JPH10316823A - Hard resin composition and extrusion molding product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition that can manifest an excellent moldability, heat resistance and deformation resistance by admixing talc to a specifically formulated thermoplastic resin composition. SOLUTION: This hard resin composition comprises (A) a thermoplastic resin composition that contains (i) 90-10 wt.% of a 60-70 wt.% chlorine- containing vinyl chloride composition, (ii) 0-80 wt.% of a vinyl chloride resin composition and (iii) 10-80 wt.% of resin composition containing 30-100 wt.% of an α-methylstyrene copolymer and 0-70 wt.% of a grafting copolymer composed of specific components and (B) talc. This hard resin composition is co- extruded together with a soft resin composition containing 30-80 wt.% of a vinyl chloride resin and 20-70 wt.% of a plasticizer to give extrusion-molded products that is expected to be used as a sealing material as gasket.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard resin composition excellent in moldability, heat resistance and deformation resistance, and a co-extruded product.

[0002]

2. Description of the Related Art Conventionally, seal materials such as packings and gaskets have been used to keep the airtightness of buildings, automobiles, kitchen appliances, etc., and to prevent rainwater, dust, and the like from entering inside them. As these sealing materials, soft resin compositions such as a soft vinyl chloride-based resin composition and crosslinked rubber materials are used. Soft resin compositions and rubber materials can be extruded, injection-molded and compression-molded by themselves to use as products, or for the purpose of maintaining the airtightness of building materials, automobiles and kitchen appliances, metal and resin in the same mold. (Hereinafter referred to as a die), and may be used as a sealing material by being melt-integrated (hereinafter referred to as coextrusion) or adhered to a metal. However, the sealing material coextruded with the metal is economically disadvantageous because it is necessary to separate the resin and the metal in order to recycle the material.

As a countermeasure, a hard resin composition is used instead of metal, and a soft resin composition comprising the hard resin composition, a vinyl chloride resin composition, a partially crosslinked acrylonitrile-butadiene copolymer and a plasticizer. A method for producing a gasket by co-extrusion of the same has been proposed (Japanese Patent Application Laid-Open No. 62-11787).

However, since the hard resin composition is a vinyl chloride resin composition or an ABS resin composition, it has insufficient heat deformation resistance, and when used in a high-temperature atmosphere, the entire sealing material such as a gasket may be deformed. there were. Therefore, it has been difficult to use it as a sealing material for gaskets and the like.

In order to improve the heat resistance of the hard resin composition, the hard material comprises a chlorinated vinyl chloride resin composition, a vinyl chloride resin composition, an α-methylstyrene copolymer or a graft copolymer. A method has been proposed in which a hard resin composition composed of a resin composition is used and coextruded with the soft resin composition (JP-A-8-90629). This co-extruded product has an effect that even when used in a high-temperature atmosphere such as 90 to 100 ° C., deformation such as warpage or bending is less likely to occur than in a conventional product.

[0006]

However, in recent years,
In order to prolong the life of a co-extruded product, it has been required to ensure heat-resistant deformation resistance for a long period of time. Specifically, the product expands in the longitudinal direction when the soft resin composition is at a high temperature, and the product shrinks in the longitudinal direction when the soft resin composition is at a low temperature. It has been required that the length of the extruded product does not change.

It is an object of the present invention to satisfy the above requirements, have good moldability, heat resistance and deformation resistance, have excellent sealing and sealing effects, and furthermore, have a heat resistance in an actual operating temperature range of 80 to 110.degree. An object of the present invention is to provide an extruded product having reduced expansion and contraction. The present inventors have conducted intensive studies on adding talc to a hard resin composition and producing a co-extruded product with the soft resin composition, and as a result, have completed the present invention.

[0008]

Means for Solving the Problems A first invention of the present invention is:
The following (a) component 90 to 10% by weight, (b) component 0 to 8
A thermoplastic resin composition comprising 0% by weight and 10 to 80% by weight of the component (c), and a hard resin composition comprising the component (d). (A) Component Chlorinated vinyl chloride resin composition having a chlorine content of 60 to 70% by weight (b) Component Vinyl chloride resin composition (c) Component 30 to 100% by weight of the following component (A) and (B) Resin composition containing 0 to 70% by weight of component (a) 65 to 85% by weight of component α-methylstyrene, 15 to 35% by weight of vinyl cyanide compound and 0 to 20 of other vinyl compounds copolymerized therewith Α-methylstyrene-based copolymer containing 2% by weight (b) Component 50 to 80% by weight of an aromatic vinyl compound, 15 to 35% by weight of a vinyl cyanide compound and 0 to 0 of other vinyl compounds copolymerized therewith Graft copolymer obtained by copolymerizing 20 to 70 parts by weight of a mixture containing 30% by weight in the presence of 30 to 80 parts by weight of a rubber having a glass transition temperature of 0 ° C. or lower (d) Component talc The present invention No. The invention of No. 2 includes the above-mentioned hard resin composition A,
(2) 30-80% by weight of vinyl chloride resin and plasticizer 2
A soft resin composition B containing 0 to 70% by weight,
An extruded article characterized by being co-extruded. The third invention of the present invention provides the above hard resin composition A,
(2) a soft resin composition B containing 5 to 75% by weight of a vinyl chloride resin, 5 to 70% by weight of a partially crosslinked acrylonitrile-butadiene copolymer and 10 to 65% by weight of a plasticizer, It is an extruded product characterized by being extruded. A fourth invention of the present invention is the extruded products of the first and second inventions, wherein the extruded product is a sealing material.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

In the present invention, the hard resin composition A is
A thermoplastic resin composition containing the components (a), (b) and (c) and a heat-resistant vinyl chloride resin composition containing the component (d).

The component (a) used in the hard resin composition A of the present invention is a chlorinated vinyl chloride resin composition having a chlorine content of 60 to 70% by weight, and the component (b) is a vinyl chloride resin composition. The component (c) is a resin composition containing an α-methylstyrene-based copolymer and a graft copolymer, and the component (d) is talc.

The chlorinated vinyl chloride-based resin composition of the component (a) used in the present invention is obtained by dispersing the vinyl chloride-based resin composition powder in a gaseous phase, in a state of being suspended in water, or in a state of being dissolved in a solvent. It can be manufactured by, for example, Methods for chlorinating vinyl chloride resin compositions are well known, and are described in JP-B-36-888 and JP-B-45-308.
This is described in detail in Japanese Patent Publication No. 33 and the like.

The chlorine content of the chlorinated vinyl chloride resin composition used in the present invention is preferably from 60 to 70% by weight. The chlorine content of the chlorinated vinyl chloride resin composition is 60% by weight.
If less than 70% by weight, the heat resistance is not sufficiently improved.
If it exceeds, thermal decomposition tends to occur, which is not preferable.

The vinyl chloride resin composition used for producing the chlorinated vinyl chloride resin composition includes a polyvinyl chloride resin composition and a mixture of vinyl chloride and a vinyl compound copolymerizable therewith. A resin composition polymerized by an ordinary method such as a suspension polymerization method, a bulk polymerization method, a fine suspension polymerization method or an emulsion polymerization method, and an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer or chlorination. A resin composition obtained by graft copolymerizing vinyl chloride with polyethylene or the like can be used.

Examples of the vinyl compound copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as methyl acrylate and butyl acrylate, and methacrylic esters such as methyl methacrylate and ethyl methacrylate. , Maleic esters such as butyl malate and diethyl malate, fumaric esters such as dibutyl fumarate and diethyl fumarate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, acrylonitrile and methacrylonitrile and the like. Α-olefins such as vinyl cyanide, ethylene, propylene and styrene, vinylidene halides and vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, and Phthalic acid esters such as diallyl phthalate. The content of these vinyl compounds is preferably 30% by weight or less, more preferably 20% by weight or less, in the components of the vinyl chloride resin composition.

The vinyl chloride resin composition of the component (b) used in the present invention may be the same as described above.

The average degree of polymerization of these vinyl chloride resin compositions is preferably from 500 to 1500 as measured by JIS K-6721.
If it is less than 500, the impact resistance may be inferior.
If it exceeds 3, the melt viscosity at the time of processing becomes extremely high, and the processability may be deteriorated.

The component (c) used in the present invention comprises α-methylstyrene-based copolymers 30 to 10 of the following component (a):
The resin composition contains 0% by weight and 0 to 70% by weight of the graft copolymer (B).

The component (a) includes 65 to 85% by weight of α-methylstyrene, 15 to 35% by weight of a vinyl cyanide compound, and 0 to 2 of another vinyl compound copolymerizable therewith.
A copolymer containing 0% by weight is used.

Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, α-methacrylonitrile and the like. Of these, acrylonitrile and / or methacrylonitrile are preferred.

Examples of the vinyl compound copolymerizable with α-methylstyrene and a vinyl cyanide compound include styrene, vinyltoluene, t-butylstyrene, halogen-substituted styrene, fumaronitrile, maleimide, maleic anhydride, and N-substituted maleimide. And at least one selected from various known vinyl compounds such as methacrylic acid, methacrylic acid esters and acrylic acid esters. Of these, styrene is preferred in terms of economy.

The method for producing the component (a) is not particularly limited, but is carried out, for example, by aqueous emulsion polymerization. Examples of the polymerization initiator in the aqueous emulsion polymerization include persulfates such as potassium persulfate. Examples of the emulsifier include sodium dodecylbenzenesulfonate and sodium stearate. Ordinarily used additives such as a molecular weight regulator such as t-dodecyl mercaptan, an emulsifying aid such as sodium naphthalene sulfonate, and a lubricant such as fatty acid amide may be added. The temperature of the emulsion polymerization is preferably from 30 to 100 ° C, more preferably from 50 to 75 ° C. The emulsion polymerization solution obtained by the above method is coagulated with a coagulant such as calcium chloride by a usual means, washed and dried to obtain a white powdery polymer.

The component (b) includes 50 to 80% by weight of an aromatic vinyl compound, 15 to 35% by weight of a vinyl cyanide compound, and 0 to 3 of other vinyl compounds copolymerizable therewith.
A graft copolymer obtained by copolymerizing 20 to 70 parts by weight of a mixture containing 0% by weight in the presence of 80 to 30 parts by weight of a rubber having a glass transition temperature of 0 ° C. or less is used.

The aromatic vinyl compound used for producing the graft copolymer of the component (b) includes styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, halogen-substituted styrene, and mixtures thereof. And the like. Of these, styrene is preferred in terms of economy.

Examples of the vinyl cyanide compound include the above-mentioned acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like. Of these, acrylonitrile and / or methacrylonitrile are preferred.

Other vinyl compounds copolymerizable with an aromatic vinyl compound or a vinyl cyanide compound include fumaronitrile, maleimide, maleic anhydride, N-substituted maleimide, methacrylic acid, acrylic acid, methacrylic acid ester and acrylic acid. One or more compounds selected from various known vinyl compounds such as acid esters can be used.

The rubber having a glass transition temperature (hereinafter referred to as Tg) of 0 ° C. or lower used in the production of the component (b) includes polymers of conjugated diene compounds such as butadiene and isoprene, and the like.
Further, a copolymer of the conjugated diene compound with another vinyl compound copolymerizable therewith can be used. Among them, polybutadiene and butadiene are used in terms of economic efficiency.
A copolymer containing 0% by weight or more is preferred. The production of the graft copolymer is carried out in a usual manner under known polymerization conditions.

In the resin composition of the component (c) used in the present invention, the weight ratio of the α-methylstyrene copolymer of the component (a) to the graft copolymer of the component (b) is (a)
30 to 100% by weight of the component and 0 to 70% by weight of the component (B), 50 to 100% by weight of the component (A) and 0 to 0 of the component (B)
Preferably it is 50% by weight. If the component (a) is less than 30% by weight, the effect of improving the heat deformation resistance is hardly obtained.

In the thermoplastic resin composition used in the present invention, the weight ratio of the component (a), the component (b) and the component (c) is 90 to 10% by weight of the component (a) and 0 to 10% by weight of the component (b). 80
% By weight and 10 to 80% by weight of the component (c). (A)
If the component exceeds 90% by weight, the impact strength is weak and the processability is poor. If the component is less than 10% by weight, there is no effect of improving heat resistance, and warpage or deformation is liable to occur. On the other hand, when the component (b) exceeds 80% by weight, the heat resistance is not sufficiently improved, and in this case, warping and deformation are liable to occur. Further, when the component (c) is less than 10% by weight, no effect of improving impact resistance and heat resistance is recognized, and when it exceeds 80% by weight, workability becomes extremely difficult.

The talc (d) used in the present invention is a kind of clay mineral, and its composition formula is MgO.Si ₂ O.H.
₂ O. By using talc as the hard resin composition, even if the soft resin composition in the co-extruded product is elongated in the longitudinal direction at a high temperature or shrinks in the longitudinal direction at a low temperature, the hard resin composition is The coextruded product does not change in length or deforms or warps due to expansion and contraction of the product, and has excellent effects such as good wettability with the resin composition and high impact strength. This effect is not observed with fillers such as calcium carbonate, silica, clay, aluminum hydroxide and antimony oxide.
Further, when mica is contained in the hard resin composition, the resin component serving as a matrix in the thermoplastic resin composition and the mica have poor wettability and low impact strength. When wollastonite is used, the appearance is poor. Further, even if talc is added to the soft resin composition, deformation and warpage cannot be suppressed.

The average particle size of talc is not particularly limited, but is preferably 0.8 μm to 12 μm, and more preferably 1.0 μm to 9 μm.
μm is more preferable, and 1.5 μm to 5 μm is most preferable. If it is less than 0.8 μm, deformation and warpage may be large, and if it exceeds 12 μm, the surface may not be smooth and the appearance may be poor.

The amount of the component (d) used is as follows:
The amount is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the thermoplastic resin composition containing the components (b) and (c). If it is less than 1 part by weight, there is no effect of heat deformation resistance, and if it exceeds 20 parts by weight, impact strength may be reduced.

The hard resin composition A according to the present invention is JIS K
It is preferable that the load deflection temperature specified by the -7207 method A is 80 ° C or higher, more preferably 85 ° C or higher. When the deflection temperature under load is less than 80 ° C., the effect of improving heat resistance is not sufficient, and the film is easily deformed when exposed to a high-temperature atmosphere, which is not preferable.

The hard resin composition A of the present invention may contain appropriate amounts of necessary stabilizers, processing aids, reinforcing agents, lubricants and contents.

The soft resin composition B of the present invention is a composition containing a vinyl chloride resin composition, a plasticizer and, if necessary, a partially crosslinked acrylonitrile-butadiene copolymer.

As the vinyl chloride resin composition used in the flexible resin composition B of the present invention, the same ones as described above can be mentioned.

The average degree of polymerization of the vinyl chloride resin composition used in the flexible resin composition B of the present invention is not particularly limited. In order to meet the object of the present invention of reducing the size and obtaining a good sealing material, the average degree of polymerization measured by JIS K-6721 is preferably 2000 or more.

The plasticizer used in the soft resin composition B of the present invention may be any plasticizer which is generally used as a plasticizer for a vinyl chloride resin composition, such as dibutyl phthalate and phthalic acid. Phthalic acid-based plasticizers such as diheptyl, di-2-ethylhexyl phthalate, diisononyl phthalate and diisodecyl phthalate; trimellitic acid-based plasticizers such as tributyl trimellitate and tri-2-ethylhexyl trimellitate; tetrabutyl pyromellitate; Pyromellitic acid plasticizers such as tetraoctyl pyromellitic acid; phosphoric acid plasticizers such as tricresyl phosphate and trioctyl phosphate; fatty acid plasticizers such as dioctyl adipate, dioctyl azelate and dioctyl sebacate; adipic polyester And polyesters such as polyester sebacate Le plasticizers, and epoxy-based plasticizers such as alkyl epoxy stearate and the like,
These may be used alone or in combination of two or more. Further, a secondary plasticizer such as epoxidized soybean oil and chlorinated paraffin may be used in combination. Among them, phthalic acid plasticizers, trimellitic acid plasticizers, fatty acid plasticizers, phosphoric acid plasticizers, fatty acid plasticizers, polyester plasticizers, and epoxy plasticizers are preferable in terms of great economic efficiency and effects.

When the composition contains a vinyl chloride resin composition and a plasticizer, the soft resin composition B has a weight ratio of 30 to 80% by weight of the vinyl chloride resin composition and 20 to 70% by weight of the plasticizer. It is preferably in the range of 40 to 80% by weight of the vinyl chloride resin composition and 60 to 20% by weight of the plasticizer.

When the amount of the vinyl chloride resin composition is less than 30% by weight, defective phenomena such as poor product appearance often occur at the time of extrusion molding, and when the amount exceeds 80% by weight, the sealing portion of the obtained gasket product is hard. , It becomes unsuitable as a sealant.

If the amount of the plasticizer is less than 20% by weight, the sealing portion of the obtained sealing material is hard and is unsuitable as a sealing material. If the amount exceeds 70% by weight, the hardness is too low and the material is easily deformed in a high temperature atmosphere. Become.

Further, when the soft resin composition B is sealed with a sealing material for a long period of time, in order to prevent the soft resin composition portion of the extruded product from being deformed and the sealing property from being reduced,
It is preferable to contain a partially crosslinked acrylonitrile-butadiene copolymer.

The partially crosslinked acrylonitrile-butadiene copolymer used in the soft resin composition B of the present invention is not limited to a production method as long as it contains a crosslinked acrylonitrile-butadiene copolymer insoluble in methyl ethyl ketone. As a crosslinking method, a method of crosslinking by copolymerizing with a polyfunctional monomer such as divinylbenzene or ethylene glycol dimethacrylate, and a method of proceeding a crosslinking reaction until a crosslinked acrylonitrile-butadiene copolymer insoluble in methyl ethyl ketone is generated. And a method of crosslinking an unvulcanized acrylonitrile-butadiene copolymer using a small amount of a crosslinking agent. Commonly available partially crosslinked acrylonitrile-butadiene copolymers include Good Chem Co., Ltd., trade name "Chemigum P83", Nippon Synthetic Rubber Co., Ltd., trade name "JSR N201", B.I. F. Goodrich Corporation, trade name “Hycar1421” and the like.

When the composition contains a vinyl chloride resin composition, a partially cross-linked acrylonitrile-butadiene copolymer and a plasticizer, the soft resin composition B is 5 to 75% by weight of the vinyl chloride resin composition, Crosslinked acrylonitrile-
5 to 70% by weight of butadiene copolymer and 10 to 6 plasticizers
Preferably it is in the range of 5% by weight.

If the amount of the vinyl chloride resin composition is less than 5% by weight, defective phenomena such as poor product appearance often occur at the time of extrusion molding, and if it exceeds 75% by weight, the sealing portion of the obtained gasket product is hard. , It becomes unsuitable as a sealant.

When the content of the partially crosslinked acrylonitrile-butadiene copolymer is less than 5% by weight, an appropriate molding temperature difference from the hard resin composition material at the time of coextrusion molding becomes large, and the obtained sealing material is pressed or compressed. Easy to be deformed. 7
If the content exceeds 0% by weight, defective phenomena such as defective product appearance are likely to occur during extrusion molding.

If the amount of the plasticizer is less than 10% by weight, the sealing portion of the obtained sealing material is hard and unsuitable as a sealing material. If the amount exceeds 65% by weight, the hardness is so low that it is easily deformed in a high-temperature atmosphere. Become.

The soft resin composition B of the present invention may contain, if necessary, stabilizers, processing aids, reinforcing agents, lubricants, fillers, pigments and the like used in general vinyl chloride resin compositions. Is also good.

In the present invention, the order of mixing the components (a), (b), (c) and (d) is not limited, and generally, the mixing method and the pelletizing method are the same as those of ordinary vinyl chloride. The method used for the production of the base resin composition is used. For both the hard resin composition A and the soft resin composition B, a high-speed mixer such as a Henschel mixer or a super mixer or a mixer such as a ribbon blender is used. As a mixing method, it is preferable that the respective components are put into the above-mentioned mixer and uniformly blended, for example, at a temperature of 150 ° C. or less for a time appropriate for each mixer. The granulation is carried out by a conventional method for producing the above-mentioned composition, such as a Banbury mixer, a mixing roll, and an extruder, which is usually used for producing a vinyl chloride resin composition.

Although there is no particular limitation on the co-extrusion apparatus,
Usually, a kneading and extruding apparatus A used for a hard material and a kneading and extruding apparatus B for a soft material are joined and integrated with the same mold C to obtain a co-extrusion apparatus D. The size of A and B, single-screw, twin-screw, horizontal and vertical devices, and the like can be appropriately selected depending on the material used and the shape and dimensions of the co-extruded product.

In the present invention, for the purpose of imparting surface design and the like, a multilayer structure of a vinyl chloride resin composition or an acrylic resin composition may be extruded on the surface during extrusion molding.
In order to improve the strength and the like of the extruded product, a metal or the like may be co-extruded.

The co-extruded product of the present invention can be used as a joint material for construction, etc., but is excellent in a sealing effect and a sealing effect, and is used for packing, gasket, weather strip, window molding, belt molding, and flush mount. It is preferably used as a sealing material for moldings and the like, and more preferably used as packing, gaskets, weather strips, window moldings, belt moldings, and flush mount moldings. FIG. 1 shows a case where the sealing material is used as a gasket for an automobile window, for example. In FIG. 1, the gasket is composed of two layers of the soft resin compositions 1 and 1 ′ (where 1 ′ is a lip portion) and the hard resin composition 2, and the soft resin compositions 1 and 1 ′ are in contact with the window glass. In addition, the airtightness is maintained by sealing to prevent rainwater or the like from entering between the soft resin compositions 1 and 1 ′ and the window glass.

[0053]

The present invention will be described below with reference to examples.

Example 1 Each raw material shown in Table 1 was put into a 75-liter Henschel mixer, stirred and mixed, and then kneaded into pellets using a 90 m / m single screw extruder (manufactured by Ikegai Iron Works Co., Ltd.). 15 kg of each of the hard resin composition A and the soft resin composition B shown in FIG. Using this, co-extrusion was performed with the following two extruders. Extruder A 65m / m single screw extruder (Ikegai Iron Works Co., Ltd.)
Extruder B 40 m / m vertical single-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd.) The die for the co-extruded molded product is designed to be composed of the hard resin composition A and the soft resin composition B. What was used was used.
About the obtained co-extrusion molded article, evaluation and measurement of each physical property were performed. Table 1 shows the results. As a result, the obtained co-extruded product had good moldability, little expansion under a hot atmosphere, and was practically usable as a sealing material.

[0055]

[Table 1]

Comparative Example 1 Each raw material shown in Table 1 was agitated, kneaded, and pelletized in the same manner as described in the above Examples, and was co-extruded. The physical properties of the obtained co-extruded product were evaluated and measured, and the results are shown in Table 1. As a result, the sealing material was impractical or had a large expansion under hot atmosphere.

Example 2 Each raw material shown in Tables 2 and 3 was agitated, kneaded, and pelletized in the same manner as described in the above Example, and co-extruded. The physical properties of the obtained co-extruded product were evaluated and measured, and the results are shown in Tables 2 and 3. As a result, each of the obtained co-extruded products had good moldability, little expansion under a hot atmosphere, and was practically usable as a sealing material.

[0058]

[Table 2]

[0059]

[Table 3]

Comparative Example 2 Each raw material shown in Table 4 was stirred, kneaded, and pelletized in the same manner as described in the above Example, and was co-extruded. The physical properties of the obtained co-extruded product were evaluated and measured, and the results are shown in Table 4. As a result, the sealing material was impractical or had a large expansion under hot atmosphere.

[0061]

[Table 4]

Example 3 Each raw material shown in Example 2-9 was stirred, kneaded, and pelletized in the same manner as in the above-mentioned Example, and was mixed with the soft resin compositions 1, 1 'as shown in FIG. Hard resin composition 2-2
A gasket for automobile windows (weatherstrip) consisting of layers was co-extruded. However, the die for the co-extruded product had a configuration of the hard resin composition A and the soft resin composition B, and was designed to be a gasket for an automobile window shown in FIG. 100 m of the obtained co-extruded product
m, and pressed against glass so that a bending load of 1 kgf / 100 mm is applied to the lip portion 1 'made of a soft resin composition as shown in FIG.
After the treatment at ° C, the application of the load was stopped, and the shape of the gasket for an automobile window was observed. The shape of the gasket for an automobile window was the same as the shape before pressing, and no deformation was observed.

Comparative Example 3 Each raw material shown in Example 1 was stirred, kneaded, and pelletized in the same manner as in Example 3, and a gasket for automobile windows shown in FIG. 1 was co-extruded and subjected to the same test. Was done.
The shape of the gasket for an automobile window was crushed due to pressure and deformed compared to the shape before pressing.

(Raw Materials Used) The raw materials used in each Example and each Comparative Example are shown below. (1) Chlorinated vinyl chloride resin composition of component (a) Nicatemp T241 (chlorine content 64.5%) manufactured by Nippon Carbide Industry Co., Ltd. (2) Vinyl chloride resin composition of component (b)- 1 Taiyo PVC TH1000 (degree of polymerization 1030) Manufactured by Taiyo PVC Co., Ltd. (3) Resin composition of component (c) 60% by weight of component (a) and 40% by weight of component (b) below are obtained by mixing. Was used. (A) Component α-methylstyrene copolymer Emulsion polymerization was started using 210 g of α-methylstyrene, 15 g of styrene, 45 g of acrylonitrile and an initiator. During the polymerization, 30 g of acrylonitrile was added during the polymerization to obtain an α-methylstyrene copolymer. (B) Graft copolymer of component Polybutadiene latex (polybutadiene solid content concentration 35%, average particle diameter 350 μm; gel content 87%) 28
Using 6 parts and an initiator, graft emulsion polymerization was carried out while adding 105 parts of styrene and 45 parts of acrylonitrile to obtain a graft copolymer. (4) Talc of component (d) Talc-1 Hytron (average particle size 4.0 μm) Talc-2 LMP (average particle size 4.0 μm) manufactured by Takehara Chemical Industry Co., Ltd. 5) Vinyl chloride resin composition used for flexible resin composition B-2 Taiyo PVC TH2500 (degree of polymerization 2500) manufactured by Taiyo PVC Co., Ltd. (6) Partially crosslinked acrylonitrile-butadiene copolymer (abbreviated as NBR in the table) JSR N201 manufactured by Nippon Synthetic Rubber Co., Ltd. (7) Plasticizer diisononyl phthalate (8) Filler Calcium carbonate (average particle size 4.0 μm) Silica (average particle size 4.5 μm) Nippon Silica Industry Co., Ltd. Mica (average particle size: 3.0 μm) Wollastonite (average particle size: 4.3 μm) manufactured by Mika Yamaguchi Corporation Hayashi Kasei Co., Ltd.

(Measurement Method) The measurement method of each example and each comparative example is shown below. Shrinkage: After cutting the co-extruded product to a length of 500 mm, it was heated in an atmosphere at 100 ° C. for 270 hours. After the removal, the length L (unit: mm) is measured, and the initial length 50
By dividing by 0 mm, shrinkage = [(500−L) / 500 ×
100]% was calculated. Deformation, warpage: After heating a co-extruded product cut to a length of 500 mm in an atmosphere of 100 ° C. for 270 hours,
The appearance of the sled was evaluated. Deflection temperature under load of hard resin composition portion: JIS K72
07 A method. Wetting: The hard resin composition portion was magnified 1000 times with an electron microscope, and the situation between the thermoplastic resin composition and the filler was observed. Impact strength: According to JIS K7110.

[0066]

According to the present invention, the moldability during production, the appearance,
It is possible to obtain a co-extruded product such as a sealing material having excellent heat deformation resistance and small thermal expansion in an actual operating temperature range. In particular, since the thermal expansion under high temperature conditions such as 100 ° C. × 270 hours or for a long time is small, it is suitable for gaskets such as gaskets and packings. In addition, it is also possible to use parts that reach a high temperature, such as building materials and automobile parts, which could not be used with conventional products, specifically, outer wall materials, window frames, and automobile interior materials.

[Brief description of the drawings]

FIG. 1 is a view showing an example of a gasket for a vehicle window according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Soft resin composition 1 'Soft resin composition (lip part) 2 Hard resin composition

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 27/06 C08L 27/06 55/02 55/02 C09K 3/10 C09K 3/10 Z F16J 15/10 F16J 15/10 X // B29K 27:06 B29L 9:00 31:26

Claims (4)

[Claims] (1) 90 to 10% by weight of the following component (a):
(B) a thermoplastic resin composition containing 0 to 80% by weight of the component and (c) 10 to 80% by weight of the component;
(D) A hard resin composition comprising a component. (A) Component Chlorinated vinyl chloride resin composition having a chlorine content of 60 to 70% by weight (b) Component Vinyl chloride resin composition (c) Component 30 to 100% by weight of the following component (A) and (B) Resin composition containing 0 to 70% by weight of component (a) 65 to 85% by weight of component α-methylstyrene, 15 to 35% by weight of vinyl cyanide compound and 0 to 20 of other vinyl compounds copolymerized therewith Α-methylstyrene-based copolymer containing 2% by weight (b) Component 50 to 80% by weight of an aromatic vinyl compound, 15 to 35% by weight of a vinyl cyanide compound and 0 to 0 of other vinyl compounds copolymerized therewith Graft copolymer obtained by copolymerizing 20 to 70 parts by weight of a mixture containing 30% by weight in the presence of 30 to 80 parts by weight of a rubber having a glass transition temperature of 0 ° C. or lower (d) Component talc 2. The (1) hard resin composition A according to claim 1.
And (2) a soft resin composition B containing 30 to 80% by weight of a vinyl chloride resin and 20 to 70% by weight of a plasticizer. 3. The (1) hard resin composition A according to claim 1.
And (2) 5 to 75% by weight of a vinyl chloride resin, and 5 to 70% by weight of a partially crosslinked acrylonitrile-butadiene copolymer
An extruded product obtained by co-extruding a soft resin composition B containing 10 to 65% by weight of a plasticizer. 4. The extruded product according to claim 2, wherein the extruded product is a sealing material.