabilizers, and hindered amine-based light stabilizers.
• foaming agent examples include azo compounds such as azodicarboxylic amide and azobisisobutyronitrile, nitroso compounds such as N, N'-dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, and p, p-oxybis (benzene).
• Organic foaming agents such as sulfonylhydrazide compounds such as sulfonylhydrazide); volatile hydrocarbon compounds such as benzene gas, carbon dioxide gas, water and pentane, and gas-based foaming agents such as microcapsules containing them; and the like.
• the vinyl chloride resin composition can be prepared by mixing the above-mentioned components without particular limitation.
• the method of mixing the vinyl chloride resin, the plasticizer, and various additives further used as needed is not particularly limited, and for example, a dusting agent containing vinyl chloride resin fine particles is used. Examples thereof include a method in which the components to be removed are mixed by a dry blend, and then a dusting agent is added and mixed.
• a Henschel mixer for the dry blend.
• the temperature at the time of 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 vinyl chloride resin molded sheet is obtained by molding the above-mentioned vinyl chloride resin composition into a sheet shape.
• the method for molding the vinyl chloride resin composition is not particularly limited, and a known molding method can be used, but powder molding is preferable, and powder slush molding is more preferable.
• 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, preferably 300 ° C. or lower, and preferably 280 ° C. The following is more preferable.
• the vinyl chloride resin composition of the present invention is sprinkled on a mold in the above temperature range, left for 5 seconds or more and 30 seconds or less, then the excess vinyl chloride resin composition is shaken off, and further, under an arbitrary temperature. , Leave it for 30 seconds or more and 3 minutes or less. Then, the mold is cooled to 10 ° C. or higher and 60 ° C. or lower, and the obtained vinyl chloride resin molded sheet is removed from the mold. Then, the demolded vinyl chloride resin molded sheet is obtained as, for example, a sheet-shaped molded body in the shape of a mold.
• the thickness of the obtained vinyl chloride resin molded sheet is not particularly limited, but is preferably 0.8 mm or more, more preferably 1.0 mm or more, and preferably 1.6 mm or less. It is more preferably 0.4 mm or less.
• the vinyl chloride resin laminated sheet of the present invention has a predetermined resin layer L arranged on at least one side in the thickness direction of the vinyl chloride resin molded sheet described above.
• the predetermined resin layer L may be arranged on both sides of the vinyl chloride resin molded sheet in the thickness direction, or may be arranged only on one side of the vinyl chloride resin molded sheet in the thickness direction. Usually, it is arranged only on one side in the thickness direction of the vinyl chloride resin molded sheet.
• the surface of one side or both sides of the vinyl chloride resin laminated sheet in the thickness direction may be partially composed of a predetermined resin layer L, or may be entirely composed of a predetermined resin layer L. ..
• the predetermined resin layer L is usually directly adhered to the vinyl chloride resin molded sheet.
• the predetermined resin layer L is formed by using the above-mentioned resin layer forming composition.
• the organometallic compound contained in the resin layer forming composition is consumed in the reaction of cross-linking the polymers constituting the resin A, but a part of the organometallic compound remains in the formed resin layer L. You may.
• the resin A contained in the resin layer forming composition is also contained in the resin layer L, but in the resin layer L, at least a part of the polymers constituting the resin A are organic metals. It is cross-linked by the structure derived from the compound.
• other components other than the resin A and the organic metal compound contained in the composition for forming the resin layer are also contained in the resin layer L.
• the solvent contained in the resin layer forming composition is removed by a drying step or the like described later, the solvent is not usually contained in the formed resin layer L, but the desired effect of the present invention can be obtained. It is assumed that the solvent may remain in the resin layer L within the obtained range.
• the plasticizer in the vinyl chloride resin molded sheet becomes the other resin member. It is considered that the transition reduces the amount of the plasticizer in the vinyl chloride resin molded sheet and causes deterioration of the vinyl chloride resin molded sheet.
• the vinyl chloride resin laminated sheet of the present invention having the resin layer L containing the resin A whose SP value is in the predetermined range, the resin is sandwiched between the vinyl chloride resin molded sheet and another resin member or the like.
• the plasticizer By interposing the layer L, it becomes difficult for the plasticizer to pass through the resin layer L from the vinyl chloride resin molded sheet and reach other resin members and the like, and as a result, the plasticizer from the vinyl chloride resin molded sheet. It is presumed that the migration of plastics can be suppressed well. Further, although the moisture and heat resistance of the resin A contained in the resin layer forming composition is usually low, the resin A is formed in the resin layer L formed by further adding an organic metal compound to the resin layer forming composition. Since at least a part of the constituent polymers is crosslinked by a structure derived from an organic metal compound, the resin layer L becomes insoluble in a solvent such as water, which can enhance the moisture and heat resistance of the resin layer L. ..
• the thickness of the resin layer L is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 5 ⁇ m or more, particularly preferably 10 ⁇ m or more, and 1000 ⁇ m or less. It is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
• the thickness of the resin layer L is 0.1 ⁇ m or more, the migration of the plasticizer from the vinyl chloride resin molded sheet can be further suppressed.
• the thickness of the resin layer L is 1000 ⁇ m or less, the weight of the entire resin layer L can be reduced.
• the resin layer L is formed on at least one side in the thickness direction of the vinyl chloride resin molded sheet.
• a method of forming the resin layer L on at least one side in the thickness direction of the vinyl chloride resin molded sheet for example, the following method can be mentioned. 1) A method in which the composition for forming a resin layer is applied to at least one side of a vinyl chloride resin molded sheet and then dried; 2) A method of immersing a vinyl chloride resin molded sheet in the resin layer forming composition and then drying it; and 3) Applying the resin layer forming composition on a release base material and drying to obtain the resin layer L.
• the method 1) is particularly preferable because it is easy to control the layer thickness of the resin layer L.
• a step of applying the resin layer forming composition to at least one side of the vinyl chloride resin molded sheet (coating step) and a step of drying the applied resin layer forming composition are performed.
• the step of forming the resin layer L (resin layer forming step) is included.
• the method of applying the resin layer forming composition to at least one side of the vinyl chloride resin molded sheet in the coating step is not particularly limited, and is, for example, a bar coating method, a doctor blade method, a reverse roll method, or a direct roll. Examples include a method, a gravure method, an extrusion method, a brush coating method, and a spray coating method. Above all, it is preferable to use the spray coating method because it is easy to handle when the vinyl chloride resin molded sheet has a complicated structure such as a curved surface shape.
• examples of the method for drying the applied resin layer forming composition include drying with warm air, hot air, and low humidity air, vacuum drying, and drying with irradiation with infrared rays or electron beams. Be done.
• the applied composition for forming a resin layer By drying the applied composition for forming a resin layer, the resin A and the organometallic compound undergo a cross-linking reaction, and the polymers constituting the resin A are cross-linked via the organometallic compound. Thereby, the moisture and heat resistance of the formed resin layer L can be enhanced.
• the drying conditions are not particularly limited, but the drying temperature is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, further preferably 30 ° C.
• drying temperature is equal to or higher than the above lower limit, the drying efficiency is improved and the crosslinking reaction is promoted.
• the drying temperature is not more than the above upper limit, pinholes do not occur in the resin layer and a uniform resin layer is formed. Further, the drying time can be arbitrarily adjusted within a range in which the desired effect of the present invention can be obtained.
• the method for producing a vinyl chloride resin laminated sheet of the present invention includes a coating step of applying the above-mentioned resin layer forming composition to at least one side in the thickness direction of a vinyl chloride resin molded sheet containing a vinyl chloride resin and a plasticizing agent. It is characterized by including a resin layer forming step of drying the applied resin layer forming composition to form a resin layer L. According to the method for producing a vinyl chloride resin laminated sheet of the present invention, the transfer of the plasticizer from the vinyl chloride resin molded sheet can be satisfactorily suppressed, and the vinyl chloride resin laminated sheet having excellent moisture and heat resistance of the resin layer L is produced. be able to.
• the vinyl chloride resin molded sheet used in the method for producing the vinyl chloride resin laminated sheet of the present invention the vinyl chloride resin molded sheet described above in the section of "vinyl chloride resin laminated sheet” can be used.
• the resin layer forming composition used in the method for producing the vinyl chloride resin laminated sheet of the present invention the above-mentioned resin layer forming composition of the present invention can be used.
• the coating step and the resin layer forming step in the method for producing the vinyl chloride resin laminated sheet of the present invention for example, the coating step and the coating step included in the method for forming the resin layer L described above in the section of "vinyl chloride resin laminated sheet" Each resin layer forming step can be carried out.
• the laminated body of the present invention has a foamed polyurethane molded body and the vinyl chloride resin laminated sheet described above.
• the laminated body of the present invention has a structure in which the above-mentioned predetermined resin layer L is interposed between the foamed polyurethane molded body and the vinyl chloride resin molded sheet.
• the foamed polyurethane molded body is lined with a resin layer L interposed below one side of the vinyl chloride resin laminated sheet, and the foamed polyurethane molded body and the vinyl chloride resin laminated sheet are adjacent to each other in the stacking direction ( That is, the foamed polyurethane molded body and the vinyl chloride resin molded sheet are laminated in the stacking direction via the resin layer L).
• the laminate of the present invention since the resin layer L is interposed between the urethane foam molded body and the vinyl chloride resin molded sheet, the migration of the plasticizer from the vinyl chloride resin molded sheet is satisfactorily suppressed. And has excellent moisture and heat resistance. Therefore, the laminate of the present invention is suitably used as an automobile interior material for automobile interior parts such as an automobile instrument panel and a door trim, and is particularly preferably used for an automobile instrument panel.
• the laminating method is not particularly limited, and for example, the following method can be used. That is, on the surface of the vinyl chloride resin laminated sheet on the side where the resin layer L is provided, isocyanates and polyols, which are raw materials for the foamed polyurethane molded product, are reacted to carry out polymerization, and polyurethane is polymerized by a known method. The foamed polyurethane molded body is directly formed on the vinyl chloride resin laminated sheet by foaming.
• the SP value of the polyurethane resin constituting the foamed polyurethane molded body is usually 8 (cal / cm 3 ) 1/2 or more, preferably 9 (cal / cm 3 ) 1/2 or more, and usually 12 ( It is cal / cm 3 ) 1/2 or less, preferably 11 (cal / cm 3 ) 1/2 or less.
• ⁇ Thickness of resin layer L> The thickness of the resin layer L was measured by observing the cross section of the resin layer L of the laminates obtained in each Example and Comparative Example with a digital microscope (“VHX-900” manufactured by KEYENCE). Observation of the cross section and measurement of the thickness were carried out at one point each near both long sides of the laminated body and one point near the center on the surface of the laminated body, and the smallest numerical value was taken as the measurement result.
• ⁇ Moisture resistance of resin layer L> A moist heat resistance test was conducted in which the vinyl chloride resin laminated sheets obtained in each Example and Comparative Example were allowed to stand for 300 hours under the conditions of a temperature of 80 ° C. and a humidity of 80% RH. Then, the surface of the vinyl chloride resin laminated sheet on the resin layer L side was visually observed, and the moisture and heat resistance of the resin layer L was evaluated according to the following criteria. The smaller the number of droplets observed, the more difficult it is for the resin layer L to dissolve under high humidity and high temperature conditions, indicating that the resin layer L is excellent in moisture heat resistance. A: The resin layer L is not melted at all, and no droplets are observed. B: The resin layer L is slightly melted, and a small number of droplets are observed. C: The resin layer L is clearly melted, and many droplets are observed.
• High Performance Liquid Chromatograph Analyzer "LC1260-II” manufactured by Agilent. Column: “ZORBAX Eclipse XDB-C8” manufactured by Agilent. Column temperature: 40 ° C Mobile phase A: acetonitrile Mobile phase B: Ion-exchanged water Gradient conditions: 0 min (20% by volume mobile phase B), 2.5 min (0% by volume mobile phase B), 8.0 min (0 volume% mobile phase B) Flow velocity: 1.0 mL / min Detector: Diode Array Detector (DAD) Signal: 254 nm Ref: 360 nm Injection volume: 1 ⁇ m
• Example 1 ⁇ Preparation of vinyl chloride resin composition> Of the ingredients shown in Table 2, the ingredients excluding the plasticizer (trimellitic acid ester), the epoxidized soybean oil as the stabilizer, and the vinyl chloride resin fine particles as the dusting agent were put into a Henschel mixer and mixed. .. Then, when the temperature of the mixture rises to 80 ° C., all of the above plasticizer and epoxidized soybean oil as a stabilizer are added, and the temperature is further raised to dry up (the plasticizer is a vinyl chloride resin). It is a state in which the above mixture is further absorbed by the vinyl chloride resin particles.) Then, when the dried-up mixture was cooled to a temperature of 100 ° C. or lower, vinyl chloride resin fine particles as a dusting agent were added to prepare a vinyl chloride resin composition.
• the plasticizer trimellitic acid ester
• the epoxidized soybean oil as the stabilizer the vinyl chloride resin fine particles as the dusting agent
• ⁇ Formation of vinyl chloride resin molded sheet> The vinyl chloride resin composition obtained above is sprinkled on a textured mold heated to a temperature of 250 ° C., left to stand for an arbitrary time of about 8 to 20 seconds to melt, and then the surplus vinyl chloride resin composition is melted. Was shaken off. Then, the textured mold sprinkled with the vinyl chloride resin composition was allowed to stand in an oven set at a temperature of 200 ° C., and 60 seconds after the standing, the textured mold was cooled with cooling water. .. When the mold temperature was cooled to 40 ° C., a 200 mm ⁇ 300 mm ⁇ 1.2 mm vinyl chloride resin molded sheet was removed from the mold.
• composition for forming resin layer ⁇ Preparation of composition for forming resin layer>
• polyvinyl alcohol as resin A PVA, "JMR-20M” manufactured by Japan Vam & Poval Co., Ltd., saponification degree from polyvinyl acetate: 65%, average degree of polymerization: 400, SP value: 16 .4 (cal / cm 3 ) 1/2 ) 100 parts were added, and heating was started while stirring. The temperature was raised to about 45 ° C., the heating was stopped when the PVA was dissolved, and the mixture was allowed to cool to around room temperature with stirring.
• PVA polyvinyl alcohol as resin A
• a polyol mixture was obtained. Further, a mixed solution was prepared by mixing the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) at a ratio of an isocyanate index of 98. Then, the prepared mixed solution was poured onto the vinyl chloride resin laminated 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 to be sealed for 5 minutes, a polyurethane foam molded product (thickness: 8.78 mm, density: 0.18 g) is adjacent to the vinyl chloride resin laminated sheet (thickness: 1.22 mm) as the skin.
• polymethylene polyphenylene polyisocyanate polymeric MDI
• a laminate lined (laminated) with / cm 3 and SP value: 10.0 (cal / cm 3 ) 1/2 ) was formed in the mold. Then, the formed laminate was taken out from the mold, and the reduction rate of the plasticizer in the vinyl chloride resin molded sheet before and after heating was measured according to the above method. The results are shown in Table 3. The thickness of the resin layer L was measured using the laminated body and found to be 30 ⁇ m.
• Example 2 In the preparation of the resin layer forming composition of Example 1, the amount of dihydroxybis (ammonium lactate) titanium used as the organic metal compound was changed from 4.10 parts to 6.15 parts. In the same manner, a vinyl chloride resin composition, a vinyl chloride resin molded sheet, a resin layer forming composition, a vinyl chloride resin laminated sheet, and a laminated body were produced, and various measurements or evaluations were performed. The results are shown in Table 3. The thickness of the resin layer L was measured and found to be 30 ⁇ m.
• Example 3 In the preparation of the resin layer forming composition of Example 1, the amount of dihydroxybis (ammonium lactate) titanium used as the organic metal compound was changed from 4.10 parts to 12.30 parts. In the same manner, a vinyl chloride resin composition, a vinyl chloride resin molded sheet, a resin layer forming composition, a vinyl chloride resin laminated sheet, and a laminated body were produced, and various measurements or evaluations were performed. The results are shown in Table 3. The thickness of the resin layer L was measured and found to be 30 ⁇ m.
• Example 1 In the production of the vinyl chloride resin laminated sheet of Example 1, the resin layer L was not formed on the surface opposite to the textured surface of the vinyl chloride resin molded sheet (that is, the vinyl chloride resin laminated sheet was not produced). In the formation of the laminate of Example 1, the same as in Example 1 except that the laminate was produced by using the vinyl chloride resin molded sheet having no resin layer L as it is instead of the vinyl chloride resin laminate sheet. To produce a vinyl chloride resin composition, a vinyl chloride resin molded sheet, and a laminate. Then, for the obtained laminate, the reduction rate of the plasticizer in the vinyl chloride resin molded sheet before and after heating was measured. The results are shown in Table 3.
• Example 3 Vinyl chloride in the same manner as in Example 1 except that dihydroxybis (ammonium lactate) titanium as the organic metal compound was not used in the preparation of the resin layer forming composition of Example 1.
• a resin composition, a vinyl chloride resin molded sheet, a resin layer forming composition, a vinyl chloride resin laminated sheet, and a laminated body were produced, and various measurements or evaluations were performed. The results are shown in Table 3. The thickness of the resin layer L was measured and found to be 30 ⁇ m.
• Comparative Example 4 In the preparation of the resin layer forming composition of Comparative Example 2, comparison was made except that the amount of dihydroxybis (ammonium lactate) titanium used as the organic metal compound as the organic metal compound was changed from 0 part to 6.15 parts. In the same manner as in Example 2, a vinyl chloride resin composition, a vinyl chloride resin molded sheet, a resin layer forming composition, a vinyl chloride resin laminated sheet, and a laminated body were produced, and various measurements or evaluations were performed. The results are shown in Table 3. The thickness of the resin layer L was measured and found to be 30 ⁇ m.
• the resin layers of Comparative Examples 2 to 4 formed by using a composition other than the above-mentioned composition for forming a resin layer can satisfactorily suppress the migration of the plasticizer from the vinyl chloride resin molded sheet, but are moisture resistant. It turns out that it is inferior in heat.
• a resin layer forming composition capable of satisfactorily suppressing the migration of a plasticizer from a vinyl chloride resin molded sheet and forming a resin layer having excellent moisture and heat resistance.
• a vinyl chloride resin laminated sheet and a method for producing the same which can satisfactorily suppress the migration of the plasticizer from the vinyl chloride resin molded sheet and have excellent moisture and heat resistance of the resin layer.

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