JPH07247393A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which has excellent moldability and can provide a molding having excellent surface slipperiness and sealing property. CONSTITUTION:A vinyl chloride resin compsn. comprising 100 pts.wt. vinyl chloride resin, 20 to 300 pts.wt. nitrile rubber, 20 to 200 pts.wt. plasticizer, and 3 to 80 pts.wt. powder, of a cross-linked resin, having an average particle diameter of 2 to 100mum; and a vinyl chloride resin compsn. prepd. by further adding either a curing agent for a rubber or a curing agent for a rubber in combination with a monomer having, in one molecule, at least two polymerizable double bonds to the above vinyl chloride resin compsn. and melt-kneading the mixture at a resin temp. of 140 to 220 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition and a molded product obtained by molding the composition. More specifically, the sliding property of the surface when sliding, flexibility, tearability and TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition capable of obtaining a molded article having excellent compression set resistance and a molded article obtained by thermoforming the composition.

[0002]

2. Description of the Related Art Molded products of compositions containing vinyl chloride resin and nitrile rubber as main components show excellent sealing properties based on excellent compression set, and the compositions have good moldability. It is used as a sealing material around windows and doors for automobiles and construction.

[0003] However, since the conventional molded product of the composition mainly containing vinyl chloride resin and nitrile rubber has poor surface slipperiness, for example, the surface of the molded product is the surface of another material (glass). , Metal, paint, plating, etc.), there is a problem that abnormal noise is generated when sliding while contacting. The generation of this abnormal noise becomes more remarkable when an external force such as vibration or wind is applied during the above sliding.

As a measure against the generation of abnormal noise, in order to prevent it by giving slipperiness to the surface of the molded product, for example, a fatty acid ester of glycerin is added to the raw material composition of the molded product, and this is gradually added to the surface of the molded product. There is known a method of using an additive for improving slipperiness, such as a method of bleeding (JP-A-2-24323) and a method of attaching silicone oil to the composition.

However, in the method of bleeding the above-mentioned additive on the surface of the molded product, it is easy for dust to adhere to the surface of the molded product, and the bleeding additive migrates to the surface of the object which comes into contact with the molded product. There is a problem that it causes dirt and the like.

Further, conventionally, various finely powdered inorganic fillers have been blended with a composition containing vinyl chloride resin and nitrile rubber as main components for the purpose of reinforcement, weight increase, abrasion resistance and heat resistance improvement. However, the surface of the molded product obtained by molding the composition does not have sufficient slipperiness, and when an inorganic powder having a large particle size is used, the particle shape is spherical silica or glass beads. As described above, even if it is spherical, there is a defect that the surface of another object that comes into contact and slides with the molded article is damaged by repeating contact and slide.

[0007]

DISCLOSURE OF THE INVENTION The present invention has a good moldability of the composition, and the molded article obtained from the composition is free from the problem of surface slipperiness and sealing without the problem of bleeding of additives. The present invention provides a vinyl chloride resin composition having excellent properties and a molded product obtained by molding the composition. As a result of intensive studies to solve the above problems, the present inventors have found that a vinyl chloride resin composition containing a specific amount of a specific resin powder crosslinked and a molded product obtained by molding the composition are obtained. The present invention has been completed based on the knowledge that the surface has excellent slipperiness and can solve the problems of the prior art.

[0008]

The first invention of the present invention is as follows:
Vinyl chloride resin 100 parts by weight, nitrile rubber 1-30
0 parts by weight, 20 to 200 parts by weight of a plasticizer, and 3 to 80 parts by weight of a crosslinked resin powder having an average particle diameter of 2 to 100 μm are contained as components constituting a vinyl chloride resin composition [hereinafter referred to as The composition may be referred to as a composition (A)], and the second invention is that the composition of the composition of the first invention further comprises (a) a rubber curing agent or (b) a rubber. The curing agent and the monomer having at least two polymerizable double bonds in one molecule are contained, and the resin temperature is 120 to
A vinyl chloride resin composition obtained by melt-kneading at 220 ° C. [hereinafter, this composition may be referred to as composition (B)], and the third invention is the first invention or the second invention. Is a molded product obtained by molding the vinyl chloride resin composition.

The present invention will be described in detail below. In the present invention, by suspension polymerization, solution polymerization, bulk polymerization or emulsion polymerization, homopolymerization of vinyl chloride monomer,
Alternatively, a vinyl chloride-based resin obtained by copolymerizing the following comonomer in combination with a vinyl chloride monomer in a proportion of 30% by weight or less can be used. The preferred polymerization method is suspension polymerization.

As the above-mentioned copolymerizable monomers, olefins such as ethylene and propylene, vinylidene halides such as vinylidene chloride, vinyl esters such as vinyl acetate, n
-Vinyl ethers such as butyl vinyl ether, acrylic acid esters such as butyl acrylate, methacrylic acid 2
Methacrylic acid esters such as ethylhexyl diallyl phthalate, divinylbenzene and the like are used. The average degree of polymerization of the vinyl chloride resin is preferably about 700 to 6,500.

The nitrile rubber used in the present invention (hereinafter referred to as NB
R) is a copolymer having butadiene and acrylonitrile as main constituent units, and the amount of bound acrylonitrile is 20 to 45% by weight, more preferably 25 to 45% by weight. NBR preferably has a Mooney viscosity of about 10 to 100. The NBR may contain one or more units of other monomers in addition to the acrylonitrile unit and the butadiene unit. Examples of other monomers include monomers having a carboxyl group such as (meth) acrylic acid and maleic acid, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, alkylene glycol di (meth) acrylate, alkylene glycol. Or of polyoxyalkylene glycol (meth)
Examples thereof include monomers having two or more polymerizable double bonds in one molecule such as acrylate.

Further, the NBR of the present invention may be either uncrosslinked or partially crosslinked, but particularly partially crosslinked NBR is preferable. This partially crosslinked NBR has a unit of a monomer having two or more polymerizable double bonds in the above molecule, and thus partially crosslinked NB
R is included.

The NBR used in the present invention may have any shape such as powder, granule and block, but it is easy to obtain a uniformly mixed compound and a homogeneous molded product, and thus the powder NBR. Is preferred, and partially crosslinked powdery NBR is particularly desirable. The average particle size of powder NBR particles is usually 1 mm or less,
More preferably, it is about 0.5 mm or less.

The NBR content of the composition of the present invention is 1 to 300 parts by weight, preferably 20 to 300 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If this amount exceeds 300 parts by weight, the processability of the composition will deteriorate and the strength of the molded product will decrease, and if it is less than 1 part by weight, the effect of adding NBR will not be obtained and sufficient sealing properties will not be obtained.

The plasticizer used in the present invention is not particularly limited as long as it is used for producing a flexible molded product of vinyl chloride resin, and examples thereof include phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, Examples include fatty acid dibasic acid ester, glycol ester, fatty acid ester, phosphoric acid ester, and citric acid ester-based plasticizers, as well as epoxy-based plasticizers and polyester-based plasticizers.

The plasticizer content of the composition of the present invention is 20 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin.
It is preferably 30 to 190 parts by weight. 2 plasticizers
If it exceeds 100 parts by weight, the molded product may have reduced slipperiness, compression set, strength and elongation, and if it is less than 20 parts by weight, the molded product may be hard and sufficient sealing properties may not be obtained.

The average particle size used in the present invention is 2 to 100 μm.
As the crosslinked resin powder of, for example, suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization, one or more kinds of the monomer (I) constituting the main component of the resin and one molecule constituting the crosslink A resin obtained by copolymerizing a monomer (II) having two or more polymerizable double bonds, the average particle diameter of which is adjusted to 2 to 100 μm by pulverization, classification, etc., if necessary. Is. It is preferable that the resin powder is subjected to antistatic treatment.

The above-mentioned monomer (I) is preferably a vinyl compound having an aromatic ring, such as styrene, α-methylstyrene, vinyltoluene and ethylvinylbenzene. Examples of the monomer (II) include divinylbenzene, trivinylbenzene,
Examples include divinyltoluene, divinylixylene, ethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate. In the copolymerization of the monomer (I) and the monomer (II), a monomer having a fluorine atom or a silicon atom is used in an amount of 20% by weight or less based on the total amount of the monomers (I) and (II). May be copolymerized. Further, as the crosslinked resin powder, a crosslinked cured product of a thermosetting resin such as a phenol resin, a melamine resin or a urea resin having an average particle diameter of 2 to 100 μm can also be used.

Among these crosslinked resin powders, a styrene resin powder obtained by copolymerizing styrene as the monomer (I) in an amount of 50% by weight or more based on the whole is preferable. The shape of the resin is preferably spherical. The crosslinked particles having a substantially spherical particle shape can be obtained, for example, by copolymerizing the monomer (I) and the monomer (II) by the above suspension polymerization method or emulsion polymerization method.

The average particle diameter of the crosslinked resin powder used in the present invention is 2 to 100 μm, preferably 5 to 50 μm. If the average particle size of the resin exceeds 100 μm, unevenness may occur on the surface of the molded product or the surface appearance may become uneven, which is not preferable. If the average particle size is 2 μm or less, the effect of slipperiness cannot be obtained.

The heat resistant temperature of the crosslinked resin powder is 230
℃ or above, preferably 250 ℃ or above,
The resin powder is preferably a solid resin powder because it is difficult to melt when it is melt-kneaded or molded. In consideration of the surface appearance of the molded product, it is also possible to use a crosslinked resin powder that has been previously colored with a pigment or a dye.

The content of the crosslinked resin powder (dry product) of the present invention is 3 to 100 parts by weight of vinyl chloride resin.
80 parts by weight. When this amount is less than 3 parts by weight, the slipperiness of the surface of the molded product is poor, and when it exceeds 80 parts by weight, the moldability,
In particular, the surface appearance of the molded product deteriorates and the strength of the molded product also tends to decrease.

As the rubber curing agent used in the composition (B) of the present invention, various curing agents can be used. Among them, organic peroxides, sulfur, sulfur-containing compounds and combinations of sulfur and sulfur-containing compounds are preferable. preferable. Examples of preferred organic peroxide curing agents are lauryl peroxide, benzoyl peroxide, bis-2,4-dichlorobenzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, 2,5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 1,1
-Bis (tert-butyl peroxy) -3,3,5
-Trimethylcyclohexane, tris-α, α-dimethyl-α- (tert-butylperoxy) methylbenzene, α, α-bis (butylperoxy) diisopropylbenzene, bis (4-tert-butylcyclohexyl) peroxydicarbonate , Tertiary butyl perbenzoate and the like. Organic peroxide is a plasticizer,
It is preferably used after being dissolved or dispersed in an organic solvent or the like.

Various kinds of sulfur can be used, and those usually used for vulcanization of rubber are used, and powdered sulfur is particularly preferable. The sulfur-containing compound is a compound having a sulfur atom used for rubber vulcanization, and examples thereof include tetramethylthiuram sulfide, dipentamethylene thiuram hexasulfide, thiuram disulfide, and triazine thiol.

The amount of the curing agent used varies depending on the type of the curing agent and the combination with the accelerator, but in consideration of such things as improvement of compression set and retention of appropriate flexibility in the molded product, vinyl chloride type is used. Usually 0.00 per 100 parts by weight of resin
It is 3 to 3 parts by weight, more preferably 0.005 to 1 part by weight.

The monomer having at least two polymerizable double bonds in one molecule used in the composition (B) of the present invention includes, for example, a monomer having two or more allyl groups in one molecule. There are monomers, monomers having an aromatic ring and two or more vinyl groups, monomers having two or more (meth) acryloyl groups, and the like. Triallyl isocyanurate, divinylbenzene, trivinylbenzene, divinyltoluene. ,
Examples include divinylxylene, alkylene glycol di (meth) acrylate, polyoxyalkylene di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate. However, among them, triallyl isocyanurate is particularly preferable.

The amount of the above-mentioned monomer having at least two polymerizable double bonds in one molecule is arbitrarily selected according to the desired properties of the composition to be obtained and the molded product thereof.
A preferable range is 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

The composition (A) and the composition (B) of the present invention may contain a filler. Examples of the filler include carbon black, calcium carbonate, titanium oxide, talc, asbestos, aluminum hydroxide, magnesium hydroxide, clay, silica, and white carbon, and these may be used alone or in combination of two or more. You can also The preferred content of the filler is 200 parts by weight or less based on 100 parts by weight of the vinyl chloride resin.

The composition (A) and the composition (B) of the present invention may contain a resin other than a vinyl chloride resin, a rubber other than NBR, etc. for modification. Examples of the above-mentioned compoundable resin and rubber include polyurethane,
Acrylic resin, methacrylic resin, ABS resin, MB
Examples thereof include S resin, nylon, polychloroprene, EPDM, modified EPDM and the like. These can be used alone or in combination of two or more. The amount of the resin other than the vinyl chloride resin that can be contained in the composition (A) and the composition (B) of the present invention is based on the vinyl chloride resin, and the amount of the rubber other than NBR is based on the NBR, respectively. It is preferably 50% by weight or less.

The composition (A) and the composition (B) of the present invention include a stabilizer against heat and ultraviolet rays, a processing aid, a lubricant,
Colorants such as pigments and dyes, flame retardants, foaming agents and the like may be contained in appropriate amounts as necessary. Examples of the heat stabilizer include lead heat stabilizers such as tribasic lead sulfate, tin heat stabilizers such as dibutyltin malate / laurate, tin heat stabilizers such as sulfur-containing tin stabilizers, and Ba-Zn. System composite stabilizer,
A Ca—Zn-based composite stabilizer, a hydrotalcite-based composite stabilizer, a metal soap such as zinc stearate, calcium stearate, or the like can be used. Examples of processing aids include low molecular weight polyethylene, higher fatty acid esters, PMMA-based processing aids, polyester-based processing aids, and the like.
What is usually used for vinyl chloride resins can be used.
Among the colorants, as the pigment, for example, color carbon black, chrome yellow, titanium oxide, phthalocyanine green and the like which are usually used for vinyl chloride resins can be used.

The composition (A) of the present invention can be obtained by almost uniformly mixing each of the essential components and, if desired, the optional components with a mixing device. At that time, the temperature of the composition usually rises due to heat generated by mixed friction or external heating, and liquid components such as plasticizers are absorbed by non-liquid components such as vinyl chloride resin or adhere to the surface. -Shaped composition (so-called powder compound)
Is obtained. The above powder compound may be cooled once, if necessary, in a powder state or at a temperature of 120-22.
The mixture is kneaded at 0 ° C., pelletized, supplied to a molding machine, and thermoformed to form a molded product.

The composition (B) of the present invention is obtained by, for example, mixing each of the essential components and, if desired, optional components in the same manner as in the case of the composition (A) using a mixing device to obtain a powder compound. Using a kneading machine, the resin temperature is 120 to 2
While melting and kneading at 20 ° C., preferably 140 to 210 ° C., the curing agent contained or the curing agent and a monomer having at least two or more polymerizable double bonds in one molecule are used for NB.
It is obtained by crosslinking R (so-called dynamic vulcanization). If this temperature exceeds 220 ° C, the composition is likely to undergo thermal decomposition, and if it is less than 120 ° C, the crosslinking reaction does not proceed sufficiently. The molten composition obtained above is molded into a molded product as it is or after being molded into pellets, while being heated if necessary.

The mixing device, kneading device and molding machine used to obtain the above-mentioned compositions (A) and (B) are all those commonly used in the production of soft vinyl chloride resin compositions and their molding processes. Can be used. Examples of the mixing device include a Henschel mixer.

Examples of the kneading device include an open roll, a closed kneader (for example, a Banbury mixer), a normal single-screw extruder, a same-direction or different-direction twin-screw extruder, and the like. Examples of the molding machine include those used for extrusion molding, injection molding, calender molding, compression molding and the like of the soft vinyl chloride resin composition.

The molded article of the present invention is a composition obtained by thermoforming the composition (A) or (B) and is not particularly limited in its shape. For example, it is simply thermoformed, or the entire molded article is foamed. , A foam formed only inside the molded product, a thermoformed part of the composition and another object (for example, a metal molded product,
Resin molded products, etc.) are integrally molded or laminated.

Since the molded product of the present invention exerts an excellent effect, it can be used as a member for windows and doors of vehicles and buildings, various industrial parts, etc., and particularly, it slides in contact with glass or metal. Suitable for use in parts. Examples of applications for molded articles include vehicle weather strips, flush mount moldings, belt moldings, west moldings, garnishes, glass run channels, wind moldings,
Examples thereof include guide channels, side end frames, door edges, protectors, and the like, and sealing materials for doors and windows of buildings, but the use of the molded product of the present invention is not limited to these. Since the composition (A), the composition (B) and the thermoformed products of the present invention all have thermoplasticity, unnecessary parts such as defective moldings and sprue runners may be subjected to treatment such as crushing as necessary. Once done, the thermoforming raw material can be reused.

[0037]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples.

Example 1 The compounding ingredients shown in Table 1 were added to a heated pressure kneader (manufactured by Moriyama Seisakusho) to obtain a front roll of 51 rpm,
The material was kneaded for 7 minutes with a post-roll 34 rpm. The temperature (resin temperature) of this melt-kneaded composition was 165 ° C.

The obtained composition was wound on a 12-inch two-roll roller having a surface temperature preset to 180 ° C. and kneaded for 10 minutes to obtain a sheet. This sheet was hot press molded at 180 ° C. for 5 minutes to prepare test pieces for each test, and a slip test, a tensile test, a tear test, and a compression set test were conducted by the following methods. In addition, a pellet was prepared using a part of the sheet, and the sheet-shaped molded product was extruded using the pellet, and the workability (appearance) was evaluated. The results of each of the above tests and evaluations are shown in Table 1.

Test Method (1) Sliding Test Polished flat glass was fixed on a metal table so that its surface was horizontal. On the other hand, a sheet of the composition obtained by press molding in the above example (length 50 × width 50 × thickness 2 mm)
Is a sample, and its surface is 50 × 50 mm and its weight is 1000.
A rectangular parallelepiped of g (both top and bottom are 50 × 50 mm) and a surface of 50 × 50 mm were bonded together with a double-sided adhesive tape to obtain a bonded body. This laminated body is placed on the glass surface so that the sheet surface is in contact with the glass surface, and the laminated body is subjected to a tensile tester (Strograph M-50 type manufactured by Toyo Seiki Co., Ltd.).
Was pulled horizontally at a speed of 100 mm / min and moved on the glass plate. The load at 100 mm between the moving distances of 30 mm and 130 mm was measured, and the dynamic friction coefficient was calculated from the average value. This dynamic friction coefficient value was defined as slipperiness. The value of the slipperiness is preferably 0.5 or less for practical use.

(2) Workability The sheet-shaped molded product was heated to a cylinder temperature of 18 with a small extruder.
Extrusion molding was performed at 0 ° C., and the surface of the molded product was visually evaluated and evaluated by touch according to the following criteria. ◎… Very good. ○: Good. X: Poor appearance.

(3) Tensile strength (T _B ) According to JIS K 6301.

[0043] (4) according to the growth (E _B) JIS K 6301.

(5) Tear (TR) According to JIS K 6301 method B.

(6) Compression set (C _S ) According to JIS K 6301, compression was performed at 70 ° C. for 22 hours at a compression rate of 25%.

Examples 2 to 14 The same procedure as in Example 1 was carried out except that the ingredients shown in Tables 1 to 3 were used. However, the resin temperature at the time of kneading with a pressure kneader was 150 ° C. in Example 12, and Example 1
In the case of 3, the temperature was 210 ° C. The results are shown in Tables 1 to 3.

Comparative Examples 1 to 7 Comparative Examples 1 to 7 were carried out in the same manner as in Example 1 except that the blending components shown in Tables 3 and 4 were used. The results are shown in Tables 3-4.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

Regarding the raw materials used in the examples and comparative examples,
This will be described below. (1) Vinyl chloride resin: Denka Vinyl SH-250, manufactured by Denki Kagaku Kogyo Co., Ltd., average degree of polymerization: 2500 (2) NBR: Goodyear, Chemicum P8B-
A, bound acrylonitrile 33%, Mooney value 56, powdery partially cross-linked NBR (3) DOP: di-2-ethylhexyl phthalate (4) Filler: calcium carbonate powder with a specific surface area of 13000 cm ² / g (5) Ba-Zn system Stabilizer: Ba-Zn fatty acid salt complex stabilizer (6) Sulfur: powdered sulfur (7) Nocceller CZ: Ouchi Shinko, N-cyclohexyl-2-benzothiazylsulfenamide (8) Zinc oxide: average Zinc oxide having a particle diameter of 4 μm (9) Organic peroxide: 1,1-bis-tert-butylperoxy-3,3,5-trimethylcyclohexane (10) Triallyl isocyanurate: manufactured by Kurogane Kasei (11) ) Cross-linked polystyrene resin powder: Fine pearl manufactured by Sumitomo Chemical Co., Ltd., spherical cross-linked polystyrene beads having an average particle size of 6 μm, 11 μm, 30 μm (heat-resistant temperature 270 ° C.), Fine styrene and divinylbenzene was suspension copolymerization, the average particle diameter of 80 [mu] m, 120 [mu] m spherical crosslinked polystyrene beads (heat-resistant temperature of about 250 ° C.)

[0053]

The vinyl chloride resin composition of the present invention has excellent processability, and the molded product obtained by thermoforming the above composition has excellent surface slipperiness and sealing properties. Since the molded product of the present invention exerts an excellent effect, it can be used as a member for windows and doors of vehicles and buildings, various industrial parts, etc., and is particularly suitable for a portion that comes into contact sliding with glass or metal. Get used to.

Front page continued (72) Inventor Tetsuo Kawakami 1135 Nakamura, Shibukawa, Gunma Denki Kagaku Kogyo Co., Ltd. (72) Inventor Hiroyuki Nagashima 2 Kirihara, Fujisawa, Kanagawa Shiroki Kogyo Co., Ltd. (72) Invention Person Yasuhisa Suzuki 2 Kirihara Town, Fujisawa City, Kanagawa Prefecture Shiroki Industry Co., Ltd.

Claims (4)

[Claims] 1. A vinyl chloride resin 100 parts by weight, a nitrile rubber 1 to 300 parts by weight, a plasticizer 20 to 200 parts by weight, and a crosslinked resin powder 3 to 3 having an average particle diameter of 2 to 100 μm.
A vinyl chloride resin composition containing 80 parts by weight as a component. 2. A single component having at least two polymerizable double bonds in one molecule, in addition to (a) a rubber curing agent or (b) a rubber curing agent as a component constituting the composition according to claim 1. A vinyl chloride resin composition obtained by containing a polymer and melt-kneading at a resin temperature of 120 to 220 ° C. 3. The vinyl chloride resin composition according to claim 1, wherein the crosslinked resin is a styrene resin. 4. A molded product obtained by molding the vinyl chloride resin composition according to claim 1 or 2.