JPWO2016152085A1 - Vinyl chloride resin composition for powder molding, vinyl chloride resin molded body, and laminate - Google Patents

Abstract

The present invention provides a vinyl chloride resin composition and a vinyl chloride resin molded article for powder molding, and a molded article having excellent flexibility at low temperature and low fluffing properties, and the vinyl chloride resin molded article and polyurethane foam molded article. It aims at providing the laminated body which has a body. The vinyl chloride resin composition for powder molding of the present invention includes (a) a vinyl chloride resin, (b) an epoxy resin, and (c) a silicone oil having a viscosity of 10 cs or more and 200 × 10 4 cs or less.

Description

  The present invention relates to a vinyl chloride resin composition for powder molding which gives a molded article having excellent flexibility at low temperatures and low fluffing properties, and vinyl chloride formed by powder molding the above-mentioned vinyl chloride resin composition for powder molding The present invention relates to a resin molded body, and a laminate having the vinyl chloride resin molded body and a foamed polyurethane molded body.

The automobile instrument panel has a structure in which a foamed polyurethane layer is provided between a skin made of a vinyl chloride resin and a base material. Here, when the skin is made of a vinyl chloride resin, the skin may discolor over time, and the heat aging resistance of the skin may decrease. One cause of the discoloration or the like is a chemical reaction associated with the transfer of the tertiary amine used as a catalyst during the formation of the foamed polyurethane layer to the skin made of vinyl chloride resin. Therefore, in order to prevent discoloration of the skin, it has been studied to introduce a granular catcher material that captures volatile organic compounds generated in the foamed polyurethane layer into the foamed polyurethane layer. Specifically, a urethane integrated foam-molded product in which the catcher material covered with the open-cell sheet material is disposed in the vicinity of the sealing portion of the foamed polyurethane layer terminal by the skin material and the base material was examined ( For example, see Patent Document 1). However, in the urethane integrated foam molded article described in Patent Document 1, since the skin and the foamed polyurethane layer are in contact with each other, discoloration of the skin material due to the chemical reaction cannot be prevented for a long period of time. The heat aging resistance is reduced.
Also, in a laminate provided with a synthetic resin foam layer that joins the core material (base material) and the skin, a laminate in which a vent hole for discharging gas generated in the foam layer is provided in the core material. The body was examined (for example, refer patent document 2). However, even in the laminate described in Patent Document 2, since the skin and the synthetic resin foam layer are in contact with each other, discoloration of the skin material due to the chemical reaction cannot be prevented for a long time, and the heat resistance of the skin material can be prevented. Aging is reduced.

  Furthermore, it comprises a polyurethane molded body, a skin layer containing a vinyl chloride resin and covering at least one surface of the polyurethane molded body, and an amine catcher agent layer interposed between the polyurethane molded body and the skin layer. Molded bodies have been studied (see, for example, Patent Document 3). However, the amine catcher agent is volatile. Therefore, even in the molded article described in Patent Document 3, it is impossible to prevent the tertiary amine from moving to the skin made of the vinyl chloride resin for a long period of time. As a result, discoloration of the skin material due to the chemical reaction cannot be prevented for a long time, and the heat aging resistance of the skin material is reduced.

By the way, a vinyl chloride resin composition for powder molding in which a specific trimellitate plasticizer is blended has been studied as a raw material for skin materials used for automobile interior materials (see, for example, Patent Document 4). However, in order to improve the heat aging resistance of the skin material obtained by powder-molding the vinyl chloride resin composition for powder molding, the amount of the plasticizer must be increased. There was a problem that a sticky feeling originated.
Further, vinyl chloride for powder molding containing 100 parts by mass of vinyl chloride resin particles composed of a vinyl chloride resin having an average degree of polymerization of 1500 or more and 110 parts by mass or more and 150 parts by mass or less of a specific trimellitate plasticizer. Based resin compositions have been studied (see, for example, Patent Document 5).
Furthermore, a resin composition containing a vinyl chloride resin, which is a kind of soft resin, and silicone oil has been studied (for example, see Patent Document 6). And since the resin composition of patent document 6 has the smooth touch feeling, the vinyl chloride resin molded object formed by shape | molding the said resin composition is useful as an outer skin of a vehicle instrument panel It is. On the other hand, the vinyl chloride resin molded body has a problem that the plasticizer contained in the material is transferred to the surface due to the influence of heat, light, etc. and loses the soft feeling. And in order to solve the said problem, it replaced with the vinyl chloride resin and the resin composition for powder molding which uses a thermoplastic polyurethane was developed. Specifically, a polyurethane resin composition for powder molding containing a powdered thermoplastic polyurethane and a hydroxyl group-modified and / or (meth) acryloxy-modified silicone oil was examined (for example, see Patent Document 7).

JP 2007-216506 A JP-A-8-90697 Japanese Patent Publication No.4-26303 Japanese Patent Laid-Open No. 2-138355 International Publication No. 2009/107463 JP 2000-204212 A JP 2005-154670 A

In recent years, in automotive instrument panel skins with polyurethane foam layers laminated, the skin is cracked as designed at low temperatures and the airbag is inflated. There has been a demand for an automobile instrument panel having a skin with excellent flexibility. However, an automobile instrument panel having such a skin has not been realized.
Further, in an automotive instrument panel using a molded body formed by powder molding of a soft resin composition as a skin, if dust or dirt adhered to the automotive instrument panel is wiped off with a cloth, the wiped dust Further, there is a problem that fiber residue contained in dirt and the like adheres to the skin, and the appearance of the automobile instrument panel is impaired. Therefore, in recent years, there has been a demand for an automobile instrument panel in which fiber residue is difficult to adhere even if the surface is wiped with a cloth (low fluffing property), but an automobile instrument panel provided with a skin that satisfies the requirement. Was not realized.

  Therefore, the problem to be solved by the present invention is to provide a vinyl chloride resin composition for powder molding which gives a molded article having excellent flexibility at low temperatures and low fuzziness. Another problem to be solved by the present invention is a vinyl chloride resin molded article having excellent flexibility at low temperatures and low fluffing properties, obtained by powder molding the above-mentioned vinyl chloride resin composition for powder molding, and The present invention provides a laminate having the vinyl chloride resin molded body and the polyurethane foam molded body.

The inventors of the present invention have intensively studied to solve the above problems, and as a result, (a) vinyl chloride resin, (b) epoxy resin, and (c) silicone oil having a viscosity of 10 cs or more and 200 × 10 ⁴ cs or less. It has been found that a vinyl chloride resin composition for powder molding containing the above solution solves the above problems, and has completed the present invention.

The vinyl chloride resin composition for powder molding of the present invention is a powder comprising (a) a vinyl chloride resin, (b) an epoxy resin, and (c) a silicone oil having a viscosity of 10 cs or more and 200 × 10 ⁴ cs or less. This is a vinyl chloride resin composition for molding.
In the present invention, “viscosity” can be measured using a Ubbelohde viscometer according to ASTM D 445-46T. When a mixture of two or more different silicone oils is used, the “viscosity” can be measured as a value of the entire mixture.

  Here, in the vinyl chloride resin composition for powder molding of the present invention, the preferable content of the (b) epoxy resin is 0.2 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the (a) vinyl chloride resin. Or less.

In the vinyl chloride resin composition for powder molding of the present invention, the preferable content of the silicone oil (c) having a viscosity of 10 cs or more and 200 × 10 ⁴ cs or less is (a) 100 parts by mass of the vinyl chloride resin. It is 0.1 mass part or more and 10 mass parts or less with respect to.

In the vinyl chloride resin composition for powder molding of the present invention, the (a) vinyl chloride resin is preferably (a1) vinyl chloride resin particles having an average degree of polymerization of 800 or more and 5000 or less, and (a2). It consists of vinyl chloride resin fine particles having an average polymerization degree of 500 or more and 5000 or less, and the content ratio of the (a1) vinyl chloride resin particles having an average polymerization degree of 800 or more and 5000 or less is 70% by mass or more and 100% by mass or less, (A2) The content ratio of the vinyl chloride resin fine particles having an average degree of polymerization of 500 or more and 5000 or less is 0% by mass or more and 30% by mass or less.
In the present invention, “resin particles” refers to particles having a particle size of 30 μm or more, and “resin particles” refers to particles having a particle size of less than 30 μm.
The “average degree of polymerization” of the vinyl chloride resin constituting the vinyl chloride resin particles and the vinyl chloride resin fine particles (hereinafter sometimes referred to as “vinyl chloride resin (fine) particles”) is defined in JIS K 6720-2. Measured in compliance.

  The vinyl chloride resin composition for powder molding of the present invention is preferably used for powder slush molding.

  Moreover, this invention is a vinyl chloride resin molded object formed by powder-molding any of the vinyl chloride resin compositions for powder molding described above.

  Here, the vinyl chloride resin molded body of the present invention is preferably a vinyl chloride resin molded body formed by powder slush molding of the above-described vinyl chloride resin composition for powder molding.

  Moreover, the vinyl chloride resin molded article of the present invention is preferably for an automotive instrument panel skin.

  And this invention is a laminated body which has a foaming polyurethane molding and one of the vinyl chloride resin moldings mentioned above.

  The laminate of the present invention is preferably for an automobile instrument panel.

  The vinyl chloride resin composition for powder molding of the present invention provides a molded article having excellent flexibility at low temperatures and low fluffing properties.

(Vinyl chloride resin composition for powder molding)
The vinyl chloride resin composition for powder molding of the present invention comprises (a) a vinyl chloride resin, (b) an epoxy resin, and (c) a silicone oil having a viscosity of 10 cs or more and 200 × 10 ⁴ cs or less, Optionally further contains additives.

<(A) Vinyl chloride resin>
(A) The vinyl chloride resin is a polymer containing units derived from vinyl chloride as a monomer, and is not particularly limited, and preferably contains vinyl chloride resin particles, and optionally contains vinyl chloride resin fine particles. In addition. The (a) vinyl chloride resin more preferably includes (a1) vinyl chloride resin particles having a predetermined polymerization degree, and optionally (a2) further includes vinyl chloride resin fine particles having a predetermined polymerization degree. The (a) vinyl chloride resin is more preferably composed of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles having a predetermined content ratio.
In the present specification, “(a1) vinyl chloride resin particles having an average degree of polymerization of 800 or more and 5000 or less” means “(a1) vinyl chloride resin particles having a predetermined degree of polymerization” or “(a1) vinyl chloride. It has the same meaning as “resin particles”. Further, “(a2) vinyl chloride resin fine particles having an average degree of polymerization of 500 to 5000” is the same as “(a2) vinyl chloride resin fine particles having a predetermined degree of polymerization” and “(a2) vinyl chloride resin fine particles”. Has the meaning of

Here, as the vinyl chloride resin that can constitute the (a1) vinyl chloride resin particles and the (a2) vinyl chloride resin fine particles, in addition to the vinyl chloride homopolymer, the vinyl chloride unit is preferably 50% by mass or more, more preferably. Is a copolymer containing 70% by mass or more.
Specific examples of comonomers of the vinyl chloride copolymer include olefins such as ethylene and propylene; halogenated olefins such as allyl chloride, vinylidene chloride, vinyl fluoride, and ethylene trifluoride; vinyl acetate and propionic acid. Carboxylic acid vinyl esters such as vinyl; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; allyl ethers such as allyl-3-chloro-2-oxypropyl ether; acrylic acid, maleic acid, itaconic acid, acrylic acid-2- Unsaturated carboxylic acids such as hydroxyethyl, methyl methacrylate, monomethyl maleate, diethyl maleate, maleic anhydride, esters thereof or anhydrides thereof; unsaturated nitriles such as acrylonitrile, methacrylonitrile; acrylamide, N- Methylo Le acrylamide, acrylamido-2-methylpropanesulfonic acid, (meth) acrylamides such as acrylamide propyl trimethyl ammonium chloride; allyl amine benzoates, allylamine and its derivatives such as diallyl dimethyl ammonium chloride; and the like. The monomer exemplified above is only a part of the monomer (comonomer) copolymerizable with vinyl chloride. As the comonomer, “polyvinyl chloride” edited by Kinki Chemical Association Vinyl Division The various monomers illustrated in Nikkan Kogyo Shimbun (1988), pages 75-104 may be used. One or more of these monomers can be used. Examples of the vinyl chloride resin constituting the (a1) vinyl chloride resin particles include resins such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, and chlorinated polyethylene. And (1) vinyl chloride or (2) a resin obtained by graft polymerization of vinyl chloride and the comonomer.
Here, in this specification, “(meth) acryl” means acryl and / or methacryl.

  The (a) vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method or bulk polymerization method.

<< (a1) Vinyl chloride resin particles >>
The (a) vinyl chloride resin preferably contains (a1) vinyl chloride resin particles having a predetermined degree of polymerization.
In the vinyl chloride resin composition for powder molding, (a1) vinyl chloride resin particles normally function as a matrix resin.
The (a1) vinyl chloride resin particles can be produced by any conventionally known production method such as suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, etc. It is preferably made of a vinyl chloride resin produced by a polymerization method.

Here, the average degree of polymerization of the (a1) vinyl chloride resin particles is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, particularly preferably 800 or more, and still more preferably. Is 1200 or more, and more preferably 1900 or more. The average degree of polymerization of the (a1) vinyl chloride resin particles is preferably 5000 or less, more preferably 3000 or less, still more preferably 2800 or less, and even more preferably 2500 or less. If the average degree of polymerization of the above (a1) vinyl chloride resin particles is equal to or more than the above lower limit, the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition for powder molding has better flexibility at low temperature. This is because sex can be imparted. If the average degree of polymerization of the (a1) vinyl chloride resin particles is not more than the above upper limit, the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition for powder molding has a lower fluffing property. This is because it can be given.
As the (a1) vinyl chloride resin particles, only one kind may be used, or two or more kinds (a1) vinyl chloride resin particles having different average polymerization degrees may be used in combination.

The average particle diameter of the (a1) vinyl chloride resin particles is usually 30 μm or more, preferably 50 μm or more, more preferably 80 μm or more, and further preferably 100 μm or more. The average particle diameter of the (a1) vinyl chloride resin particles is preferably 500 μm or less, more preferably 300 μm or less, still more preferably 200 μm or less, and even more preferably 180 μm or less. (A1) If the average particle diameter of the vinyl chloride resin particles is not less than the above lower limit, lower fluffing properties can be imparted to a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding. Because. Moreover, if the average particle diameter of the (a1) vinyl chloride resin particles is not more than the above upper limit, a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding at a better low temperature This is because flexibility can be imparted.
The “particle diameter” and “average particle diameter” of the (a1) vinyl chloride resin particles can be measured by a laser diffraction method in accordance with JIS Z8825.

  The content ratio of the (a1) vinyl chloride resin particles in 100% by mass of the (a) vinyl chloride resin is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more. And can be 100% by mass, preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. If the content ratio of the (a1) vinyl chloride resin particles is equal to or more than the above lower limit, good heat aging resistance can be imparted to the vinyl chloride resin molded body produced using the vinyl chloride resin composition for powder molding. . Moreover, it is because the powder fluidity | liquidity of the vinyl chloride resin composition for powder molding will become more favorable if the content rate of (a1) vinyl chloride resin particle is 95 mass% or less.

<< (a2) Vinyl chloride resin fine particles >>
The (a) vinyl chloride resin may contain (a2) vinyl chloride resin fine particles having a predetermined degree of polymerization as required.
In the vinyl chloride resin composition for powder molding, (a2) vinyl chloride resin fine particles function as a dusting agent (powder fluidity improver) that improves the powder fluidity of the vinyl chloride resin composition.
Further, (a2) vinyl chloride resin fine particles can be produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method, bulk polymerization method, etc. A vinyl chloride resin produced by a legal method is preferred.

The average degree of polymerization of the vinyl chloride resin constituting the (a2) vinyl chloride resin fine particles is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, preferably 5000 or less, More preferably, it is 3000 or less, More preferably, it is 2500 or less, More preferably, it is 1800 or less. If the average polymerization degree of the vinyl chloride resin constituting the (a2) vinyl chloride resin fine particles is not less than the above lower limit, the powder flowability of the vinyl chloride resin composition for powder molding is further improved, and the composition This is because even better heat aging resistance can be imparted to the vinyl chloride resin molded article produced using the above. Moreover, it is because the powder fluidity | liquidity of the vinyl chloride resin composition for powder shaping | molding will become still more favorable if the average degree of polymerization of the vinyl chloride resin which comprises (a2) vinyl chloride resin fine particle is below the said upper limit.
Incidentally, as the (a2) vinyl chloride resin fine particles, only one kind may be used, or two or more kinds of (a2) vinyl chloride resin fine particles having different average polymerization degrees may be used. From the viewpoint of further improving the powder fluidity of the resin composition, it is preferable to use two different types of (a2) vinyl chloride resin fine particles in combination.

The average particle size of the above (a2) vinyl chloride resin fine particles is usually less than 30 μm, preferably 25 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, preferably 0.00. It is 1 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm or more.
(A2) The “particle diameter” and “average particle diameter” of the vinyl chloride resin fine particles can be measured by a laser diffraction method in accordance with JIS Z8825.

  The content ratio of (a2) vinyl chloride resin fine particles in 100% by mass of (a) vinyl chloride resin is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. Preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less. If the content ratio of the above (a2) vinyl chloride resin fine particles is not less than the above lower limit, the powder flowability of the vinyl chloride resin composition for powder molding is further improved and the vinyl chloride produced using the composition is used. This is because even better heat aging resistance can be imparted to the resin molded body. Moreover, it is because the powder fluidity | liquidity of the vinyl chloride resin composition for powder molding will become still more favorable if the content rate of the said (a2) vinyl chloride resin fine particle is below the said upper limit.

<(B) Epoxy resin>
The vinyl chloride resin composition for powder molding of the present invention contains (b) an epoxy resin.
Here, in the present invention, (b) epoxy resin does not include epoxidized vegetable oil such as epoxidized soybean oil used as a plasticizer. That is, (b) an epoxy resin excludes epoxidized vegetable oil.
Moreover, (b) epoxy resin is not specifically limited except the said conditions, Any of an aromatic epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin can be used. Preferable (b) epoxy resin is an aromatic epoxy resin. Specific examples of the aromatic epoxy resin include bisphenol A liquid epoxy resin, bisphenol A solid epoxy resin, bisphenol F and epichlorohydrin obtained by reacting bisphenol A and epichlorohydrin in the presence of alkali. Bisphenol F-type epoxy resins obtained by reaction in the presence, brominated resins of these resins, urethane-modified resins of these resins, phenol novolac type epoxy compounds, cresol novolak type epoxy compounds, cresol type epoxy compounds, polyphenol type epoxy Examples thereof include glycidyl ether type epoxy compounds such as compounds and hydrogenated bisphenol A type epoxy compounds. Among the above-mentioned, more preferable (b) epoxy resins are bisphenol A type liquid epoxy resin, bisphenol A type solid epoxy resin, and bisphenol F type epoxy resin. Further preferred (b) epoxy resin is bisphenol A type liquid epoxy resin. These may use only 1 type and may use 2 or more types of (b) epoxy resins.
In addition, the epoxy resin being “liquid” means that the epoxy resin is in a liquid state under a normal temperature and a normal pressure of a temperature of 25 ° C. and a pressure of 1 atm.

  Bisphenol A type liquid epoxy compounds are commercially available, and specific examples thereof include, for example, trade names “jER828, jER828, jER828EL, jER828XA, jER834” (manufactured by Mitsubishi Chemical Corporation), trade names “EPICLON840, EPICLON840-”. S, EPICLON 850, EPICLON 850-S, EPICLON 850-CRP, EPICLON 850-LC ”(above, manufactured by DIC Corporation,“ EPICLON ”is a registered trademark), and the like. Further, bisphenol A type solid epoxy compounds are commercially available, and specific examples thereof include, for example, trade names “EPICLON 860, EPICLON 1050, EPICLON 1055, EPICLON 3050, EPICLON 4050, EPICLON 7050, EPICLON AM-020-P, EPICLON AM-040-P, EPICLON HM-091, EPICLON HM-101 "(manufactured by DIC Corporation). Furthermore, bisphenol F type epoxy resins are commercially available, and specific examples thereof include, for example, trade names “EPICLON 830, EPICLON 830-S, EPICLON 830-LVP, EPICLON 835, EPICLON 835-LV” (manufactured by DIC Corporation). is there.

Here, the epoxy group equivalent of the (b) epoxy resin is preferably 100 g / eq. Or more, more preferably 150 g / eq. Or more, preferably 5000 g / eq. Or less, more preferably 1000 g / eq. Or less, more preferably 600 g / eq. It is as follows.
In the present invention, the “epoxy group equivalent” can be measured in accordance with JIS K7236: 2001.

  Further, the content of (b) epoxy resin with respect to 100 parts by mass of (a) vinyl chloride resin is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and further preferably 0. 0.5 parts by mass or more, more preferably 1.5 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less. Preferably it is 7 mass parts or less. (B) If the content of the epoxy resin is within the above range, a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding can be given more favorable flexibility at low temperatures. It is.

  Further, the content of the (b) epoxy resin is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the plasticizer when the vinyl chloride resin composition for powder molding further contains a plasticizer described later. More preferably 1.0 part by mass or more, still more preferably 1.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass. Or less. (B) If the content of the epoxy resin is within the above range, the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition for powder molding is better while maintaining low fluffing properties. This is because flexibility at a low temperature can be imparted.

<(C) Silicone oil>
The vinyl chloride resin composition for powder molding of the present invention comprises (c) a silicone oil having a viscosity of 10 cs or more and 200 × 10 ⁴ cs or less (in this specification, simply “(c) silicone oil” or “(c) It may be referred to as “silicone oil having a predetermined viscosity”). (C) The silicone oil may be a polar group-unmodified silicone oil or a polar group-modified silicone oil. The polar group-unmodified silicone oil is a polymer having a polysiloxane structure. Specific examples of the polar group-unmodified silicone oil include polydimethylsiloxane, polydiethylsiloxane, poly (methylethyl) siloxane, and mixtures thereof. Examples of the polar group-modified silicone oil include silicone oils in which polar groups such as carboxyl group, hydroxyl group, mercapto group, amino group, epoxy group, and (meth) acryloyloxy group are introduced into a polymer having a polysiloxane structure. It is done. The site into which the polar group is introduced is the terminal and / or side chain of a polymer having a polysiloxane structure.

Here, the viscosity of (c) silicone oil needs to be 10 cs or more and 200 × 10 ⁴ cs or less. The viscosity of the (c) silicone oil is preferably 50 cs or more, more preferably 1000 cs or more, still more preferably 5000 cs or more, still more preferably 8000 cs or more, particularly preferably 5 × 10 ⁴ cs or more, preferably 150 × 10 ^4. cs or less, more preferably 100 × 10 ⁴ cs or less, and even more preferably 50 × 10 ⁴ cs or less. (C) If the viscosity of the silicone oil is equal to or higher than the above lower limit, the releasability of the vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition for powder molding is improved, and the vinyl chloride resin molded article This is because the fluffing property of can be further reduced. In addition, if the viscosity of the (c) silicone oil is not more than the above upper limit, even if a plasticizer is used, (c) the vinyl chloride resin molded product is not sticky without excessively containing the silicone oil. This is because it is possible to realize good release properties and fluffing properties while suppressing the above.

  Further, the content of (c) silicone oil with respect to 100 parts by mass of (a) vinyl chloride resin is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and further preferably 0.5 parts by mass or more. 1 part by mass or more is more preferable, 10 parts by mass or less is preferable, 8 parts by mass or less is more preferable, 5 parts by mass or less is further preferable, 3 parts by mass or less is more preferable, and 2 parts by mass or less is particularly preferable. (C) If the content of silicone oil is not less than the above lower limit, the releasability of a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding is improved, and the vinyl chloride resin molding is performed. This is because the fluffiness of the body can be further reduced. Further, if the content of (c) silicone oil is not more than the above upper limit, even when a plasticizer is used, (c) the vinyl chloride resin molded body is not excessively contained without containing silicone oil. This is because better releasability and fluffiness can be achieved while suppressing sticking.

  Furthermore, when the vinyl chloride resin composition for powder molding further contains a plasticizer described later, the content of (c) silicone oil is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the plasticizer. Is preferably 9 parts by mass or more, more preferably 1.5 parts by mass or less, and even more preferably 1.1 parts by mass or less. (C) If the content of silicone oil is not less than the above lower limit, the release property of a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding is further improved, and the vinyl chloride resin This is because the fluffing property of the molded product can be further reduced. Further, if the content of (c) silicone oil is not more than the above upper limit, (c) the vinyl chloride resin molded product is better while suppressing stickiness due to the plasticizer without excessively containing silicone oil. This is because it is possible to achieve excellent mold release properties and fluffiness.

<Additives>
Additives that the vinyl chloride resin composition for powder molding may further contain in addition to (a) vinyl chloride resin, (b) epoxy resin, and (c) silicone oil having a viscosity of 10 cs or more and 200 × 10 ⁴ cs or less For example, plasticizer, perchloric acid-treated hydrotalcite, zeolite, β-diketone, fatty acid metal salt, (a2) dusting agent other than vinyl chloride resin fine particles, and other additives. Can further be included.

<< Plasticizer >>
The vinyl chloride resin composition for powder molding of the present invention preferably further contains a plasticizer. Specific examples of the plasticizer include the following primary plasticizer and secondary plasticizer.

As so-called primary plasticizers,
Trimellitic acid tri-n-hexyl, trimellitic acid tri-n-heptyl, trimellitic acid tri-n-octyl, trimellitic acid tri- (2-ethylhexyl), trimellitic acid tri-n-nonyl, trimellitic acid Tri-n-decyl, trimellitic acid triisodecyl, trimellitic acid tri-n-undecyl, trimellitic acid tri-n-dodecyl, trimellitic acid tri-n-alkyl ester (however, the number of carbon Is an ester having 2 or more types in the molecule), trimellitic acid trialkyl ester (alkyl group having the same or different carbon number [however, the carbon number is 8 to 10). An ester having two or more types in the molecule);
Pyromellitic acid tetra-n-hexyl, pyromellitic acid tetra-n-heptyl, pyromellitic acid tetra-n-octyl, pyromellitic acid tetra- (2-ethylhexyl), pyromellitic acid tetra-n-nonyl, pyromellitic acid Tetra-n-decyl, pyromellitic acid tetraisodecyl, pyromellitic acid tetra-n-undecyl, pyromellitic acid tetra-n-dodecyl, pyromellitic acid tetra-n-alkyl ester (an alkyl group having a different carbon number [however, An ester having two or more carbon atoms in the molecule), pyromellitic acid tetraalkyl ester (an alkyl group having the same or different carbon number, provided that the carbon number is 8 to 10). An ester having two or more types in the molecule);
Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dibenzyl phthalate, Phthalic acid derivatives such as butylbenzyl phthalate, dinonyl phthalate, dicyclohexyl phthalate;
Isophthalic acid derivatives such as dimethyl isophthalate, di- (2-ethylhexyl) isophthalate, diisooctyl isophthalate;
Tetrahydrophthalic acid derivatives such as di- (2-ethylhexyl) tetrahydrophthalate, di-n-octyltetrahydrophthalate, diisodecyltetrahydrophthalate;
Adipic acid derivatives such as di-n-butyl adipate, di (2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate;
Azelaic acid derivatives such as di- (2-ethylhexyl) azelate, diisooctylazelate, di-n-hexylazelate;
Sebacic acid derivatives such as di-n-butyl sebacate, di- (2-ethylhexyl) sebacate, diisodecyl sebacate, di- (2-butyloctyl) sebacate;
Maleic acid derivatives such as di-n-butyl maleate, dimethyl maleate, diethyl maleate, di- (2-ethylhexyl) maleate;
Fumaric acid derivatives such as di-n-butyl fumarate and di- (2-ethylhexyl) fumarate;
Citric acid derivatives such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri- (2-ethylhexyl) citrate;
Itaconic acid derivatives such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate;
Oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate;
Ricinoleic acid derivatives such as methylacetylricinoleate, butylacetylricinoleate, glycerylmonoricinoleate, diethylene glycol monoricinoleate;
stearic acid derivatives such as n-butyl stearate and diethylene glycol distearate;
Other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester;
Phosphoric acid derivatives such as triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate;
Diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexoate), dibutylmethylene bisthioglycolate, etc. A glycol derivative of
Glycerol derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate;
Polyester plasticizers such as adipic acid polyester, sebacic acid polyester, phthalic acid polyester;
Etc. The primary plasticizer mentioned above may use 1 type (s) or 2 or more types. Among them, as the primary plasticizer, trimellitic acid ester and pyromellitic acid ester are preferable, trimellitic acid ester is more preferable, trimellitic acid tri-n-octyl, trimellitic acid tri- (2-ethylhexyl), trimellitic acid Tri-n-nonyl acid and tri-n-decyl trimellitic acid are more preferable, and tri- (2-ethylhexyl) trimellitic acid is particularly preferable.

  In addition, so-called secondary plasticizers include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; chlorinated paraffins; fatty acid esters of glycols such as triethylene glycol dicaprylate; phenyl oleate; methyl dihydroabietic acid And the like. The secondary plasticizer mentioned above may use together 1 type (s) or 2 or more types with a primary plasticizer. Especially, as a secondary plasticizer, an epoxidized vegetable oil is preferable and an epoxidized soybean oil is more preferable.

  The content of the plasticizer with respect to 100 parts by mass of the vinyl chloride resin (a) is preferably 30 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 90 parts by mass or more, and preferably 190 parts by mass or less. The amount is more preferably equal to or less than mass parts, and still more preferably equal to or less than 160 parts by mass. This is because if the content of the plasticizer is at least the above lower limit, good flexibility at low temperatures can be imparted to a vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition for powder molding. . Further, if the content of the plasticizer is not more than the above upper limit, the fluffiness of a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding can be reduced, and the plasticizer This is because (a) the vinyl chloride resin is well absorbed and the powder moldability of the vinyl chloride resin composition for powder molding is improved.

<< Perchloric acid-treated hydrotalcite >>
The vinyl chloride resin composition for powder molding of the present invention may contain perchloric acid-treated hydrotalcite. Perchloric acid-treated hydrotalcite, for example, by adding hydrotalcite to a dilute aqueous solution of perchloric acid, stirring, and then filtering, dehydrating or drying as necessary, thereby allowing carbonate anions in hydrotalcite It can be easily produced by substituting at least a part of (CO ₃ ²⁻ ) with a perchlorate anion (ClO ₄ ⁻ ) (2 mol of perchlorate anion is substituted for 1 mol of carbonate anion). Although the molar ratio of the hydrotalcite to the perchloric acid can be arbitrarily set, it is generally 0.1 mol or more and 2 mol or less of perchloric acid with respect to 1 mol of hydrotalcite.

  The substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted) hydrotalcite is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 85 mol% or more. Further, the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted) hydrotalcite is preferably 95 mol% or less. Chloride formed by powder molding a vinyl chloride resin composition for powder molding because the substitution rate of carbonate anions in untreated (unsubstituted) hydrotalcite to perchlorate anions is within the above range. This is because the vinyl resin molded body can be imparted with good flexibility at low temperatures and the fluffiness of the vinyl chloride resin molded body can be lowered.

Hydrotalcite 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− It is an inorganic substance having a layered crystal structure composed of a layer [Mg _1−x Al _x (OH) ₂ ] ^{x +} and a negatively charged intermediate layer [(CO ₃ ) _{x / 2} · mH ₂ O] ^x− . Here, in the above general formula, x is a number in the range of greater than 0 and less than or equal to 0.33. Natural hydrotalcite is Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O is commercially available as the synthesized hydrotalcite. A method for synthesizing a synthetic hydrotalcite is described in, for example, Japanese Patent Publication No. 61-174270.

  The content of perchloric acid-treated hydrotalcite with respect to 100 parts by mass of (a) vinyl chloride resin is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, preferably 1.5 parts by mass or more, and 7 parts by mass. Part or less, preferably 6 parts by weight or less, more preferably 5.5 parts by weight or less. When the content of the perchloric acid-treated hydrotalcite is within the above range, better flexibility at low temperatures is imparted to a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding. This is because the fluffiness of the vinyl chloride resin molded product can be further reduced.

<< Zeolite >>
The vinyl chloride resin composition for powder molding of the present invention can contain zeolite as a stabilizer. Zeolite is represented by the general formula: M _{x / n} · [(AlO ₂ ) _x · (SiO ₂ ) _y ] · zH ₂ O (in the above general formula, M is a metal ion of valence n, x + y is four sides per unit cell) The number of bodies, z is the number of moles of water), and the type of M in the general formula is a monovalent or divalent metal such as Na, Li, Ca, Mg, Zn And mixed types thereof.

  The content of zeolite is not limited to a specific range. The content of the zeolite is preferably 0.1 parts by mass or more and preferably 5 parts by mass or less with respect to 100 parts by mass of the (a) vinyl chloride resin. When the zeolite content is within the above range, a vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition for powder molding can be imparted with good flexibility at low temperatures and a vinyl chloride resin molded article. This is because the fluffiness of can be lowered.

<< β-diketone >>
β-diketone can be used to more effectively suppress fluctuations in the initial color tone of a vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition for powder molding of the present invention. Specific examples of β-diketone are dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, and the like. These β-diketones may be used singly or in combination of two or more.
In addition, content of (beta) -diketone is not limited to a specific range. The content of β-diketone is preferably 0.1 parts by mass or more and preferably 5 parts by mass or less with respect to 100 parts by mass of (a) vinyl chloride resin.

<< Fatty acid metal salt >>
The vinyl chloride resin composition for powder molding of the present invention may contain a fatty acid metal salt. Preferred fatty acid metal salts are monovalent fatty acid metal salts, more preferred fatty acid metal salts are monovalent fatty acid metal salts having 12 to 24 carbon atoms, and more preferred fatty acid metal salts having 15 to 21 carbon atoms. It is a monovalent fatty acid metal salt. Specific examples of the fatty acid metal salt include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, 2-ethylhexane Barium acid, zinc 2-ethylhexanoate, barium ricinoleate, zinc ricinoleate and the like. The metal constituting the fatty acid metal salt is preferably a metal capable of generating a polyvalent cation, more preferably a metal capable of generating a divalent cation, and a divalent cation of the third to sixth periods of the periodic table. Is more preferable, and a metal capable of generating a divalent cation in the fourth period 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 with respect to 100 parts by mass of the (a) vinyl chloride resin is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 5 parts by mass or less, and more preferably 1 part by mass or less. Preferably, 0.5 mass part or less is still more preferable. When the content of the fatty acid metal salt is in the above range, a vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition for powder molding can be imparted with good flexibility at low temperatures and a vinyl chloride resin. This is because the fluffing property of the molded product can be lowered, and further the discoloration after the heat resistance test can be reduced.

<< Other dusting agents >>
The vinyl chloride resin composition for powder molding of the present invention may further contain (a2) a dusting agent other than the vinyl chloride resin fine particles (hereinafter sometimes referred to as “other dusting agent”). Specific examples of other dusting agents 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 Organic fine particles such as fine particles and polyamide resin fine particles; Among these, inorganic fine particles having an average particle size of 10 nm to 100 nm are preferable.

  The content of other dusting agents is not limited to a specific range. The content of other dusting agents is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and can be 0 parts by mass with respect to 100 parts by mass of (a) the vinyl chloride resin. .

<< Other additives >>
The vinyl chloride resin composition for powder molding of the present invention comprises a colorant, an impact modifier, a perchloric acid compound other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.), oxidation Other additives such as an inhibitor, an antifungal agent, a flame retardant, an antistatic agent, a filler, a light stabilizer, and a foaming agent may be further contained.

Specific examples of the colorant are quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, titanium white, and carbon black. One or more pigments are used. The quinacridone pigment is obtained by treating p-phenylene dianthranilic acid with concentrated sulfuric acid, and exhibits a yellowish red to reddish purple hue. Specific examples of the quinacridone pigment are quinacridone red, quinacridone magenta, and quinacridone violet.
The perylene pigment is obtained by a condensation reaction of perylene-3,4,9,10-tetracarboxylic anhydride and an aromatic primary amine, and exhibits a hue from red to magenta and brown. Specific examples of the perylene pigment are perylene red, perylene orange, perylene maroon, perylene vermilion, and perylene bordeaux.
The polyazo condensation pigment is obtained by condensing an azo dye in a solvent to obtain a high molecular weight, and exhibits a hue of a yellow or red pigment. Specific examples of the polyazo condensation pigment are polyazo red, polyazo yellow, chromophthal orange, chromophthal red, and chromophthal scarlet.
The isoindolinone-based pigment is obtained by a condensation reaction of 4,5,6,7-tetrachloroisoindolinone and an aromatic primary diamine, and exhibits a hue from greenish yellow to red and brown. A specific example of the isoindolinone pigment is isoindolinone yellow. The copper phthalocyanine pigment is a pigment in which copper is coordinated to phthalocyanines, and exhibits a hue of yellowish green to vivid blue.
Specific examples of the copper phthalocyanine pigment are phthalocyanine green and phthalocyanine blue.
Titanium white is a white pigment made of titanium dioxide and has a large hiding power, and there are anatase 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.

  Specific examples of the impact modifier include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, chlorosulfonated polyethylene and the like. In the vinyl chloride resin composition for powder molding of the present invention, one or more impact resistance improvers can be used. The impact resistance improver is dispersed as a heterogeneous phase of fine elastic particles in the vinyl chloride resin composition for powder molding. In the vinyl chloride resin composition for powder molding of the present invention, the chain and polar group graft-polymerized on the elastic particles are compatible with (a) the vinyl chloride resin, and the impact resistance of the vinyl chloride resin composition is improved.

  Specific examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.

  Specific examples of the antifungal agent include aliphatic ester antifungal agents, hydrocarbon antifungal agents, organic nitrogen antifungal agents, organic nitrogen sulfur antifungal agents, and the like.

  Specific examples of the flame retardant include halogen-based flame retardants such as chlorinated paraffins; phosphorus-based flame retardants such as phosphate esters; inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide;

  Specific examples of the antistatic agent include anionic antistatic agents such as fatty acid salts, higher alcohol sulfates 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;

  Specific examples of the filler are silica, talc, mica, calcium carbonate, clay and the like.

  Specific examples of the light stabilizer include benzotriazole-based, benzophenone-based, nickel chelate-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

  Specific examples of the blowing agent include azo compounds such as azodicarbonamide and azobisisobutyronitrile, nitroso compounds such as N, N'-dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, p, p-oxybis (benzene). Organic foaming agents such as sulfonyl hydrazide compounds such as sulfonyl hydrazide; volatile hydrocarbon compounds such as chlorofluorocarbon gas, carbon dioxide gas, water and pentane; gas-based foaming agents such as microcapsules enclosing these.

<Preparation of vinyl chloride resin composition for powder molding>
Here, the mixing method of (a) vinyl chloride resin particles, (b) epoxy resin, (c) silicone oil having a viscosity of 10 cs to 200 × 10 ⁴ cs, and additives added as necessary is limited. Not. In a preferred mixing method, components other than the dusting agent (including (a2) vinyl chloride resin fine particles and other dusting agent added as necessary) are once mixed by dry blending, and then the dusting agent. Is added and mixed. The Henschel mixer is preferably used for dry blending. The temperature during dry blending is preferably 50 ° C or higher, more preferably 70 ° C or higher, and preferably 200 ° C or lower.

(Vinyl chloride resin molding)
The vinyl chloride resin molded article of the present invention is obtained by powder molding, preferably powder slush molding, of the vinyl chloride resin composition for powder molding of the present invention. The vinyl chloride resin molded article of the present invention is suitably used as an automobile interior material, for example, a skin of an automobile instrument panel, a door trim or the like.

<Manufacture of vinyl chloride resin molding>
Here, the mold temperature at the time of powder slush molding is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, preferably 300 ° C. or lower, more preferably 280 ° C. or lower.
In addition, the vinyl chloride resin molded body of the present invention is obtained by, for example, sprinkling a powder molding vinyl chloride resin composition on a mold in the above temperature range and leaving it for 5 seconds to 30 seconds, and then surplus vinyl chloride resin. The composition is shaken off, and is further allowed to stand for 30 seconds to 3 minutes at an arbitrary temperature. Thereafter, the mold is cooled to 10 ° C. or more and 60 ° C. or less, and the obtained vinyl chloride resin molded article is removed from the mold to be suitably obtained.

(Laminate)
The laminate of the present invention can be obtained by providing the vinyl chloride resin molded body and the foamed polyurethane molded body described above. The lamination method is as follows: (1) A vinyl chloride resin molded body and a foamed polyurethane molded body are separately manufactured, and then bonded together by using thermal fusion, thermal bonding, or a known adhesive; (2) Chlorination Polymerization is performed by reacting isocyanates, which are raw materials of the foamed polyurethane molded body, and polyols on the vinyl resin molded body, and polyurethane is foamed by a known method, and the polyurethane foam is formed on the vinyl chloride resin molded body. And a method of directly forming a molded body. In the latter method (2), the process is simple, and even when a laminated body having various shapes is obtained, the vinyl chloride resin molded body and the foamed polyurethane molded body can be reliably bonded. Therefore, it is more preferable.

  And the laminated body of this invention is used suitably as a vehicle interior material, for example, a vehicle instrument panel, a door trim, etc.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In addition, the measuring method of various physical properties is as follows.

<Viscosity of silicone oil>
The viscosity of the silicone oil was measured as a kinematic viscosity η ^{CS / 25} (unit: mm ² / s = cs) at a temperature of 25 ° C. using an Ubbelohde viscometer according to ASTM D 445-46T.

<Average polymerization degree of vinyl chloride resin>
The average degree of polymerization of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin constituting the vinyl chloride resin fine particles is in accordance with JIS K6720-2. (A1) Vinyl chloride resin particles and (a2) vinyl chloride resin Each fine particle was calculated by dissolving in cyclohexanone and measuring the viscosity.

<Average particle diameter of vinyl chloride resin (fine) particles>
The average particle diameter of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles is a volume average particle diameter, and each of the vinyl chloride resin particles and the vinyl chloride resin fine particles is dispersed in a water tank, and the following apparatus is used. Then, the diffraction / scattering intensity distribution of light was measured and analyzed, and the particle diameter distribution based on the particle diameter and volume was measured.
Apparatus: Laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model number “SALD-2300”)
Measurement method: Laser diffraction and scattering Measurement range: 0.017 μm to 2500 μm
Light source: Semiconductor laser (wavelength 680 nm, output 3 mW)

<Low temperature tensile test (initial)>
The obtained vinyl chloride resin molded sheet as a vinyl chloride resin molded article was used as a sample, and the sample was punched with a No. 1 dumbbell described in JISK6251. Then, based on JIS K 7113, tensile stress (MPa) and tensile elongation (%) were measured at a tensile rate of 200 mm / min and a low temperature of −35 ° C. A larger tensile elongation at a low temperature of −35 ° C. indicates that the vinyl chloride resin molded article is more excellent in flexibility at a low temperature. The results are shown in Table 1.

<Low temperature tensile test (after heating)>
The obtained laminate with a foamed polyurethane molded article was used as a sample, the sample was put in an oven, and the sample was heated in an environment at a temperature of 130 ° C. for 250 hours. Thereafter, the polyurethane foam layer was peeled from the sample, and the tensile stress (MPa) and the tensile elongation (%) were measured at a low temperature of −35 ° C. under the same conditions as in the low temperature tensile test (initial). It shows that the larger the tensile elongation at −35 ° C., the better the vinyl chloride resin molded body is in heat resistance (flexibility at low temperature after heating). The results are shown in Table 1.

<Fuzzy property test>
The obtained laminate on which the polyurethane foam molded article was lined was cut into a size of 170 mm × 300 mm to obtain a test piece. In addition, arbitrary 20 places which measure a color difference were previously defined about the vinyl chloride resin molded object side of the said test piece. And about the said 20 places, the brightness (L value) of the surface of the test piece (vinyl chloride resin molding side) before an abrasion test was measured using the color difference meter (the product name "CR-400" by Konica Minolta Sensing Co., Ltd.). did.
Next, the sample piece was placed on a sample stand of a Gakushin abrasion tester (manufactured by Daiei Kagaku Seiki Seisakusho, product name “RT-200”) with the vinyl chloride resin molded article side facing up. . And the load of 500g was attached to the said abrasion tester, and the total load applied to a test piece was set to 500g. Next, after attaching one paper towel (Nippon Paper Crecia Co., Ltd., product name “COMFORT”) to the tip of the abrasion tester, the paper towel is attached to the surface of the test piece on the side of the vinyl chloride resin molded product. The test piece surface and the paper towel were brought into contact with each other by reciprocating 10 times while in contact with the test piece. And about 20 places on the vinyl chloride resin molded body of the above-mentioned predetermined test piece, using the same color difference meter as described above, the brightness of the surface of the test piece (vinyl chloride resin molded body side) after the wear test ( L value) was measured. And the average value of the brightness difference (ΔL value = L value obtained after the wear test−L value obtained before the wear test) at the 20 locations before and after the wear test was calculated. The smaller the ΔL value, the lower the fluffing property of the vinyl chloride resin molded product, and the less the fiber residue adheres. The results are shown in Table 1.

(Examples 1-5 and Comparative Example 1)
<Preparation of vinyl chloride resin composition>
Of the ingredients shown in Table 1, ingredients except trimellitic acid ester plasticizer and epoxidized soybean oil as plasticizer and two kinds of vinyl chloride resin fine particles as dusting agents A and B are put in a Henschel mixer. And mixed. When the temperature of the mixture rises to 80 ° C., all the plasticizer is added to obtain a mixture, and the mixture is further heated to dry up (the plasticizer is absorbed by the vinyl chloride resin particles). , Refers to a state in which the mixture is further improved.). Thereafter, when the dried-up mixture was cooled to a temperature of 100 ° C. or lower, two kinds of vinyl chloride resin fine particles as dusting agents A and B were added to prepare a vinyl chloride resin composition for powder molding. .

<Manufacture of vinyl chloride resin molding>
The obtained powdered vinyl chloride resin composition for powder molding is sprinkled on a mold with a texture heated to a temperature of 250 ° C., and an arbitrary time of about 10 seconds to 20 seconds so that the thickness of the vinyl chloride resin molded sheet becomes 1 mm. After leaving it to melt, the excess vinyl chloride resin composition was shaken off. Thereafter, the embossed mold sprinkled with the vinyl chloride resin composition was allowed to stand in an oven set at a temperature of 200 ° C., and when 60 seconds had elapsed from the standing, the embossed mold was cooled with cooling water. When the mold temperature was cooled to 40 ° C., a vinyl chloride resin molded sheet of 150 mm × 200 mm × 1 mm was removed from the mold as a vinyl chloride resin molded body.
And the low-temperature tensile test (initial stage) was implemented about the obtained vinyl chloride resin molded sheet according to the above-mentioned method. The results are shown in Table 1.

<Manufacture of laminates>
Two sheets of the obtained vinyl chloride resin molded sheet were laid in a 200 mm × 300 mm × 10 mm mold so as not to overlap with the embossed surface down.
Separately, propylene oxide / propylene oxide / ethylene oxide (PO / EO) block adduct (hydroxyl value 28, content of terminal EO unit = 10%, content of internal EO unit 4%), 50 parts by mass of glycerin PO. EO block adduct (hydroxyl value 21, terminal EO unit content = 14%) 50 parts by mass, water 2.5 parts by mass, ethylene glycol solution of triethylenediamine (manufactured by Tosoh Corporation, trade name “TEDA-” L33 ") 0.2 parts by mass, 1.2 parts by mass of triethanolamine, 0.5 parts by mass of triethylamine, and 0.5 parts by mass of a foam stabilizer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name" F-122 ") A polyol mixture consisting of parts was prepared. Then, the prepared polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) were mixed at a ratio of an index of 98 to prepare a mixed solution. And the prepared liquid mixture was each poured on 2 sheets of vinyl chloride resin molding sheets spread | laid in the metal mold | die as above-mentioned. Thereafter, the mold was sealed by covering the mold with an aluminum plate of 348 mm × 255 mm × 10 mm. 5 minutes after sealing the mold, a laminate of 9 mm thick and 0.18 g / cm ³ density foamed polyurethane molded product on the skin made of 1 mm thick vinyl chloride resin molded sheet is taken out from the mold. It was.
And about the obtained laminated body, the low temperature tension test (after heating) and the fluffiness test were implemented according to the above-mentioned method. The results are shown in Table 1.

1) ZEST (registered trademark) 2500Z manufactured by Shin Daiichi PVC Co., Ltd. ((a1) vinyl chloride resin particles, average degree of polymerization: 2500, average particle diameter: 130 μm)
2) TOTM manufactured by Mitsubishi Gas Chemical Company, Inc.
3) Adeka Sizer O-130S manufactured by ADEKA Corporation
4) Alkamizer 5 manufactured by Kyowa Chemical Industry Co., Ltd.
5) Mizukaizer DS, manufactured by Mizusawa Chemical Co., Ltd.
6) Karenz DK-1, manufactured by Showa Denko K.K.
7) SAKAI SZ2000, manufactured by Sakai Chemical Industry Co., Ltd.
8) Shin-Etsu Silicone Co., Ltd., KF-96H-10,000cs
9) Shin-Etsu Silicone Co., Ltd., KF-96H-300,000 cs
10) EPICLON 850 manufactured by DIC Corporation (bisphenol A type liquid epoxy resin, epoxy group equivalent: 188 g / eq.)
11) ZEST (registered trademark) PQLTX manufactured by Shin Daiichi PVC Co., Ltd. ((a2) vinyl chloride resin fine particles obtained by emulsion polymerization, average degree of polymerization: 800, average particle size: 2 μm)
12) manufactured by Tosoh Corporation, Leuron Paste (registered trademark) 860 ((a2) vinyl chloride resin fine particles obtained by emulsion polymerization, average degree of polymerization: 1600, average particle size: 2 μm)
13) DAPX-1720 Black (A), manufactured by Dainichi Seika Kogyo Co., Ltd.

In the vinyl chloride resin molded bodies obtained by powder slush molding of the powder molding vinyl chloride resin compositions of Examples 1 to 5, the tensile properties after heating at low temperatures and after heating are excellent, so Excellent flexibility and low fuzziness. Further, it was obtained by powder slush molding of (b) an epoxy resin and (c) a vinyl chloride resin composition for powder molding of Comparative Example 1 which does not contain silicone oil having a viscosity of 10 cs to 200 × 10 ⁴ cs. In the vinyl chloride resin molded article, the tensile stress after heating at low temperature and the tensile elongation after heating were low, so the vinyl chloride resin molded article after heating was inferior in flexibility at low temperature and had high fuzziness.

  The vinyl chloride resin composition for powder molding of the present invention is suitably molded on the skin of automobile interior materials, such as automobile instrument panels and door trims.

Claims (10)

(A) a vinyl chloride resin, (b) an epoxy resin, and (c) a silicone oil having a viscosity of 10 cs or more and 200 × 10 ⁴ cs or less,
Vinyl chloride resin composition for powder molding.   The vinyl chloride resin for powder molding according to claim 1, wherein a content of the (b) epoxy resin is 0.2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (a) vinyl chloride resin. Composition. Content of the silicone oil whose (c) viscosity is 10 cs or more and 200 × 10 ⁴ cs or less is 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (a) vinyl chloride resin. Item 3. The vinyl chloride resin composition for powder molding according to Item 1 or 2. The (a) vinyl chloride resin comprises (a1) vinyl chloride resin particles having an average degree of polymerization of 800 or more and 5000 or less, and (a2) vinyl chloride resin fine particles having an average degree of polymerization of 500 or more and 5000 or less,
The content ratio of the vinyl chloride resin particles (a1) having an average degree of polymerization of 800 or more and 5000 or less is 70% by mass or more and 100% by mass or less,
4. The powder molding according to claim 1, wherein a content ratio of the vinyl chloride resin fine particles having an average degree of polymerization of 500 to 5000 is 0% by mass to 30% by mass. Vinyl chloride resin composition.   The vinyl chloride resin composition for powder molding according to any one of claims 1 to 4, which is used for powder slush molding.   A vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition for powder molding according to any one of claims 1 to 5.   A vinyl chloride resin molded article obtained by powder slush molding the powder molding vinyl chloride resin composition according to any one of claims 1 to 5.   The vinyl chloride resin molded article according to claim 6 or 7, which is used for an automobile instrument panel skin.   The laminated body which has a foaming polyurethane molded object and the vinyl chloride resin molded object of any one of Claims 6-8.   The laminate according to claim 9, which is used for an automobile instrument panel.