JP6215685B2 - Vinyl chloride-based resin composition, vinyl chloride-based resin powder slush molded body, resin laminate, and production method thereof - Google Patents

Description

  The present invention relates to a vinyl chloride resin composition, a vinyl chloride resin powder slush molded body, a resin laminate, and a method for producing them, and in particular, to an improvement in characteristics of a vinyl chloride resin powder slush molded body.

  The vinyl chloride resin powder slush molded body is preferably used, for example, for interior parts of automobiles such as instrument panels (see, for example, Patent Documents 1 and 2).

JP 2011-173974 A JP 2012-007026 A

  However, in the conventional vinyl chloride resin powder slush molded body, for example, the problem that the flexibility is impaired by exposure to a relatively high temperature, or the fiber adheres when the surface is wiped with a cloth There was a problem that rubbing marks remained. In particular, when the former problem is suppressed, the latter problem becomes remarkable, and when the latter problem is suppressed, the former problem becomes remarkable.

  The present invention has been made in view of the above problems, and achieves both excellent surface properties and excellent flexibility, a vinyl chloride resin composition, a vinyl chloride resin powder slush molding, a resin laminate, and It is an object to provide these manufacturing methods.

  The vinyl chloride resin composition according to one embodiment of the present invention for solving the above-mentioned problems is a vinyl chloride resin particle having an average particle size of 50 to 500 μm made of a vinyl chloride resin having an average polymerization degree of 1500 or more. 100 parts by weight, 110 to 150 parts by weight of plasticizer, vinyl chloride resin fine particles having an average particle diameter of 0.01 to 50 μm and smaller than the average particle diameter of the vinyl chloride resin particles, and an average particle diameter And 0.5 to 8 parts by weight of modified polyorganosiloxane particles having a size of 0.1 to 100 μm. ADVANTAGE OF THE INVENTION According to this invention, the vinyl chloride resin composition which provides both the outstanding surface characteristic and the outstanding softness | flexibility to a powder slush molded object can be provided.

  A vinyl chloride resin powder slush molded article according to an embodiment of the present invention for solving the above problems is a vinyl chloride resin having an average particle diameter of 50 to 500 μm made of a vinyl chloride resin having an average polymerization degree of 1500 or more. 100 parts by weight of resin particles, 110 to 150 parts by weight of plasticizer, vinyl chloride resin fine particles having an average particle diameter of 0.01 to 50 μm and smaller than the average particle diameter of the vinyl chloride resin particles, and average particles And 0.5 to 8 parts by weight of modified polyorganosiloxane particles having a diameter of 0.1 to 100 μm. ADVANTAGE OF THE INVENTION According to this invention, the vinyl chloride-type resin powder slush molded object provided with both the outstanding surface characteristic and the outstanding softness | flexibility can be provided.

  In order to solve the above problems, a resin laminate according to an embodiment of the present invention includes a vinyl chloride resin layer made of the vinyl chloride resin powder slush molded article, and a polyurethane foam laminated on the vinyl chloride resin layer. And a layer. ADVANTAGE OF THE INVENTION According to this invention, the resin laminated body containing the vinyl chloride-type resin layer provided with both the outstanding surface characteristic and the outstanding softness | flexibility can be provided. Moreover, the said resin laminated body is good also as being an interior material for vehicles.

  The method for producing a vinyl chloride resin composition according to an embodiment of the present invention for solving the above-mentioned problems is a vinyl chloride having an average particle size of 50 to 500 μm made of a vinyl chloride resin having an average degree of polymerization of 1500 or more. 100 parts by weight of resin particles, 110 to 150 parts by weight of plasticizer, vinyl chloride resin particles having an average particle diameter of 0.01 to 50 μm and smaller than the average particle diameter of the vinyl chloride resin particles, and an average And 0.5 to 8 parts by weight of modified polyorganosiloxane particles having a particle size of 0.1 to 100 μm. ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the vinyl chloride-type resin composition which provides both the outstanding surface characteristic and the outstanding softness | flexibility to a powder slush molded object can be provided.

  A method for producing a vinyl chloride resin powder slush molding according to an embodiment of the present invention for solving the above-described problems includes performing powder slush molding of the vinyl chloride resin composition. ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the vinyl chloride resin powder slush molding provided with both the outstanding surface characteristic and the outstanding softness | flexibility can be provided.

  The manufacturing method of the resin laminated body which concerns on one Embodiment of this invention for solving the said subject includes laminating | stacking a foaming polyurethane layer on the vinyl chloride resin layer which consists of the said vinyl chloride resin powder slush molding. It is characterized by that. ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the resin laminated body containing the vinyl chloride-type resin layer provided with both the outstanding surface characteristic and the outstanding softness | flexibility can be provided.

  According to the present invention, it is possible to provide a vinyl chloride resin composition, a vinyl chloride resin powder slush molded article, a resin laminate, and a production method thereof that achieve both excellent surface characteristics and excellent flexibility. .

It is explanatory drawing which shows an example of the result of having evaluated the characteristic of the powder slush molded object manufactured from the mixing | blending of the vinyl chloride resin composition used in the Example which concerns on one Embodiment of this invention, and the said vinyl chloride resin composition. is there. It is explanatory drawing which shows an example of the result of having evaluated the characteristic of the powder slush molded object manufactured from the mixing | blending of the vinyl chloride resin composition used in the comparative example which concerns on one Embodiment of this invention, and the said vinyl chloride resin composition. is there.

  Hereinafter, an embodiment of the present invention will be described. Note that the present invention is not limited to this embodiment.

  The vinyl chloride resin composition (this composition) according to the present embodiment has 100 parts by weight of vinyl chloride resin particles having an average particle size of 50 to 500 μm made of a vinyl chloride resin having an average degree of polymerization of 1500 or more, 110 to 150 parts by weight of plasticizer, vinyl chloride resin fine particles having an average particle diameter of 0.01 to 50 μm and smaller than the average particle diameter of the vinyl chloride resin particles, and an average particle diameter of 0.1 to 100 μm And 0.5-8 parts by weight of modified polyorganosiloxane particles.

  The vinyl chloride resin powder slush molded body (this molded body) according to the present embodiment has 100 parts by weight of vinyl chloride resin particles having an average particle diameter of 50 to 500 μm made of a vinyl chloride resin having an average degree of polymerization of 1500 or more. 110 to 150 parts by weight of a plasticizer, vinyl chloride resin fine particles having an average particle diameter of 0.01 to 50 μm and smaller than the average particle diameter of the vinyl chloride resin particles, and an average particle diameter of 0.1 And 0.5 to 8 parts by weight of the modified polyorganosiloxane particles that are ˜100 μm.

  This composition is a vinyl chloride resin composition used for powder slush molding. The molded body is a vinyl chloride resin molded body produced by powder slush molding of a vinyl chloride resin composition.

When a cross section of a vinyl chloride resin powder slush molding (for example, a sheet manufactured by powder slush molding of a vinyl chloride resin composition) is observed, the vinyl chloride resin used for powder slush molding at the time of manufacture is observed. By confirming the interface between the particles, it can be confirmed that the molded body is manufactured by powder slush molding (the molded body is a powder slush molded body).

  Further, when the cross section of the vinyl chloride resin powder slush molding is observed, for example, the vinyl chloride resin particles used in the powder slush molding at the time of production and the modified polyorganosiloxane adhered to the surface of the vinyl chloride resin particles The presence of particles can also be confirmed.

  The vinyl chloride resin constituting the vinyl chloride resin particles (PVC particles) is not particularly limited as long as the average degree of polymerization is 1500 or more. That is, this vinyl chloride resin is a vinyl chloride homopolymer and / or copolymer having an average degree of polymerization of 1500 or more.

  The average degree of polymerization of the vinyl chloride resin is not particularly limited as long as it is 1500 or more. For example, it may be 1700 or more. Although the upper limit of the average degree of polymerization of the vinyl chloride resin is not particularly limited, the average degree of polymerization may be, for example, 4000 or less (for example, 1500 to 4000 or 1700 to 4000), and 3000 or less (for example, 1500 to 3000 or 1700 to 3000). That the average degree of polymerization of the vinyl chloride resin constituting the PVC particles is in the above range particularly contributes to the provision of the molded article with excellent flexibility.

  The vinyl chloride resin constituting the PVC particles may have a gel content insoluble in tetrahydrofuran of less than 5% by weight. The amount of gel contained in the vinyl chloride resin may be 3% by weight or less, or 1% by weight or less. The amount of gel contained in the vinyl chloride resin may be 0% by weight. That is, in this case, the vinyl chloride resin is an uncrosslinked vinyl chloride resin. That the gel content contained in the vinyl chloride resin constituting the PVC particles is in the above-described range contributes particularly to the provision of the molded article with excellent flexibility.

  The average particle diameter of the PVC particles is not particularly limited as long as it is within a range of 50 to 500 μm, but may be, for example, 100 μm or more (for example, 100 to 500 μm), or 150 μm or more (for example, 150 to 500 μm). It is good also as being. Moreover, the average particle diameter of PVC particle | grains is good also as being 300 micrometers or less (for example, 50-300 micrometers), for example, and good also as being 200 micrometers or less (for example, 50-200 micrometers). Moreover, the average particle diameter of PVC particle | grains is good also as being 100-300 micrometers, for example, and good also as being 100-200 micrometers. The average particle diameter of the PVC particles is measured according to JIS K7369: 2009.

  In addition, the PVC particles may be, for example, particles having an average particle diameter as described above and having a particle diameter of 500 μm or less. Moreover, the PVC particles are porous particles. PVC particles are produced, for example, by suspension polymerization.

  The amount of PVC particles contained in the present composition and the present molded body is not particularly limited, and may be, for example, 25% by weight or more, or 30% by weight or more. Moreover, although the upper limit of the quantity of the PVC particle contained in this composition and this molded object is not restricted in particular, the quantity of the said PVC particle is good also as being 60 weight% or less, for example. That is, the present composition and the present molded body may contain, for example, 25 to 60% by weight of PVC particles or 30 to 60% by weight.

  The plasticizer is not particularly limited as long as it is used as a plasticizer for a vinyl chloride resin. That is, the plasticizer includes, for example, trimellitic acid plasticizer, aliphatic plasticizer, pyromellitic acid plasticizer, phthalic acid plasticizer, polyester plasticizer, epoxy plasticizer, and phosphoric acid plasticizer. It is good also as being 1 or more types selected from the group which consists of.

  The amount of the plasticizer contained in the present composition and the present molded body is not particularly limited as long as it is within the range of 110 to 150 parts by weight with respect to 100 parts by weight of the PVC particles, but is, for example, 120 to 150 parts by weight. It is good also as it being 120 weight part or more and less than 150 weight part, and good also as being 120-145 weight part. That the content of the plasticizer is not less than the above-described lower limit value contributes particularly to the provision of the molded article with excellent flexibility. Further, the plasticizer content being equal to or less than the above upper limit value contributes particularly to the provision of excellent surface characteristics of the molded article.

Vinyl chloride resin fine particles (paste PVC) are fine particles made of vinyl chloride resin. The vinyl chloride resin constituting the paste PVC is not particularly limited, and is a homopolymer and / or copolymer of vinyl chloride. The average degree of polymerization of the vinyl chloride resin is not particularly limited, and may be 500 or more, for example, or 800 or more. Moreover, although the upper limit of the average degree of polymerization of this vinyl chloride resin is not particularly limited, the average degree of polymerization may be, for example, 2000 or less, or 1500 or less. More specifically, the average degree of polymerization of the vinyl chloride resin may be, for example, 500 to 2000 or 800 to 1500. Moreover, the average polymerization degree of the vinyl chloride resin constituting the paste PVC may be smaller than the average polymerization degree of the vinyl chloride resin constituting the PVC particles.

  The average particle size of the paste PVC is not particularly limited as long as it is in the range of 0.01 to 50 μm and smaller than the average particle size of the PVC particles. For example, it is 0.1 μm or more (for example, 0.1 to 50 μm). It is good also as being 0.5 micrometer or more (for example, 0.5-50 micrometers). Moreover, the average particle diameter of paste PVC is good also as being 20 micrometers or less (for example, 0.01-20 micrometers), for example, and good also as being 10 micrometers or less (for example, 0.01-20 micrometers). Moreover, the average particle diameter of paste PVC is good also as being 0.1-20 micrometers, for example, and good also as being 0.5-10 micrometers. The average particle size of the paste PVC is measured according to JIS K7369: 2009.

  Since the average particle size of the paste PVC is smaller than the average particle size of the PVC particles, the paste PVC is disposed so as to cover a part of the surface of the PVC particles. The paste PVC may be, for example, fine particles having the above average particle diameter and a particle diameter of 50 μm or less. The paste PVC may be non-porous particles. The paste PVC is produced, for example, by suspension polymerization, micro suspension polymerization, emulsion polymerization or the like.

  The amount of paste PVC contained in the present composition and the present molded body is not particularly limited. For example, it may be 5 parts by weight or more with respect to 100 parts by weight of PVC particles, and is 10 parts by weight or more. It is good as well. Moreover, the amount of paste PVC contained in the present composition and the present molded body may be, for example, 40 parts by weight or less, or 30 parts by weight or less with respect to 100 parts by weight of PVC particles. . More specifically, the present composition and the present molded body may contain, for example, 5 to 40 parts by weight of paste PVC or 10 to 30 parts by weight with respect to 100 parts by weight of PVC particles.

  The modified polyorganosiloxane constituting the modified polyorganosiloxane particles (modified POS particles) is not particularly limited as long as it is a polyorganosiloxane chemically modified by introducing a functional group.

  That is, the modified polyorganosiloxane constituting the modified POS particles is, for example, from the group consisting of acrylic modified polyorganosiloxane, epoxy modified polyorganosiloxane, amino modified polyorganosiloxane, carboxyl modified polyorganosiloxane, and alcohol modified polyorganosiloxane. It may be one or more selected, preferably one or more selected from the group consisting of acrylic-modified polyorganosiloxane, carboxyl-modified polyorganosiloxane, and alcohol-modified polyorganosiloxane, particularly preferably acrylic-modified. Polyorganosiloxane.

  Acrylic-modified polyorganosiloxane, carboxyl-modified polyorganosiloxane, and alcohol-modified polyorganosiloxane have, for example, the same polarity as the halogen group of vinyl chloride and relatively high affinity (compatibility) with vinyl chloride. preferable. Acrylic-modified polyorganosiloxane is particularly preferable because it does not have reactivity, and thus hardly adversely affects the flexibility such as tensile elongation characteristics of the vinyl chloride resin powder slush molded article.

  Specifically, the modified polyorganosiloxane constituting the modified POS particles may be, for example, an acrylic modified polyorganosiloxane obtained by emulsion graft copolymerization of the following (a) and the following (b).

(A) A compound (polyorganosiloxane) represented by the following general formula (I).

In the general formula (I), R ¹ , R ² and R ³ are the same or different hydrocarbon groups having 1 to 20 carbon atoms (for example, alkyl groups or aryl groups (for example, aryl groups having 6 to 10 carbon atoms). )) Or a halogenated hydrocarbon group (for example, a halogenated alkyl group or a halogenated aryl group (for example, a halogenated aryl group having 6 to 10 carbon atoms)), and Y is a radical reactive group (for example, a vinyl group). , Allyl group, γ-acryloxypropyl group, γ-methacryloxypropyl group or γ-mercaptopropyl group), SH group, or an organic group containing the radical reactive group and SH group, and Z ¹ and Z ² are Each represented by the same or different hydrogen atom, lower alkyl group (for example, alkyl group having 1 to 4 carbon atoms) or triorganosilyl group (for example, represented by the following general formula (II)) In triorganosilyl group (said general formula (II) that, ^{R 4} and ^{R 5} are the same or different hydrocarbon group having 1 to 20 carbon atoms (e.g., alkyl or aryl group (e.g., a carbon number 6 to 10 Aryl group)) or halogenated hydrocarbon group (for example, halogenated alkyl group or halogenated aryl group (for example, halogenated aryl group having 6 to 10 carbon atoms)), R ⁶ is a hydrocarbon having 1 to 20 carbon atoms Group (for example, alkyl group or aryl group (for example, aryl group having 6 to 10 carbon atoms)), halogenated hydrocarbon group (for example, halogenated alkyl group or halogenated aryl group (for example, halogen having 6 to 10 carbon atoms) Aryl group)), radical reactive group (for example, vinyl group, allyl group, γ-acryloxypropyl group, γ-methacryloxypropyl group or γ Mercaptopropyl group), SH group, or an organic group containing the radical organic group and the SH group.)), M is a positive integer of 10,000 or less (for example, 500 to 8000), and n is 1 or more. It is an integer (for example, 1 to 500).

(B) (meth) acrylic acid ester represented by the following general formula (III) (for example, alkyl (meth) acrylate (for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( The group consisting of (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate One or more selected from), alkoxyalkyl (meth) acrylate (for example, methoxyethyl (meth) acrylate and / or butoxyethyl (meth) acrylate), cycloalkyl (meth) acrylate (for example, cyclohexene) Sil (meth) acrylate) and aryl (meth) acrylate (for example, one or more selected from the group consisting of phenyl (meth) acrylate and / or benzyl acrylate), or the (meth) acrylic acid ester and the (meta) ) A mixture comprising a monomer copolymerizable with an acrylate ester (for example, a hydroxyl group-containing unsaturated monomer (for example, 2-hydroxyethyl (meth) acrylate and / or 2-hydroxypropyl (meth) acrylate)).

In the above general formula (III), R ⁷ is a hydrogen atom or a methyl group, R ⁸ is an alkyl group (for example, an alkyl group having 1 to 18 carbon atoms) or an alkoxy-substituted alkyl group (for example, having 3 to 6 carbon atoms). An alkoxy-substituted alkyl group), a cycloalkyl group (for example, a cycloalkyl group having 6 or 7 carbon atoms) or an aryl group (for example, an aryl group having 6 to 10 carbon atoms).

The molecular weight of the modified polyorganosiloxane constituting the modified POS particle is not particularly limited as long as the modified polyorganosiloxane is formed into particles, but for example, the weight average molecular weight of the modified polyorganosiloxane is 0.00. 5 × may be is 10 ⁵ or more, may be at 1 × 10 ⁵ or more. Although the upper limit of the weight average molecular weight of the modified polyorganosiloxane is not particularly limited, the weight average molecular weight may be, for example, 0.5 × 10 ^{5 to} 5 × 10 ⁵ , and 1 × 10 ^{5 to} 5 × may be a range of 10 ^5, may be a 1 × ¹⁰ 5 to 4 × 10 ^5.

  The average particle diameter of the modified POS particles is not particularly limited as long as it is in the range of 0.1 to 100 μm, but may be, for example, 1 μm or more (for example, 1 to 100 μm), and may be 5 μm or more (for example, 5 ˜100 μm). Moreover, the average particle diameter of the modified POS particles may be, for example, 80 μm or less (for example, 0.1 to 80 μm), or 50 μm or less (for example, 0.1 to 50 μm). The average particle diameter of the modified POS particles may be, for example, 1 to 80 μm or 5 to 50 μm.

  The average particle diameter of the modified POS particles may be smaller than the average particle diameter of the PVC particles in the above-mentioned range. Moreover, the average particle diameter of the modified POS particles may be larger than the average particle diameter of the paste PVC in the above-described range. Furthermore, the average particle size of the modified POS particles may be within the above-described range, and may be smaller than the average particle size of the PVC particles and larger than the average particle size of the paste PVC. The average particle size of the modified POS particles is measured according to JIS K7369: 2009.

  When the average particle diameter of the modified POS particles is smaller than the average particle diameter of the PVC particles, the modified POS particles are arranged so as to cover a part of the surface of the PVC particles. That is, in this case, the paste PVC and the modified POS particles are arranged so as to cover a part of the surface of the PVC particles.

  The amount of the modified POS particles contained in the present composition and the present molded body is not particularly limited as long as it is within the range of 0.5 to 8 parts by weight with respect to 100 parts by weight of the PVC particles. It may be 5 parts by weight, may be 0.5 parts by weight or more and less than 5 parts by weight, and may be 0.5 to 4 parts by weight.

  Further, the amount of the modified POS particles contained in the present composition and the present molded body may be, for example, 1 to 8 parts by weight, or 1 to 5 parts by weight with respect to 100 parts by weight of the PVC particles. It may be 1 part by weight or more and less than 5 parts by weight, or 1 to 4 parts by weight. The amount of the modified POS particles contained in the composition and the molded body within the above range contributes to the fact that the molded body has both excellent surface properties and excellent flexibility.

  The amount of each component contained in the composition and the molded body is not particularly limited as long as it is within the above-mentioned range. For example, the ratio of the amount of modified POS particles to the amount of plasticizer (modified POS particles / plasticizer) For example) may be 0.005 or more, or may be 0.007 or more. The weight ratio of the modified POS particles / plasticizer may be, for example, 0.062 or less, or 0.050 or less. More specifically, the weight ratio of modified POS particles / plasticizer may be, for example, 0.005 to 0.062, or 0.007 to 0.062. The weight ratio of modified POS particles / plasticizer may be, for example, 0.005 to 0.050.

  The composition and the molded body may contain other components. In this case, the other component may include, for example, one or more selected from the group consisting of a stabilizer, a lubricant, and a pigment. As these other components, components suitable for powder slush molding are appropriately selected and used.

  This composition has 100 parts by weight of vinyl chloride resin particles having an average particle size of 50 to 500 μm, and an average particle diameter of 110 to 150 parts by weight of a plasticizer. Vinyl chloride resin fine particles 0.01 to 50 μm smaller than the average particle size of the vinyl chloride resin particles, and modified polyorganosiloxane particles 0.5 to 8 weights having an average particle size of 0.1 to 100 μm And a part.

  That is, this composition is manufactured by mixing PVC particles, a plasticizer, paste PVC, and a modified polyorganosiloxane under the above-described conditions. In addition, when this composition further contains the above-mentioned other components (for example, one or more selected from the group consisting of a stabilizer, a lubricant, and a pigment), this composition contains PVC particles and trimellitic acid. It is manufactured by mixing the plasticizer, paste PVC, modified polyorganosiloxane, and other components. The composition thus produced is a powder composition containing the above-described PVC particles, a plasticizer, a paste PVC, and a modified polyorganosiloxane.

  The molded body is produced by a method including performing powder slush molding of the above-described vinyl chloride resin composition (present composition). That is, the molded body is, for example, a slush molding machine including a powder box and a slush molding mold, and the composition is charged into the powder box and the mold is kept at a predetermined temperature (for example, 230 to 280 ° C.), and then the slush molding machine is inverted, and the composition is brought into contact with the surface of the mold heated to the predetermined temperature and held for a predetermined time (eg, 3 to 15 seconds). Thereafter, the slush molding machine is turned over again to cool the mold, and the molded body is peeled off from the cooled mold.

  The shape of the molded body is not particularly limited, but the molded body may be, for example, a sheet shape. When the molded body is in a sheet form, the thickness is not particularly limited, but may be, for example, 3.0 mm or less, 2.0 mm or less, and 1.6 mm or less. It may be there. In addition, the thickness of the sheet-like main molded body may be, for example, 0.5 mm or more, 0.6 mm or more, or 0.8 mm or more. More specifically, the thickness of the sheet-shaped formed article may be, for example, 0.5 to 3.0 mm, 0.6 to 2.0 mm, 0.8 to It may be 1.6 mm.

  In addition, in JIS K6251, the molded body after being heated at 125 ° C. for 500 hours is measured by a method modified so as to adopt a distance between a pair of chucks holding a sample in place of the distance between marked lines. The tensile elongation at −10 ° C. (tensile elongation after heat aging) is, for example, preferably 140% or more, more preferably 145% or more, and further preferably 150% or more. It is evaluated that this molded body showing the tensile elongation after heat aging in the above-described range has excellent flexibility.

  The resin laminate according to the present embodiment includes a vinyl chloride resin layer composed of the above-described vinyl chloride resin powder slush molding (main molding), and a polyurethane foam layer laminated on the vinyl chloride resin layer. Including.

  This resin laminate is manufactured by a method including laminating a foamed polyurethane layer on a vinyl chloride resin layer composed of the above-described vinyl chloride resin powder slush molding (main molding). That is, for example, a resin laminate can be produced by foaming polyurethane on the surface of the vinyl chloride resin layer made of the molded body.

  More specifically, for example, a raw material liquid prepared by mixing a first liquid containing polyol and a second liquid containing polyisocyanate is mixed on the surface of the sheet-like vinyl chloride resin layer made of the molded body. By performing foam molding, a resin laminate having the vinyl chloride resin layer and a foamed polyurethane layer formed by the foam molding can be produced.

  In addition, the resin laminate includes a polyurethane foam layer, a vinyl chloride resin layer made of the molded article laminated on one surface of the polyurethane foam layer, and another layer laminated on the other surface of the polyurethane foam layer. It is good also as having a resin layer.

  The other resin layer may be, for example, a polyolefin resin (for example, polypropylene and / or polyethylene-polypropylene copolymer) layer or an ABS (acrylonitrile butadiene styrene) resin layer.

  A resin laminate having a vinyl chloride resin layer, a foamed polyurethane layer, and another resin layer is, for example, a polyurethane layer as described above between the vinyl chloride resin layer and the other resin layer. Manufactured by foam molding.

  Further, the resin laminate may be a vehicle interior material. That is, in this case, the resin laminate is used, for example, for interior materials such as instrument panels and door trims of vehicles such as automobiles.

  The resin laminate that is an interior material for a vehicle includes, for example, a sheet-like vinyl chloride resin layer (this molded article) and a polyurethane foam layer formed only on one surface of the vinyl chloride resin layer. It is good. Moreover, the resin laminated body which is a vehicle interior material may contain the above-mentioned vinyl chloride-type resin layer, a foaming polyurethane layer, and another resin layer.

  Next, specific examples according to the present embodiment will be described.

[Production of vinyl chloride resin composition]
As the PVC particles, vinyl chloride resin particles having an average particle size of 80 to 180 μm made of an uncrosslinked vinyl chloride resin (vinyl chloride homopolymer) having an average polymerization degree of 1300, 2500 or 3000, or an average polymerization degree Of vinyl chloride resin particles having an average particle diameter of 80 to 200 μm made of a partially cross-linked (gel content 20% by weight) vinyl chloride resin (a homopolymer of vinyl chloride). As the paste PVC, vinyl chloride resin fine particles having an average particle size of 10 μm made of a vinyl chloride resin (vinyl chloride homopolymer) having an average degree of polymerization of 1000 were used.

  As a plasticizer, trimellitic acid type plasticizer (trimellitic acid type-A) containing trimellitic acid tri (n-octyl) or trimellitic acid tri (n-octyl) is used. A trimellitic acid plasticizer (trimellitic acid-B) having a viscosity higher than that of the agent A was used. In some examples, sebacic acid plasticizers containing di2-ethylhexyl sebacate and pyromellitic acid plasticizers containing pyromellitic acid alkyl esters were also used.

  Polyorganosiloxane particles (POS particles) were used as part of the additive. That is, acrylic modified POS particles (R-170S, manufactured by Nissin Chemical Industry Co., Ltd.) having an average particle size of 30 μm were used as the modified POS particles. Further, as the unmodified POS particles, the average particle diameter is 5 μm, the unmodified POS particles (unmodified POS particles-A) which are spherical silicone rubber powders coated with a silicone resin on the surface, or the average particle diameter is 5 μm. In addition, unmodified POS particles (unmodified POS particles-B), which is a silicone rubber powder having a structure in which linear dimethylpolysiloxane is crosslinked, were used. Further, as other part of the additive, stabilizers and lubricants generally used in the production of a vinyl chloride resin composition for powder slush molding were also used.

  Using the above-described components, a vinyl chloride resin composition (PVC composition) for powder slush molding was produced. That is, first, a plasticizer and a part of the additive (stabilizer and the like) were added to the PVC particles and mixed at 70 ° C. with a super mixer. Next, after drying up the obtained mixture, it was cooled to 50 ° C. or lower, and paste PVC and other additives (POS particles, etc.) were added and mixed. In this way, 23 types (Examples 1 to 11 and Comparative Examples 1 to 11) of powdery PVC compositions containing PVC particles, a plasticizer, paste PVC, and POS particles and having different compositions were manufactured.

[Manufacture of vinyl chloride resin powder slush molding]
A vinyl chloride resin powder slush molding (PVC powder slush molding) was produced by powder slush molding of the PVC composition obtained as described above. That is, powder slush molding was performed using a box-type slush molding machine provided with a slush molding die having a flat plate with a texture (29.4 cm × 20.4 cm) and a powder box.

  Specifically, first, 2 kg of the PVC composition was put into a powder box, and a slush molding die heated to 280 ° C. was set in a slush molding machine. Next, when the mold reached 250 ° C., the slush molding machine was inverted and the PVC composition was held in the mold for about 6 seconds.

  After that, the slush molding machine was inverted. When 60 seconds passed, the mold was cooled to 50 ° C. with cooling water. The vinyl chloride resin sheet (PVC sheet) (thickness 1.0 mm) thus formed was peeled from the mold to obtain a PVC powder slush molded body.

[Evaluation of non-adhesion and wear resistance]
From the PVC sheet obtained as described above, a test piece of 30 mm × 250 mm × 1 mm was cut out and fixed on a table of a Gakushin type abrasion tester (manufactured by Suga Test Instruments Co., Ltd.). In addition, 4 cm × 4 cm medical gauze (manufactured by White Cross Co., Ltd., pure cotton single yarn, standard: type 1) was attached to the tip of the wearer having a 200 g load. Thereafter, the gauze was brought into contact with the surface of the test piece and reciprocated 30 times.

  Based on the amount of gauze fibers attached to the surface of the test piece after the test, the non-adhesiveness of the test piece was evaluated in five stages. That is, “5 points” when no fibers are attached to the surface of the test piece, “4 points” when a very small amount of fibers are attached, “3 points” when a small amount of fibers are attached, When a large amount of fibers adhered, “2 points” was assigned, and when an extremely large amount of fibers adhered, “1 point” was assigned.

  Further, based on the degree of wear of the surface of the test piece after the test, the wear resistance of the test piece was evaluated in five stages. That is, “5 points” when no traces of wear were formed on the surface of the test piece, “4 points” when traces of traces were formed, and “a few points” when traces of wear were formed. “3 points”, “2 points” when a large amount of wear marks were formed, and “1 point” when a very large amount of wear marks were formed. For both non-adhesiveness and abrasion resistance, a PVC sheet given a score of “3 points” or more was evaluated as having favorable surface characteristics.

[Manufacture of resin laminates]
A resin laminate having a vinyl chloride resin layer made of the PVC sheet obtained as described above and a polyurethane foam layer laminated on the PVC sheet was produced. That is, first, a polypropylene resin plate (thickness 2 mm) obtained by injection molding of polypropylene is attached to the inner surface of one side of a foam molding die (190 mm × 240 mm × 11 mm), and the opposite side of the die A PVC sheet manufactured by powder slush molding as described above was laid on the inner surface of.

  And on this PVC sheet, 36 g of liquid A containing 4,4′-diphenylmethane diisocyanate, 78 g of liquid B containing polyether polyol (containing 1.0% by weight of triethylenediamine and 1.6% by weight of water) The raw material liquid prepared by mixing was poured and the mold was sealed.

  Thus, a PVC sheet (skin) having a thickness of 1 mm, a polyurethane foam layer (lining material) having a thickness of 7 mm laminated on the PVC sheet, and a polypropylene resin plate having a thickness of 2 mm laminated on the polyurethane foam layer ( The resin laminated body which consists of a base material was manufactured.

[Evaluation of tensile elongation after heat aging]
As the tensile elongation characteristic of the PVC sheet, the tensile elongation characteristic at a low temperature of the PVC sheet was evaluated. That is, in JIS K6251, the tensile elongation property at −10 ° C. of the PVC sheet after heat aging was evaluated by a method modified so as to adopt the distance between a pair of chucks holding a sample instead of the distance between marked lines. .

  Specifically, first, the resin laminate obtained as described above was put in an oven and heated at 125 ° C. for 500 hours, whereby the resin laminate was thermally aged. Thereafter, the PVC sheet (vinyl chloride resin layer) was peeled from the resin laminate. Then, the peeled PVC sheet was punched into a No. 1 dumbbell shape to obtain a No. 1 dumbbell-shaped test piece. And after hold | maintaining a test piece for 3 minutes within a -10 degreeC chamber, the tensile elongation (tensile elongation (%) after heat aging) of the said test piece was measured at the tensile speed of 200 mm / min. As a practical characteristic, a PVC sheet having a tensile elongation of 140% or more after heat aging was evaluated as having favorable flexibility.

[result]
FIG. 1 (Examples 1 to 11) and FIG. 2 (Comparative Examples 1 to 11) show the composition of the PVC composition and the results of evaluating the characteristics of the PVC sheet produced from the PVC composition. As shown in FIG. 1, the PVC composition and the PVC sheet are composed of 100 parts by weight of PVC particles made of vinyl chloride resin having an average degree of polymerization of 1500 or more, 110 to 150 parts by weight of plasticizer, paste PVC, and acrylic modified POS. In the case of containing 0.5 to 8 parts by weight of the particles, the PVC sheet has excellent surface characteristics to which a score of 3 or more is given, and excellent flexibility that exhibits a tensile elongation of 140% or more after heat aging, and It was confirmed to have

  Also, when the content of acrylic modified POS particles is more than 0.5 parts by weight and the weight ratio of POS particles / plasticizer is more than 0.005 (Examples 1 to 3-11), the PVC sheet is more excellent. It has been confirmed that it has excellent surface properties and flexibility.

  Moreover, in the range of 3 to 8 parts by weight of the acrylic-modified POS particles, particularly excellent surface characteristics and flexibility were achieved. Therefore, for example, when the content of the acrylic modified POS particles is 1 part by weight or more and less than 8 parts by weight, 5 parts by weight or less, or less than 5 parts by weight, the surface characteristics are particularly excellent at lower cost. It was confirmed that flexibility was achieved.

  On the other hand, as shown in FIG. 2, when the PVC composition and the PVC sheet do not contain acrylic-modified POS particles (for example, Comparative Examples 4 to 6), the surface properties of the PVC sheet were not sufficient. That is, in Comparative Example 4 in which the PVC composition and the PVC sheet do not include acrylic modified POS particles and unmodified POS particles, and in Comparative Examples 5 and 6 that do not include acrylic modified POS particles and include unmodified POS particles, The surface properties were not sufficient.

  Moreover, in Comparative Example 1, the surface properties of the PVC sheet are improved by reducing the plasticizer content of the PVC composition and the PVC sheet not containing acrylic-modified POS particles and unmodified POS particles to 100 parts by weight. However, the flexibility of the PVC sheet was not sufficient.

  Moreover, in the comparative example 2 whose acrylic modified POS particle content of a PVC composition and a PVC sheet was 0.3 weight part, the surface characteristic of the said PVC sheet was not enough. Moreover, in the comparative example 3 whose acrylic modified POS particle content of a PVC composition and a PVC sheet was 10 weight part, the softness | flexibility of the said PVC sheet was not enough.

  Moreover, in the comparative example 7 whose plasticizer content of a PVC composition and a PVC sheet was 160 weight part, the surface characteristic of the said PVC sheet was not enough. Moreover, in Comparative Examples 8 and 9 in which the average degree of polymerization of the PVC particles was 1300, the PVC sheet could not be molded (Comparative Example 10), or the flexibility of the PVC sheet was not sufficient.

  Moreover, in Comparative Example 10 (5% by weight of gel) and Comparative Example 11 (10% by weight of gel) in which the PVC particles were composed of partially crosslinked vinyl chloride resin, could a PVC sheet be molded? Comparative Example 11) or the flexibility of the PVC sheet was not sufficient (Comparative Example 10).

  Although the results are not shown, the PVC composition and the PVC sheet do not contain acrylic-modified POS particles and unmodified POS particles, and contain 1.2 parts by weight of carbinol-modified silicone oil with respect to 100 parts by weight of PVC particles. In some cases, the non-adhesiveness of the PVC sheet was evaluated as 2 points, and the wearability was evaluated as 3 points, and the surface characteristics were not sufficient.

Claims (7)

100 parts by weight of vinyl chloride resin particles having an average particle size of 50 to 500 μm made of a vinyl chloride resin having an average degree of polymerization of 1500 or more;
110-150 parts by weight of plasticizer;
Vinyl chloride resin fine particles having an average particle diameter of 0.01 to 50 μm and smaller than the average particle diameter of the vinyl chloride resin particles;
0.5 to 8 parts by weight of modified polyorganosiloxane particles having an average particle size of 0.1 to 100 μm;
A vinyl chloride resin composition (however, an embodiment including 0.05 to 5 parts by mass of (meth) acryloxy-modified silicone oil and an aspect including 0.05 to 5 parts by mass of hydroxyl-modified silicone oil) Except.) 100 parts by weight of vinyl chloride resin particles having an average particle size of 50 to 500 μm made of a vinyl chloride resin having an average degree of polymerization of 1500 or more;
110-150 parts by weight of plasticizer;
Vinyl chloride resin fine particles having an average particle diameter of 0.01 to 50 μm and smaller than the average particle diameter of the vinyl chloride resin particles;
0.5 to 8 parts by weight of modified polyorganosiloxane particles having an average particle size of 0.1 to 100 μm;
Including a vinyl chloride resin powder slush molded product (including (meth) acryloxy-modified silicone oil 0.05 to 5 parts by mass, and hydroxyl-modified silicone oil 0.05 to 5 parts by mass) Except for the aspect.) A vinyl chloride resin layer comprising the vinyl chloride resin powder slush molding according to claim 2;
A foamed polyurethane layer laminated on the vinyl chloride resin layer;
A resin laminate comprising: It is a vehicle interior material. The resin laminated body of Claim 3 characterized by the above-mentioned. 100 parts by weight of vinyl chloride resin particles having an average particle size of 50 to 500 μm made of a vinyl chloride resin having an average degree of polymerization of 1500 or more;
110-150 parts by weight of plasticizer;
Vinyl chloride resin fine particles having an average particle diameter of 0.01 to 50 μm and smaller than the average particle diameter of the vinyl chloride resin particles;
0.5 to 8 parts by weight of modified polyorganosiloxane particles having an average particle size of 0.1 to 100 μm;
A method of producing a vinyl chloride resin composition, wherein the vinyl chloride resin composition comprises 0.05 to 5 parts by mass of (meth) acryloxy-modified silicone oil, And an embodiment containing 0.05 to 5 parts by mass of a hydroxyl group-modified silicone oil) . A method for producing a vinyl chloride resin powder slush molded article, comprising performing powder slush molding of the vinyl chloride resin composition according to claim 1. A method for producing a resin laminate, comprising: laminating a foamed polyurethane layer on a vinyl chloride resin layer comprising the vinyl chloride resin powder slush molded article according to claim 2.

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