JP2005036110A - Vinyl chloride resin plate for vacuum forming - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vinyl chloride resin plate for vacuum forming slight in generation of hydrogen chloride gas when burned, and excellent in impact resistance, tensile elongation and vacuum formability. <P>SOLUTION: The vinyl chloride resin plate for vacuum forming has the following properties: Hydrogen chloride gas generation 4 min after starting the test is ≤500 ppm in the smoking test in accordance with ASTM E662, Izod impact strength at 23°C measured in accordance with JIS K7110 is 4.9-196.2 kJ/m<SP>2</SP>, and tensile elongation at 130°C measured in accordance with JIS K7113 is 200-700%. This resin plate comprises 100 pts. wt. of a vinyl chloride resin, 50-150 pts. wt. of precipitated calcium carbonate with a mean primary particle size of ≤0.3μm, 1-30 pts. wt. of an impact modifier and 1-30 pts. wt. of an acrylic processing auxiliary with a weight-average molecular weight of 1,000,000-5,000,000. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

TECHNICAL FIELD The present invention relates to a vinyl chloride resin plate for vacuum forming that generates a small amount of hydrogen chloride during combustion and has excellent impact resistance, vacuum formability, and the like.

Conventionally, vinyl chloride resin is a material for plant plates, pipes, pipe joints, and sheets as materials with excellent physical properties such as impact resistance and heat resistance, and chemical properties such as solvent resistance and acid resistance. It is used for many applications such as film.

However, since hydrochloric acid gas is generated when it is burned, it is required to reduce the amount of hydrochloric acid gas generated at the time of combustion in order to hinder the safety of passengers in the event of fire.

Examples of a method for reducing the amount of hydrochloric acid gas generated during combustion of a vinyl chloride resin include, for example, magnesium oxide, lead oxide, calcium carbonate, magnesium carbonate having an average particle size of 250 mμm or less in 100 parts of a soft vinyl chloride resin. A method of adding 60 parts or more of a filler capable of fixing an acid such as the above has been proposed (for example, see Patent Document 1).
Japanese Patent Publication No. 48-6168

As another method, there has been proposed a vinyl chloride resin composition obtained by adding 50 to 120 parts by weight of heavy calcium carbonate having a particle size of 1.3 μm or less to 100 parts by weight of a vinyl chloride resin (for example, , See Patent Document 2).
Japanese Patent Laid-Open No. 64-9259

Furthermore, it is a vinyl chloride resin composition obtained by adding 30 to 80 parts by weight of calcium carbonate powder as a hydrogen chloride scavenger per 100 parts by weight of vinyl chloride resin, and the calcium carbonate powder is surface-treated with an organic fatty acid. There has been proposed a vinyl chloride resin composition characterized in that it is a calcium carbonate powder made of (see, for example, Patent Document 3).
JP 11-293074 A

However, since the molded body molded from the above-mentioned vinyl chloride resin composition has a large amount of filler added, it has a drawback that it has low impact resistance and is easily cracked during transportation and use. or,
When tensile elongation is reduced and vacuum forming is attempted, there is a drawback that the formed body is broken at the time of forming and cannot be vacuum formed.

The present invention has been made in view of the above-mentioned problems of the prior art, and is a vinyl chloride resin plate for vacuum forming that has a small amount of hydrochloric acid gas generated during combustion and is excellent in impact resistance, tensile elongation, and vacuum formability. The purpose is to provide.

The vinyl chloride resin plate for vacuum forming according to claim 1 has a hydrochloric acid gas generation amount of 500 ppm or less 4 minutes after the start of the test in a smoke generation test according to ASTM E662, JIS K
The Izod impact strength at 23 ° C. measured according to 7110 is 4.9 to 196.2 kJ /
m ² and a tensile elongation at 130 ° C. according to JIS K7113 is 200 to 700%.
It is characterized by being.

The vinyl chloride resin plate for vacuum forming according to claim 1 has a limited amount of hydrochloric acid gas generated, Izod impact strength and tensile elongation as described above. Excellent in tensile properties, tensile elongation and vacuum formability.

The amount of hydrochloric acid gas generated was measured in the smoke emission test according to ASTM E662.
The amount of hydrochloric acid gas measured after a minute, and if it exceeds 500 ppm, the safety is lowered, so it is limited to 500 ppm, preferably 150 ppm or less.

The Izod impact strength is an impact strength measured at 23 ° C. in accordance with JIS K7110. When the Izod impact strength is reduced, the molded body vacuum-formed from the plate and the plate is destroyed when the impact is applied from the outside. When it becomes large, it becomes difficult to destroy the molded body vacuum-formed from the plate and the plate when it receives an impact from the outside. However, in order to enlarge it, it is necessary to add a large amount of impact modifier, etc. , The mechanical properties such as bending strength and tensile strength are lowered, so that it is 4.9 to 196.2 kJ / m ² , preferably 6.9 to 14
7.2 kJ / m ² .

The tensile elongation is a tensile elongation measured at 130 ° C. in accordance with JIS K7113. If the tensile elongation is small, the vacuum formability is insufficient, and if it is large, the vacuum formability is improved, but processing aids, etc. Is required to be added in a large amount, and mechanical properties such as elasticity, bending strength, and tensile strength are lowered, so that it is 200 to 700%, preferably 300 to 600%.

The vinyl chloride resin plate for vacuum forming according to claim 2 comprises 100 parts by weight of vinyl chloride resin, 50 to 150 parts by weight of precipitated calcium carbonate having an average primary particle size of 0.3 μm or less, and impact modifier 1 to Acrylic processing aid 1 having 30 parts by weight and a weight average molecular weight of 1 to 5 million
The vinyl chloride resin plate for vacuum forming according to claim 1, which comprises ˜30 parts by weight.

Since the vinyl chloride resin plate for vacuum molding according to claim 2 is the vinyl chloride resin plate for vacuum molding having the above composition and the physical properties according to claim 1, the amount of hydrochloric acid gas generated during combustion And has excellent impact resistance, tensile elongation and vacuum formability.

The vinyl chloride resin includes a vinyl chloride homopolymer, a copolymer of a monomer having an unsaturated bond copolymerizable with a vinyl chloride monomer and a vinyl chloride monomer, and a graft copolymer obtained by graft-copolymerizing a vinyl chloride monomer to a polymer. A polymer etc. are mentioned. The vinyl chloride resin preferably contains 50% by weight or more of vinyl chloride. In the present invention, these polymers may be used alone or in combination of two or more.

Examples of the monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer include α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl acetate and vinyl propionate; butyl vinyl ether, cetyl vinyl ether, and the like. Vinyl ethers; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
(Meth) acrylic acid esters such as acrylate and phenyl methacrylate; styrene,
aromatic vinyls such as α-methylstyrene; vinyl halides such as vinylidene chloride and vinylidene fluoride; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, and the like, Two or more are used.

The polymer for graft copolymerization of vinyl chloride is not particularly limited as long as it is a polymer capable of graft polymerization of vinyl chloride. For example, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer Polymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, A chlorinated polypropylene etc. are mentioned, These may be used independently or 2 or more types may be used together.

The polymerization method of the vinyl chloride resin is not particularly limited, and any conventionally known polymerization method may be employed, and examples thereof include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method. .

When the degree of polymerization of the vinyl chloride resin decreases, the mechanical properties decrease, and when it increases, the vacuum moldability decreases, so 400 to 2500 is preferable, and 600 to 1600 is more preferable.
It is.

The average primary particle diameter of the precipitated calcium carbonate is 0.3 μm or less, preferably 0.2 μm or less, because the hydrochloric acid scavenging ability during combustion is reduced when it is increased.

Precipitated calcium carbonate is chemically produced using limestone or sodium carbonate as a raw material, and is classified into a crystalline form and an indeterminate form by a production method, and means a crystalline form. A material obtained by mechanically pulverizing limestone, calcite, oyster shell, etc. is called heavy calcium carbonate and generally has a large particle size.

The precipitated calcium carbonate may be subjected to a surface treatment as long as the achievement of the object of the present invention is not hindered. The surface treatment agent is not particularly limited, and examples thereof include fatty acids such as stearic acid and stearic acid esters; resin acids such as rosin acid soap; silane coupling agents; titanate coupling agents; surfactants and the like. May be used alone or in combination of two or more.

Further, the amount of precipitated calcium carbonate added is 50 to 150 parts by weight, preferably 80 to 120 parts by weight because the ability to trap hydrochloric acid during combustion is lowered when the amount is decreased, and the mechanical properties are lowered when the amount is increased.

The impact modifier is not particularly limited as long as it is used as an impact modifier for vinyl chloride resins. For example, methyl methacrylate-butadiene-styrene graft copolymer (MBS resin), chlorine Polyethylene (CPE), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylic modifier and the like. These impact modifiers may be used alone or in combination of two or more.

When the amount of the impact modifier added is small, there is almost no effect of improving the impact resistance, and when it is increased, the heat resistance, mechanical strength and the like are lowered, so that it is 1-30 parts by weight, preferably 3-25.
Parts by weight.

The acrylic processing aid is a polymer mainly composed of (meth) acrylate monomers, for example, (meth) acrylate monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. And a copolymer of the above (meth) acrylate monomer and a vinyl monomer such as styrene, vinyl toluene and acrylonitrile.

When the weight average molecular weight of the acrylic processing aid is less than 1,000,000, the vacuum formability is deteriorated, and when it exceeds 5,000,000, the surface smoothness of the obtained plate is lowered.

The amount of the acrylic processing aid added is from 1 to 30 parts by weight, preferably from 3 to 25, since the vacuum formability is lowered when the amount is decreased, and the surface smoothness of the obtained plate is lowered when the amount is increased.
Parts by weight.

When molding a vinyl chloride resin plate for vacuum molding from a vinyl chloride resin composition comprising the above vinyl chloride resin, precipitated calcium carbonate, impact modifier and acrylic processing aid, A compounding agent generally added when producing a vinyl resin molded article,
For example, thermoplastic elastomers, inorganic fillers, pigments, lubricants, heat stabilizers, heat stabilization aids, heat resistance improvers, light stabilizers, UV absorbers, antioxidants (anti-aging agents), antistatic agents, etc. It may be added.

1 type, or 2 or more types of the said compounding agent may be added. Moreover, the addition method and order of addition of these compounding agents are not particularly limited, and may be any method or any order.

The thermoplastic elastomer is not particularly limited as long as it is a thermoplastic elastomer used when molding a vinyl chloride resin. For example, acrylonitrile-butadiene copolymer (NBR), ethylene-vinyl acetate copolymer Polymer (EVA), ethylene-vinyl acetate-carbon monoxide copolymer (EVACO), vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, etc., styrene-based thermoplastic Examples include elastomers, olefin-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and urethane-based elastomers. These thermoplastic elastomers may be used alone or in combination of two or more.

The inorganic filler is not particularly limited as long as it is an inorganic filler used when molding a vinyl chloride resin. For example, inorganic carbonate such as calcium carbonate other than precipitated calcium carbonate, talc, clay, silica, etc. A filler is mentioned. These inorganic fillers may be used independently and 2 or more types may be used together.

The pigment is not particularly limited as long as it is a pigment used when molding a vinyl chloride resin. For example, organic pigments such as azo, phthalocyanine, selenium, and dye lake, and oxides Inorganic pigments such as molybdenum chromate, sulfide / selenide, ferrocyanide, and the like. These may be used independently and 2 or more types may be used together.

Examples of the lubricant include an internal lubricant and an external lubricant used when molding a vinyl chloride resin composition.

The internal lubricant is a lubricant added for the purpose of reducing the flow viscosity of the molten resin during thermoforming and preventing frictional heat generation. For example, lauryl alcohol, stearyl alcohol, stearic acid, butyl stearate, glycerin monostearate is used. Rate, epoxidized soybean oil, bisamide and the like. These may be used independently and 2 or more types may be used together.

The external lubricant is a lubricant added for the purpose of enhancing the sliding effect between the molten resin and the mold surface during thermoforming, and examples thereof include montanic acid wax, paraffin wax, polyethylene wax, and ester wax. These may be used independently and 2 or more types may be used together.

The heat stabilizer is not particularly limited as long as it is a heat stabilizer used in molding a vinyl chloride resin. For example, dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin malate, Organic tin stabilizers such as dibutyltin malate polymer, dioctyltin malate, dioctyltin malate polymer, dioctyltin laurate, dibutyltin laurate, dibutyltin laurate polymer, lead white, lead stearate, dibasic lead stearate Lead stabilizers such as dibasic lead phosphite, basic lead sulfite, dibasic lead sulfite, tribasic lead sulfate, silica gel coprecipitated lead oxalate, lead benzoate, lead naphthenate, calcium stearate, Metal soap stabilizers such as barium stearate and zinc stearate, calcium-zinc stabilizers, barium Zinc-based stabilizer, barium - cadmium stabilizer, hydrotalcite, and inorganic-based stabilizers such as zeolites. These may be used independently and 2 or more types may be used together.

The stabilizing aid is not particularly limited as long as it is a stabilizing aid used when molding a vinyl chloride resin. For example, epoxidized soybean oil, epoxidized linseed bean oil, epoxidized tetrahydrophthalate , Epoxidized polybutadiene, phosphate ester and the like. These may be used independently and 2 or more types may be used together.

The heat resistance improver is not particularly limited as long as it is a heat resistance improver used when molding a vinyl chloride resin. For example, a heat improver such as α-methylstyrene or N-phenylmaleimide Is mentioned. These may be used independently and 2 or more types may be used together.

The light stabilizer is not particularly limited as long as it is a light stabilizer used in molding a vinyl chloride resin, and examples thereof include hindered amine light stabilizers. These may be used independently and 2 or more types may be used together.

The ultraviolet absorber is not particularly limited as long as it is a light stabilizer used when molding a vinyl chloride resin, and examples thereof include salicylic acid ester, benzophenone, benzotriazole, and cyanoacrylate. An ultraviolet absorber is mentioned. These may be used independently and 2 or more types may be used together.

The antioxidant (anti-aging agent) is not particularly limited as long as it is an antioxidant (anti-aging agent) used when molding a vinyl chloride resin. For example, dilauryl thiodipropionate. , Dimyristyl thiodipropionate, distearyl thiodipropionate, 2,6-di-tert-butyl-P-cresol, 2,6-di-tert-butyl-4
-Ethylphenol, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and the like. These may be used alone,
Two or more kinds may be used in combination.

The method of mixing the vinyl chloride resin composition comprising the vinyl chloride resin, precipitated calcium carbonate, impact modifier and acrylic processing aid, and the above compound is not particularly limited. For example, the hot blend method, the cold The blend method etc. are mentioned.

The method of molding a vinyl chloride resin plate for vacuum molding from the vinyl chloride resin composition or a mixture of the same and the above compound is not particularly limited. For example, a method of melt extrusion with an extruder and calender molding, a press machine Examples of the method include press molding.

The vinyl chloride resin plate for vacuum forming according to the present invention is formed by a vacuum forming method. In the vacuum forming method, after a thermoplastic resin plate is heated and softened, it is deformed by being sucked into a mold under a reduced pressure. A forming method to be processed, and any conventionally known vacuum forming method may be adopted,
For example, after heating the vinyl chloride resin plate for vacuum forming, it is pushed up and extended by a mold, and then a drape forming method for drawing a vacuum, straight forming for drawing a vacuum immediately after heating, and the like.

The configuration of the vinyl chloride resin plate for vacuum molding of the present invention is as described above, and has a suitable tensile elongation and excellent vacuum moldability, so that it can be easily vacuum-molded, and a vacuum-molded molded body. Is excellent in impact resistance and generates a small amount of hydrochloric acid gas during combustion, and is therefore suitably used as an interior material for aircraft and vehicles.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Examples 1-3, Comparative Examples 1-5)
A predetermined amount of vinyl chloride resin, calcium carbonate, impact modifier, processing aid, heat stabilizer and lubricant shown in Table 1 are supplied to a 200 L super mixer (manufactured by Kawata), and mixed with stirring to produce a vinyl chloride resin composition. I got a thing.

The vinyl chloride resin, calcium carbonate, impact modifier, processing aid, heat stabilizer and lubricant used are as follows.
(1) Vinyl chloride resin, manufactured by Tokuyama Sekisui Industry Co., Ltd., trade name “TS-800E”, polymerization degree 800

(2) Calcium carbonate Precipitated calcium carbonate A Shiraishi Calcium Co., Ltd., trade name “CCR” (surface treatment product),
Average primary particle size 0.12 μm

Precipitated calcium carbonate B, manufactured by Kamishima Chemical Industry Co., Ltd., trade name “PLS2301” (surface treated product), average primary particle size 0.07 μm
・ Heavy calcium carbonate, Sankyo Seimitsu Co., Ltd., trade name “SCPE2300”, average primary particle size 1.6 μm

(3) Impact modifier • MBS resin, manufactured by Kaneka Chemical Co., Ltd., trade name “M511”
・ Acrylic rubber Rohm and Haas, trade name “KM-334”

(4) Processing aid Acrylic processing aid A, manufactured by Mitsubishi Rayon Co., Ltd., trade name “P-501A”, weight average molecular weight 800,000

Acrylic processing aid B, manufactured by Mitsubishi Rayon Co., Ltd., trade name “P-551A”, weight average molecular weight 1.45 million • Acrylic processing aid C, manufactured by Mitsubishi Rayon Co., Ltd., trade name “P-530A”, weight average molecular weight 3.1 million

(5) Tin-based heat stabilizer dibutyltin mercapto, manufactured by Sansha Co., Ltd., trade name “JF-10B”
"
(6) Lubricant • Lubricant A, trade name “Hiwax 2203A” manufactured by Mitsui Chemicals, Inc.
・ Lubricant B manufactured by Kao Corporation, trade name "Lunac S30"
・ Lubricant C Product name "Loxiol G21" manufactured by Cognis

The obtained vinyl chloride resin composition was supplied to a biaxial different-direction rotary extruder having a diameter of 50 mm (trade name “SLM-50” manufactured by Nagata Seisakusho Co., Ltd.), melt-extruded at a resin temperature of 190 ° C., and 2 mm and 3 mm in thickness. A vacuum forming plate was obtained.

Using the obtained vacuum forming plate, the amount of hydrochloric acid gas generated, Izod impact strength, tensile elongation, vacuum formability and surface smoothness were measured, and the results are shown in Table 1. In addition, the measuring method of each physical property is as follows.

(Hydrochloric acid gas generation amount)
The obtained vacuum forming plate having a thickness of 2 mm was cut to prepare a 7.5 cm square sample piece,
A combustion test was performed in a smoke generation test in accordance with ASTM E662, and 6 liters of gas was sampled after 4 minutes of combustion to measure the amount of hydrochloric acid gas generated.

(Izod impact strength)
The obtained vacuum forming plate having a thickness of 3 mm was cut to prepare a test piece, and JIS K71
10 was measured at 23 ° C.

(Tensile elongation)
The obtained vacuum forming plate having a thickness of 3 mm was cut to prepare a dumbbell according to JIS K7113, and a tensile test was performed at 130 ° C. according to JIS K7113 to measure the tensile elongation rate.

(Vacuum formability)
The obtained 3 mm-thick vacuum forming plate was cut to prepare a 50 cm square test piece, which was supplied to a vacuum forming machine (manufactured by Fuse Vacuum Co., Ltd.) to obtain a cylindrical mold having a height of 90 cm and a diameter of 180 mm. And vacuum forming at a processing temperature of 210 ° C.

The obtained molded body was evaluated according to the following criteria.
○: The dimension according to the mold was obtained.
X: The dimension according to a metal mold | die was not obtained.

(Surface smoothness)
The surface of the vacuum forming plate was evaluated by visual observation according to the following criteria.
○: There is no surface roughness.
X: The surface is rough.

Claims (2)

In the smoke emission test according to ASTM E662, the amount of hydrochloric acid gas generated 5 minutes after the start of the test is 5
00 ppm or less, Izod impact strength at 23 ° C. measured according to JIS K7110 is 4.9 to 196.2 kJ / m ² , and tensile elongation at 130 ° C. according to JIS K7113 is 200 to 700%. A vinyl chloride resin plate for vacuum forming characterized by being. 100 parts by weight of a vinyl chloride resin, 50 to 150 parts by weight of precipitated calcium carbonate having an average primary particle size of 0.3 μm or less, 1 to 30 parts by weight of an impact modifier, and a weight average molecular weight of 100 to 50
The vinyl chloride resin plate for vacuum forming according to claim 1, comprising 1 to 30 parts by weight of 100,000 acrylic processing aids.