JP2003012741A - Inorganic substance-containing polyvinyl chloride-based resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inorganic substance-containing polyvinyl chloride-based resin which has good physical properties such as good mechanical strengths and good heat resistance and is obtained by a simple method and wherein the inorganic substance is easily dispersed in the resin under the control of the transfer of the inorganic substance to an aqueous phase without using the inorganic substance in an excessive amount, when the inorganic substance is introduced into the vinyl chloride resin, and to provide a method for producing the vinyl chloride-based resin. SOLUTION: The inorganic substance-containing polyvinyl chloride-based resin comprising a resin-adhered inorganic substance prepared by carrying (B) a resin consisting mainly of a thermoplastic resin obtained by a radical polymerization method on the periphery of (A) the inorganic substance, and (C) polyvinyl chloride or a resin consisting mainly of the polyvinyl chloride is characterized in that the thermoplastic resin is graft-copolymerized with the polyvinyl chloride-based resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition containing an inorganic filler.

[0002]

2. Description of the Related Art A resin composition in which polyvinyl chloride is reinforced with an inorganic filler such as calcium carbonate is widely known.
However, these reinforcing materials have a poor affinity with polyvinyl chloride, and when they are filled, the mechanical strength and heat resistance of the reinforced polyvinyl chloride are improved, but the toughness is reduced. Moreover, the resin composition reinforced with these inorganic fillers has a problem that the mechanical strength and heat resistance cannot be improved unless a large amount of the filler is blended.

When a molded product is prepared from an inorganic-containing polyvinyl chloride resin, it is usually prepared by mixing an inorganic filler with a polyvinyl chloride resin powder to prepare a vinyl chloride resin composition. , Products are obtained through the molding process. For the purpose of reducing the mixing step and improving the dispersibility of the inorganic material in the vinyl chloride resin, a method has been proposed in which an inorganic filler is introduced into the resin in advance during suspension polymerization to prepare a polyvinyl chloride resin. There is. For example, JP-A-60-
No. 228505 proposes a method of introducing an inorganic substance into a resin by using a nonionic surfactant, but depending on the inorganic substance, the amount of the inorganic substance introduced into the resin is smaller than the amount used, resulting in reduction of process steps and physical properties. Poor improvement effect. Also,
Japanese Patent Laid-Open No. 10-110004 discloses a method of polymerizing a vinyl chloride-based monomer in the presence of an inorganic substance to obtain a vinyl chloride-based resin containing an inorganic substance.
Since the inorganic substance migrates into water during suspension polymerization in an aqueous medium, an excessive amount of the inorganic substance must be used to improve the physical properties, which is a cost disadvantage. In addition, since the inorganic substance precipitates by itself, there is a problem that a step of separating the inorganic substance and the resin is required after the polymerization, and it is difficult to introduce a large amount into the resin.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and when introducing an inorganic substance into a polyvinyl chloride resin, it suppresses the transition to the aqueous phase and is excessive. It is easy to disperse in a resin without using it, and various physical properties such as mechanical strength and heat resistance are good, and a polyvinyl chloride resin which can be obtained by a simple method is provided and the polyvinyl chloride resin It is to provide a manufacturing method.

[0005]

Means for Solving the Problems As a result of repeated studies on the above problems, the present inventors carried a thermoplastic resin obtained by polymerizing a radically polymerizable monomer around an inorganic substance, and the surface of the inorganic substance was By using a resin-adhered inorganic material coated with a thermoplastic resin and polymerizing a vinyl chloride-based monomer in the coexistence of the resin-adhered inorganic material, it is easy to introduce the inorganic material into the polyvinyl chloride-based resin, and the inorganic material is It was found that a polyvinyl chloride resin composition having various physical properties can be obtained with the same inorganic content as compared with the method of blending with a resin. Further, by using a general-purpose monomer having a high radical polymerization activity as the radical-polymerizable monomer, a more cost-effective product can be efficiently produced. This effect is particularly remarkable when an acrylic monomer such as (meth) acrylate is used.

The inorganic material used in the present invention is not particularly limited as long as it is used as a filler and a physical property enhancer of polyvinyl chloride resin, and examples thereof include metal powder, calcium carbonate and potassium titanate. Metal inorganic acid salts, metal hydroxides such as aluminum hydroxide, metal oxides such as aluminum oxide and titanium oxide, smectite group phyllosilicates such as vermiculite, montmorillonite, beidellite, nontronite and saponite, muscovite, soda mica , Mica, phyllosilicates such as sericite, celadonite, phlogopite, fluorophlogopite, kaolin minerals such as kaolinite, pyrophyllite and talc, tectosilicate,
Examples thereof include graphite, and preferably phyllosilicate having a layered structure is used. These may be used alone or in combination of two or more.

The present invention is characterized in that a thermoplastic resin obtained by polymerizing a radical-polymerizable monomer is carried on the surface of an inorganic material. Regarding the shape of the resin-adhered inorganic material composed of the inorganic material and the thermoplastic resin, the shape in which the individual inorganic particle surface is covered with the resin layer, the individual inorganic material or a plurality of particles are covered with the resin particles smaller than the single inorganic particle Shape, such as a particle shape formed by individually or in a plurality of inorganic particles in the resin particles formed by one or more resin walls made of a thermoplastic resin,
These are not particularly limited.

The present invention is characterized in that a thermoplastic resin that can be synthesized by radical polymerization is used as a material to be supported around the inorganic material. As the thermoplastic resin, poly (meth) acrylate, polystyrene derivative,
Alternatively, a general-purpose resin synthesized from a monomer having a high radical polymerization activity such as a polyvinyl acetate derivative is preferably used, and particularly preferably poly (meth) acrylate is used. These are used alone or as a copolymer.

Examples of the radical-polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cumyl (meth) acrylate,
Alkyl (meth) acrylates such as hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, etc. Styrene derivatives, vinyl acetate such as vinyl acetate and vinyl propionate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, maleic anhydride, vinylidene chloride,
Maleimide derivatives and the like can be mentioned, and these can be used alone or
A combination of two or more species can be used.

A polyfunctional monomer capable of radical polymerization may be added to the above radical polymerizable monomer by improving the mechanical strength of the thermoplastic resin. The polyfunctional monomer is not particularly limited, for example,
Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropane di (meth) acrylate.
Examples thereof include acrylates, and examples of tri (meth) acrylates include trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate. Further, as other polyfunctional monomers, di- or triallyl compounds such as pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diallyl phthalate and diallyl fumarate, divinylbenzene and butadiene, etc. Examples thereof include compounds, and these can be used alone or in combination of two or more kinds. If the polyfunctional monomer is used in a large amount, the mechanical strength is greatly improved and, as a result, the introduction thereof into the vinyl chloride resin is suppressed. Therefore, it is preferable that the polyfunctional monomer is not used in a large amount or is not used.

The ratio of the inorganic substance to the radical-polymerizable monomer at the time of producing the resin-adhered inorganic substance in which the thermoplastic resin obtained by radical polymerization is carried around the above-mentioned inorganic substance is 1 to 75% by weight of the inorganic substance and the radical. The polymerizable monomer content is preferably 25 to 99% by weight. The amount of inorganic substances is 7
More than 5% by weight and 25% by weight of radically polymerizable monomer
If it is less than less, the amount of resin attached to the inorganic substance decreases,
It becomes difficult to recognize the effect of the present invention that the resin is supported on the inorganic substance to facilitate introduction into the polyvinyl chloride resin and improve the physical properties.

The resin-adhered inorganic substance of the present invention is roughly classified into a method of producing by suspension polymerization in an aqueous medium and a method of producing by emulsion polymerization, but it is not particularly limited.

The resin-attached inorganic substance produced by the suspension polymerization method in an aqueous medium is prepared by, for example, first mixing a radical-polymerizable monomer, an inorganic substance and a polymerization initiator, and then,
It is obtained by emulsifying and suspending the mixture in water containing a dispersant and radically polymerizing the monomers in the oil droplets. At this time, the inorganic substance is mixed with the monomer in advance, so that when it is emulsified and suspended in water and during the polymerization,
Since the inorganic substance exists in the oil droplets of the monomer, the resin-adhered inorganic substance in which the thermoplastic resin covers the inorganic substance can be prepared in a water-suspension polymerization, which is a facility-friendly and simple polymerization mode.

The above-mentioned suspension polymerization methods are roughly classified into a batch polymerization method and an emulsion addition method depending on the difference in the monomer addition method, and are not particularly limited.

In the batch polymerization method during suspension polymerization, for example, an inorganic substance, a radically polymerizable monomer, and a polymerization initiator are first mixed in advance to prepare a monomer / inorganic substance mixture. On the other hand, after ion exchanged water and a dispersant were put into a jacketed polymerization reaction tank and the pressure inside the polymerization tank was reduced to remove oxygen, the pressure was returned to atmospheric pressure with nitrogen, and under a nitrogen atmosphere,
The above monomer / inorganic mixture is added all at once into the polymerization tank. This is a method in which a monomer / inorganic mixture is emulsified and suspended by a stirring blade, and then the temperature in the tank is raised to a predetermined temperature by a jacket for polymerization. Further, the monomer / inorganic substance mixture may be mixed and emulsified with the dispersant and a part of the charging water in advance and added to the polymerization tank.

The emulsion addition method at the time of suspension polymerization is, for example, to first add the above-mentioned monomer / inorganic substance mixture into a dispersant and ion-exchanged water and sufficiently emulsify the mixture by stirring to obtain an emulsified monomer / inorganic substance mixture in advance. Prepare the solution. Next, ion-exchanged water was put into a polymerization reaction tank with a jacket to depressurize the inside of the polymerization tank to remove oxygen, and then the pressure was returned to atmospheric pressure with nitrogen, and under a nitrogen atmosphere, the inside of the tank was covered with a jacket by a predetermined amount. After the temperature is reached, the above-mentioned monomer / inorganic mixture solution is added all at once or added dropwise at a constant amount for polymerization.

The resin-adhered inorganic substance produced by the emulsion polymerization method in an aqueous medium is, for example, first added to an inorganic substance in water and stirred to be in a swollen or suspended state, and then a polymerization initiator, a radical-polymerizable monomer and It is obtained by adding a dispersant and radically polymerizing the monomer. At this time, if the inorganic substance is dispersed in water in advance, the frequency with which it approaches the resin particles produced by emulsion polymerization increases. As a result, the resin adheres to the periphery of the inorganic substance, and it can be prepared in a simple polymerization mode in terms of equipment such as emulsion polymerization of an aqueous medium.

The emulsion polymerization method is roughly classified into a monomer addition method and an emulsion addition method depending on the difference in the addition of the monomer, and is not particularly limited.

With respect to the method of adding a monomer during emulsion polymerization, for example, first, an inorganic substance is added to a polymerization reaction tank with a jacket together with ion-exchanged water, and the inorganic substance is swollen or suspended by a stirring blade. Further, after decompressing the inside of the polymerization tank to remove oxygen, the pressure is returned to atmospheric pressure with nitrogen, a dispersant and a polymerization initiator are added to the polymerization tank under a nitrogen atmosphere, and the inside of the tank is predetermined by a jacket. Up to the temperature of
This is a method in which the radical-polymerizable monomer is added all at once to the polymerization tank, or a fixed amount of it is added dropwise to perform polymerization.

The emulsion addition method at the time of emulsion polymerization is, for example, that the inside of the polymerization tank is heated to a predetermined temperature by the same operation as the above-mentioned monomer addition method, and then the radical polymerizable monomer is added to the dispersant and the charged water. This is a method in which a part of the mixture and emulsified in advance are polymerized by adding them all at once to the polymerization tank or dropping a fixed amount each.

In the suspension polymerization method, the above-mentioned dispersant is added for the purpose of improving the dispersion stability of the mixed emulsion suspension of the inorganic substance and the monomer and efficiently carrying out the polymerization at the stage of obtaining the resin-attached inorganic substance. In addition, in the emulsion polymerization method, it is added for the purpose of improving the dispersion stability of the resin obtained by polymerizing the radical-polymerizable monomer and efficiently obtaining the uniformly attached inorganic substance. For example, anionic surfactants, nonionic surfactants, partially saponified polyvinyl acetate, cellulose-based dispersants, gelatin and the like, particularly preferably anionic surfactants, specifically, for example, Examples thereof include sodium alkylbenzene sulfonate and ammonium polyoxyethylene alkyl ether sulfate ester.

As the polymerization initiator in the above suspension polymerization method, a compound capable of generating an oil-soluble free radical, for example, benzoyl peroxide, lauroyl peroxide, dibutyl peroxydicarbonate, α-cumyl peroxy neodecano. Examples thereof include organic peroxides such as ates, azo initiators such as azobisisobutyronitrile, and redox initiators.

As the polymerization initiator in the above emulsion polymerization method, a water-soluble free radical-generating compound, for example, an inorganic peroxide such as hydrogen peroxide, ammonium persulfate, potassium persulfate or sodium persulfate, 4 , 4'-
Examples thereof include azo-based initiators such as azobis-4-cyanovaleric acid and redox initiators. Further, in any of the above suspension polymerization method and emulsion polymerization method, a pH adjusting agent, an antioxidant and the like may be added as necessary.

The solid content concentration of the inorganic material and the resin in the slurry containing the resin-adhered inorganic material obtained as a result of the polymerization is
Although not particularly limited, 10 to 50% by weight is preferable in view of productivity and stability of polymerization reaction. The average particle diameter of the resin-adhered inorganic material in the slurry is not particularly limited, but the preferred particle diameter differs depending on the method of use, for example, when used as a slurry, the larger the particle diameter of the resin-adhered inorganic material and the water, the more likely it is to cause separation of 30 μm.
The following are appropriate: On the other hand, when the resin-adhered inorganic substance is dried and used as a powder, it is 10
˜3000 μm is suitable.

In the present invention, by coating an inorganic substance with a thermoplastic resin to form a resin-adhered inorganic substance, vinyl chloride or a vinyl chloride-based monomer containing vinyl chloride as a main component is present in an aqueous medium, and the presence of the above resin-adhered inorganic substance. By carrying out suspension polymerization below, it becomes possible to efficiently introduce an inorganic substance into the polyvinyl chloride resin.

The vinyl chloride-based monomer containing vinyl chloride as a main component is a mixture of 50% by weight or more of vinyl chloride and another monomer copolymerizable with vinyl chloride. Other monomers copolymerizable with vinyl chloride include, for example, alkyl vinyl esters such as vinyl acetate; α-monoolefins such as ethylene and propylene; methyl (meth) acrylate, ethyl (meth) acrylate,
Alkyl (meth) acrylates such as octyl acrylate; alkyl vinyl ethers; maleimides; vinylidene chloride, styrene derivatives and the like, and at least one of them is used.

The above polyvinyl chloride resin is generally produced by a batch type water suspension polymerization method by carrying out the following series of operations in a polymerization vessel equipped with a jacket for heating and cooling and a stirring device. To be done. The batch-type water suspension polymerization method that is generally carried out is to first charge an aqueous medium and a dispersant into a polymerization vessel, then a polymerization initiator, and then degas the inside of the polymerization vessel in a vacuum and then use a vinyl chloride system. Charge with monomer,
The temperature is raised to start the polymerization reaction, and after the reaction heat comes out, cooling water is passed through the polymerization vessel jacket to maintain the polymerization temperature, and then the unreacted monomer is recovered to obtain a vinyl chloride resin. However, the method is not limited to this.

The polyvinyl chloride resin according to the present invention is
The batch type water suspension polymerization is characterized by the coexistence of resin-attached inorganic matter, as the time to be added to the polymerization vessel,
It may be any time from the addition of the aqueous medium to the step of collecting the unreacted monomer after the polymerization reaction is started, and in particular, it is facility-friendly to add the monomer before the inside of the polymerization vessel has a high pressure. Therefore, it is desirable. Further, the amount of the resin-adhered inorganic substance to be coexistent may be appropriately determined depending on the required physical properties, but it is desirable that the amount is equal to or less than that of the polyvinyl chloride resin to be produced. Will be insufficiently introduced.

Examples of the polymerization initiator used in the aqueous suspension polymerization of the polyvinyl chloride resin include the same ones as those used in the suspension polymerization method described above, and at least one of them is used. Is used.

The dispersant used in the aqueous suspension polymerization of the polyvinyl chloride resin is not particularly limited, and examples thereof include partially saponified polyvinyl alcohol; methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, etc. Water-soluble polymers such as water-soluble cellulose, polyacrylic acid, gelatin, polyethylene oxide; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan monostearate, glycerin tristearate; polyoxyethylene sorbitan monolaurate, Examples thereof include water-soluble emulsifiers such as polyoxyethylene glycerin oleate and sodium laurate, and these can be used alone or in combination of two or more kinds. Furthermore, a polymerization regulator, a chain transfer agent, a pH regulator, a gelation improving agent, an antistatic agent, a polymerization scale adhesion preventing agent, etc., which are appropriately used in general polymerization, may be added.

The polymerization temperature during the suspension polymerization of the polyvinyl chloride resin may be any known polymerization temperature and is not particularly limited. Also, regarding the polymerization vessel,
The shape and structure are not particularly limited, and a conventionally known polymerization vessel is used.

[0032]

EXAMPLES Examples of the present invention will be described below.
It is not limited to the following example. Based on the composition shown in Table 1 and Table 2, resin-adhered inorganic substances were prepared by the following procedure, and water suspension polymerization was carried out together with vinyl chloride monomer to obtain various polyvinyl chloride resin compositions.

[Production of Resin-Deposited Inorganic Material] Examples 1 to 8 (Suspension Polymerization Method) Based on the composition shown in Table 1, a predetermined amount of an inorganic material, a radical-polymerizable monomer, and 2,2-azobisisobutyi Ronitrile (0.5% by weight based on the total weight of inorganic and monomer)
Were mixed and stirred. Next, ion-exchanged water (200% by weight based on the total weight of inorganic substances and monomers: 80% of the total amount used)
Sodium dodecylbenzenesulfonate (3.0% by weight based on the total weight of the inorganic substance and the monomer) as a dispersant is added to the above, and the above-mentioned monomer / inorganic substance mixture is added thereto,
The emulsion monomer liquid was prepared by stirring. On the other hand, the remaining ion-exchanged water (5% to the total weight of inorganic substance and monomer)
0% by weight) was added and stirring was started. After depressurizing the inside of the polymerization vessel to deoxygenate the inside of the vessel, the pressure was returned to atmospheric pressure with nitrogen, the inside was made into a nitrogen atmosphere, and then the emulsified monomer liquid was added all at once. The temperature of the polymerization tank was raised to 80 ° C. to start polymerization. Polymerization was completed in 30 minutes, and after the aging period of 1 hour, the polymerization tank was cooled to room temperature. A slurry containing a resin-attached inorganic substance having a solid content concentration of about 30% by weight and an average particle size of about 10 μm was obtained.

Examples 9 to 16 (Emulsion Polymerization Method) Based on the composition shown in Table 1, a predetermined amount of monomer and ion-exchanged water (50% by weight based on the total weight of the inorganic substance and the monomer: 20% of the total amount used). ), And sodium dodecylbenzenesulfonate (3.0% by weight based on the total weight of the inorganic substance and the monomer) as a dispersant were mixed and stirred to prepare an emulsified monomer liquid. On the other hand, the remaining ion-exchanged water (200% by weight based on the total weight of the inorganic substance and the monomer) and a predetermined amount of the inorganic substance were put in the polymerization vessel, and stirring was started. After depressurizing the inside of the polymerization vessel to deoxygenate the inside of the vessel, the pressure was returned to atmospheric pressure with nitrogen and the inside was made a nitrogen atmosphere, and then the polymerization tank was heated to 80 ° C.
The temperature was raised to. After adding ammonium persulfate (0.5% by weight to the weight of the monomer) to the polymerization tank, the above emulsion monomer liquid was dropped into the polymerization tank to start polymerization. The monomer was dropped for 90 minutes, and after the aging period of 1 hour, the polymerization tank was cooled to room temperature. Solid content concentration about 30
A slurry containing a resin containing inorganic substance having a weight percentage of about 10 μm and an average particle diameter of about 10 μm was obtained.

Example 17 (Emulsion Polymerization Method) Two kinds of monomers shown in Table 1 (methyl methacrylate,
Ion-exchanged water for each n-butyl acrylate (25% by weight based on the total weight of the inorganic substance and the monomer: 10 of the total amount used)
%) And sodium dodecylbenzenesulfonate (3.0% by weight based on the total weight of the inorganic substance and the monomer) were mixed and stirred to prepare two types of emulsion monomer liquids. On the other hand, the remaining ion-exchanged water (200% by weight based on the total weight of the inorganic substance and the monomer) and a predetermined amount of the inorganic substance were put in the polymerization vessel, and stirring was started. After depressurizing the inside of the polymerization vessel to deoxidize the inside of the vessel, the pressure was returned to atmospheric pressure with nitrogen, the inside was made into a nitrogen atmosphere, and then the temperature of the polymerization tank was raised to 80 ° C. Ammonium persulfate (0.5% based on total monomer weight) in the polymerization tank
(Wt%), one of the emulsion monomer liquids (emulsion liquid of methyl methacrylate) was added dropwise to the polymerization tank to start polymerization. The monomer was dropped for 45 minutes. Then, the other emulsion monomer liquid (emulsion liquid of n-butyl acrylate) was added dropwise to the polymerization tank over 45 minutes, and after the aging period of 1 hour, the polymerization tank was cooled to room temperature. A slurry containing a resin-attached inorganic substance having a solid content concentration of about 30% by weight and an average particle size of about 10 μm was obtained.

[Production of Vinyl Chloride Resin Composition] Examples 1 to 17 and Comparative Examples 1 to 8 After degassing a stainless steel polymerization vessel equipped with a jacket and having an internal volume of 20 liters, 9.5 kg of deionized water, Partially saponified polyvinyl acetate (saponified 72 mol% average degree of polymerization 80
0) 4.2 g, hydroxypropyl methylcellulose 1
g, a predetermined amount of the slurry containing the resin-adhered inorganic substance, 7.2 kg of vinyl chloride monomer, and 2 g of polymerization initiator di-2-ethylhexyl peroxydicarbonate. The temperature inside the polymerization vessel was raised to 57 ° C. to start the polymerization reaction.
Then, when the pressure in the polymerization vessel dropped by 0.2 MPa, the unreacted vinyl chloride monomer was recovered and dehydrated and dried to obtain a polyvinyl chloride resin composition.

[Preparation of Molded Sample of Polyvinyl Chloride Resin Composition] 100 parts by weight of dried polyvinyl chloride resin was added to an organic tin stabilizer (manufactured by Sansha Machinery Co., Ltd., trade name "ON").
Z-6F ") 1 part by weight and a lubricant (manufactured by Mitsui Chemicals, Inc., trade name" Hiwax 2203A ") 0.5 part by weight were mixed with stirring to obtain a polyvinyl chloride resin compound. In Comparative Examples 2, 6 and 8, the inorganic substances shown in Table 1 were further mixed at the same time. The obtained compound was kneaded with a 6-inch roll molding machine at 190 ° C. for 3 minutes, and then made into a sheet having a thickness of 1 mm, which was press-molded (pressure 200 ° C. preheating 3 minutes-pressurization 4 minutes: pressure 4). 1.9 MPa) to obtain a polyvinyl chloride resin composition molded sample.

[Evaluation] Each of the obtained polyvinyl chloride resin compositions and vinyl chloride resin composition molded samples was evaluated as follows. The results are shown in Tables 1 and 2. (Amount of Inorganic Material) Dried various polyvinyl chloride-based resin compositions and polyvinyl chloride-based resin composition molded samples were ignited in a crucible, and after incinerating the organic content completely at 1000 ° C., from the remaining ash content, The amount of inorganic substances in each resin composition and the molded sample was calculated. (Tensile strength) Using the above-mentioned molded product sample, 23 ° C in accordance with the plastic tensile test method (JIS K 7113).
In, a tensile test was performed on the No. 1 type test piece to determine the tensile strength. (Vicat softening temperature) Using the above-mentioned molded product sample, in accordance with the plastic method (JIS K 7206), 10
The measurement was performed at N weight and a heating rate of 50 ° C./hr. (Linear Expansion Coefficient) Using the above-mentioned molded product sample, the linear expansion coefficient was measured at a measurement temperature of 23 ° C. to 70 ° C. and a heating rate of 5 ° C./min in accordance with the plastic linear expansion test method (JIS K 7197).

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

EFFECT OF THE INVENTION The polyvinyl chloride resin composition of the present invention is a resin-adhered inorganic material in which a resin is supported around the inorganic material by a thermoplastic resin obtained by polymerizing a radical-polymerizable monomer and the surface is coated. A vinyl chloride resin that can be easily introduced into a vinyl chloride resin simply by adding it during the aqueous suspension polymerization of vinyl chloride, and has various inorganic content compared to that at the time of compounding and which has good physical properties. A composition is obtained,
It can be produced inexpensively by a simple method in terms of equipment.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J011 BA04 HA02 PA03 PA07 PA13                       PC06 PC07                 4J026 AA17 AA21 AA24 AA37 AA38                       AA45 AA49 AA54 AA57 BA02                       BA05 BA10 BA15 BA20 BA27                       BA38 DA03 DA04 DA12 DA13                       DA14 DA15 DB03 DB11 FA03                       FA07 GA01 GA02 GA06

Claims (6)

[Claims] 1. A resin (B) containing, as a main component, a thermoplastic resin obtained by radical polymerization around an inorganic material (A).
And a polyvinyl chloride resin (C) made of polyvinyl chloride or a resin containing polyvinyl chloride as a main component. The thermoplastic resin and the polyvinyl chloride resin are graft-copolymerized. An inorganic substance-containing polyvinyl chloride resin characterized by being polymerized. 2. The inorganic substance-containing polyvinyl chloride resin according to claim 1, wherein the thermoplastic resin is poly (meth) acrylate. 3. Based on 100 parts by weight of polyvinyl chloride or polyvinyl chloride resin (C) containing polyvinyl chloride as a main component, a thermoplastic resin obtained by radical polymerization around the inorganic substance (A) is contained as a main component. The inorganic substance-containing polyvinyl chloride resin according to claim 1 or 2, wherein the resin-attached inorganic substance (A + B) carrying the resin (B) is 1 to 100 parts by weight. 4. The inorganic substance-containing polyvinyl chloride according to claim 1, wherein the resin-attached inorganic substance comprises 25 to 99% by weight of a radical-polymerizable monomer and 1 to 75% by weight of an inorganic substance. Resin. 5. The resin-deposited inorganic material is obtained by suspension-polymerizing a mixture of 25-99% by weight of a radical-polymerizable monomer and 1-75% by weight of an inorganic material in water. The method for producing a polyvinyl chloride-based resin containing an inorganic substance according to any one of claims. 6. The resin-attached inorganic substance is an inorganic substance 1 to 75.
The inorganic-containing polyvinyl chloride system according to any one of claims 1 to 4, wherein 25 to 99% by weight of the radical-polymerizable monomer is emulsion-polymerized in water in which the weight% is swollen or suspended. Resin manufacturing method.