JPH0561301B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a polymer composition, and more specifically,
The present invention relates to a polymer composition that has improved heat resistance and wax removal resistance and is suitable for molding encapsulant windows. [Prior Art] Conventionally, the work of attaching glass and window frames to fixed windows of automobile bodies such as front windows, rear quarter windows, and side windows has been carried out using profile extrusion molded products or injection molded products. It is carried out using In other words, in the case of the profile extrusion molding method, first a string-shaped molded product is molded using a thermoplastic resin such as soft polyvinyl chloride, and then an adhesive is applied to the periphery of the glass that has been temporarily assembled into the car body. Then, the string-like molded product is attached to this, and the main assembly is performed. In addition, in the case of injection molding, a glass peripheral structure corresponding to a window frame is formed from rubber such as EPDM,
Glass is then fitted into this molded product and attached to the vehicle body using adhesive. However, in the former method, string-like molded products,
When the glass and the vehicle body are brought into close contact with each other, or in the latter method, when the glass is fitted into the surrounding structure or the window frame is attached to the vehicle body, the urethane adhesive used is It goes out of the frame. The so-called "burr" finishing work to remove this protrusion is extremely complicated, and streamlining of the process is desired in these methods. [Problem to be solved by the invention] As a method for simplifying the work of assembling automobile window glass into a car body, the window glass is inserted into a mold and soft vinyl chloride resin is injected around the periphery of the encapsulated glass. Some methods of forming windows have been put into practical use. However, since soft vinyl chloride resin has poor thermal stability during injection molding at high temperatures, the encapsulant window obtained by the above method is unsatisfactory in that weld lines are noticeable and the appearance is impaired. . Adhesives are also used to bond the glass, but it has been pointed out that the stability of the adhesive is unsatisfactory, and that the adhesive applied to the glass protrudes from the window frame, making it difficult to finish the burrs. ing. Therefore, as an alternative to soft vinyl chloride resin, ethylene acid copolymers, such as ethylene/methacrylic acid copolymers, which have excellent adhesion to glass and injection moldability, and high surface gloss of molded products, and can be colored with carbon or pigments, are being used. The use of polymers, ethylene/methacrylic acid/acrylic acid ester copolymers, etc. is being considered. However, these ethylene-based acid copolymers do not have sufficient heat resistance; for example, the temperature is the standard for high-temperature physical properties of automotive exterior parts.
There are concerns as to whether a window frame formed from the copolymer will be able to hold a window glass attached to a vehicle body against external pressure at 80°C. Also, guard wax is applied to the car body to prevent rust during transportation of new cars, but car dealers use the following methods to remove this guard wax:
Steam containing a few percent of kerosene is injected onto the car body at high pressure (called kerosene steam cleaning), but during this cleaning, the surface of the molded ethylene acid copolymer is eroded by the heat and kerosene. There is a problem that it loses its luster or becomes whitish. That is, ethylene acid copolymers have the disadvantage of poor wax remover resistance. The present inventors incorporated an olefin-based thermoplastic elastomer described in Japanese Patent Publication No. 56-15743 into the ethylene-based acid copolymer as a measure to improve the heat resistance and wax remover resistance of the copolymer. We investigated a method of blending linear polyethylene with an ethylene-based acid copolymer as proposed in Japanese Patent Application No. 173,675/1982, but these methods do not have the advantages of the ethylene-based acid copolymer: It was found that there was a problem that the surface glossiness was impaired, and furthermore, the effect of improving heat resistance and wax remover resistance was insufficient. Therefore, an object of the present invention is to provide a polymer composition that improves the heat resistance and wax remover resistance, which are the disadvantages of ethylene acid copolymers, without impairing their various advantages. [Means for solving the problem] According to the present invention, the ethylene acid copolymer 90 to 60
parts by weight and 10 to 40 parts by weight of a polyamide resin consisting only of amide repeating units, and the ethylene acid copolymer contains 90 to 98 mol% of ethylene units and 2 to 10 mol% of (meth)acrylic acid units. Alternatively, there is provided a polymer composition characterized in that it is a random copolymer comprising 6 mol% or less of (meth)acrylic acid ester units. This polymer composition is highly suitable as a molding material for automobile enclosure windows, for example by injection molding. Ethylene-based acid copolymer The ethylene-based acid copolymer used in the polymer composition of the present invention comprises ethylene units and (meta)
It is a random copolymer having acrylic acid units as a constituent unit, and may further have (meth)acrylic acid ester units as a constituent unit. It should be noted that this random copolymer contains (meth)acrylic acid in free, ie non-salt, form. For example, with copolymers in which carboxylic acid units are neutralized with cations, such as ionically crosslinked olefin copolymers (ionomers), it is extremely difficult to form a strong adhesive bond with glass. . Here the ethylene units are 90-98 mol%, (meta)
The acrylic acid unit is contained in an amount of 2 to 10 mol%, and the (meth)acrylic acid ester unit, which is a structural unit if necessary, is contained in an amount of 6 mol% or less. For example, if the content of this (meth)acrylic acid unit is less than 2 mol%, when injection molding is performed using this polymer composition as described above, the polymer molded product that becomes the window glass and the window frame will be Adhesion may be insufficient, and
When the amount exceeds 10 mol%, the heat resistance of the acid copolymer and, ultimately, the polymer composition decreases. In addition, in the random copolymer, the (meth)acrylic acid ester unit has the effect of imparting flexibility to the copolymer and improving affinity for glass, but it contains more than 6 mol% of the (meth)acrylic acid ester unit. When it happens,
The heat resistance of the resulting polymer composition becomes unsatisfactory. Note that (meth)acrylic acid may be either acrylic acid or methacrylic acid, and (meth)acrylic acid esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and n-butyl acrylate. , isobutyl acrylate, butyl methacrylate, isobutyl methacrylate, etc. having 4 to 8 carbon atoms are preferred;
Most preferred are n-butyl (meth)acrylate and isobutyl (meth)acrylate. The ethylene acid random copolymer consisting of the above-mentioned structural units is produced by bulk polymerizing ethylene and (meth)acrylic acid or (meth)acrylic acid ester in the presence of an organic peroxide. be able to. Polyamide resin In the present invention, the polyamide resin used in combination with the random copolymer is an acid amide bond (-
CONH-), it is a synthetic polymer consisting only of amide repeating units, and does not contain other comonomer units, such as so-called soft segments such as polyether units and polyester units. When a polyamide having such a soft segment is used, as is clear from Comparative Example 7, which will be described later, the wax remover resistance cannot be improved. Specific examples of the polyamide resin used in the present invention include nylon 6, nylon 66, nylon 11, nylon 12, nylon 601, and copolymerized nylons thereof. Polymer Composition The polymer composition of the present invention is easily prepared by uniformly blending 90 to 60 parts by weight of the random copolymer described above and 10 to 40 parts by weight of the polyamide resin. If the random copolymer is used in an amount greater than 90 parts by weight, the effect of improving the heat resistance and wax remover resistance of the polymer composition will be insufficient; If the amount is less than 100%, adhesion to glass and fluidity during injection molding will be impaired, making it difficult to obtain a thin molded product. The polymer composition of the present invention may contain fillers such as clay, talc, calcium carbonate, silica, carbon black, etc., within a range that does not impair its performance.
Coloring agents such as titanium oxide, zinc, azo pigments, and phthalocyanine pigments, and other known additives such as antioxidants, heat stabilizers, weather stabilizers, etc. can be blended. Incidentally, the random copolymer and the polyamide resin are blended by dry blending or melt blending them simultaneously or sequentially. Dry blending can be performed using various blenders such as a Henschel mixer, tumbler mixer, and ribbon blender, and melt blending can be performed using a single screw extruder, twin screw extruder, Banbury mixer, and the like. When making these blends, there is no particular restriction on the mixing order of the ingredients. As mentioned above, the polymer composition of the present invention has the following features:
It is suitable as a molding material for integrally molding an automobile window glass and a window frame to form an encapsulant window by injection molding.
This integral molding can be performed as follows. That is, after washing the glass with water using a surfactant, an aqueous solution of a silane coupling agent such as γ-aminopropyltriethoxysilane (for example, Shin-Etsu Chemical KBE903) is applied to the glass surface, and then air-dried or air-sprayed. The glass is then dried, inserted into an injection mold, and in this state the polymer composition of the present invention is injected onto the periphery of the glass to integrally mold the window glass and window frame.
In this case, in order to stabilize the adhesion between the window frame, which is a molded product of the polymer composition, and the glass, it is also possible to perform post-heating if necessary. [Effects of the Invention] According to the present invention, by blending a specific amount of polyamide resin into an ethylene acid random copolymer, the random copolymer has excellent adhesion to glass, excellent surface gloss, It has become possible to improve heat resistance and wax remover resistance without impairing properties such as scratch resistance. The polymer composition of the present invention having such properties is
In addition to being suitable as an injection molding material for automobile encapsulant windows, it is also effectively used as a molding material for plastic gaskets formed around the edges of glass products such as architectural windows, mirrors, and underwater glasses. Ru. In addition, Japanese Patent Application Publication No. 193959, Japanese Patent Application Publication No. 59-1939-
Publication No. 140258, Japanese Patent Application Publication No. 1982-8246, Japanese Patent Application Publication No. 1982
-151348, JP-A-52-80352, JP-A-52-47051, JP-A-42-12546, etc. disclose ethylene-α,β-unsaturated carboxylic acid copolymers and polyamides. Blends with polyamides have been disclosed, but all of these are aimed at improving the properties of polyamides, such as impact resistance, and in particular are mainly composed of polyamides.
This is clearly different from the polymer composition of the present invention, which is mainly composed of an ethylene acid random copolymer and has improved heat resistance and wax remover resistance. The invention is illustrated by the following example. In the following Examples and Comparative Examples, the amount of deformation under weight, adhesion to glass, and wax remover resistance of the compositions were measured and evaluated by the following methods. (1) Amount of deformation due to its own weight A specimen (70mm x 20mm x 2mm) from a press sheet of a polymer composition created using a heat press at 160℃
was cut out, and while holding one end of the specimen and keeping the specimen horizontal, it was placed in a heated oven at a predetermined temperature for 3 hours. The heat resistance of the polymer composition was evaluated by measuring the amount of sagging of the other end of the sample after heating and displaying it in mm. (2) Adhesion to glass (i) Method for preparing specimens After carefully washing a glass plate (68 mm x 168 mm x 8 mm) with water, apply a primer solution (Shin-Etsu Silicone manufactured by Shin-Etsu Chemical Co., Ltd.).
KBE903, 0.1 part by volume, 50 parts by volume of methanol, water
50 parts by volume) was applied, immediately immersed in water to remove excess primer solution, and dried by blowing air. This glass plate is used in an injection molding mold (cavity).
70 mm x 170 mm x 10 mm), and the polymer composition was injection molded at a nozzle temperature of 260°C, and a 2 mm thick polymer composition was laminated on the entire surface of an 8 mm thick glass plate.
The obtained glass laminate was heated at 80° C. for 1 hour. (ii) Method for measuring adhesive strength The polymer composition of the glass laminate thus obtained was slit into a 10 mm width, and one end of the slit was held.
The glass and polymer composition were peeled off at a rate of 200 mm/min in a 90° direction and the peeling status was observed. If the adhesion is good, the polymer composition may be cut or the peeled surface may undergo cohesive failure. In cases where adhesion was poor, interfacial peeling occurred. (3) Wax remover resistance Wax remover resistance during steam kerosene cleaning was evaluated as follows. That is, after the above glass laminate was immersed in kerosene at room temperature for 10 minutes, steam at an original pressure of 3 kg/cm ² -G was immediately sprayed onto the surface of the polymer composition from a distance of 10 cm for 1 minute using a hose with a nozzle diameter of 10 mm. Changes in the surface appearance of the polymer compositions were investigated. When the wax remover resistance is good, there is no change in the black glossy appearance of the molded product, but when it is poor, the surface gloss decreases and becomes dull, or in severe cases, it turns white. Example 1 70 parts by weight of ethylene-methacrylic acid copolymer (methacrylic acid content 5.0 mol% MFR25), amylan
A dry blend of 30 parts by weight of CM1017C (Toray product nylon 6) and 3 parts by weight of carbon black was prepared and kneaded using a 30 mmφ twin screw extruder at a die temperature of 200°C to prepare a polymer composition shown in Table 1. Physical property items were evaluated. Comparative Example 1 The physical property items shown in Table 1 were evaluated using only the ethylene-methacrylic acid copolymer used in Example 1. Comparative Example 2 High-density polyethylene Hi-Zex 2200J (density
A polymer composition was prepared in the same manner as in Table 1 except that 0.968MFR5.5) was used, and the physical property items shown in Table 1 were evaluated. Comparative Example 3 Olefin thermoplastic elastomer milastomer was used instead of Amilan CM1017 used in Example 1
A polymer composition was prepared in the same manner as in Table 1 except that 8530B (density 0.89, A hardness 88) was used, and the physical property items shown in Table 1 were evaluated.

[Table] Example 2-3 Comparative Example 4-5 A polymer composition was prepared in the same manner as in Example 1 except that the blending ratio of Example 1 was changed, and the physical properties of the obtained polymer composition were as described in Example 1. It was evaluated according to.

【table】

[Table] Wax remover resistance
Almost good Good Poor Good
Example 4 70 parts by weight of ethylene-methacrylic acid-butyl acrylate copolymer (methacrylic acid 4.0 mol%, butyl acrylate 2.5 mol%, MFR35) and amylan
A polymer composition was prepared using 30 parts by weight of CM1007 (Toray product nylon 6) in the same manner as in Example 1, and its physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 3. Comparative Example 6 Using only the ethylene-methacrylic acid-butyl acrylate copolymer shown in Example 4, its physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Table] Example 5 A polymer composition was prepared in exactly the same manner as in Example 1, except that nylon 12 (Rilsan AESN 0 TL; manufactured by Toray Industries, Inc.) was used instead of Amiran CM1017C. The same evaluation as in Example 1 was performed. The results are shown in Table 4. Comparative Example 7 In Example 1, polyamide elastomer (Pebax 3533
A polymer composition was prepared in exactly the same manner as in Example 1, except that SN 00 (manufactured by AT0chem) was used.
The same evaluation as in Example 1 was performed. The results are shown in Table 4.

【table】

Claims (1)

[Scope of Claims] 1 Consists of 90 to 60 parts by weight of an ethylene acid copolymer and 10 to 40 parts by weight of a polyamide resin consisting only of amide repeating units, the ethylene acid copolymer being 90 to 98 mol% 2 to 10 mol% of (meth)acrylic acid units, or further 6 mol% or less of (meth)acrylic acid ester units.