JP2001347604A - Extruded molding and automobile molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an extruded molding having excellent weatherability and moldability, and decreased compressive permanent set. SOLUTION: The extruded molding is formed by compounding a soft resin composition containing a vinyl chloride resin, an acrylic rubber polymer and a plasticizer, and a metal. A filler is used as required. A weather strip 1 comprising the soft resin composition 2 and the metal 3 is included in the extruded molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an extruded article using a soft resin composition having excellent weather resistance, heat deformation resistance, and moldability, and having a reduced compression set.

[0002]

2. Description of the Related Art Soft vinyl chloride resin compositions and EPDM
Soft materials such as rubber, which have unique physical properties and textures not found in natural materials, have the disadvantage that their strength, heat resistance, and dimensional accuracy such as expansion and contraction are inferior. In order to remedy this drawback, composite extrusion molding of a composite of a soft material and a metal has been conventionally performed.

[0003] In this composite extrusion molding, when a rubber material such as EPDM is used as a soft material, a vulcanization step is required after molding, which makes the manufacturing process longer and economically disadvantageous. Extruded products of soft vinyl chloride resin composition and metal for a wide range of applications, such as gaskets for building materials such as window frames, belt moldings, window moldings, and side moldings. Has been adopted.

[0004] However, on the other hand, when a soft vinyl chloride resin composition is used as a soft material, there is a drawback that the shape retention at high temperatures and the compression set are significantly inferior to products using vulcanized rubber. Was.

As a method for improving these disadvantages, for example, a method using a high polymerization degree vinyl chloride resin having an average polymerization degree of 2500 to 3800 is mentioned. By using this method, the compression set defined in JIS K6262 (70 ° C. × 22 hours) can be reduced from 60-70% of the conventional product to nearly 50%. However, the vinyl chloride-based resin composition obtained by this method is insufficient as a material for an automobile molding, which requires a lower and better compression set characteristic. Even if a vinyl chloride resin having a higher degree of polymerization is used to improve this drawback, the compression set cannot be further reduced, but the moldability of the obtained vinyl chloride resin composition is rather deteriorated. There was a disadvantage.

In order to improve this drawback, a method is generally used in which a partially cross-linked nitrile rubber is added to a soft vinyl chloride resin composition comprising a vinyl chloride resin and a plasticizer to improve the compression set characteristics. ing.

In order to further improve the compression set characteristics, a crosslinking agent is added to a soft vinyl chloride resin composition comprising a vinyl chloride resin, a plasticizer and a partially crosslinked nitrile rubber, and a partially crosslinked nitrile is formed during molding. Methods for dynamically crosslinking rubber have been proposed.

[0008]

However, the vinyl chloride resin composition obtained by these methods can certainly improve the shape retention at high temperatures and the compression set characteristics, but it is difficult to obtain a molten resin during molding. Molded products with complicated cross-sections because the viscosity is high and the moldability is inferior, and furthermore the color change and the physical properties due to outdoor exposure due to the partially cross-linked nitrile rubber contained in the resin composition may be large and the weather resistance may be inferior. When severe weather resistance is required, there is a problem that it cannot be used.

The present invention solves the above-mentioned problems and provides a resin composition having improved shape retention at high temperatures and compression set characteristics without deteriorating the moldability and weatherability of the vinyl chloride resin composition. The purpose is to provide.

[0010]

That is, the present invention relates to an extruded product obtained by compounding a soft resin composition containing a vinyl chloride resin, an acrylic rubber polymer, and a plasticizer with a metal. The average degree of polymerization of vinyl chloride resin is 800
The extruded product, wherein the extruded product further comprises a filler; the extruded product wherein the filler is calcium carbonate and / or talc; and an acrylic rubber polymer. Is an extruded product having a core-shell type structure. And it is an automobile molding made of the extruded product.

[0011]

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

As the vinyl chloride resin used in the present invention, a mixture of vinyl chloride and a vinyl compound copolymerizable therewith can be prepared by a suspension polymerization method, a bulk polymerization method, a fine suspension polymerization method or an emulsion polymerization method. And a resin composition obtained by graft copolymerization of vinyl chloride with ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, or the like. Further, a chlorinated vinyl chloride resin may 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. Vinyl cyanides, α-olefins such as ethylene, propylene and styrene, vinylidene halides and vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, and di- Phthalic acid esters such as Rirufutareto like. The content of these vinyl compounds is preferably 30% by mass or less in the components of the vinyl chloride resin.
% By mass or less is more preferable.

The average degree of polymerization of these vinyl chloride resins is preferably from 800 to 4000, more preferably from 1300 to 3800, more preferably from 1300 to 3800, as measured by JIS K6721.
2500 is most preferred. If the degree of polymerization is less than 800, the compression set of the obtained resin composition may be inferior,
If it exceeds 4,000, the melt viscosity during molding of the obtained resin composition will be extremely high, and the processability may be deteriorated.

[0015] Among the acrylic rubber polymers used in the present invention, the core material is different from the core material in terms of compression set characteristics and weather resistance.
An acrylic rubber polymer having a core-shell structure composed of a shell material covering the surface of the core material is preferable.

The core material is a monomer having butyl acrylate as a main component and having the same reactivity as butyl acrylate and having two or more double bonds, for example, an aromatic divinyl monomer such as divinylbenzene or butylene glycol. It refers to one crosslinked with diacrylate or the like.

The shell material preferably has a structure containing at least one monomer having excellent compatibility with the vinyl chloride resin. As a shell material with excellent compatibility with vinyl chloride resin,
Polymethacrylates such as polymethyl methacrylate and polyethyl methacrylate; polyesters such as polycaprolactone; polyester-based polyurethanes; resin compositions such as ethylene-vinyl acetate copolymer and styrene-acrylonitrile copolymer; .

As the acrylic rubber polymer having a core-shell type structure, Sanigam P7395 (Good Y
ear Co., Ltd.).

The amount of the acrylic rubber polymer used is preferably from 10 to 300 parts by mass, more preferably from 20 to 200 parts by mass, per 100 parts by mass of the vinyl chloride resin. If the amount is less than 10 parts by mass, the compression set characteristics and weather resistance may be inferior. If the amount exceeds 300 parts by mass, the melt viscosity at the time of molding may be significantly increased, and the processability may be deteriorated.

The plasticizer used in the present invention is not particularly limited, and those used in conventional soft vinyl chloride resin compositions can be used. Among the plasticizers,
Phthalates such as di-2-ethylhexyl phthalate and dibutyl phthalate, adipic esters such as di-2-ethylhexyl adipate, sebacates such as dibutyl sebacate, and trimellits such as tri-2-ethylhexyl trimellitate One of the group consisting of acid esters and epoxy compounds such as epoxidized soybean oil;
Species or two or more are preferred.

The amount of the plasticizer used is preferably from 20 to 200 parts by mass, more preferably from 30 to 200 parts by mass, based on 100 parts by mass of the vinyl chloride resin in view of hardness, flexibility, physical properties and moldability required for the product. 150 parts by mass is more preferred. If the amount is less than 20 parts by mass, it is difficult to impart flexibility, and the obtained resin composition has a large compression set, and the weather resistance and processability may be deteriorated. It is difficult to absorb the agent, and the plasticizer may ooze out of the molded product, resulting in poor shape retention and moldability.

In the present invention, it is preferable to use a filler from the viewpoint of satisfying hardness, flexibility, physical properties and moldability required for products.

The filler used in the present invention includes calcium carbonate, talc, silica, clay, aluminum hydroxide and antimony oxide. Among these, calcium carbonate and / or talc are preferred from the viewpoint of greatly improving the shapeability of the soft resin composition during molding.

The calcium carbonate used in the present invention may be either heavy calcium carbonate or light calcium carbonate.

The average particle size of calcium carbonate is not particularly limited, but is usually preferably from 0.03 to 4.0 μm, more preferably from 0.03 to 4.0 μm.
4 to 2.0 μm is more preferred. If it is less than 0.03 μm, the effect of imparting shapeability may not be recognized, and it may be 4.0.
If it exceeds μm, the surface of the molded article may not be smooth and the appearance may be poor.

Talc used in the present invention is a kind of clay mineral.

Although the average particle size of talc is not particularly limited, it is usually 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 or more than 12 μm, the surface may not be smooth and the appearance may be poor.

The amount of the filler used is 10
3 to 200 parts by mass, preferably 5 to 15 parts by mass, per 0 parts by mass.
0 parts by mass is more preferred. If the amount is less than 3 parts by mass, the molding processability of the detailed shape of the molded product may be poor,
If the amount exceeds the mass part, the moldability of the detailed shape of the molded product is poor, and the surface of the molded product may not be smooth.

The metal used in the present invention is not particularly limited as long as it is a generally rigid metal such as stainless steel, iron, copper and aluminum.

The resin composition of the present invention may be prepared by adding a solvent such as ethylene-vinyl acetate copolymer, acrylic resin, chlorinated polyethylene, polyurethane and acrylonitrile-butadiene copolymer within a range that does not extremely deteriorate the performance of the resin composition. Thermoplastic resin with excellent compatibility with vinyl resin, flame retardant represented by antimony trioxide and zinc borate usually added to vinyl chloride resin, barium stearate, zinc stearate, and tribasic lead sulfate Various additives such as a heat stabilizer, an antioxidant, an ultraviolet absorber, a lubricant, and a colorant can be added as necessary.

In the present invention, the method of mixing and kneading the components constituting the resin composition and the method of molding and processing the obtained resin composition are not particularly limited, and general kneading methods and molding and processing are not limited. A method can be used.

That is, each component is put into a mixer such as a high-speed mixer such as a Henschel mixer or a super mixer or a ribbon blender, and is uniformly blended at a temperature of, for example, 150 ° C. or less for a time appropriate for each mixer. .
The resulting mixture can be granulated by an ordinary method using a kneader such as a Banbury mixer, a mixing roll, and an extruder, which is used for a usual production of a vinyl chloride resin.

In order to manufacture the extruded product of the present invention, a long metal plate or, if necessary, a long metal plate obtained by roll-homing and bending is introduced into a die of a resin kneading extruder. It is manufactured as a composite extruded product joined with a soft resin composition in the inside. It is effective to further improve the effect of the present invention by providing an adhesive application device, an adhesive heating device, and an adhesive drying device in the production line in order to firmly join the metal and the resin composition during this time. It is.

In the present invention, for the purpose of imparting surface design and the like, during the extrusion molding, a vinyl chloride resin composition, an acrylic resin composition, or the like may be extruded in multiple layers on the surface.

Since the extruded product of the present invention is excellent in weather resistance and compression set characteristics, it can be used for various automobile molding members such as weather strip, glass run channel, window molding and belt molding, and architectural members such as glazing for window frames. It can be widely used.

The weather strip of the present invention has, for example, the structure shown in FIG. The weather strip 1 is made of a soft resin composition 2 and a metal 3 and is assembled to the vehicle body 4 at a portion having a detailed shape (marked by a circle). Soft resin composition 2
A flocked portion 6 may be provided by flocking at a contact portion between the window glass 5 and the window. In the weatherstrip 1, since the reaction force with the window glass 5 is determined by the detailed shape portion, strict dimensional accuracy is required for the detailed shape.

[0037]

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

Experimental Example 1 Raw materials having the composition shown in Table 1 were charged into a 75-liter Henschel mixer. After stirring and mixing, the mixture was kneaded into pellets by a 90 m / m single screw extruder (manufactured by Ikegai Iron Works Co., Ltd.) to obtain 15 kg of soft resin resin composition pellets. This was kneaded with a 40 m / m single screw extruder (manufactured by Ikegai Iron Works, Ltd.)
It was joined on a stainless steel plate having a width of 25 mm and a thickness of 1 mm as metal. Before the introduction of the stainless steel belt, after applying Hamatite A1104B (produced by Yokohama Rubber Co., Ltd.) as an adhesive to the joint with the soft resin composition to a thickness of about 0.05 mm,
The mixture was heated to 198 ° C. by a high-frequency heater and the roll was pulled off at a speed of 1.5 m / min to obtain a composite extruded product. The obtained composite extruded product was evaluated and measured for various physical properties.

(Raw Materials) Vinyl Chloride Resin-1: Degree of Polymerization 2000 Acrylic Rubber Polymer-1: Good Year Co., Ltd.
Product name "Sanigam P7395", having a core-shell structure Plasticizer: Commercial product, di-2-ethylhexyl phthalate Filler-1: Commercial product, calcium carbonate, average particle size 1.8
μm Heat stabilizer-1: Commercial product, barium stearate Heat stabilizer-2: Commercial product, zinc stearate Partially crosslinked nitrile rubber: Partially crosslinked acrylonitrile-butadiene copolymer, trade name “N201” manufactured by JSR Corporation

[Test Method] (Degree of polymerization) The degree of polymerization was based on JIS K6721. (Evaluation of Compression Set) In accordance with JIS K6262, the compression set of the soft resin composition was evaluated under the test conditions of 70 ° C. × 22 hours. (Evaluation of weather resistance) Using a No. 3 dumbbell specified in JIS K6251 using a carbon arc sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.), a black panel temperature of 63 ° C., a cycle of 108 minutes of fine weather and 12 minutes of rain For 1000 hours, and the change in color tone before and after the exposure was evaluated using a color difference meter (Color Computer SM5, manufactured by Suga Test Instruments Co., Ltd.). Color difference ΔE is JIS Z8
730. (Evaluation of Formability) The weather strip shown in FIG. 1 was formed as a composite extruded product, and the composite extrudability was evaluated. When the molded article was smooth and had a good shape, it was evaluated as ○, when the surface of the molded article was smooth but rough, was evaluated as Δ, and when the surface of the molded article was wavy and the end was torn, it was evaluated as ×.

[0041]

[Table 1]

EXPERIMENTAL EXAMPLE 2 An objective product was obtained and evaluated under the same conditions as in Experimental Example 1 except that the raw materials used in the composition shown in Table 2 were used. Table 2 shows the results.

(Raw materials) Vinyl chloride resin-2: Degree of polymerization 1300 Vinyl chloride resin-3: Degree of polymerization 1700 Vinyl chloride resin-4: Degree of polymerization 2500 Vinyl chloride resin-5: Degree of polymerization 3800

[0044]

[Table 2]

Experimental Example 3 An objective product was obtained and evaluated under the same conditions as in Experimental Example 1 except that the raw materials having the composition shown in Table 3 were used. Table 3 shows the results.

[0046]

[Table 3]

Experimental Example 4 An objective product was obtained and evaluated under the same conditions as in Experimental Example 1 except that the raw materials having the composition shown in Table 4 were used. Table 4 shows the results.

(Raw materials) Filler-2: commercial product, talc, average particle size 4 μm Filler-3: commercial product, aluminum hydroxide Filler-4: commercial product, clay

[Test Method] (Evaluation of Formability of Detailed Shape) Evaluation of the formability of the weather strip shown in FIG.
The detailed shape (indicated by a circle in FIG. 1) was evaluated. The surface condition was particularly smooth and the mold shape was shaped to details. The result was marked with “○”, the shape where the details were not shaped slightly was marked as “Δ”, and the shape where the details were not shaped was marked as “x”.

[0050]

[Table 4]

Experimental Example 5 The objective product was obtained and evaluated under the same conditions as in Experimental Example 1 except that the raw materials having the composition shown in Table 5 were used. Table 5 shows the results.

(Raw materials) Acrylic rubber polymer-2: commercially available product, having no core-shell structure

[0053]

[Table 5]

[0054]

According to the present invention, it is possible to provide a resin composition having improved shape retention at high temperatures and improved compression set without deteriorating the moldability and weatherability of the vinyl chloride resin. In particular, since the compression set specified in JIS K6262 (70 ° C. × 22 hours) is smaller and better than that of the conventional product, it can be used as a molding, particularly a molding for vehicles (preferably a weather strip).

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a weather strip.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Weather strip 2 Soft resin composition 3 Metal 4 Body 5 Window glass 6 Flocked part

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 3/08 C08K 3/26 3/26 3/34 3/34 5/11 5/11 5/12 5/12 C08L 27/06 C08L 27/06 51/06 51/06 B29K 19:00 // B29K 19:00 27:06 27:06 105: 16 105: 16 105: 22 105: 22 B29L 31:30 B29L 31:30 B60J 5/00 501L F term (reference) 3D024 AA05 AB06 AB21 AB24 AB27 AB57 4F071 AA24 AA31 AA77 AA81 AB06 AB21 AC10 AH10 BA01 BB06 BC07 4F100 AA08A AA08H AB01B AB04 AC10A AC10H AH02H AK15A02 AK25A02 AK25A02 AK15A EH23 GB36 JA07A JK13A JK20 JL04 JL09 YY00A 4F207 AA15 AA45 AB07 AD03 AD08 AG03 AH23 KA01 KA17 KB11 4J002 BD04W BD05W BD08W BD09W BD18W BN08W BN12X CD163 DA078 DA088 DA098 DC008 DE127E0137 DJ008

Claims (6)

[Claims] 1. An extruded product obtained by compounding a metal with a soft resin composition containing a vinyl chloride resin, an acrylic rubber polymer, and a plasticizer. 2. The average degree of polymerization of the vinyl chloride resin is 800.
The extruded product according to claim 1, wherein the number is from 4,000 to 4,000. 3. The method according to claim 1, further comprising a filler.
Or the extruded product according to 2. 4. The extruded product according to claim 3, wherein the filler is calcium carbonate and / or talc. 5. The extruded product according to claim 1, wherein the acrylic rubber polymer has a core-shell type structure. 6. An automobile molding comprising the extruded product according to claim 1. Description: