JP2001047857A - Vinyl chloride resin component for vehicle window molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin material capable of sufficiently satisfying seal characteristic which is an important performance of a material for vehicle window molding and useful characteristic of vinyl chloride resin as the material for vehicle window molding and preventing the generation of abnormal sound during running of an automobile when temperature is low, in particular, in winter, preferably, a resin material capable of reducing hydrogen chloride gas generated at the time of combustion. SOLUTION: This material for molding arranged around a window glass of a vehicle is composed of 100 pts.wt. of vinyl chloride resin whose average degree of polymerization is 700 to 3800 and 60 to 140 pts.wt. of plasticizer as main components, and its material characteristic satisfies the following conditions (1) and (2). (1) storage modulus of elasticity E' of dynamic viscoelasticity is 5.0 to 30.0 (MPa) at 20 deg.C to 200 (MPa) at -20 deg.C, and E' (-20 deg.C)/E' (20 deg.C) is a scope of 2 to 15. (2) The reduction of amount after heating and aging test at 100 deg.C for 120 hr according to JISK6723 is 1.0% or less.

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 suitable as a material for moldings installed around a window glass of a vehicle.

[0002]

2. Description of the Related Art Conventionally, various materials have been studied as materials for moldings installed around window glasses of vehicles. Among them, vinyl chloride resin compositions have been widely used for the same purpose because of their original properties, that is, easy moldability, adhesion to other materials, flexibility of hardness, economical efficiency and the like. However, in the conventional vinyl chloride resin composition, when used for molding materials installed around vehicles such as automobiles, in particular, windows that cannot be opened and closed during automobiles, during automobile driving, especially at low temperatures such as winter. During traveling of the vehicle, noises such as wind noise and squeak noise are often generated from this portion, which has been a problem in that the comfort inside the vehicle may be impaired.

[0003] Therefore, as a countermeasure, a method of improving lubrication at the time of contact by adding a lubricant such as paraffin wax to a soft PVC material (JP-A-63-175030), or adding a rubber-like substance such as nitrile rubber Method (JP-A-7-6)
2183) and a method of adding a thermoplastic polyurethane or the like (JP-A-6-32958).
None of them has yet achieved a sufficient improvement effect. Furthermore, when these vinyl chloride resins are incompletely burned at the time of disposal, toxic hydrogen chloride gas is generated, so that there has been a problem that environmental problems may occur in waste disposal at the time of recovery. .

[0004]

SUMMARY OF THE INVENTION The present inventors have found that, as a material for a vehicle window molding, the sealing properties and the useful properties of the vinyl chloride resin, which are important properties, are sufficiently satisfied. In order to obtain a resin material that does not generate abnormal noise when the vehicle is running at low temperatures, particularly in winter, and more preferably a resin material that can reduce hydrogen chloride gas generated during combustion, it is made of various combinations of resin compositions. Molding the wind molding material, as a result of repeated studies such as running tests at low temperature, etc., the vinyl chloride resin composition showing a specific range of physical properties obtained by a special combination was found to solve the above problems, The present invention has been completed.

[0005]

That is, the gist of the present invention is to provide a molding material to be installed around a window glass of a vehicle, the vinyl polymer resin having an average degree of polymerization of 700 to 3800, which is 100% by weight. Parts, a plasticizer comprising 60 to 140 parts by weight as a main component, and having a material property satisfying the following conditions (1) and (2) in a vinyl chloride resin composition for a vehicle window molding. A vinyl chloride-based resin composition having an average molecular weight of 430 or more, or calcium carbonate having an average particle size of 0.2 μm or less is 10 to 1%.
It is present in a vinyl chloride resin composition containing 50 parts by weight.

(1) The storage elastic modulus E ′ of dynamic viscoelasticity is 20
5.0 to 30.0 (MPa) at 20 ° C, 20 to 2 at -20 ° C
00 (MPa) and E ′ (−20 ° C.) / E ′
(20 ° C.) is in the range of 2 to 15. (2) Weight loss after heat aging test at 100 ° C. for 120 hours according to JIS K6723 is 1.0% or less.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As described above, the vinyl chloride resin composition for a vehicle window molding according to the present invention contains a vinyl chloride resin having a specific molecular weight and a specific amount of a plasticizer as main components, that is, 50% of the total amount of the composition.
It is a specific composition that occupies at least% by weight and has both the physical property ranges of the above (1) and (2). By selecting such a composition, the effects of the present invention can be obtained. is there.

The composition of the present invention has a dynamic viscoelasticity storage modulus E ′ of 5.0 to 30.degree.
0 (MPa), 20 to 200 (MPa) at −20 ° C., and E ′ (−20 ° C.) / E ′ (20 ° C.) of 2 to 15
It is essential to be within the range. Those that do not satisfy this condition are not preferable because when mounted as a molding around a window glass of a vehicle, abnormal noise is generated during low-temperature running such as in winter. Preferably, the storage elastic modulus E ′ of dynamic viscoelasticity is 8.0 to 23.0 (MP) at 20 ° C.
a) It is 40 to 150 (MPa) at −20 ° C., and E ′ (−20 ° C.) / E ′ (20 ° C.) is in the range of 2 to 10.

Further, the vinyl chloride resin composition of the present invention may satisfy the condition (2) according to JIS K6723.
It is essential that the weight loss after the heat aging test at 00 ° C. for 120 hours is 1.0% or less. If the composition is such that the weight loss exceeds 1%, the material with a low boiling point gradually evaporates and the material hardens while being used as a molding formed around the window glass. It is not preferable because sudden noise starts to occur during running. Preferably,
It is preferably 0.6% or less, more preferably 0.4% or less.

The vinyl chloride resin composition which satisfies the above conditions is limited among the various combinations of generally known vinyl chloride resins with plasticizers and other compounding agents, which are obtained by a fairly special combination. Range of compositions. The type of the vinyl chloride resin, the type of the plasticizer and the compounding ratio thereof can be appropriately selected to obtain a resin that meets the above conditions, but for example, usually used in consideration of productivity and cost. A vinyl chloride which satisfies the above-mentioned conditions by using a high-molecular weight plasticizer, for example, a plasticizer having a molecular weight of 430 or more, and making the compounding amount larger than the normal compounding amount (for example, 90 parts or more). A resin composition is obtained.

As the vinyl chloride resin contained in the vinyl chloride resin composition of the present invention, vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith can be prepared by a suspension polymerization method, a bulk polymerization method, Any of those produced by a conventional method such as a suspension polymerization method or an emulsion polymerization method can be arbitrarily selected and used. Examples of the comonomer include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylates such as methyl methacrylate and ethyl methacrylate; and dibutyl. Maleates such as maleate 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; cyanides such as acrylonitrile and methacrylonitrile Α-olefins such as vinyl chloride, ethylene, propylene and styrene, vinylidene chloride and vinyl halide 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 is contained in the component of the vinyl chloride resin in an amount of 30% by weight or less, preferably 20% by weight or less.

The average degree of polymerization of the vinyl chloride resin used in the present invention is determined by JIS based on its workability, moldability and physical properties.
It is essential that the average degree of polymerization based on K6721 is in the range of 700 to 3800, preferably 1100 to 2800.
500, preferably in the range of 1500-2500.
If the average degree of polymerization is less than 700, it cannot be used because physical properties are inferior. If it exceeds 3,800, processability and moldability deteriorate, so that it cannot be used.

The plasticizer contained in the vinyl chloride resin composition of the present invention is indispensable for softening the composition to facilitate kneading and processing, and furthermore, the conditions (1) and (2) of the present invention. The type and amount are important in satisfying (3). In particular, it is desirable to use a plasticizer having an average molecular weight of 430 or more from the viewpoint of low volatility when used as a molding material. When two or more plasticizers are used, if the average molecular weight of the added amount ratio is 430 or more, the effects intended by the present invention can be satisfied. The upper limit of the average molecular weight is not particularly limited.
It is desirable to use one having a value of 00 or less.

Accordingly, the plasticizer used in the present invention includes:
From the known plasticizers exemplified below, one or two or more plasticizers are combined, and the conditions (1) and (2) of the present invention are satisfied together with the relationship with the physical properties of the vinyl chloride resin used. Can be arbitrarily selected and used. For example, plasticizers that can be used include di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or carbon atoms. Phthalate ester plasticizers such as phthalate esters of about 10 to 13 higher alcohols or mixed alcohols; di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-decyl adipate, diisodecyl adipate, di-2 Aliphatic dibasic ester plasticizers such as -ethylhexyl azelate, dibutyl sebacate and di-2-ethylhexyl sebacate; tri-2-ethylhexyl trimellitate (TO
TM), trimellitate plasticizers such as tri-n-octyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, di-n-octyl-n-decyl trimellilate, tributyl phosphate,
Tricresyl phosphate (TCP), triphenyl phosphate, trixylyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2
-Chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3- Phosphate ester plasticizers such as dichloropropyl phosphate and bis (chloropropyl) monooctyl phosphate; biphenyltetracarboxylic acid tetraalkyl ester plasticizers such as 2,3,3 ', 4'-biphenyltetracarboxylic acid tetraheptyl ester ;
Polyester polymer plasticizers; Epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, and liquid epoxy resin; chlorinated paraffins; chlorinated fatty acid esters such as alkyl pentachlorostearate; I can do it.

However, as described above, in order to satisfy the performance as the molding material of the present invention, for example, diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), phthalic acid ester of a mixed higher alcohol of C10 to C13, etc. It is desirable to use a plasticizer having an average molecular weight of 430 or more. Thus, the content of the plasticizer depends on the type of the vinyl chloride resin used, the type of the plasticizer used, the type and the amount of the other additives, etc. in order to satisfy the conditions (1) and (2). Although different, it is essential that the amount be in the range of 60 to 140 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the plasticizer is less than 60 parts by weight, it is too hard to obtain a sufficient effect as a sealing material for the molding material, and if it exceeds 140 parts by weight, it is too soft to obtain the minimum necessary strength as a sealing material. It is not suitable because it cannot be done. Particularly preferably, 90 to 13
It is preferred to contain 0 parts by weight.

In the vinyl chloride resin composition of the present invention, for example, carbon black, calcium carbonate,
Titanium oxide, talc, aluminum hydroxide, magnesium hydroxide, hydrotalcite, clay, silica, white carbon, and the like can be added, and the type and amount of addition are not limited to these. Considering the environmental problems described above, it is preferable that 10 to 150 parts by weight of calcium carbonate having an average particle size of 0.2 μm or less is added to 100 parts by weight of the vinyl chloride resin. Calcium carbonate has a characteristic of trapping an acidic gas such as hydrogen chloride due to its chemical property, but the trapping ability is remarkably improved by increasing the surface area.
Desirably, it is 2 microns or less. Although the amount of calcium carbonate of 0.2 μm or less is added, if less than 10 parts by weight, the effect of capturing hydrogen chloride is not seen.
Exceeding the weight parts is unsuitable because physical properties such as strength are impaired.

The vinyl chloride resin composition of the present invention contains, in addition to the above essential components, a stabilizer, a lubricant, an antioxidant, an ultraviolet absorber, a flame retardant, an antistatic agent, a coloring agent, a foaming agent, and an impact modifier. Various additives such as an agent, a thermoplastic resin other than the vinyl chloride resin, a rubber, and the like can be compounded as necessary. Stabilizers include inorganic salts such as tribasic lead sulfate, lead silicate, and basic lead carbonate, lead, cadmium, barium, calcium, zinc, and the like. Two types, for example, Ba-Zn, Ca-Z
n, a fatty acid complex such as Cd-Ba or a fatty acid (phosphite) -based, a carboxylate (phosphite) -based composite metal soap or a composite liquid metal soap, an organic tin-based compound, and the like, and the like. Not something. As the flame retardant, antimony trioxide, barium borate, zinc borate, zinc oxide, chlorinated polyethylene, and other halogen-based flame retardants are used.

The vinyl chloride resin composition of the present invention is obtained by charging each component such as a vinyl chloride resin, a plasticizer, a filler, a stabilizer, a lubricant, etc. into a predetermined mixer or kneader. Temperature range, for example, 100 to 230
It is easily prepared by uniformly mixing or kneading while heating to a temperature of 130 ° C, preferably 130 to 200 ° C. The mixer or kneader used for mixing or kneading used for mixing the above-mentioned components is not particularly limited as long as it is a device capable of substantially uniformly mixing and kneading the compound, and as the mixer, for example, , Henschel mixer, ribbon blender, planetary mixer, etc.,
Examples of the kneader include a single-screw extruder, a twin-screw extruder, a roll mill, a Banbury mixer, a kneader, an intensive mixer, and the like which can be kneaded under a shearing force while heating. The vinyl chloride resin composition of the present invention may be in the form of a powder or a pellet, and the composition may be formed by various molding methods such as extrusion molding, injection molding, rotational molding, and press molding. Therefore, it must be used as a mall material installed around the window glass of vehicles. By using this material, it is possible to suppress abnormal noise generated around the window glass when the vehicle is running.

[0019]

EXAMPLES Next, the vinyl chloride resin composition of the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless departing from the gist thereof. The evaluation of the dynamic viscoelastic storage modulus, the generation of abnormal noise, the evaluation of heat aging, and the evaluation of the amount of generated hydrogen chloride for the vinyl chloride resin composition were performed as follows.

(Evaluation of Dynamic Viscoelastic Storage Elastic Modulus) R manufactured by Orientec
HEOVIBRON Automatic Dynamic Viscoelasticity Analyzer Frequency 11Hz, Amplitude 0.025mm (Evaluation of heat aging) JIS K67236.4. Item 10
0 ° C. × 120 hr Performed in accordance with the heat aging test, measure the mass before / after heating, and indicate the weight loss by%.

(Evaluation of Hydrogen Chloride Generation) JCS (Japan Electric Cable Manufacturers Association) Standard No. C-53 3.7. (Evaluation of noise generation) The compositions of the following Examples and Comparative Examples are molded into a window molding of an automobile using an extruder.

<Evaluation of standard condition>: The molded article was mounted as it was around the rear glass of an automobile, and the vehicle was run in an atmosphere of -15 ° C to evaluate the degree of noise generation. <Evaluation after heat resistance test>: After heating the molded article in an oven at 100 ° C for 100 hours, it was mounted around the rear glass of an automobile,
The vehicle was run in an atmosphere of -15 ° C, and the degree of generation of abnormal noise was evaluated. ◎ No unusual noise can be seen near the rear glass in the vehicle interior. ○ In the vehicle cabin, a slight noise near the rear glass can be slightly observed, but it is smaller than other sounds and is not bothersome. × Noise in the vicinity of the rear glass can be clearly seen in the cabin, and the noise is bothersome.

(Examples 1 to 7, Comparative Examples 1 to 5) Ba-Z was added to 100 parts by weight of a vinyl chloride resin having an average polymerization degree of 1800.
3 parts by weight of the n-type composite stabilizer, 2 parts by weight of carbon black, a plasticizer and a filler described below were added in the amounts shown in Table 1, and the mixture was stirred and mixed at 120 ° C. or lower by a high-speed mixer. The mixture was kneaded with a Banbury mixer until the resin temperature reached 165 ° C., formed into a sheet with a mill roll, and then pelletized with a pelletizer. The pellet was used as an evaluation material.

DOP: di (2-ethylhexyl) phthalate, molecular weight 391 DIDP: diisodecyl phthalate, molecular weight 447 DUP: diundecyl phthalate, molecular weight 475 DOA: di (2-ethylhexyl) adipate, molecular weight 371 DOZ: dioctyl azelatate DIN, molecular weight of P13: 4 Molecular weight 419

[0025]

[Table 1]

[0026]

EFFECT OF THE INVENTION The vinyl chloride resin composition for a vehicle window molding according to the present invention, in addition to the characteristics of conventional PVC, does not generate any unusual noise during traveling even when installed as a molding for a vehicle window glass, and is comfortable in a vehicle. In a more preferred embodiment, the hydrogen chloride gas generated at the time of combustion is reduced without impairing the feeling, so that disposal treatment is easy.

Continued on the front page (72) Inventor Hirotoshi Fujiwara 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Inventor Takanori Tanaka 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Corporation F-term (reference 3D023 AA01 AB01 AC26 AD02 AD22 4J002 BB041 BB051 BB081 BB091 BB242 CD002 CD162 CF002 DE237 EH036 EH096 EH146 EW046 EW056 FA087 FD010 FD017 FD022 FD026 FD030 GN00

Claims (3)

[Claims] 1. A molding material to be installed around a window glass of a vehicle, wherein the main components are 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 700 to 3800, and 60 to 140 parts by weight of a plasticizer. A vinyl chloride resin composition for a vehicle window molding whose material properties satisfy the following conditions (1) and (2). (1) The storage elastic modulus E ′ of dynamic viscoelasticity is 5.0 at 20 ° C.
30.0 (MPa), 20 to 200 (MP
a) and E ′ (−20 ° C.) / E ′ (20 ° C.) is in the range of 2 to 15. (2) Weight loss after heat aging test at 100 ° C. for 120 hours according to JIS K6723 is 1.0% or less. 2. The vinyl chloride resin composition for a vehicle window molding according to claim 1, wherein the plasticizer has an average molecular weight of 430 or more. 3. The vinyl chloride resin composition for a vehicle window molding according to claim 1, further comprising 10 to 150 parts by weight of calcium carbonate having an average particle size of 0.2 μm or less.