JPH02155943A - Bonding of polyphenylene sulfide resin to tetrafluoroethylene-ethylene copolymer resin - Google Patents

Abstract

PURPOSE:To form a resin compsn. capable of bonding a polyphenylene sulfide resin molding to a tetrafluoroethylene-ethylene copolymer resin by compounding a polyphenylene sulfide, a tetrafluoroethylene-ethylene copolymer and an ultrafine particle. CONSTITUTION:A resin compsn. obtd. by compounding a polyphenylene sulfide (PPS), a tetrafluoroethylene-ethylene copolymer (ETFE) and an ultrafine particle is used as an adhesive for bonding a PPS molding to an ETFE molding. Namely, bonding parts of said moldings and the adhesive are melted at a temp. above the m.p. of PPS and ETFE but below 400 deg.C and in a molten state, both members are joined together by using the adhesive and cooled down while keeping the bonded state.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field This invention relates to polyphenylene sulfide (hereinafter abbreviated as PPS) resin and tetrafluoroethylene-ethylene copolymer (
The present invention relates to an adhesive resin composition that enables adhesion to a resin (hereinafter abbreviated as ETFE) and a laminate using the same.

(b) Conventional technology ETFE has excellent properties such as heat resistance, chemical resistance, flexibility, weather resistance, electrical properties, weather resistance, stain resistance, and abrasion resistance, and PPS has a high melting point and is heat resistant. chemical resistance,
It is known as a highly elastic resin, and it is expected that a more highly functional material can be obtained by bonding the two, but there are almost no known adhesives that can bond the two.

(c) Problems to be Solved by the Invention: To obtain an adhesive and an adhesive method that enable bonding of PPS molded products with TFE molded products.

(d) Means for solving the problem As a result of intensive research for the above purpose, it was found that a mixture of ETFE and PPS in a specific mixing ratio and further blending of inorganic solid fine particles achieves the object of the present invention. They discovered this and completed the present invention.

That is, the present invention provides a bonding method using a resin composition obtained by mixing ETFE and PPS, a resin obtained by further mixing these compositions with inorganic solid fine particles, and a bonding method using a resin composition obtained by mixing ETFE and PPS. The gist is a laminate made of ETFE resin and PPS resin.

Each component of the adhesive resin composition of the present invention will be explained below.

ETFE in the present invention is a polymer having the following molecular structure, and is an alternating copolymer of tetrafluoroethylene and ethylene as heptamers, and the copolymerization ratio thereof is about 1.

(-CH2-CH2-CF2-CF2-)n-As the ETFE having the above molecular structure, injection molding, extrusion molding grade, etc. can be used. ET like this
In Japan, Asahi Kasei Corporation's ``Afron C'' is an FE.
OP”, Daikin Industries, Ltd. [Neofron ETFEJ
, as a foreign product Hochst (West German Confederation)
rHostaflon ETJ, Du Pont,
Chew, (USA) r Tefzel
J etc. are known as commercial products.

PPS in the present invention is a polymer having the following molecular structure.

(-C6H4-5-)n- C6H4- is a benzene ring.

As PPS having the above molecular structure, injection molding, extrusion molding grade, etc. can be used.
Examples of S include "Toprene PPS" by Topren Co., Ltd., "Polyphenylene Sulfide" by Asahi Glass Co., Ltd., "Shin-Etsu PPS" by Shin-Etsu Chemical Co., Ltd., and "Sasteel" by Hodogaya Chemical Co., Ltd., and foreign products include Ph1lip.
s Che, Co.

(USA) r RYTON J etc. are known as commercial products.

The ultrafine particles in the present invention are ETFE, melted with PPS,
It is necessary that the mixture be chemically and morphologically stable.

The reason why it is called ultrafine particles is that the particle size of the particles must be 10 μm or less, and more preferably 1 to 0.01 μm.
It is a layer thing. Materials with this property include various iron oxides for electromagnetic products, chromium oxide, metal powders produced by vacuum evaporation, aluminum oxide used as abrasives or manufacturing raw materials,
Examples include inorganic glass powder, boron nitride, which is a ceramic raw material, silicon oxide powder, and fly ash, which is a factory waste.

The adhesive composition is produced by melt-mixing ETFE, PPS, filler, etc. to obtain a resin composition, and then the resulting resin mass is further formed into a sheet using a heat press and used as an adhesive.

It is accurate to adjust the raw materials during mixing by weight, but the specific gravity of ultrafine particles varies significantly depending on the type, and ETFE has a slight difference in the copolymerization ratio of monomers.
Specific gravity changes. Limiting the blending ratio by weight ratio requires description of each type of resin grade and ultrafine particles, so in the present invention, the blending ratio for the polymer needs to be expressed not by weight but by the volume ratio of the polymer. .

The following definition is used for the resin mixing ratio of ETFE to PPS (hereinafter abbreviated as resin mixing ratio) described in the claims of the present invention. PPS and ETFE volume refers to the true volume as a polymer.

Resin mixing ratio = 100 x ETFE volume/(ET
FE 10pps) Volume % Filling rate = 100x Fine particle volume/(Ultrafine particle ETF
E + PPS) volume %adherent is PPS,
When it is a molded product of ETFE and the adhesive is a mixed resin that is not filled with PPS and ETFE ultrafine particles, the range of resin mixture that can be bonded is wide, but the adhesive strength obtained is low, with a tensile adhesive strength of 10! kg/cm", and was not strong enough for practical use. The results are shown for reference in the examples.

The filling effect of ultrafine particles is recognized from the filling rate of 2x, and at 15x or more, the adhesive force decreases.It is related to the viscosity of PPS, but as the filling rate increases, the adhesive coagulated layer becomes hard and brittle, and the adhesive force decreases. In practice it is less than 20×.
The most preferable range is a filling rate of 2.5 to 5%.

In this case, the resin mixture ratio (ETFE/
(ETFE+PP5) x 100 volume z) range is 1
0 to 70%, preferably 15 to 60%. In this case, the adhesive strength is approximately 30
Kg/cm2 has been changed.

The optimum conditions for the mixing ratio differ slightly depending on the type, particle size, and shape of the fine particles.

The mixing temperature and adhesion temperature must be higher than the temperature at which both PPS and ETFE melt. The melting point of pps is 2.
The temperature is around 82°C, and since ETFE starts thermal decomposition at around 255 to 265°C and 340°C or higher, the temperature is preferably in the range of 305 to 340°C. In actual heating, in order to shorten the heat transfer time, heating may be performed in an even higher temperature atmosphere, and the upper limit temperature is approximately 4.
00℃.

As a method for producing the adhesive, any device capable of thermal melting and mixing, such as a screw type extrusion device, a twin-screw roller, a Weissenberg pump, etc., can be used for mixing. An adhesive suitable for the form of the adherend can be produced by using a press or other molding device from a resin mixture produced by melt-mixing.

The manufacturing method of the adhesive, the adhesion method, and the measurement of adhesive strength are described in detail in Examples.

Research has already been published on the effect of ultrafine particle filling on adhesiveness, but in the present invention it can be considered to be the stabilization of the mixed state of polymers.

PPS is known as a polymer that is not compatible with ETFE. However, although it is possible to create a mixture by mechanically mixing, the mixed state is thermodynamically unstable, and in the molten state, they separate from each other, and the same polymers tend to aggregate together.For this reason, when adhering If the melting temperature of the tip of the adhesive or adherend is too high or the bonding time is too long, polymer separation will occur, and the entanglement of PPS and ETFE polymers will decrease, causing a significant decrease in adhesive strength. Become.
As a result of experiments, it was found that filling with ultrafine particles is effective in preventing a decrease in adhesive strength and expanding the range of adhesion-capable mixing ratios.

For example, without ultrafine particle filling, the resin mixing ratio is 50% (ET
If FE/PP5=1), the adhesive strength is approximately 10 kg.
7cm2, but when iron oxide fine powder for magnetic materials (chemical structure is Fe2O3, particle size 0.5μ■, called ferrite fine particles) is filled as ultrafine particles with care so that it is mixed almost equally into each polymer. Adhesive strength 3 with a filling rate of 3%
3 Kg/cm", and it was found that it was possible to coat the surface of PPS plastic moldings with an ETFE film using this adhesive.

(e) Effect The ETFE molded product and the PPS molded product are bonded together.

(f) Example adhesive, ETF as a resin that is a raw material for producing adherends
E is Daikin Co., Ltd. [Neofron ETFE EP 5
20 J, and "Toprene T-4" manufactured by Tovren Co., Ltd. was used as the PPS.

As ultrafine particles, ferrite fine particles (Toda Kogyo Co., Ltd. 7-Fe20S-KFA-N H1) are used.
Average grain size 0.5~0.6μm or less Ferrite is Fe
abbreviated as O), and alumina ultrafine particles (Baikowsk
ieChimie BP BAIKALOX A-12
5. Alumina with an average particle size of 0.01 μm or less (abbreviated as AIO), and others were used.

A Weissenberg-type resin mixing and extrusion device was used to mix the resins and the like for producing the adhesive, and the supply amount was determined based on the specific gravity of each raw material at a predetermined mixing ratio, and the mixing was performed in the following procedure. First, the surface temperature of the fixed plate and rotating plate of the Weisenberg mixing and extrusion device was maintained at 320°C, the gap between the rotating plate and the fixed plate was set to 2 m, and the rotating plate started rotating, and the raw materials mixed in a solid state were transferred from the hopper. supply In general, it is difficult to uniformly mix materials with different specific gravities, pellets, and powders of different shapes and sizes, so it is necessary to supply them in small quantities.The diameter of the disk of the device used in the experiment was 12 cm.
Since the internal volume of the apparatus was about 10 cc, the volume of polymer was supplied in units of 5 cc, the nozzle hole was plugged at the start, and when mixing was sufficient, the plug was opened to start extrusion. Furthermore, the extrudate was extruded again to ensure sufficient mixing.

The extrudate was formed into a sheet with a thickness of 0.31 by heat press, and used as an adhesive sheet.

To prepare a test piece for evaluating adhesive strength, a rod-shaped object with a tip diameter of 6 cm and a length of 6 to 9 cm was prepared in advance from ETFE and PPS molded materials as adherends, and the tip was The adhesive part and the other part near the tip will be used as the gripping part during the tensile test.

To bond sticks of different adherend materials, cut a sheet with a diameter of 5cm from an adhesive sheet, use a heated metal plate with a smooth surface and a thin PTFE sheet, and fuse the adhesive to the tip of the ETFE stick. . The surface temperature of the metal plate at this time is 300 to 330°C, and the fusion of the tip and adhesive must be confirmed. Next, using an air burner, 2 rods,
In other words, heat the tips of the ETFE rod and the PPS rod, which have the welding agent fused to the tips, and after confirming that the tips are both melted, bring the tips into contact and press lightly to fuse them together, then cool while maintaining that state. and complete the gluing.

In order to measure adhesive strength, the axes of the glued rods need to be on almost the same straight line, but if the length of the melted part at the tip is too long or the pressing force is too strong, the melted part may flow and cause problems during the test. Since it is not possible to make a test piece, some care must be taken when adhering. The adhesive force was measured using a Tensilon UTM 3 model at a tensile rate of 4 shoes/min, and the adhesive force was determined by dividing the strength by the area of the fractured surface. In such tests, the adhesive surface is the weakest, and the adhesive can be treated as having no elongation. There are cases where anisotropy occurs in the resin flow during adhesive preparation, and a circular adhesive changes into an elliptical shape during bonding, so the fracture surface area was calculated approximately as a circle or an ellipse. Since there is a lot of variation in the data, we decided to show the average value of the top three out of the five samples that could be bonded. The measurement results of adhesive strength are summarized below.

(1) The figure shows the adhesive force measurement results when the adherend was a molded product of ETFE and PPS and the adhesive was a mixed resin of ETFE and PPS.

○ in the figure indicates no filler, this is for reference only,・4
．． When filled with 3.85 to 4 Vol % of tAlo ultrafine particles, the vertical axis represents the tensile adhesive force (g/c+n”
), the horizontal axis is the resin mixture ratio (ETFE) / (ETFE +
It is expressed in volume % of PP5).

(2) An ETFE pellet filled with FeO ultrafine particles was prepared in advance with a filling rate of 3%, and an attempt was made to bond it with an adhesive with a resin mixture rate of 50%. As a result, the adhesive strength was 33 kg /
cm'', which was more than twice as strong as that without filler, and the strength was practically usable. Examples of particles that were effective for
%.

The numbers in parentheses are the average or average particle diameter, and the unit is μ■.

Crushed glass peas (0,2), silica powder (2~0°5
), nickel (0,3), nickel-iron alloy (0,3
), abrasive jewelry (1 or less).

(4) For comparison, we attempted to bond PPS and PVDF molded objects in the same way using a mixed resin composition of ETFE and PPS filled with ferrite and glass beads with an average particle size of 50 μm as an adhesive. No performance improvement was observed.

(G) In addition to the effects of the invention, the adhesive resin composition of the present invention is a combination of ETFEs and PPS.
It enables adhesion to resin molded products, such as ETFE, P
It is also possible to bond PS fiber-reinforced molded products.

Therefore, ETFE, which has excellent properties such as heat resistance, chemical resistance, weather resistance, sliding properties, and electrical properties, is used instead of PPS, which is strong and can maintain high elasticity even at high temperatures, but has a weak point in weather resistance. Lamination on the surface can facilitate outdoor use of PPS materials.

In addition, the laminated composite of the present invention can be used for various industrial materials, and is particularly useful for structural materials, electronic materials, etc.

[Brief explanation of the drawing]

In the figure, the adherends are ETFE and PPS molded products, and the adhesive is E
Adhesive force measurement results when using a mixed resin of TFE and PPS. The vertical axis is the tensile adhesive force, and the weight is kilograms per square centimeter (Kg/cm"). The horizontal axis is the resin mixture ratio of the adhesive (ETFE) / (ETFE).
+PPS) is expressed as volume %. In the figure, O indicates no filler, and O indicates ultrafine alumina particles (A
The figure shows the case where IO>3.85 to 4 Vol% is filled.

Claims (3)

[Claims] (1) A resin composition obtained by mixing three components: polyphenylene sulfide, tetrafluoroethylene-ethylene copolymer, and ultrafine particles. (2) A resin composition obtained by mixing three components: polyphenylene sulfide, tetrafluoroethylene-ethylene copolymer, and ultrafine particles is used as an adhesive, and a polyphenylene sulfide resin molded product and tetrafluoroethylene-ethylene copolymer are used as adhesives. The polymer resin molded product is used as an adherend, and the part of the adherend to be joined and the adhesive are melted at a temperature above the melting point of polyphenylene sulfide and tetrafluoroethylene-ethylene copolymer and below 400°C, and in a molten state. A method for adhering polyphenylene sulfide resin moldings and tetrafluoroethylene-ethylene copolymer resin moldings, which involves joining adherends using an adhesive and cooling them while maintaining the joined state. (3) A laminated structure in which polyphenylene sulfide resin and tetrafluoroethylene-ethylene copolymer resin are bonded together using a resin composition in which polyphenylene sulfide, tetrafluoroethylene-ethylene copolymer, and ultrafine particles are mixed as an adhesive layer.