JP3076222B2 - Extruded products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an extruded product made of synthetic resin having excellent heat resistance, moldability and deformation resistance, and more particularly to a sealing material.

[0002]

2. Description of the Related Art Conventionally, a soft synthetic resin such as a soft vinyl chloride resin or a soft material such as a cross-linked rubber material has been used as a seal material for a packing, a gasket or the like of buildings, automobiles, kitchen appliances and the like.

[0003] Soft synthetic resins or crosslinked rubber materials are used alone as extrusion, injection and compression molded products. In addition, a metal and a resin are melted and integrated (hereinafter, referred to as coextrusion) in the same mold (hereinafter, referred to as a die) or adhered to a metal to be used as a sealing material.

However, a co-extruded sealing material made of metal is economically disadvantageous because it is necessary to separate resin and metal in order to recycle the material.

[0005] As a countermeasure, coextrusion using a hard synthetic resin instead of metal has been studied. A co-extruded sealing material using a hard synthetic resin is processed and manufactured after co-extrusion molding of a hard synthetic resin and a soft material, or after bonding a hard synthetic resin and a soft material.
Examples of the hard synthetic resin include an ABS resin and a hard vinyl chloride resin. However, when the ABS resin is adhered or co-extruded with the soft vinyl chloride resin, cracks and the like are easily generated, which is not suitable for practical use.

[0006] Therefore, as a hard material to be co-extruded with a soft material, a hard vinyl chloride resin is generally used.

[0007] Examples of the soft material include soft vinyl chloride resin, olefin-based resin, and rubber. In the case of co-extrusion, in general, the heat-fusing property with the hard material and the workability are poor. Excellent soft vinyl chloride resin is used.

The sealing material thus obtained is used for building,
Used for automobiles, kitchen appliances, etc.

However, when these are used outdoors, the temperature of the sealing material can reach 70 ° C. or more, and when they are used for the interior of automobiles, the temperature inside the automobile can reach 90 ° C. at the maximum. There is.

When a sealing material obtained by co-extrusion of a hard vinyl chloride resin and a soft vinyl chloride resin is exposed to a high-temperature atmosphere at 70 ° C., the hard vinyl chloride resin is deformed, and Since the deformation of the vinyl resin due to pressing and compression increases, the sealing and sealing effects are reduced during use, and a sealing material having good sealing performance cannot be obtained.

In the case of a gasket using a heat-resistant vinyl chloride resin as a hard resin material and a soft vinyl chloride resin as a soft material in order to increase the heat resistance of the hard material, the heat resistance of the hard material is improved. The deformation of the vinyl chloride resin used as a soft material in a high-temperature atmosphere could not be prevented.

On the other hand, when a crosslinked rubber material is used as a soft material, a product having excellent deformation resistance and good sealing performance can be obtained, but due to a difference in molding temperature from the rubber material and a crosslinking treatment of the rubber portion, the adhesive is required. Therefore, the co-extruded product with the hard synthetic resin could hardly be a product.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide an extruded product which solves the above-mentioned drawbacks, has good heat resistance, moldability and deformation resistance, and has excellent sealing and sealing effects. It is in. The present inventors have intensively studied the production of a co-extruded product by using a thermoplastic resin composition as a hard material and a soft resin composition as a soft material, and as a result, completed the present invention.

[0014]

Means for Solving the Problems A first invention of the present invention is:
(1) a thermoplastic resin composition A comprising the following (a) component 90 to 20% by weight and (b) component 10 to 80% by weight;
(2) An extruded product obtained by co-extruding a soft resin composition B comprising 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. (A) Component Vinyl chloride resin (b) Component A resin composition comprising the following (A) component: 30 to 100% by weight and (B) component: 0 to 70% by weight (A) Component: α-methylstyrene: 65 to 85% by weight An α-methylstyrene-based copolymer comprising 15 to 35% by weight of a vinyl cyanide compound and 0 to 20% by weight of another vinyl compound copolymerized therewith; 50 to 80% by weight of an aromatic vinyl compound; A glass transition temperature (hereinafter abbreviated as Tg) of 20 to 70 parts by weight of a mixture comprising 15 to 35% by weight of a vinyl chloride compound and 0 to 30% by weight of another vinyl compound copolymerized with these compounds
Graft copolymer obtained by copolymerization in the presence of 80 to 30 parts by weight of rubber having a temperature of 0 ° C. or less

[0015] The second invention of the present invention is the extruded product according to the first invention, wherein the extruded product is a sealing material.

Hereinafter, the present invention will be described in detail. In the present invention, the thermoplastic resin composition A includes the component (a) and the component (b).
It is a composition comprising components.

The component (a) used in the thermoplastic resin composition A of the present invention is a vinyl chloride resin, and the component (b) is α.
A resin composition comprising a methylstyrene-based copolymer and a graft copolymer.

The weight ratio of component (a) to component (b) of the thermoplastic resin composition A of the present invention is 90 to 20% by weight of component (a) and 10 to 80% by weight of component (b).

Examples of the vinyl chloride resin as the component (a) used in the present invention include, in addition to polyvinyl chloride, a mixture of vinyl chloride and a vinyl compound copolymerized with vinyl chloride, a suspension polymerization method, a bulk polymerization method, What was polymerized by a usual method such as a fine suspension polymerization method or an emulsion polymerization method, and further, a vinyl chloride was graft-copolymerized to an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer or a chlorinated polyethylene. Everything is used.

Examples of the vinyl compound copolymerized 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. Vinyl cyanides, α-olefins such as ethylene, propylene and styrene; vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide; and halogenation. Cycloalkenyl such, as well as, phthalic acid esters such as diallyl phthalate, and the like. These vinyl compounds, 30% by weight in the preferred components of the vinyl chloride resin or less, particularly preferably 20 wt% or less. Of course, the vinyl compound is not limited to the above.

The amount of the vinyl compound used in these vinyl chloride copolymers is preferably 30% by weight or less, more preferably 20% by weight, of the components of the vinyl chloride resin.
The range is as follows.

The average degree of polymerization of the vinyl chloride resin used for the thermoplastic resin composition A is 500 as an average degree of polymerization (hereinafter referred to as a degree of polymerization) measured according to JIS K-6721.
~ 1500 are preferred. If the degree of polymerization is less than 500, the impact resistance will be poor, and if the degree of polymerization is 1500
If it exceeds, the melt viscosity during processing becomes extremely high, and processing becomes difficult.

The component (b) used in the thermoplastic resin composition A is composed of the α-methylstyrene copolymer 30 of the component (a).
To 100% by weight and the graft copolymer (B)
Consists of 70% by weight.

The component (a) includes 65 to 85% by weight of an α-methylstyrene copolymer, a vinyl cyanide compound 1
Copolymers consisting of 5 to 35% by weight and 0 to 20% by weight of other vinyl compounds copolymerized with them are used.

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

Examples of the vinyl compound copolymerized with α-methylstyrene and a vinyl cyanide compound include styrene, vinyltoluene, t-butylstyrene, halogen-substituted styrene, acenaphthylene, fumaronitrile, maleimide, maleic anhydride, N- One or more selected from various known vinyl compounds such as substituted maleimide, methacrylic acid, acrylic acid, methacrylic acid ester and acrylic acid ester are preferable, and styrene is particularly preferable.

The method for producing the component (a) is not particularly limited, but is, for example, an aqueous emulsion polymerization method. As a polymerization initiator in the aqueous emulsion polymerization, for example, a persulfate such as potassium persulfate is used.

As the emulsifier, for example, sodium dodecylbenzenesulfonate and sodium stearate are used. A molecular weight regulator such as t-dodecyl mercaptan;
Usually used additives such as emulsifying aids such as sodium naphthalene sulfonate and lubricants such as fatty acid amides may be added.

The temperature of the emulsion polymerization is preferably from 30 to 100 ° C., particularly preferably from 50 to 75 ° C. The emulsion polymerization liquid obtained by the above method is coagulated with a coagulant such as calcium chloride by usual means, washed, dehydrated 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 30% of another vinyl compound copolymerized therewith.
A graft copolymer obtained by copolymerizing 20 to 70 parts by weight of a mixture consisting of 100% 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, but styrene is particularly preferred.

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

Other vinyl compounds copolymerized with an aromatic vinyl compound and a vinyl cyanide compound include, for example, acenaphthylene, fumaronitrile, maleimide, maleic anhydride, N-substituted maleimide, methacrylic acid, acrylic acid, methacrylic acid ester And at least one selected from various known vinyl compounds such as acrylic acid esters.

Examples of the rubber having a Tg of 0 ° C. or lower used in the production of the component (b) include, for example, polymers of conjugated diene compounds such as butadiene and isoprene, and copolymers thereof with other vinyl compounds. And the like. In particular, polybutadiene or a copolymer containing 50% by weight or more of butadiene is preferable. The production of the graft copolymer is carried out in a usual manner under known polymerization conditions.

As the graft copolymer (b), an ABS graft copolymer obtained by graft copolymerizing styrene and acrylonitrile with polybutadiene is typical.

In the resin composition of the component (b) used in the present invention, the weight ratio of the α-methylstyrene copolymer (a) to the graft copolymer (ii) is as follows:
30-100% by weight of the component and 0-70% by weight of the component (b), 50-100% by weight of the component (a) and 0 of the component (b)
Preferably, it consists of 〜50% by weight. (A) component is 3
When the amount is less than 0% by weight, the effect of improving heat resistance is hardly obtained.

The thermoplastic resin composition A of the present invention comprising the components (a) and (b) is JIS K-720.
The deflection temperature under load defined by the method 7A is preferably 80 ° C. or higher, particularly preferably 85 ° C. or higher. When the deflection temperature under load is less than 80 ° C., the effect of improving the heat resistance is insufficient, and the film is easily deformed when exposed to a high-temperature atmosphere, which is not preferable.

In the present invention, the soft resin composition B is a composition comprising a vinyl chloride resin, a partially crosslinked acrylonitrile-butadiene copolymer and a plasticizer.

The vinyl chloride resin used in the flexible resin composition B of the present invention may be a mixture of polyvinyl chloride and the above-mentioned vinyl compound copolymerized with vinyl chloride in a suspension polymerization method, a bulk polymerization method, or the like. All those produced by ordinary methods such as a fine suspension polymerization method or an emulsion polymerization method are used.

Examples of the vinyl compound copolymerized with vinyl chloride include the same vinyl compounds as those described above. The amount of these vinyl compounds used is also preferably 30% by weight or less in the components of the vinyl chloride resin,
Particularly preferably, it is used in a range of 20% by weight or less.

The average degree of polymerization of the vinyl chloride resin used in the soft resin composition B of the present invention is not particularly limited. In order to meet the object of the present invention of obtaining a suitable sealing material, it is preferable that the average degree of polymerization measured by JIS K-6721 is 2000 or more.

The partially crosslinked acrylonitrile-butadiene copolymer used for the flexible 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. , A method of obtaining by copolymerization with a polyfunctional compound such as divinylbenzene or ethylene glycol dimethacrylate, a method of increasing the reaction rate until a cross-linked acrylonitrile-butadiene copolymer insoluble in methyl ethyl ketone is formed, or using a small amount of a cross-linking agent Any method can be used, such as a method obtained by crosslinking an unvulcanized acrylonitrile-butadiene copolymer.

Examples of commonly available partially crosslinked acrylonitrile-butadiene copolymers include, for example, Good Chem Co., Ltd., trade name "Chemigum P83", Nippon Synthetic Rubber Co., Ltd .;
Product name "JSR N201" and B.I. F. Goodrich Corporation, trade name “Hycar1421” and the like.

The plasticizer used in the flexible resin composition B of the present invention is not limited as long as it is used as a plasticizer for the vinyl chloride resin. For example, dibutyl phthalate, diheptyl phthalate, diphthalic phthalate, etc. Phthalic acid plasticizers such as 2-ethylhexyl, diisononyl phthalate and diisodecyl phthalate; trimellitic acid plasticizers such as tributyl trimellitate and tri-2-ethylhexyl trimellitate; tetrabutyl pyromellitate and tetraoctyl pyromellitate Pyromellitic plasticizers such as, phosphate plasticizers such as tricresyl phosphate and trioctyl phosphate,
Fatty acid-based plasticizers such as dioctyl adipate, dioctyl azelate and dioctyl sebacate, and polyester-based plasticizers such as polyester adipate and polyester sebacate Epoxy-based plasticizers such as alkyl epoxy stearate, and the like. They are used alone or in combination of two or more. Also, a secondary plasticizer such as epoxidized soybean oil and chlorinated paraffin can be used in combination.

The soft resin composition B is 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.
% By weight.

When the content of the vinyl chloride resin is less than 5% by weight,
In extrusion molding, defective phenomena such as poor product appearance often occur, and when the content exceeds 75% by weight, the sealing portion of the obtained sealing material becomes hard, so that it is not suitable as a sealing material.

When the content of the partially crosslinked acrylonitrile-butadiene copolymer is less than 5% by weight, the difference in proper molding temperature from the hard material at the time of coextrusion molding becomes large, and the obtained sealing material is deformed by pressing, compression and the like. Easy to receive. On the other hand, 7
If the content is more than 0% by weight, poor phenomena such as poor product appearance are likely to occur during extrusion molding, which is inappropriate.

Further, when the plasticizer is less than 10% by weight, the obtained sealing material is unsuitable as a sealing material because the sealing portion is hard, and when it exceeds 65% by weight, the hardness is too low to be used in a high temperature atmosphere. It is easy to deform and unsuitable.

A filler can be added to the thermoplastic resin composition A and the soft resin composition B of the present invention in order to improve properties. The thermoplastic resin composition A has an advantage that heat resistance and moldability are improved by adding a filler.
As the filler, a filler that can be used for a vinyl chloride resin can be used. Specifically, calcium carbonate, silica, clay, talc, aluminum hydroxide, antimony oxide and the like are used alone or in combination. The average particle size of the filler is not particularly limited, but is usually 0.01 μm to 10 μm, preferably 0.03 μm to 7 μm, particularly preferably 0.03 μm to 7 μm.
μm to 5 μm are used. Among the fillers, calcium carbonate is preferred, and particularly preferred is calcium carbonate having an average particle size of 0.03 μm to 5 μm.

The amount of the filler to be added to the thermoplastic resin composition A is 40 parts by weight or less, preferably 1 to 30 parts by weight, based on 100 parts by weight of the resin composition. The filler is
If it exceeds 40 parts by weight, pelletization becomes impossible, and no performance as a resin composition can be obtained.

The thermoplastic resin composition A and the soft resin composition B of the present invention may contain, if necessary, stabilizers, processing aids, reinforcing agents, lubricants, pigments and the like used for general vinyl chloride resins. May be added.

In the present invention, the order of addition and mixing of each raw material is not limited, and generally, mixing and pelletizing are performed in the same manner as in the case of ordinary vinyl chloride resin. For mixing both the thermoplastic resin composition A and the soft resin composition B, for example, a mixer such as a high-speed mixer such as a Henschel mixer or a super mixer, or a ribbon blender is used. In the mixing method, it is preferable that the respective components are put into the above-mentioned mixer, and the components are uniformly blended at a temperature of, for example, 150 ° C. or less for a time appropriate for each mixer.

Granulation is performed by mixing the above mixture with a Banbury mixer,
Using a mixing roll, an extruder, or the like, it is carried out by a method used in the production of ordinary vinyl chloride resins.

There is no particular limitation on the coextrusion 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. Selection of the sizes of A and B, single-shaft, twin-shaft and the like, and horizontal and vertical apparatuses can be appropriately selected depending on the material to be used and the shape and dimensions of the co-extruded product.

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

[0056]

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

Examples 1 to 5 Each of the raw materials shown in Table 1 was placed in a 75-liter Henschel mixer, mixed by stirring, and kneaded into pellets using a 90 m / m single screw extruder (manufactured by Ikegai Iron Works Co., Ltd.). 15 kg of each pellet of the thermoplastic resin composition A and the soft resin composition B were obtained. Using this, co-extrusion was performed with the following two extruders. Extruder A 65m / m single screw extruder (Ikegai Iron Works Co., Ltd.)
(For thermoplastic resin composition A) Extruder B 40 m / m vertical single screw extruder (Plastic Engineering Laboratory Co., Ltd.) (for soft resin composition B)

As a die for a co-extruded product, a die designed to have a constitution of a thermoplastic resin composition A and a soft resin composition B was used.

The obtained co-extruded article had good moldability, and was cut into a length of 500 mm.
Was heated for 48 hours in an atmosphere of. After removal, the length L was measured, divided by the initial length of 500 mm, and the contraction rate ((5
00-L) / 500 × 100)% was calculated. Also, 5
The appearance of the deformation and warpage after heating the co-extruded product cut to a length of 00 mm in an atmosphere of 80 ° C. for 48 hours was evaluated. In addition, JIS K of thermoplastic resin composition A
The deflection temperature under load according to the -7207A method was measured. The physical properties are shown in Table 1. As a result, the obtained co-extruded product was good and was practically usable as a sealing material.

[0060]

[Table 1]

Comparative Examples 1-2 Each raw material shown in Table 2 was stirred, kneaded and pelletized in the same manner as described in the above Example, and co-extruded. The obtained co-extruded product was evaluated and measured, and the physical properties are shown in Table 2. As a result, it was not practical as a sealing material.

[0062]

[Table 2]

Raw Materials Used The raw materials used in Examples 1-4 and Comparative Examples 1-2 are shown below. (1) Vinyl chloride resin Vinyl chloride resin-1 Denka Vinyl SS110 (degree of polymerization 1100) manufactured by Denki Kagaku Kogyo Co., Ltd. Vinyl chloride resin-2 Denka Vinyl SH380 (degree of polymerization 3800) Denki Kagaku Kogyo Co., Ltd. Made

(2) Resin composition of component (b) A resin composition obtained by mixing the following components (a) and (b) as shown in Tables 1 and 2 was used.

(A) Component α-methylstyrene copolymer Emulsion polymerization was initiated 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 performed while dispensing 105 parts of styrene and 45 parts of acrylonitrile.
A graft copolymer was obtained.

(3) Partially crosslinked acrylonitrile-butadiene copolymer (abbreviated as NBR in the table) JSR N201 manufactured by Nippon Synthetic Rubber Co., Ltd.

(4) Plasticizer Diisononyl phthalate (5) Filler Surface-treated calcium carbonate having an average particle size of 0.08 μm

[0069]

As described above, according to the present invention, an extruded product excellent in heat resistance, moldability and deformation resistance, specifically, a sealing material can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // B29K 25:00 27:06 B29L 9:00 31:26 (56) References JP-A-6-340038 (JP, A) JP-A-4-253786 (JP, A) JP-A-4-46944 (JP, A) JP-A-2-311547 (JP, A) JP-A-62-259655 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B29C 47/00-47/96 B32B 1/00-35/00 C08L 1/00-101/16

Claims (2)

(57) [Claims] 1. A thermoplastic resin composition A comprising (1) 90 to 20% by weight of the following component (a) and 10 to 80% by weight of component (b), and (2) 5 to 75% by weight of a vinyl chloride resin. %, Partially crosslinked acrylonitrile-butadiene copolymer 5
An extruded product obtained by co-extrusion of a soft resin composition B comprising from 70 to 70% by weight and a plasticizer from 10 to 65% by weight. (A) Component Vinyl chloride resin (b) Component A resin composition comprising the following (A) component 30 to 100% by weight and (B) component 0 to 70% by weight (A) Component 65 to 85% by weight of α-methylstyrene %, A vinyl cyanide compound of 15 to 35% by weight and another vinyl compound copolymerized therewith with 0 to 20% by weight of an α-methylstyrene-based copolymer (b) component, an aromatic vinyl compound of 50 to 80% by weight, 20 to 70 parts by weight of a mixture of 15 to 35% by weight of a vinyl cyanide compound and 0 to 30% by weight of another vinyl compound copolymerized therewith are mixed with a rubber 8 having a glass transition temperature of 0 ° C. or lower.
Graft copolymer obtained by copolymerization in the presence of 0 to 30 parts by weight 2. The extruded product according to claim 1, wherein the extruded product is a sealing material.