JPH0615185B2 - Method for manufacturing laminated body - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a laminate of a sheet glass with a thermoplastic elastomer, and in particular, a production of a simultaneous laminate obtained by integrally molding an automobile window glass and a gasket. It is about the method.

[Prior Art] At present, a window for an automobile is prepared by separately preparing glass and a gasket and combining them to finish them integrally, but the work efficiency is poor and there is a demand for rationalization.

[Problems to be solved by the invention] Gasket materials currently used for automobile window glass are ethylene-propylene rubber (EPR), styrene-
Vulcanized rubber such as Budadiene rubber (SBR) is used. Since these rubbers are not thermoplastic, a system is adopted in which the extruded and shaped product is vulcanized and produced according to the profile of the gasket, and then it is mounted around the glass. This method takes time and labor for the construction method,
This method is not suitable for diversifying the needs of free design in the future.

[Means for Solving the Problems] In order to improve the inefficiency in mounting a window glass of an automobile, the present invention uses a specific thermoplastic elastomer instead of a vulcanized rubber to replace a window glass and a gasket. By integrally molding, the above problems were successfully solved all at once, and the present invention was achieved.

That is, the present invention contains 0.2 to 10% by weight of a polyrefin resin containing a carboxyl group or an anhydride group thereof,
S K-6301, JIS-A hardness is 60 ~ 95, 2.16Kg load, MFR at 230 ℃ 0.5 ~ 10g / 10 minutes styrene thermoplastic elastomer having physical properties and silane coupling in advance A method for producing a laminated body, which comprises laminating, by insert injection molding, a plate glass having at least a part of its surface treated with an agent.

The thermoplastic elastomer used in the present invention (hereinafter sometimes referred to simply as an elastomer, an olefin-based or styrene-based thermoplastic elastomer was selected from the viewpoint of material flexibility.

The olefin thermoplastic elastomer is a blend of EPR or butyl rubber and an olefin resin, and there is also a blend of a partially crosslinked rubber component and a polyolefin resin. Specific methods for producing these include, for example, JP-A-47-18942, JP-A-48-26838, and JP-A-47-18942.
55-71738, etc. On the other hand, a styrene-based thermoplastic elastomer can be easily obtained by blending an SBS (styrene / butadiene / styrene) block copolymer or SEBS (styrene / ethylene / butyle / styrene) block copolymer with a polyolefin resin. As a typical manufacturing method,
-37618, Japanese Patent Publication No. 59-31540, and Japanese Patent Laid-Open No. 58-206644.

In the present invention, in consideration of the adhesiveness to glass, the polyolefin resin containing a carboxyl group or an anhydride group thereof is added to these elastomers in an amount of 0.2 to
Add 10% by weight. By modifying the elastomer itself,
By introducing a carboxyl group or its anhydride group into the elastomer, the effect of improving the adhesiveness of the elastomer to glass can be obtained, but it is slightly inferior to the production efficiency and economical efficiency, and therefore it is generally difficult to use.

A polyolefin resin containing a carboxyl group or an anhydride group thereof is a modified polyolefin resin containing a compound having these groups by copolymerization or graft modification, and examples of such a compound include acrylic acid and methacrylic acid. An α, β-unsaturated carboxylic acid such as an acid, maleic acid or fumaric acid, or an acid anhydride thereof is often used. Preferred is acrylic acid or maleic anhydride. The polyolefin resin containing carboxyl or its anhydride group generally has a melt index (180 ° C., 2.16 Kg load) of about 10 to 1000 g / 10 min, preferably 50 to 800 g / 10 min. The content of the carboxyl group or its anhydride group (however, the anhydride group is calculated to have two carboxyl groups) is preferably in the range of 1 to 20% by weight from the viewpoint of the adhesive effect and the production efficiency.
Particularly preferably, it is selected in the range of 3 to 10% by weight. If the content exceeds 20% by weight, the production is difficult.

If the content of such a modified polyolefin resin in the elastomer component is less than 0.2% by weight, sufficient adhesive strength with glass cannot be obtained, and if it exceeds 10% by weight, a significant effect is recognized. Not only that, but it is not economically desirable.

The hardness of the elastomer is preferably in the range of 60 to 95. If it is less than 60, the mechanical strength will be weak, and it will be disadvantageous in that it will turn over at the contact interface with the glass or will be fixed in the mounting jig with the vehicle. On the other hand, if it exceeds 95, the rubber elasticity is inferior, which may cause rain stains.

The MFR of the elastomer is preferably 0.5 to 10 g / 20 minutes. If the MFR is less than 0.5, problems such as short shots will occur when molding large glass. On the other hand, those having a viscosity of more than 10 are not preferable because they have too much fluidity and are likely to cause defective appearance such as voids and sink marks in the mold, and also have poor mechanical strength in terms of physical properties of the elastomer.

Regarding the glass to be inserted, it is more preferable to use glass that has been preheated to about 70 to 200 ° C. from the viewpoint of adhesiveness.

The silane coupling agent for pretreating glass has a general formula
In the compound represented by the formula X Si (OR) ₃ , X may or may not have a functional group (amino group, vinyl group, epoxy group, metalcapto group, fluoro group, etc.) that reacts with an organic substance. In the organic group, R 1 is a hydrolyzable group (methoxy group, ethoxy group, etc.). As the silane coupling agent, specifically, methyltrimethoxysilane, vinyltriacetoxysilane, aminosilane, γ-glycidoxypropyltrimethoxysilane and the like are preferably used.

[Examples] Next, the present invention will be specifically described with reference to Examples. The modified resins blended with the elastomer in the examples and comparative examples are as follows.

Modified resin MFR 0.8g / 10min Polypropylene 500g, maleic anhydride 50g and chlorobenzene 10 were put in a polymerization tank of 20 and heated to 120 ° C with stirring to dissolve the polymer, and then to 105 ° C. After cooling, 40 g of benzoyl peroxide dissolved in 250 ml of chlorobenzene was added dropwise through the dropping funnel over 1 hour, and after the addition, the polymerization was completed at 105 ° C for 4 hours. After completion of the reaction, the mixture was cooled to about 60 ° C., the reaction solution was added to a large amount of acetone, and the precipitated polymer was separated by filtration. The obtained polymer was repeatedly washed with a large amount of acetone to obtain a maleic anhydride modified polypropylene. The content of maleic anhydride in the obtained polymer was 6% by weight (4.4% by weight as an anhydride group) as determined by infrared absorption spectroscopy.

In addition, various physical properties were measured and the effects were determined by the following methods.

(1) Hardness JIS-A: Conforms to JIS K6301.

Shore D: Conforms to ASTM D2240.

(2) Strength at break (Kg / cm ² ) According to JIS K6301.

(3) Elongation at break (%) Conforms to JIS K6301.

(4) Compression set (%) Complies with JIS K6301. 25% compression, 70 ℃, 22 hours.

(5) MFR (g / 10 minutes) Complies with JIS K7210. 230 ℃, load 2.16Kg.

(6) Glass adhesion JIS K6854, the adhesion performance measurement part 3 in Figure 2, JIS
180 ° peeling was performed according to K6854.

⊚: No peeling, cohesive failure ◯: Adhesive strength 3 to 5 kg / inch ×: Adhesive strength 3 Kg / inch or less (7) Rubber elasticity Judgment was made by the compression set of (4) above.

◯: Compression set of 60% or less ×: Compression set of more than 60% (8) Appearance of molding Visual inspection of molded test pieces.

◯: No flow marks, short shots, sink marks, etc. ×: Same as above (9) Mechanical strength Judgment based on the strength at break point in (2) above.

◯: Strength at break 50 kg / cm ² or more ×: Strength at break less than 50 kg / cm ² Examples 1 to 6 and Comparative Examples 1 to 8 Using an 8 ounce injection molding machine, preheating, and silane coupling Agent (Nippon Unicar, Aminosilane A-11
20) The glass plate with a diameter of 92 mm and a thickness of 2.8 mm coated with vulcanized rubber spacers is inserted into the mold and the test piece shown in the figure at an injection pressure of 550 Kg / cm ² and a temperature of 240 ° C is applied. Molded. FIG. 1 is a plan view showing only half of the test piece, and FIG. 2 is an end view of the AA cross section of FIG. In the figure, 1 is a glass plate, 2 is an elastomer laminated on the periphery of the glass plate, and 3 is an adhesiveness measuring portion. Four
Are side gates provided at two opposite points for injection molding.

A test piece was molded using an elastomer material having various physical properties shown in Table 1, and the obtained test piece was contacted with the elastomer and the glass surface. I grasped the wear level. The experimental results are shown in Table 1.

It can be seen that the elastomer of the present invention exhibits very good adhesion.

[Brief description of drawings]

FIG. 1 is a plan view of a test piece for evaluating the adhesiveness of laminated glass, and FIG. 2 is an end view of the AA cross section of FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location B29L 31:30 4F

Claims (1)

[Claims] 1. A carboxyl group or its anhydride is 1 to 20.
Contains 0.2 to 10% by weight of polyolefin resin, and has a hardness of 60 to 95 according to JIS K-6301.JIS-A method.
With a load of 2.16Kg and MFR at 230 ℃, 0.5-10g / 10
A method for producing a laminate, comprising laminating a styrene-based or olefin-based thermoplastic elastomer having physical properties and a plate glass whose surface has been treated with a silane coupling agent in advance by insert injection molding.