JP3322087B2 - ABS resin composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ABS resin composite which has excellent creep resistance and adhesive strength and can be used as a packing, joint material, sealing material or gasket.

[0002]

2. Description of the Related Art Packings, jointing materials, sealing materials, gaskets, and the like for maintaining confidentiality of automobiles, electric equipment, buildings, and the like include:
Soft vinyl chloride resin, vulcanized rubber and the like are used as the material. These gaskets are made of soft vinyl chloride resin or vulcanized rubber by extrusion or injection molding alone.
Alternatively, it is used after being formed into a desired shape by in-mold vulcanization, and is generally used by fixing it to a supporting substrate such as a metal or a hard synthetic resin with a screw or an adhesive. However, natural rubber, nitrile rubber, chloroprene rubber,
When vulcanized rubber materials such as EPDM are used, expensive vulcanizing equipment is indispensable to pass through the vulcanizing step at the time of production, and heating equipment is also required to raise a sufficient vulcanizing effect. And the production efficiency is poor, resulting in an expensive product. On the other hand, when a product made of a soft vinyl chloride resin is used, the productivity is excellent, but the creep resistance is inferior, and there is a drawback that the sealing effect due to long-term use cannot be maintained.

In recent years, particularly in the automobile industry, there has been a strict demand for reducing the weight of automobile parts for the purpose of improving fuel efficiency of automobiles, and the use of resin parts has been spurred.
Further, development of easily recyclable resin materials is desired from the viewpoint of resource reuse. For example, when vulcanized rubber is used as an automobile part, it is difficult to recycle, and when a metal is used as a support for a soft resin, it is disadvantageous from the viewpoint of weight reduction. Separation was required, and recycling was inferior.

[0004]

SUMMARY OF THE INVENTION The present inventors impair the superior characteristics of chlorinated polyethylene elastomer compositions, such as creep resistance, compression set, flexibility, moldability, weatherability, low temperature properties, and the like. Intensive study of recyclable parts such as automobiles, electric equipment, buildings, etc. without any problems revealed that the chlorinated polyethylene elastomer composition was combined with an ABS resin having a large flexural modulus to achieve a light weight and Have been found to exhibit excellent physical properties, can be used for a long time in applications such as gaskets, and can be easily recycled, and have completed the present invention. That is, an object of the present invention is to provide a packing, a joint material, a sealing material, a gasket, or the like that is excellent in high-temperature creep characteristics (compression set), weather resistance, adhesive strength, and is easy to recycle. Another object of the present invention is to provide a composite of a chlorinated polyethylene elastomer composition and an ABS resin that can be used for a gasket.

[0005]

The gist of the present invention is to provide an ABS resin having a flexural modulus of 1000 kg / cm ² or more according to JIS K7203;
Chlorination degree 20-45 wt%, heat of crystal fusion 5-35 cal /
g of crystalline chlorinated polyethylene and 100 parts by weight of a chlorinated polyethylene elastomer composition in which 5 to 200 parts by weight of a plasticizer are blended, and an ABS resin composite and a method for producing the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The ABS resin which is a constituent element of the ABS resin composite of the present invention is acrylonitrile (A
N) and an acrylonitrile-styrene (AS) copolymer which is a copolymer of styrene (ST) and polybutadiene (PBD) which is a rubber component. The content of the rubber component in the ABS resin is 5%. It is desirable that the content be from 80 to 80% by weight, preferably from 10 to 30% by weight. The composition ratio of the AS copolymer is in the range of 90/10 to 50/50 in ST / AN ratio. Monomers such as methyl methacrylate, α-methylstyrene, and N-phenylmaleimide may be used as a copolymer component of the AS copolymer. Further, acrylonitrile-butadiene rubber, acrylic rubber, ethylene-propylene rubber, or the like may be used as the rubber component. If necessary, a stabilizer, a lubricant, an antioxidant, an ultraviolet absorber, a foaming agent, a coloring agent, a shock absorber, a processing aid, and the like may be added to the ABS resin.

[0007] A chlorinated polyethylene elastomer composition to be composited with an ABS resin contains crystalline chlorinated polyethylene and a plasticizer as essential components. The crystalline chlorinated polyethylene needs to have a degree of chlorination of 20 to 45% by weight and a DSC crystal melting heat of 5 to 25 cal / g.
The range of the heat of crystal fusion is such that the polyethylene crystal residue, the so-called crystallinity, is in the range of 10 to 50%. DSC (differential scanning calorimetry) method Crystal melting heat is a value calculated from the total crystal peak area of the DSC chart measured at a heating rate of 10 ° C./min using a differential calorimeter, and if it is less than 5 cal / g. This indicates that there is substantially no residual crystal.

[0008] The crystal melting point of the DSC method described below is defined as DSC
It is the temperature showing the highest peak among all the crystal peaks at the time of the method crystal melting heat measurement. The crystalline melting point of the chlorinated polyethylene used in the present invention is in the range of 110 to 140 ° C. If the chlorinated polyethylene has a degree of chlorination of less than 20%, the compatibility with the plasticizer is poor, the hardness cannot be lowered, and the weather resistance is poor. Permanent set and low temperature properties cannot be obtained. On the other hand, if the heat of crystal fusion is less than 5 cal / g, the effect of improving the compression set is lost, while if it exceeds 25 cal / g, the hardness cannot be lowered and the workability is poor.

The chlorinated polyethylene used in the present invention preferably has a DOP oil absorption of 25 or more. DOP
Is the amount of DOP added in 100 ml of chlorinated polyethylene powder and stirred at a temperature of 23.degree. 25 or more means DO
Even if 25 ml of P is added, the powder is not clumped and is in the form of a powder, or even if it appears to be hardened, slight force,
It means dispersing by impact. The measurement method is
The measurement was performed according to JIS K5101. DOP oil absorption 25
By using the above chlorinated polyethylene, low-temperature properties of the crystalline chlorinated polyethylene elastomer composition,
The blocking resistance and the extrudability can be improved.

The plasticizer as one component of the chlorinated polyethylene elastomer composition is not particularly limited as long as it is used for a vinyl chloride resin.
Phthalate ester plasticizers such as ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate and dihexyl phthalate; linear dibasic ester plasticizers such as dioctyl adipate and dioctyl sebacate; trimellitate ester Plasticizers: Polyester-based polymer plasticizers; Epoxy-based plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and epoxy resin; Phosphate-based plasticizers such as triphenyl phosphate, trixylyl phosphate, and tricresyl phosphate And these may be used alone or in combination of two or more.

The amount of the plasticizer to be used is appropriately determined depending on the type and amount of the additive used in combination, which will be described later, or the hardness of the target product. And a range of 15 to 75 parts by weight is particularly preferable. If the amount of the plasticizer is too small, a material with low hardness cannot be obtained, and if the amount is too large, it is difficult to suppress the bleeding phenomenon.

The chlorinated polyethylene elastomer composition preferably contains a vinyl chloride resin for the purpose of improving its melt fluidity, adhesion to an ABS resin, and appearance of extrusion molding. Vinyl chloride resin is produced by a usual method such as suspension polymerization, bulk polymerization, fine suspension polymerization or emulsion polymerization of vinyl chloride or a mixture of vinyl chloride and a copolymerizable monomer. Everything is used. Examples of the comonomer include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylic esters such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylic esters such as methyl methacrylate and ethyl methacrylate; and dibutyl maleate. Maleates such as ate and diethyl maleate; fumaric esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; cyanide such as acrylonitrile and methacrylonitrile Vinyls, α-olefins such as ethylene, propylene, and styrene; vinylidene halides and vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide Diallyl phthalate, polyfunctional monomers such as ethylene glycol dimethacrylate and the like, of course, the comonomer is not limited to those described above. The comonomer accounts for 30% by weight or less, preferably 20% by weight, of the components of the vinyl chloride resin.
% By weight or less.

The average degree of polymerization of the vinyl chloride resin thus produced is usually in the range of 400 to 8000, preferably 400 to 1500, particularly 40.
Those having about 0 to 1000 are used. The amount of the vinyl chloride resin used is preferably in the range of 5 to 100 parts by weight, particularly 5 to 70 parts by weight, based on 100 parts by weight of the crystalline chlorinated polyethylene. If the added amount is too small, fluidity,
Adhesiveness and the like are not remarkably improved, and if too large, physical properties such as compression set tend to be inferior.

The chlorinated polyethylene elastomer composition used in the composite of the present invention can further improve the creep resistance and compression set by incorporating a rubber substance containing a tetrahydrofuran (THF) insoluble crosslinking component into the chlorinated polyethylene elastomer composition. it can. Acrylonitrile-butadiene rubber (NB) is used as a rubber material containing a THF-insoluble crosslinking component.
R), methyl methacrylate-butadiene-styrene rubber (MBS), acrylic rubber (AR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), ethylene-vinyl acetate rubber (EVA), urethane rubber (U
R) such as by adding a polyfunctional monomer to the polymerization system during the production of various rubbers, or by introducing a crosslinked structure into rubber molecules by a method such as crosslinking after treatment with an organic peroxide after the production of the rubber. . Among these, it is desirable to use a rubber having a crosslinked structure by adding a polyfunctional monomer during the production of the rubber substance. In particular, in the present invention, NBR
Is preferably used. The THF-insoluble crosslinking component is desirably at least 20% by weight of the rubber substance, preferably at least 50% by weight, particularly preferably at least 80% by weight. THF
If the amount of the insoluble cross-linking component is less than 20% by weight, the effect of improving the creep resistance is not clear, and it is desirable to use one having a high degree of cross-linking as much as possible.

The amount of the rubber substance to be added is 400 parts by weight or less based on 100 parts by weight of the crystalline chlorinated polyethylene.
Preferably it is in the range of 20 to 300 parts by weight. If the added amount of the rubber substance is too small, the effect of improving the creep resistance is not recognized, and if it is more than 400 parts by weight, the processability and moldability of the elastomer composition tend to be inferior. In the case where the chlorinated polyethylene elastomer composition contains a rubber substance, it is desirable to contain a plasticizer in an amount of 15 parts by weight or more. If the amount of the plasticizer is too small, the hardness is high,
The elasticity of the elastomer composition may be impaired.

It is desirable to add a filler to the chlorinated polyethylene elastomer composition as long as the compression set is not impaired. The filler has an effect of absorbing an excessive amount of the plasticizer and smoothing the kneading and molding. Examples of the filler include carbon black, calcium carbonate, titanium oxide, talc, aluminum hydroxide, magnesium hydroxide, hydrotalcite, clay, silica, and white carbon. The addition amount of the filler is selected from the range of 500 parts by weight or less based on 100 parts by weight of the crystalline chlorinated polyethylene, and preferably 10 to 200 parts by weight in consideration of various properties of the elastomer composition. If the added amount of the filler is too small, the effect of improving kneading and moldability is small, and if it is more than 500 parts by weight, the moldability tends to deteriorate, and it is economical to add the filler within a range that does not impair moldability. It is desirable from the viewpoint of sex. Further, various additives such as a stabilizer, a lubricant, an antioxidant, an ultraviolet absorber, a foaming agent, a flame retardant, and a coloring agent may be added to the elastomer composition as needed.

To prepare the chlorinated polyethylene elastomer composition, the crystalline chlorinated polyethylene, the plasticizer, and various additives described above, if necessary, are heated to a temperature not lower than the crystal melting point of the crystalline chlorinated polyethylene. It is desirable to knead under shearing force. By kneading under these conditions, an elastomer composition having excellent compression set and low-temperature properties can be obtained. At temperatures below the crystal melting point, the plasticizer penetrates only into the amorphous portion of the crystalline chlorinated polyethylene, and the crystal structure after kneading does not change much, but it is heated to a temperature above the crystal melting point and kneaded under shearing force. It is presumed that the plasticizer penetrates into the crystal part as well, and when the chlorinated polyethylene is recrystallized, a new network structure between the molecular chains is generated and the rubber elasticity such as compression set is improved. Is done.

The apparatus used for mixing the above-mentioned components may be any apparatus as long as it can be substantially uniformly mixed, and examples thereof include a Henschel mixer, a ribbon blender, and a planetary mixer. Are extruders, rolls, Banbury mixers,
A device such as a kneader capable of kneading under a shearing force while heating is used. As a kneading method, chlorinated polyethylene and various additives are charged in the former stage with an extruder having a multistage addition port,
It is also possible to adopt a method of injecting a plasticizer at a later stage.
The upper limit of the heating temperature is desirably within a range where thermal deterioration of the chlorinated polyethylene can be ignored, specifically, 210 ° C. or less. The kneading temperature is desirably in the range of 130 to 210 ° C, preferably 150 to 200 ° C.

The ABS-based resin composite of the present invention is a composite of an ABS-based resin and a chlorinated polyethylene elastomer composition. The method of compounding is, for example, a method of extrusion-coating the above-mentioned chlorinated polyethylene elastomer composition on a strip-shaped or strip-shaped extruded ABS-based resin molded article, a plurality of extruders of the ABS-based resin and the elastomer composition. And various methods such as a method of coextrusion and compounding in or near an extrusion die, a method of producing a molded article from each of the ABS resin and the elastomer composition by various molding methods, and a method of heat-sealing the two. Further, a method of forming a composite by so-called insert molding, in which a molded article made of an ABS resin is set in a mold and then injection-molding a chlorinated polyethylene elastomer composition, furthermore, double injection molding, sandwich injection molding For example, a method of forming a complex by the method described above may be used.

In particular, a composite having a long structure in which an ABS resin is formed in a belt-like or band-like shape, and a band-like end of a band-like or band-like shape-formed product made of an elastomer composition is fused or adhered to the band-like surface; A long composite formed by fusing or adhering the band-shaped ends of an ABS resin and a chlorinated polyethylene elastomer composition to each other in the form of a strip or a strip-shaped article is a gasket for vehicles such as automobiles, electric equipment, buildings and the like. It has high utility value (including packing, jointing agent, and sealant). Of course, the gasket is not limited to the above structure.

[0021]

According to the present invention, the ABS resin composite is made of ABS.
Since the chlorinated polyethylene elastomer composition is formed as a composite with the base resin, the heat deformation resistance is remarkably good.
Thermal deformation of the elastomer composition composited with the BS resin does not occur, and the elastomer composition has excellent creep resistance.
Compression set, low temperature properties (flexibility), weather resistance are maintained,
Exposure to high temperatures or sunlight, eg for cars, construction,
Further, when used as a gasket, packing, joint material, or sealant for electric equipment such as an electric refrigerator or a freezer maintained at a low temperature, the effect is exhibited over a long period of time. When the ABS resin composite of the present invention is produced by coextrusion, the adhesion between the ABS resin and the elastomer composition is good, and the peel strength is high. Furthermore, since the ABS resin composite of the present invention does not use a support such as a metal, the unnecessary composite is crushed as it is,
It can be recycled as pillar and outer groove material.

[0022]

EXAMPLES Next, the ABS-based resin composite of the present invention will be described in detail in Examples, but the present invention does not depart from the gist thereof.
The present invention is not limited to the following embodiments. <Preparation of chlorinated polyethylene elastomer composition> Table-
The raw materials of chlorinated polyethylene, plasticizer, polyvinyl chloride, rubber substance and filler shown in Table 1 were added in the amounts (parts by weight) shown in Table 3 and 5 parts by weight of a Ba-Zn-based composite stabilizer in a Henschel mixer. The mixture was heated and mixed, and kneaded with a Banbury mixer having a jacket temperature of 120 ° C. for 80 rotations for 3 minutes. At this time, the composition was discharged at a resin temperature of 180 ° C. The composition was formed into a sheet by a roll and pelletized by a sheet cutting method. Further, the roll sheet was press-formed at 180 ° C. for 5 minutes to prepare a predetermined test piece, and compression set and rebound resilience were measured.

[0023]

[Table 1] Table-1 {Raw materials} ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ (1) Chlorinated polyethylene Chlorination degree Crystal heat of fusion Crystal melting point DOP oil absorption (%) (cal / g) (° C) A 31 8.3 118 50 or more B 30 10.7 122 50 or more C 26 14.5 120 50 or more ────────────────── ────────────────── (2) Plasticizer di-2-ethylhexyl phthalate ───────────────────── ─────────────── (3) Polyvinyl chloride polymerization method Degree of polymerization Suspension polymerization 800 ───────────────────── ─────────────── (4) Rubber material AN content THF insoluble crosslinking component Mooney viscosity (% by weight) (% by weight) (JIS K6300) NBR 40 95 60 ───────────────────────── ─────────── (5) Filler calcium carbonate ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━

Test method: (1) Compression set Based on JIS K6301, 25
% Compression, measured at 70 ° C. for 22 hours. (2) Rebound resilience 23 ° C based on JIS K6301
Measured with <Production method of ABS-based resin composite> Using the ABS-based resin shown in Table 2, a composite was produced by co-extrusion with the chlorinated polyethylene elastomer composition described above. 40mm
An ABS resin pellet is extruded with a φ extruder, and a chlorinated polyethylene elastomer composition pellet is extruded with a 20 mm φ extruder.
mm, thickness 1.5 mm) on the back surface of a chlorinated polyethylene elastomer composition strip (height 10 mm, thickness 2)
mm), a composite having a pseudo E-shaped cross section to which one end was fused was produced by continuous coextrusion. The die temperature at the time of fusion was 190 ° C. The fusion strength between the ABS resin and the chlorinated polyethylene elastomer composition was evaluated by a 180 ° peel test using an autograph, and the results are shown in Table-3.

[0025]

[Table 2] Table 2 Ａ ABS resin Flexural modulus Hardness MFR ^{* 1} (kg / cm ² ) (g / 10 min) ───────────────────────────────── Toughflex YT- 346 22000 70 or more 10━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ * 1 220 ° C, 10kgf (JIS K7210)

[0026]

[Table 3] * 2 The higher the value, the greater the holding force as a packing. * 3 Olefin-based thermoplastic elastomer * 4 Peeled off during extrusion molding.

As described above, an ABS-based resin composite using an olefin-based elastomer does not fuse at all, and a desired molded product cannot be obtained. On the other hand, the composite with the chlorinated polyethylene elastomer composition of the present invention has good molded appearance, high fusion strength, and strong adhesion.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-62-41039 (JP, A) JP-A-4-335047 (JP, A) JP-A-6-336542 (JP, A) JP-A-4- 339845 (JP, A) JP-A-6-336541 (JP, A) JP-A-5-1187 (JP, A) JP-A-5-247289 (JP, A) JP-A 5-247290 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C08L 23/28

Claims (6)

(57) [Claims] 1. An ABS resin having a flexural modulus of not less than 1000 kg / cm ² according to JIS K7203, and a crystalline chlorination having a chlorination degree of 20 to 45% by weight and a heat of crystal fusion of 5 to 25 cal / g. Plasticizer 1 in 100 parts by weight of polyethylene
An ABS-based resin composite which is composited with a chlorinated polyethylene elastomer composition containing 0 to 160 parts by weight. 2. The ABS resin composite according to claim 1, wherein the chlorinated polyethylene has an oil absorption of 25 or more when di-2-ethylhexyl phthalate (DOP) is used as an oil. 3. The ABS resin composite according to claim 1, wherein the chlorinated polyethylene elastomer composition contains a vinyl chloride resin. 4. The ABS resin composite according to claim 1, wherein the chlorinated polyethylene elastomer composition contains a rubber substance containing a tetrahydrofuran (THF) -insoluble crosslinking component. 5. The method for producing an ABS resin composite according to claim 1, wherein the ABS resin and the chlorinated polyethylene elastomer composition are co-extruded. 6. A gasket comprising the ABS-based resin composite according to any one of claims 1 to 4.