JPS61255853A - Two layer type synthetic resin tube and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a two-layer synthetic resin tube for conveying water, agricultural chemicals, other liquids, and the like.

(Prior Art) A two-layer synthetic resin tube consisting of two inner and outer layers made of different materials and molded into one body is conventionally known.

In particular, in recent years, fluororesins have attracted attention for their outstanding heat resistance and chemical resistance, and urethane resins have attracted attention for their excellent rubber elasticity, mechanical properties, oil and solvent resistance, etc., and demand for these is growing and applications are expanding. However, it would be desirable if a practical two-layer tube with both of these excellent properties could be developed.

(Problems to be solved by the invention) Conventional two-layer tubes made of different types of synthetic resins are
It is extremely difficult to strongly adhere the inner and outer molded layers to each other simply by using a synthetic resin adhesive, depending on the selection of the resin. For example, when using the above-mentioned fluororesin, since fluororesin is non-adhesive and non-polar, when creating a one-piece tube consisting of two layers of fluororesin and, for example, urethane resin, simply use urethane resin and other various types of resin. Even if an attempt was made to bond the inner and outer layers to each other using a synthetic resin adhesive, the resulting two-layer tube easily peeled off due to manual tension, and a practical tube could not be obtained. As a trial, either 10,000 yen of molded tubes of fluororesin, urethane resin or other synthetic resins, or both.
Even if the adhesive surface area is increased by etching the surface by chemical or physical means, a large mutual adhesion suitable for practical use cannot be obtained, and the problem of easy peeling cannot be solved.

Ta.

(Means for Solving the Problems) The present invention provides a new adhesive means that can also use fluororesin, which could not be bonded using conventional adhesive means.
This product provides a layered synthetic resin tube, consisting of two inner and outer layers made of different materials and molded into one body.
In a layered synthetic resin tube, the joint surface t-
.

The two layers are bonded to each other through an inorganic filler exposed and embedded in the bonding surface of one of the layers and a silane coupling agent.

Furthermore, the present invention provides a method for producing the two-layer synthetic resin tube of the present invention using an ordinary extrusion molding machine, in which a synthetic resin such as a fluororesin containing an inorganic filler is used as the inner layer tube. It is characterized in that it is molded, and a synthetic resin such as urethane resin to which a silane coupling agent is added is molded into a single body as an outer skin tube on the upper surface thereof.

(Example) An example of the present invention will be described with reference to a two-layer tube made of a fluororesin and a urethane resin and a method for manufacturing the same.

The drawing is a schematic representation of a two-layer synthetic resin tube of the present invention manufactured by the specific example T described below of the manufacturing method of the present invention, and (1) shows an inner layer tube (2
) indicates an outer layer tube made of urethane resin that is firmly bonded to the outer layer surface, and the mutual joint surface of both layer tubes (11T21) is made of countless inorganic fillers ( Among 3), countless powdered inorganic fillers (3) which function as anchors are exposed on the outer joint surface of the filler, and one end is chemically bonded to this, and the other end is attached to the inner peripheral joint surface of the urethane resin outer layer. It is a two-layered tube molded in one piece that is extremely strongly bonded to one piece by extremely strong adhesive means with a chemically bonded silane coupling agent (4).

This was tested for peel strength by applying a considerable tensile peel force between the two layers, but no peeling was observed. Thus, the two-layer synthetic resin tube of the present invention is a two-layer synthetic resin tube that is excellent in all aspects such as chemical resistance, heat resistance, flexibility, and mechanical properties that can exhibit the excellent properties of both resins. As a practical product, it can satisfactorily transport various fluids depending on the purpose, such as various chemical liquids such as agricultural chemicals, and can be used as a good hose with a long service life.

Next, one example of a method for manufacturing a tube made of two layers of fluororesin and urethane resin, shown in the above embodiment, will be described in detail.

The fluororesin may be any fluororesin as long as it fully satisfies the requirements for a thermoplastic resin, and since there is a step of mixing an inorganic filler with it, it is preferable to use a fluororesin that is easy to mix, that is, has good flow characteristics. Examples include polychlorotrifluoroethylene (POTIF]I+), tetrafluoroI
Ethylene-hexafluoropropylene (TlcP), Tetrafluoroethylene-perfluoroalkyl vinyl ether (PIF), Tetrafluoroethylene-ethylene (1+TIFK), Polyvinylidene hexafluoride (PVD)
7) etc., particularly preferably Xτym.

The POT is 7m.

Inorganic fillers mixed into fluororesin include quartz, silicas such as Koda silica, kaolin, and! Squid, talc, silicates such as calcium silicate, aluminum silicate, iron oxide, 7N mit.

1 of desired fine inorganic fillers such as metal oxides such as aluminum oxide, metals such as aluminum and copper, etc.
Select and use one or more species.

These inorganic fillers have good chemical bonding with adhesion aids.
The amount of the inorganic filler added to the fluororesin is preferably in the range of 1 to 10 parts per 100 parts of the fluororesin, but is not limited to this range.

As the urethane resin, it is sufficient as long as it satisfies the requirements of heat-fallenability, and generally, 1) adipic acid-based polyester polyol consisting of adipic acid and glyfur, II
) Any type may be used as long as an organic diisocyanate is addition-polymerized to a caprolactone-based polyester polyol obtained by ring-opening g-caprolactone or an ether-based polyol obtained by ring-forming a cyclic ether such as ray. In particular, Y of the silane coupling agent YR8iX is M
In the case of H, groups, those that are compatible with and react with H, are preferred, and from this point of view, those containing residual NOD groups are more suitable, and any commercially available products can be used.

As the adhesion aid, it is sufficient that it chemically bonds with the above-mentioned inorganic filler and the reactive group of the synthetic resin such as urethane resin, but in the case of urethane resin, a silane coupling agent [general formula YR8i @s Y is ME,
, Ha, 01! , ==b-, etc., and X is (
These are reactive groups such as OOI(,OH,) and (OOH,)3. It is preferable to use ], and in particular, it is preferable because the NH* group is easily compatible with or reacts with the remaining Woo group of the urethane resin.

For example, r-aminopropyltriethoxysilane (MH,
Oh! OR,01! ,81 (OOH,OH,),
, N-β-(aminoethyl)-r-amylablepyrtrimethoxysilane CNH,0HfOHIHHOHffiO
H,OH,! 31 (OOH), 7'-ureidopropylethoxysilane (NH,0ONHOH).

81 (OOII, OH,), etc.

The amount of the silane coupling agent added to the urethane resin is generally preferably α5 to 10% by weight, and optimally 1 to 5% by weight, based on the total amount of the urethane resin.

The silane coupling agent can be added by mixing it inside the urethane resin or adhering or coating it to the surface of the urethane resin.

Next, a preferred specific example of manufacturing a two-layer synthetic resin tube formed in one piece, with the fluororesin as the inner layer and the urethane resin as the outer layer, will be described.

Specific example Fluororesin (pellets of tetrafluoro-a ethylene and ethylene copolymer 11i'l"1FEt) 100ky
aluminum silicate powder 5 to 9 @ 330 in twin screw extruder
It was blended and pelletized at a temperature of ~350°C.

The aluminum silicate-containing fluororesin pellets thus obtained were molded using a 30 mm diameter single-screw extruder to an inner diameter of 1 m.
A tube with an outer diameter of 1.5 m and an outer diameter of 1.5 mm was prepared.

On the other hand, thermoplastic urethane resin pellets (Vandex 5067, manufactured by Dainippon Ink Chemical) 100 to 9, silane coupling agent (γ-aminopropyltriethoxysilane)
5- was mixed in a tumbler, uniformly adhered to the surface of a thermoplastic urethane resin pellet, and heat-treated in an electric furnace at 100° C. for 2 hours.

Next, the extrusion-molded tube made of the aluminum silicate-containing 7-component resin is used as an inner layer, and the outer circumferential surface (the urethane resin to which the silane coupling agent is attached) is extrusion coated so as to form an outer layer tube with a thickness of 5 ms. A two-piece type tube having an inner diameter of 1 and an outer diameter of Swa was manufactured as a whole.

For reference, the above-mentioned fluororesin pellets with no inorganic filler added and the above-mentioned urethane resin pellets not attached to the silane coupling agent were used as materials and were combined in the same manner as above to create a two-layer tube.

When we manually applied a tensile force to the two-layered tube of the present invention and the two-layered tube of the reference example to forcibly peel off the two layers by hand, the product of the present invention did not peel off at all, whereas the two-layered tube of the reference example did not peel off at all. The item peeled off easily.

(Effects of the Invention) The present invention provides a two-layered tube in which the inner and outer layers are made of different synthetic resins, and a countless number of inorganic fillers are anchored and fixed to one of the joint surfaces of the two layers as a means of adhering the two layers. At the same time, a silane coupling agent was attached to the other surface, so both the inner and outer layers were extremely firmly bonded together through the inorganic filler and the silane coupling agent.
A layered tube has been created, and a two-layered tube consisting of a fluororesin layer and a urethane resin layer has become practical, and the product exhibits the excellent characteristics of each layer and can be used in an extremely wide range of industrial applications. It has the effect of

[Brief explanation of drawings]

The drawing shows a cross-sectional view of a portion of an example of a product implementing the invention. (1) Inner tube (2) Outer tube (3) Inorganic filler (4) Silane coupling agent procedure amendment

Claims (1)

[Scope of Claims] 1. In a two-layer synthetic resin tube consisting of two inner and outer layers made of different materials and molded into one body, the bonding surface of both layers is the bonding surface of one of the layers. A two-layer synthetic resin tube that is bonded to each other via an inorganic filler exposed and embedded on the surface and a silane coupling agent. 2 One synthetic resin is a fluororesin, which serves as the inner tube, and the other synthetic resin is a urethane resin, which serves as the outer tube.
Layered synthetic resin tube. 3 A synthetic resin such as a fluororesin containing an inorganic filler is molded as an inner layer tube, and a synthetic resin such as a urethane resin containing a silane coupling agent is molded into one body on the upper surface as an outer tube. A method for manufacturing a two-layer synthetic resin tube.