JP4093046B2 - Adhesive laminate of thermoplastic elastomer substrate and glass - Google Patents

Description

【００４４】
【表２】

【００４５】
表１及び表２の結果から明らかな様に、本発明で使用する接着剤成分は、幅広い硬度範囲の汎用オレフィン系エラストマー、スチレン系エラストマー及びガラスに対して優れた接着性能を発揮し、特に接着剤Ａの性能は顕著である。
【００４６】
【発明の効果】
以上説明した本発明によれば、ハロゲン含有成分を使用せず、接着剤を１度塗布するだけで汎用の熱可塑性エラストマーとガラスを接着させることが可能で、特に、モール付き自動車用窓ガラスとして好適な、熱可塑性エラストマー製基体とガラスとの接着積層体が提供され、本発明の工業的価値は顕著である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adhesive laminate of a thermoplastic elastomer substrate and glass, and more particularly to an adhesive laminate suitable as a window glass for automobiles with a molding.
[0002]
[Prior art]
Usually, a window molding structure is adopted as a structure for fixing a window glass to a vehicle body. Conventionally, a soft vinyl chloride resin is used for a window molding, and in the case of a windshield or a rear glass, they are bonded and laminated with an adhesive.
[0003]
In recent years, demands for converting the material of malls from soft vinyl chloride to elastomers are increasing due to weight savings for improving fuel efficiency and environmental problems. However, in general, an elastomer is a material that is chemically inactive and has extremely poor adhesion because it does not have a polar group in the molecule.
[0004]
Thus, a method has been proposed in which a chlorinated polyolefin and a silane coupling agent are used as an adhesive component to bond a thermoplastic elastomer substrate and glass (for example, see Patent Document 1). However, in the case of this method, the adhesive laminate of the thermoplastic elastomer substrate and glass contains a halogen, and it does not completely solve the environmental problem during the incineration process.
[0005]
In addition, a method has been proposed in which an olein-based resin containing a carboxyl group or an anhydride thereof is blended with an olefin-based or styrene-based elastomer and adhered to glass (for example, see Patent Document 2). However, in this method, the adhesiveness is insufficient unless a large amount of carboxyl groups or anhydrides are added, so that a special elastomer is required and is difficult to realize.
[0006]
[Patent Document 1]
Japanese Patent No. 3142985 [Patent Document 2]
Japanese Examined Patent Publication No. 6-15185 [0007]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and its object is to use a thermoplastic elastomer that does not use a halogen-containing component and has sufficient adhesiveness, and is particularly suitable as a window glass for automobiles with moldings. The object is to provide an adhesive laminate of a substrate and glass.
[0008]
[Means for Solving the Problems]
As a result of intensive studies, the present inventor has obtained knowledge that the above object can be easily achieved by using a specific adhesive component, and has completed the present invention.
[0009]
That is, the gist of the present invention is an adhesive laminate of a thermoplastic elastomer substrate and glass, and a modified olefin polymer having a graft ratio of maleic anhydride of 0.1 to 10% by weight as an adhesive component. It exists in the laminated body of the base material made from a thermoplastic elastomer and glass characterized by using.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0011]
First, the thermoplastic elastomer substrate used in the present invention will be described. In the present invention, an olefin-based or styrene-based elastomer is preferably used as the thermoplastic elastomer.
[0012]
Olefin-based elastomers include ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber (EPDM), ethylene-1-butene-nonconjugated diene copolymer rubber, propylene-1-butene-nonconjugated. It is an elastic copolymer mainly composed of an olefin such as a diene copolymer rubber. Further, it may be a mixture of an olefin elastomer and an olefin resin such as polypropylene or polyethylene.
[0013]
On the other hand, the styrene elastomer is an elastic polymer containing styrene as a main component, such as a styrene block copolymer. Further, it may be a mixture of a styrene elastomer and an olefin resin such as polypropylene or polyethylene.
[0014]
The thermoplastic elastomers as described above are commercially available. For example, in the case of olefin-based elastomers, “Thermorun” manufactured by Mitsubishi Chemical, “Miralastomer” manufactured by Mitsui Chemicals, “Santoprene” manufactured by AES Japan, and Sumitomo Chemical Examples of “Sumitomo TPE” and styrene elastomer include “Lavalon” manufactured by Mitsubishi Chemical Corporation, “Sumiflex” manufactured by Apco Corporation, and the like.
[0015]
In the thermoplastic elastomer in the present invention, in addition to the above-described components, other arbitrary blending components can be blended according to various purposes within a range not significantly impairing the effects of the present invention. Examples of such components include fillers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, Examples include flame retardants, antistatic agents, conductivity-imparting agents, metal deactivators, antibacterial agents, antifungal agents, fluorescent brighteners, and other additives, thermoplastic resins and fillers other than the essential components, and the like. .
[0016]
Examples of the thermoplastic resin other than the essential components include ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid ester copolymer, ethylene / methacrylic acid. Ethylene / α-olefin copolymers such as ester copolymers, polyphenylene ether resins, polyamide resins such as nylon 6 and nylon 66, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyoxymethylene homopolymers, Examples include polyoxymethylene resins such as polyoxymethylene copolymers and polymethyl methacrylate resins. Further, a polyolefin resin containing a carboxyl group or an anhydride thereof may be blended, and in that case, further improvement in adhesiveness can be expected.
[0017]
Examples of the filler include glass fiber, hollow glass sphere, carbon fiber, talc, calcium carbonate, mica, potassium titanate fiber, silica, titanium dioxide, and carbon black.
[0018]
For preparing the thermoplastic elastomer composition, for example, an ordinary kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll, a Brabender, a plastograph, a kneader or the like is used.
[0019]
As a base molding means, for example, an extrusion molding method, an injection molding method, or the like is applied.
[0020]
Next, the adhesive component used in the present invention will be described. In the present invention, a modified olefin polymer having a graft ratio of maleic anhydride of 0.1 to 10% by weight is used.
[0021]
The olefin polymer used for the adhesive component may be a single polymer or a plurality of copolymers. For example, a homopolymer such as ethylene, propylene, 1-butene, ethylene- Examples include propylene, ethylene-1-butene, and propylene-1-butene copolymers. Among these, a propylene homopolymer or a copolymer is preferable. In view of adhesion to glass, a propylene-based copolymer containing 1-butene is particularly preferable. The content of 1-butene is usually 3 to 35% by weight, preferably 6 to 35% by weight. When the content is less than 3% by weight, the low-temperature adhesiveness is inferior. Becomes worse.
[0022]
As described above, the graft ratio of maleic anhydride is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. When the graft amount is less than 0.1% by weight, the adhesiveness is inferior, and when it exceeds 10% by weight, no improvement in performance is observed, which is economically disadvantageous. The graft ratio means the ratio (% by weight) of maleic anhydride to the modified olefin polymer (grafted olefin polymer).
[0023]
As a method for introducing maleic anhydride into the olefin polymer, a method in which an olefin polymer, maleic anhydride and an organic peroxide are supplied to an extruder and melt kneaded, or an aromatic hydrocarbon such as xylene or chlorobenzene is used. For example, a method in which a mixture of an olefin copolymer and maleic anhydride is heated and dissolved in a halogenated aromatic hydrocarbon solvent such as the above, and an organic peroxide is sequentially added and reacted.
[0024]
In the production of an adhesive laminate of a thermoplastic elastomer substrate and glass, the adhesive component is used as an organic solvent solution or dispersion. Examples of the organic solvent used for preparing such a solution or dispersion include aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as isoparaffin and normal paraffin. The ratio (weight ratio) between the adhesive component and the organic solvent is usually in the range of 5/95 to 25/75.
[0025]
In many cases, the adhesive component is prepared as a dispersion of an organic solvent. For example, when a maleic anhydride-grafted olefin polymer is stirred and dissolved in a hydrocarbon solvent under heating, the maleic anhydride-grafted olefin polymer precipitates to form a dispersion when the temperature is lowered to room temperature. The average particle diameter of the dispersed particles can be controlled by appropriately selecting the dissolution temperature, the stirring rotation speed, and the like. In the present invention, an example of a commercially available adhesive that can be suitably used is “Unistal” manufactured by Mitsui Chemicals.
[0026]
A predetermined amount of the adhesive (solution or dispersion) prepared as described above is applied to a substrate by a gravure coater, a reverse coater, a roll coater, a spray or the like. The coating amount is usually 0.5 to 5 mμ.
[0027]
Next, the glass used in the present invention will be described. In the present invention, for example, a window glass mounted on the front, rear or side of an automobile is applied. A ceramic coating layer is usually formed on the surface of the automobile window glass in contact with the adhesive layer in order to prevent the adhesive layer from being deteriorated by ultraviolet rays and to improve the design.
[0028]
Next, an adhesive laminate of a thermoplastic elastomer substrate and glass according to the present invention will be described. The adhesive laminate of the present invention uses a modified olefin polymer having a graft ratio of maleic anhydride of 0.1 to 10% by weight as an adhesive component, and is made of a thermoplastic elastomer substrate / adhesive layer / It has a laminated structure of glass.
[0029]
When the above laminated structure is formed, both may be laminated after the adhesive layer is formed on the thermoplastic elastomer substrate side, or both may be laminated after the adhesive layer is formed on the glass side. The method for laminating the adhesive is performed by a normal coating method. At this time, the glass is preferably preheated to 70 to 200 ° C.
[0030]
The adhesive laminate of a thermoplastic elastomer substrate and glass according to the present invention does not cause interfacial delamination between the substrate and glass when the substrate and glass peel test is performed. Especially, it is suitable as a window glass for automobiles with a molding.
[0031]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, the following raw materials were used.
[0032]
(1) Olefin thermoplastic elastomer having a hardness of 70 according to JIS K6253: TPO (hardness 70)
[0033]
(2) Olefin thermoplastic elastomer having a hardness of 90 according to JIS K6253: TPO (hardness 90)
[0034]
(3) Styrenic thermoplastic elastomer having a hardness of 70 according to JIS K6253: TPS (hardness 70)
[0035]
(4) Glass: 150 × 25 × 5 mm glass plate with a ceramic coating layer on one side
(5) Adhesive A: Toluene dispersion of maleic anhydride-modified propylene-1-butene copolymer prepared by the following method
That is, 100 parts by weight of a propylene-1-butene copolymer having a 1-butene content of 15% by weight and 500 parts by weight of xylene are charged into a 2 l flask equipped with a cooling tube and heated to a boiling point with stirring to dissolve. did. Next, 15 parts by weight of benzoyl peroxide and 15 parts by weight of maleic anhydride were added in 3 divided portions every 1 hour, and after addition of the whole amount, stirring and heating were continued for an additional hour. After cooling, the precipitate was washed with acetone. Thus, a maleic anhydride-modified polypropylene copolymer was obtained. The maleic anhydride content was 4.8% by weight. Next, 12 parts by weight of the above resin and 88 parts by weight of toluene were charged in a 1.5 L autoclave, dissolved under stirring at 100 ° C. for 15 minutes, then cooled down to 1 at 60 ° C. and 500 rpm. After being held for a period of time, it was held at 10 ° C. and 700 rpm for 2 hours, and returned to room temperature to obtain an adhesive A.
[0038]
(6) “Chemlock 459X” manufactured by Load in Corp .: Chlorinated olefin adhesive
(7) “Chemlock AP-134” manufactured by Load in Corporation: Silane-based adhesive
<Creation of thermoplastic elastomer substrate>
Each thermoplastic elastomer (TPO) was processed with a press molding machine to obtain a sheet having a thickness of 2 mm. The substrate was cut into a width of 25 mm and a length of 150 mm to obtain an elastomer substrate (test piece).
[0041]
Example 1
A test piece of TPO (hardness 70) was heated to 100 ° C. in an oven, and immediately after removal, the adhesive A was applied. Similarly, the glass preheated at 100 ° C. in the oven was taken out and bonded to the surface of the above test piece on which the adhesive A was applied. After drying, a 180 ° C. peel test was performed, resulting in material destruction.
[0042]
Test Examples 1 to 8 and Comparative Examples 1 to 6 for Comparative Examples
In an oven, the elastomeric substrate marked with a circle in Tables 1 and 2 was heated to 100 ° C., and immediately after taking out, the adhesive marked with a circle in Tables 1 and 2 was applied. Similarly, the glass plate is heated to 100 ° C. in an oven, and immediately after taking out, the ceramic coating layer forming surface or the glass surface marked with ○ in Table 1 and Table 2 is shown in Table 1 and Table 2. The adhesive marked with ○ was applied. And after leaving at room temperature for 24 hours, the cross-cut tape peeling test was done based on JIS-K5400. And the remaining number after a peeling test was measured. This test is intended to individually evaluate the adhesion performance to each material before constructing an adhesive laminate of a thermoplastic elastomer substrate and glass. The results are shown in Tables 1 and 2.
[0043]
[Table 1]

[0044]
[Table 2]

[0045]
As is apparent from the results of Tables 1 and 2, the adhesive component used in the present invention exhibits excellent adhesion performance to general-purpose olefin elastomers, styrene elastomers and glass in a wide range of hardness, and in particular, adhesion. The performance of agent A is remarkable.
[0046]
【The invention's effect】
According to the present invention described above, it is possible to bond a general-purpose thermoplastic elastomer and glass without using a halogen-containing component and only by applying an adhesive once. A suitable adhesive laminate of a thermoplastic elastomer substrate and glass is provided, and the industrial value of the present invention is remarkable.

Claims (4)

An adhesive laminate comprising a thermoplastic elastomer substrate , an adhesive layer and glass, wherein a modified olefin polymer having a graft ratio of maleic anhydride of 0.1 to 10% by weight is used as the adhesive layer. A laminate of a thermoplastic elastomer substrate and glass , wherein the modified olefin polymer is a modified propylene copolymer containing 1 to 35% by weight of a 1-butene component .   The laminate according to claim 1, wherein the thermoplastic elastomer is an olefin-based or styrene-based elastomer. The laminate according to claim 1 or 2 , wherein a ceramic coating layer is formed on the surface of the glass in contact with the adhesive layer.   It is a window glass for motor vehicles with a molding, The laminated body in any one of Claims 1-3.