JP2008150588A - Resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that can give a molded article excellent in sealing effect and having high flame retardancy and dimensional stability. <P>SOLUTION: The resin composition comprises 100 pts.mass vinyl chloride resin, 1-30 pts.mass phosphoric acid plasticizer and 1-50 pts.mass inorganic filler. The resin composition uses talc as the inorganic filler. The resin composition has an average degree of polymerization of the vinyl chloride resin of not less than 500. The resin composition contains as the vinyl chloride resin a chlorinated vinyl chloride resin having a chlorine content of not less than 60 mass%. A molded article using the resin composition, a sealing material using the same and a compound produced by granulation of the resin composition are provided. A process for producing a molded article comprises subjecting the resin composition and a soft vinyl chloride resin to co-extrusion molding. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a resin composition, a molded body using the resin composition, a sealing material, a compound, and a method for producing the molded body.

  Sealing materials such as packing and gaskets are used in order to maintain the airtightness of structures such as buildings, automobiles, and kitchen appliances, and prevent rainwater and dust from entering the structure. The sealing material is required to have a structure having conflicting elements, that is, a characteristic of a soft member having an excellent sealing effect and a characteristic of a hard member having rigidity necessary for assembly work.

  As a material for the sealing material, vinyl chloride resin, chloroprene rubber, and silicon rubber are known. When chloroprene rubber or silicon rubber is used, the rigidity required for the assembly work may be insufficient, and a vinyl chloride resin that can easily control the rigidity has been attracting attention.

  As a method of forming a vinyl chloride resin to form a sealing material, methods of extrusion molding and injection molding are known. In extrusion molding, a coextrusion method in which a metal and a resin are melted and integrated inside a mold is used. The sealing material coextruded with the metal requires a labor for separating the vinyl chloride resin and the metal in the recycling process, which may cause an increase in cost.

  In order to save labor in the recycling process, a method is known in which a hard vinyl chloride resin is used in place of metal, and this hard vinyl chloride resin and soft vinyl chloride resin are coextruded to form a sealing material ( (See Patent Document 1).

In order to improve the heat resistance of the sealing material, a molded product made by co-extrusion molding of a chlorinated vinyl chloride resin or a hard vinyl chloride resin mainly composed of a vinyl chloride resin and this. Is known as a sealing material (see Patent Document 2, etc.).

  In order to prolong the life of the sealing material, dimensional stability in the actual use temperature range of 80 to 110 ° C. is required. As a method for reducing thermal expansion and shrinkage on the soft resin side of the sealing material, a method of adding talc to a vinyl chloride resin is known (see Patent Document 3).

  In automobile applications and architectural applications, especially in architectural applications called “Otsunoue fire doors”, flame retardancy is required from the viewpoint of fire prevention in the event of a fire.

JP 62-011787 A Japanese Patent Application Laid-Open No. 08-099343 JP-A-11-279360

  An object of this invention is to provide the resin composition which can obtain the molded object which is excellent in the sealing effect, and has a high flame retardance and dimensional stability, and such a molded object.

  The resin composition of the present invention contains 100 parts by mass of a vinyl chloride resin, 1 to 30 parts by mass of a phosphoric acid plasticizer, and 1 to 50 parts by mass of an inorganic filler.

  A molded body such as a sealing material using the resin composition of the present invention has an excellent sealing effect, and has high flame retardancy and dimensional stability. Therefore, it is suitable for uses such as parts that require flame retardance among building materials, such as outer wall materials, window frames, and glass gaskets, and is particularly suitable for multilayer glass gaskets.

Hereinafter, the present invention will be described in detail. In the present specification, the monomer unit means a structural unit derived from a monomer. Further, parts and% in this specification are based on mass unless otherwise specified.

<Vinyl chloride resin>
The vinyl chloride resin may be any resin having a vinyl chloride unit or a chlorinated vinyl chloride unit in the main chain, and examples thereof include a homopolymer of vinyl chloride. In addition, vinyl chloride resin
It may be a copolymer having monomer units derived from vinyl compound monomers other than vinyl chloride in the main chain or side chain. Examples of such a copolymer include a vinyl chloride graft polymer having an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, a chlorinated polyethylene, or the like in the side chain.

Examples of vinyl compound monomers other than vinyl chloride used for vinyl chloride resins include (1) vinyl esters such as vinyl acetate and vinyl propionate,
(2) acrylic acid esters such as methyl acrylate and butyl acrylate,
(3) Methacrylic acid esters such as methyl methacrylate and ethyl methacrylate,
(4) Maleic acid esters such as butyl maleate and diethyl maleate,
(5) fumaric acid esters such as dibutyl fumarate and diethyl fumarate,
(6) Vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether,
(7) Vinyl cyanides such as acrylonitrile and methacrylonitrile,
(8) Olefin such as ethylene, propylene and styrene,
(9) Vinylidene halides and vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide,
(10) Phthalic acid esters such as diallyl phthalate.

The vinyl chloride resin preferably contains a chlorinated vinyl chloride resin such as a chlorinated vinyl chloride resin alone or a mixture of a chlorinated vinyl chloride resin and a vinyl chloride resin. In this case, the chlorine content of the chlorinated vinyl chloride resin is preferably 60% by mass or more. If the chlorine content of the chlorinated vinyl chloride resin is 60% by mass or more, it is difficult to ignite and flame during heating, and the heat resistant temperature is improved.

The proportion of chlorinated vinyl chloride units in the vinyl chloride resin is preferably 50 parts by mass or more of chlorinated vinyl chloride units in a total of 100 parts by mass of vinyl chloride units and chlorinated vinyl chloride units. When the chlorinated vinyl chloride unit is 50 parts by mass or more, the heat resistant temperature is improved and the mechanical strength is high.

For example, a vinyl chloride resin can be produced by, for example, a monomer such as vinyl chloride by suspension polymerization, bulk polymerization,
Examples of the polymerization method include a fine suspension polymerization method and an emulsion polymerization method. In addition, vinyl chloride resin having a vinyl chloride unit chlorinated vinyl chloride unit is a powder of vinyl chloride resin in the gas phase.
Alternatively, it can be produced by chlorination in a state suspended in water or dissolved in a solvent. (For example, see Japanese Patent Publication No. 36-888 and Japanese Patent Publication No. 45-30833)

(Degree of polymerization of vinyl chloride resin)
The average degree of polymerization of the vinyl chloride resin is 5 as an average degree of polymerization measured according to JIS K-6721.
00 or more is preferable, and 500-1500 is more preferable. If the average degree of polymerization is within the above range, the molding processability is good, so that various shapes can be used as the core material of the gasket.

<Phosphoric plasticizer>
The phosphate plasticizer is not particularly limited as long as it is a phosphate plasticizer for a vinyl chloride resin. For example, tricresyl phosphate (TCP), triphenyl phosphate, trixyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, Cresyl diphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) ) Phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl phosphate, halogen-containing polyphosphate, etc. Resorcinol bis (phenyl) phosphate (RDP
), Resorcinol bis (2,6-dixylenyl) phosphate, bisphenol A bis (diphenyl) phosphate (BPADP), bisphenol A bis (dicresyl) phosphate (BPADC), and the like. Condensed phosphoric acid plasticizers are preferably used from the viewpoint of not lowering the softening point, and these phosphoric acid plasticizers may be used alone or in combination of two or more.

The compounding quantity of a phosphoric acid type plasticizer is 1-30 mass parts with respect to 100 mass parts of vinyl chloride-type resin, and 2-15 mass parts is more preferable. If it is the said range, since fusion property with a soft vinyl chloride resin is good, the hardness of a molded object is high, and there is little deformation | transformation in high temperature atmosphere, it is preferable.

When a phosphoric acid plasticizer and a non-phosphoric acid plasticizer such as a polyester plasticizer, trimellitic acid plasticizer, and phthalic acid plasticizer are used in combination, the phosphoric acid plasticizer is preferably hardly volatilized.

<Inorganic filler>
Examples of the inorganic filler include talc, calcium carbonate, aluminum hydroxide, and silica powder, and talc is preferably used. As the inorganic filler, a mixed powder of a plurality of components or a powder having a plurality of particle size distributions may be used in combination.

When a molded product is produced by coextrusion using talc as an inorganic filler, the deformation of the molded product due to thermal expansion and contraction of the soft vinyl chloride resin is small, and at the contact portion between the soft vinyl chloride resin and the resin composition Is preferable because of good adhesion and high impact strength.

Talc is a kind of clay mineral of hydrous magnesium silicate, and its composition is (MgO) _x (SiO ₂ ) _y · zH ₂ O (x, y, z are positive values). A part of Mg in talc may be substituted with a divalent metal ion such as Ca ²⁺ . The particle size of talc is not particularly limited, but is preferably 0.8 μm to 30 μm, more preferably 1.0 μm to 25 μm, and most preferably 1.5 μm to 20 μm as a median particle size by laser scattering. Within this range, a smooth surface with good dispersibility can be obtained as compared with the case where the median particle size of talc is small, and the surface of the molded product becomes smooth compared with the case where the median particle size is large, and the appearance is good. Become.

When using calcium carbonate, aluminum hydroxide, and silica, a powder having a BET specific surface area of 1 to 100 m ² / g is preferably used.

The compounding amount of the inorganic filler is 1 to 50 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
It is preferable that it is 2-25 mass parts. Within the above range, it is preferable that the glass does not easily come off from the window when the sealing material burns due to a fire or the like, the surface of the molded body is smooth, and molding is easy.

<Other ingredients>
The resin composition may contain an appropriate amount of various additives such as a stabilizer, a filler, a reinforcing agent, a processing aid, a lubricant and a pigment as necessary. These additives are preferably used with a small or zero lead content in consideration of environmental aspects.

A stabilizer is not specifically limited, A lead type stabilizer and a non-lead type stabilizer are mentioned. When a lead-based stabilizer is used, a resin having excellent continuous lubricity and good moldability can be obtained. The stabilizer is preferably a lead-free stabilizer from the viewpoint of the environment, and a barium-zinc stabilizer, a calcium-zinc stabilizer, and the like are preferably used.

The pigment is preferably an inorganic substance that does not contain lead, antimony, and chromium, such as titanium oxide,
Inorganic pigments such as iron oxide, ultramarine, carbon black, monoazo, disazo, phthalocyanine,
Organic pigments such as quinacridone, perylene, and isoindolinone are preferably used.

  Various additives such as processing aids and lubricants may be appropriately added to the resin composition.

<Vicat softening point temperature of resin composition>
The resin composition preferably has a Vicat softening point temperature defined by JIS K 7206 of 80 ° C. or higher, more preferably 85 ° C. or higher. When the Vicat softening point temperature is within this range, the deformation of the molded product is small and preferable when exposed to a high temperature atmosphere.

<Method for producing resin composition>
The manufacturing method of a resin composition is not specifically limited, For example, the method of mixing each component of a resin composition and melt-molding is mentioned. The means used to manufacture the resin composition and the mixing procedure of each component are not limited. For example, (1) a method in which raw materials are mixed and directly molded into a sealing material, or (2) a phosphoric acid plasticizer and an inorganic filler are used. There is a method in which the compound to be contained is produced in advance, and the compound and the vinyl chloride resin are heated and melted and molded with an extruder. The compound is preferably granulated and formed into a pellet.

As a method for mixing the raw materials of the resin composition, for example, a high speed mixer such as a Henschel mixer or a super mixer, a mixer such as a ribbon blender, or the like is used. As a mixing method, it is preferable that each component is charged into the above mixer and uniformly blended at a temperature of, for example, 150 ° C. or less for a time commensurate with each mixer. A Banbury mixer, a mixing roll, an extruder, etc. can be used for granulation.

The pellets can be produced by a granulator such as a single screw extruder, a twin screw extruder, a slant shaft extruder, a kneader, or a Banbury mixer.

<Molded body>
A method for obtaining a molded body from the resin composition or compound of the present invention is, for example, using a plurality of kneading and extruding apparatuses, and injecting the resin composition of the present invention and a soft vinyl chloride resin into the same mold from different kneading and extruding apparatuses. A co-extrusion molding method, that is, a two-color molding method is preferably used.

The use of the molded body is not limited, and it can be used as a sealing material for packing and gaskets for general building materials. For example, it is suitable for use in building gaskets, packing and joint materials that require flame resistance. Used for.

The molded body is suitable for uses such as building materials that require flame retardancy, such as outer wall materials, window frames, glass gaskets, etc., and is suitably used for multilayer glass gaskets.

As an example of the molded article of the present invention, a multilayer glass gasket for construction formed by coextrusion molding of the resin composition of the present invention and a soft vinyl chloride resin will be described. The gasket core material is made of the resin composition of the present invention, and the gasket lip material is made of a soft vinyl chloride resin. The gasket lip material consists of two layers of soft vinyl chloride resin. The gasket lip material and the gasket core material are in contact with the window glass and sealed to maintain airtightness. To prevent intrusion.

<Materials used>
The raw materials used in each example and comparative example are shown below.

(1) Vinyl chloride resin Chlorinated vinyl chloride resin: H-527 (chlorine content 65.0%), manufactured by Kaneka Chemical Co., Ltd., average polymerization degree 700

(2) Phosphate plasticizer tricresyl phosphate, commercial product

(3) Inorganic filler Inorganic filler A: Talc, made in China, average particle size 13 μm, commercial product Inorganic filler B: Talc, made in China, average particle size 3 μm, commercial product Inorganic filler C: Calcium carbonate, Nitto flour NS400N manufactured by Kagaku Kogyo Co., Ltd.
Inorganic filler D: Aluminum hydroxide, Hygielite H42S manufactured by Showa Denko KK

(4) Others Stabilizer: Barium-zinc system, commercial product Pigment: Titanium oxide, commercial product

(5) Soft vinyl chloride resin composition Soft vinyl chloride resin composition A: Pellet containing 100 parts by weight of vinyl chloride resin (polymerization degree 1700, commercially available product) and 90 parts by weight of a phosphoric acid plasticizer Soft vinyl chloride resin composition B: Pellet containing 100 parts by mass of vinyl chloride resin (degree of polymerization 1300, commercially available) and 90 parts by mass of phosphoric acid plasticizer

<Evaluation method>
The sample evaluation methods in each Example and Comparative Example are shown below.

(1) Evaluation of composition a) Tensile yield stress JIS K 7113, bending elastic modulus and bending strength JIS K 7171, Vicat softening point temperature Measured according to JIS K 7206.

b) Flame Retardancy Evaluated by a heat generation characteristic test for Type B fire door. A sample was placed in a 500 ° C. heating furnace for 10 minutes and examined for the presence or absence of flame. The flame was evaluated for flame arrival time. ○: No flame ×: Flame is present c) Oxygen index

  Evaluation was made based on JIS K7201.

(2) Evaluation of molded body a) Deformation After the coextruded molded body cut to a length of 10 mm × 10 mm × 500 mm was heated in an atmosphere at 70 ° C. for 24 hours, the appearance was evaluated for deformation and warpage. ○: No deformation ×: Deformation

b) Shrinkage rate The coextruded product was cut to a length of 500 mm and then heated in an atmosphere at 70 ° C for 24 hours. After removal, the length L was measured and divided by the initial length of 500 mm, and the shrinkage rate = [(500−L) / 500 × 100]% was calculated. ○: Shrinkage ratio over 0.1% ×: Shrinkage ratio 0.1% or more

<Example 1>
A vinyl chloride resin 100 parts by weight, a phosphoric acid plasticizer 1 part by weight, talc A 20 parts by weight, a stabilizer 4 parts by weight, and a pigment 1 part by weight are placed in a 75 liter Henschel mixer and stirred, and then 90 mm uniaxial The mixture was kneaded and pelletized with an extruder (manufactured by Ikekai Tekko Co., Ltd.) to obtain 15 kg of pellets of the resin composition. The properties of the obtained resin composition are shown in Table 1.

The obtained resin composition pellets were extruded with an extruder A, and the soft vinyl chloride resin composition A pellets were extruded with an extruder B, and coextruded at a die temperature of 170 ° C. to produce a gasket. Extruder A: 65mm single screw extruder (Ikegai Iron Works)
Extruder B: 40mm single screw extruder (Plastic Engineering Laboratory Co., Ltd.)

  The die for the co-extrusion molded body had two injection ports, and the one having a structure in which the resin composition and the soft vinyl chloride resin were separately injected from the two injection ports was used.

  Table 2 shows the characteristics of the obtained molded body.

<Examples 2 to 7, Comparative Examples 1 and 2>
A resin composition was obtained in the same manner as in Example 1 except that the composition was changed as shown in Table 1. The evaluation results are shown in Table 1.

Further, a molded body was obtained in the same manner as in Example 1 except that the soft vinyl chloride resin shown in Table 2 was used. The evaluation results are shown in Table 2.

Claims (8)

  A resin composition comprising 100 parts by mass of a vinyl chloride resin, 1 to 30 parts by mass of a phosphoric acid plasticizer, and 1 to 50 parts by mass of an inorganic filler.   The resin composition according to claim 1, wherein the inorganic filler is talc.   The resin composition according to claim 1 or 2, wherein the vinyl chloride resin has an average degree of polymerization of 500 or more.   The resin composition according to any one of claims 1 to 3, wherein the vinyl chloride resin contains a chlorinated vinyl chloride resin having a chlorine content of 60% by mass or more.   A molded body comprising the resin composition according to any one of claims 1 to 4.   A sealing material comprising the resin composition according to any one of claims 1 to 4.   A compound obtained by granulating the resin composition according to any one of claims 1 to 4.   A method for producing a molded body, comprising coextruding the resin composition according to any one of claims 1 to 4 and a soft vinyl chloride resin.