JPS61153086A - Resin hose - 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 [Industrial Application Field] The present invention relates to a resin hose, and more specifically, a resin hose having a nylon tube, an organic fiber reinforcing layer, and a thermoplastic resin cover. After treatment with an active halogen compound or without treatment, polytetramethylene glycol and 4.4'-
A one-component moisture-curing adhesive consisting of a urethane polymer with an isocyanate group/hydroxyl group equivalent ratio within a specific range obtained by reacting with an isocyanate compound whose main component is diphenylmethane diisocyanate, or a short-chain diol containing this urethane prepolymer. Apply a one-component moisture-curing adhesive made of urethane prepolymer modified with
The present invention relates to a resin hose in which the nylon tube and the organic fiber reinforcing layer are bonded together.

[Prior art] As a method for adhering a nylon tube made of 6-nylon or 6.6-nylon to an organic fiber reinforcing layer in a resin hose, the surface of the nylon tube is coated with resorcinol, formic acid,
Plasticized with nylon solvents such as phenol and methanol,
How to embed an organic MT4 reinforcing layer to obtain structural adhesion, and especially when the nylon tube is 11-nylon, 12-nylon, etc., coextrusion with a resin such as polyurethane that can easily be made sticky in polar solvents. There is a method of structurally adhering polyurethane and an organic fiber reinforcing layer (Japanese Patent Publication No. 10367/1983), and the adhesion work is carried out while taking advantage of the characteristics of each.

[Problems to be Solved by the Invention] However, in the method using a nylon solvent such as resorcinol, the nylon solvent remains in the tube, resulting in a decrease in heat resistance and a usage limit of 100°C.

Furthermore, since the nylon solvent is a powerful drug, it also has the disadvantage of not being easy to handle. On the other hand, in the method using polyurethane, the resin with poor heat resistance forms the surface layer of the tube, so the heat resistance decreases, and the
The limit is ℃.

[Means for Solving the Problems] An object of the present invention is to provide a resin hose in which a nylon tube and an organic fiber reinforcing layer have high adhesive strength and excellent heat resistance.

As a result of extensive studies in line with this objective, the present inventors have discovered that isocyanate groups/hydroxyl groups obtained by reacting polytetramethylene glycol with a specific molecular weight with an isocyanate compound whose main component is a 4,4'-diphenylmethane diisocyanate compound. A one-component moisture-curing adhesive made of a urethane polymer with an equivalent ratio within a specific range, or a one-component moisture-curing adhesive made of a urethane prepolymer modified with a short-chain diol, is used to create a nylon tube. It has been discovered that by bonding the resin hose with the organic fiber reinforcing layer, the resin hose has high adhesive properties and also has excellent heat resistance.

By using this liquid-based moisture-curing adhesive (hereinafter simply referred to as adhesive), a nylon tube made of 6-nylon, 6.6-nylon, or a copolymer nylon thereof and organic fiber reinforcement made of polyester fiber, etc. Adhesion of layers is now possible without the need for heating. However, even if the above adhesive is used, 10-nylon, 11-nylon, 1
The adhesion between the nylon tube made of 2-nylon and the organic fiber reinforcing layer was still insufficient.

As a result of further study, the present inventor found that by treating the adhesive interface of a nylon tube such as 10-nylon with an organic active halogen compound and then applying the above adhesive,
- It was discovered that a nylon tube made of nylon, 11-nylon, and 12-nylon and an organic fiber reinforcing layer adhere with high adhesive strength, and the present invention was achieved.

That is, the present invention provides a resin hose having a nylon tube, an organic fiber reinforcing layer, and a thermoplastic resin cover, in which the adhesive interface of the nylon tube is treated with a mechanically active halogen compound in the molecule, or after being untreated, the average Obtained by reacting polytetramethylene glycol with a molecular weight of 100 to 1,800 with an isocyanate compound containing 4,4'-diphenylmethane diisocyanate as a main component such that the isocyanate group/hydroxyl group equivalent ratio is 1.3 to 2.0. A one-component moisture-curing adhesive made of a urethane prepolymer, or a urethane prepolymer,
A one-component moisture-curing adhesive made of a urethane prepolymer modified with a short-chain diol such that the molar ratio of short-chain diol/polytetramethylene glycol is 0.5 or less is applied, and the nylon tube and the organic fiber are bonded together. This is a resin hose characterized by having a reinforcing layer bonded to it.

The nylon tube used in the present invention is not particularly limited, and includes, for example, 6-nylon, 6.6-nylon, or copolymers thereof, or 10-nylon, 11-nylon, and 1-nylon.
Examples include 2-nylon, but as described later, 10
- For nylon tubes such as nylon, 11-nylon, and 12-nylon, sufficient adhesive strength cannot be obtained with the tatIA fiber reinforced layer by applying adhesive alone, so it is necessary to treat the adhesive interface with an organic halogen compound. It is. Also,
As the organic fiber reinforcing layer, a material obtained by braiding polyester fibers is used.

In the present invention, 10-nylon, 11-nylon,
12-Adhesion to the organic fiber reinforcing layer is not sufficient only by applying an adhesive such as nylon. Treat with a nylon Tugen compound. Examples of the organic halogen compounds used here include halogenated succinimides such as N-promsuccinimide, halides of isocyanuric acid such as trichloroisocyanuric acid and cyclosocyanuric acid, and halogenated hydantoins such as dichlorodimethylhydantoin. . Among these, trichloroisocyanuric acid is preferred.

It is preferable that the concentration of such an organic halogen compound be 2 to 10% using an appropriate soluble solvent such as methyl ethyl ketone or ethyl acetate as an organic solvent.

In the present invention, 10-nylon, 11-nylon,
Nylon tubes such as 12-nylon are treated after the adhesive interface is treated with the organic active halogen compound, while nylon tubes made of 6-nylon, 6,6-nylon, or copolymers thereof are not treated at all. Apply adhesive as is.

The adhesive used here is a urethane polymer with an equivalent ratio of isocyanate groups/hydroxyl groups within a specific range, which is obtained by reacting polytetramethylene glycol with an isocyanate compound containing 4,4'-diphenylmethane diisocyanate as a main component, or It consists of a urethane prepolymer modified with a short chain diol.

Polytetramethylene glycol (PTMG) is used as a polyol to form this urethane polymer. Among polyols, PTMG has the best adhesion to the nylon tube to which it is bonded. In the present invention,
It is also possible to use PTMG whose ends are modified with propylene oxide or the like. The average molecular weight of PTMG is 70
0 to 1800, preferably 800 to 1700, and adhesives using PTMG in this range have an adhesive strength of 5 #/in or more when bonded to nylon at room temperature.

If the average molecular weight of PTMG is less than 700 or more than 1,800, the adhesive force will decrease. Note that the average molecular weight of this PTMG is a value calculated from the hydroxyl value.

On the other hand, as the isocyanate compound forming the urethane prepolymer, an isocyanate compound containing 4,4'-diphenylmethane diisocyanate as a main component is used.

There are various compounds containing isocyanate groups (-NGO), but aliphatic isocyanate compounds are not suitable for moisture-curing adhesives because they react slowly with moisture in the atmosphere, and they also have poor heat resistance. Even if you look at it, it's not enough. On the other hand, aromatic isocyanate compounds include tolylene diisocyanate (TDI), bitolylene diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI>, 4,4'-diphenylmethane diisocyanate (MDI>), etc. However, like aliphatic isocyanate compounds, TDI reacts slowly with atmospheric moisture (and is not suitable for moisture-curing adhesives, and NDI, TODI, etc. are expensive). It is not practical. In addition, NDI is not practical due to its poor storage stability when used as an adhesive.

Therefore, the adhesive used in the present invention is an isocyanate compound (hereinafter referred to as MDI) whose main component is 4,4'-diphenylmethane diisocyanate, which has good reactivity with atmospheric moisture and good compatibility with nylon tubes. (collectively) is used. This MDI may be pure MDI with a high purity of approximately 100%, or modified MDI that has been partially decarboxylated, such as I5O manufactured by Kasei Upjohn Co., Ltd.
nate 143L or crude MDI (n=0.1 or 2) shown by the following chemical formula may be used, but hydrogenated MDI is not preferred from the viewpoint of safety and health.

In the present invention, the adhesive made of the urethane polymer is used by replacing a part of MDI with TDI, TODESNDI, or an aliphatic isocyanate compound in order to adjust the curing speed, viscosity, cohesive force, physical properties, adhesiveness, etc. It is also possible.

In the adhesive used in the present invention, the urethane prepolymer obtained by reacting PTMG and MDI has an isocyanate group/hydroxyl group equivalent ratio of 1.3 to 2.0, preferably 1.
4 to 1.9.

Urethane prepolymers obtained by reacting polyols with isocyanate compounds usually have isocyanate groups/
It is obtained by reacting so that the equivalent ratio of hydroxyl groups is 1.9 to 2.5.

Moisture-curing adhesives have a curing mechanism in which atmospheric moisture reacts with isocyanate groups to form urea bonds and generate carbon dioxide gas. When a large amount of carbon dioxide gas is generated, or when carbon dioxide gas is generated rapidly, the dissipation of gas is delayed.
Air bubbles remain in the adhesive layer, making it impossible to obtain sufficient adhesive strength.

Methods for eliminating air bubbles include reducing isocyanate groups in the prepolymer, ie, reducing the amount of gas generated, and reducing free MDI, ie, reducing the amount of rapid gas generated. In addition, addition of carbon dioxide absorbents, fillers, plasticizers, solvents, etc. is also an effective method. Moisture-curing urethane prepolymers reduce the amount of free MDI to total IMDI.
It is desirable to reduce the amount to 1% or less. Free MDIfE
One method for reducing 1 is to reduce the isocyanate group/hydroxyl group equivalent ratio. Furthermore, the method of reducing the equivalent ratio is effective in reducing the number of active isocyanate groups. Therefore, in the present invention, the upper limit of the equivalent ratio is set to 2.0, preferably 1.9.

In addition, if this equivalent ratio is too small, the molecular weight of the urethane prepolymer becomes too large than necessary, which inevitably increases the viscosity and makes it difficult to handle as an adhesive. This results in poor wetting of polyamide resin, etc., and sufficient adhesion cannot be obtained.

Also, since the amount of free isocyanate groups is reduced, the amount of urea bonds formed during the curing reaction is reduced.

Comparing urethane bonds and urea bonds, urea bonds contribute more to heat resistance, so a decrease in haze due to urea bonds means a decrease in heat resistance. Therefore, in the present invention, the lower limit of the equivalent ratio is set to 1.3, preferably 1.4.

In the adhesive used in the present invention, by further modifying the urethane prepolymer obtained as described above with a short chain diol, the reaction shown by the above formula proceeds, improving the adhesive strength to the resin. be able to.

0CN-R+ -NGO+HO-B-OH+0CN-R
2-NCO→ 0CN-R+ (in the above formula, HO-
B-OH is a short-chain diol; 0CN-R+ -NCO and 0CN-R2NGO are the urethane prepolymers described above, respectively.) If free MDI is present while this reaction is proceeding, short-chain diols are preferentially The presence of short chain diols also has the function of removing free MDI.

In carrying out this modification, the molar ratio of PTMG and short chain diol is important. In other words, the presence of short chain diol has an effect of improving the adhesive force, and increasing the short chain diol decreases the adhesive force.
As the molar ratio of MG approaches 0.5, the adhesive strength is no longer different from that before modification. In the relationship between the two, as the molar ratio becomes sufficiently large, the molecular weight of the prepolymer begins to increase and becomes a polymer around 1.0, so that the moisture curing function is lost.

Therefore, when modifying with a short chain diol, the molar ratio of short chain diol/PTMG is set to 0.5 or less, preferably 0.4 or less.

The short chain diol used here is a diol having a molecular weight of at least about 400 or less, such as ethylene glycol, 1,4-butanediol, diethylene glycol, beta-human O-oxyethyl benzoate, beta-hydroxyethyl terephthalate, etc., and modified products thereof. Alternatively, it may be a mixture. Among these short chain diols, 1,4-butanediol is most preferred.

The adhesive used in the present invention obtained in this way is treated with a solvent that does not react with isocyanate groups, such as methyl ethyl ketone (MEK), toluene, ethyl acetate, cellosolve acetate, thinner, and hexane, for degreasing and viscosity adjustment. It is desirable to use it diluted. Furthermore, various additives may be optionally added as desired.

As explained above, in the resin hose of the present invention, the nylon tube and the organic fiber reinforcing layer made of polyester fiber or the like adhere with high adhesive strength, and the resulting resin hose has excellent heat resistance.

The present invention will be specifically described below based on Examples and Comparative Examples.

衷IJLL PTMG with average molecular weight 1300 (Product name PTG-30
0, manufactured by Nippon Polyurethane Co., Ltd.) 100/(f (76
, 9 mol) was put into the reaction vessel, the temperature was adjusted to 50°C, and then 34.6 kg of pure M[) 1 was added. After the rapid exothermic reaction had passed for 1 hour and the reaction had subsided, the reaction was further carried out at 80° C. for 5 hours to obtain a urethane prepolymer.

10% by weight of dry methyl ethyl ketone was added to the urethane prepolymer thus obtained and mixed uniformly by stirring to obtain a one-component moisture-curing adhesive.

This adhesive was applied with a brush to the outer periphery of a nylon tube made of 8/6.6 copolymerized nylon, and an organic fiber reinforcing layer made of braided polyester fibers was placed thereon and lightly pressed.

A peel test was conducted to evaluate the adhesive strength between this nylon tube and the mIN reinforcing layer. Peel test at 20℃, 6
The test was carried out after being allowed to stand for one day under the condition of 5% relative humidity, and the test was carried out at 20° C. at a tensile speed of 50 am/inch. The results are shown in Table 1.

After adhering the organic IS, M reinforcing layer to the nylon tube in this way, a urethane-based adhesive was further applied to the outer periphery of the organic fiber reinforcing layer, a polyester thermoplastic resin cover was adhered, and the resin was bonded as shown in Figure 1. Got a hose.

In FIG. 1, 1 is a nylon tube, 2 is a one-component moisture-curing adhesive layer, 3 is an organic fiber reinforcing layer, 4 is a urethane adhesive layer, and 5 is a thermoplastic resin cover.

The thus obtained resin hose was subjected to a high temperature impulse test. The test is JIS B 83428.4
Pressure 200* f/cd square wave,
The test was carried out under the following conditions: oil temperature 120°C, U-shaped mounting, R-50+U. The results are shown in Table 1.

Examples 2 to 3 Trichloroisocyanuric acid diluted with ethyl acetate at a concentration of 3% was brushed onto the adhesion interface of each of the nylon tube made of 6/6.6 copolymerized nylon and the tube made of 11-nylon used in Example 1. Apply it for about 5 minutes,
A nylon tube treated with trichloroisocyanuric acid was obtained by air drying at 20° C. and 65% relative humidity.

The adhesive used in Example 1 was applied with a brush to the outer periphery of this trichloroisocyanuric acid-treated nylon tube, and an organic fiber reinforcing layer made of braided polyester fibers was placed and lightly pressed.

In order to evaluate the adhesion test between this nylon tube and the organic fiber reinforced layer, a peel test was conducted in the same manner as in Example 1. The results are shown in Table 1.

After the organic III reinforcing layer was bonded to the nylon tube in this manner, a urethane adhesive was further applied to the outer periphery of the organic fiber reinforcing layer, and a polyester thermoplastic resin cover was bonded to obtain a resin hose.

This resin hose was subjected to a high temperature impulse test according to Example 1, and the results are shown in Table 1.

The adhesive interface of the nylon tube made of 6/6.6 copolymerized nylon on LLL was plasticized with a nylon solvent, and the organic reinforcement III layer was adhered. In order to evaluate the adhesive strength between this nylon tube and the organic reinforcing fiber layer, a peel test was conducted in the same manner as in Example 1. The results are shown in Table 1.

After the organic fiber reinforcing layer was bonded to the nylon tube in this manner, a urethane adhesive was further applied to the outer periphery of the organic fiber reinforcing layer, and a polyester thermoplastic resin cover was bonded to obtain a resin hose.

This resin hose was subjected to a high temperature impulse test according to Example 1, and the results are shown in Table 1.

Comparative Example 2 The adhesive interface of a nylon tube obtained by coextruding 11-nylon and polyurethane was plasticized with a urethane solvent,
An organic reinforcing fiber layer was adhered. In order to evaluate the adhesive strength between this nylon tube and the organic reinforcing fiber layer, a peel test was conducted in the same manner as in Example 1. The results are shown in Table 1.

After the organic fiber reinforcing layer was bonded to the nylon tube in this manner, a urethane adhesive was further applied to the outer periphery of the organic fiber reinforcing layer, and a polyester thermoplastic resin cover was bonded to obtain a resin hose.

This resin hose was subjected to a high temperature impulse test according to Example 1, and the results are shown in Table 1.

As shown in Table 1, Examples 1 to 3 in which the nylon tube was treated with an organic active halogen compound or without treatment, and then coated with a liquid moisture curing adhesive and bonded to the organic fiber reinforcing layer. The resin hose has excellent adhesion between the nylon tube and the organic fiber reinforcing layer, and also has excellent heat resistance as a resin hose, compared to the conventionally used resin hoses of Comparative Examples 1 and 2.

[Effects of the Invention] As explained above, the resin of the present invention can be bonded to an organic fiber reinforcing layer by applying a liquid moisture curing adhesive to a nylon tube after treating it with an organic active halogen compound or without treatment. The hose must be able to bond the nylon tube and the organic fiber reinforcing layer with high adhesive strength without suffering thermal deformation in the temperature range from low temperatures to approximately 80 degrees Celsius or below, which does not cause residual strain on the tube, and has high heat resistance. Therefore, it has excellent fitting properties and can be used at high temperatures of 110 to 120°C.

Therefore, the resin hose of the present invention can be used in various fields where heat resistance is required.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing the structure of the resin hose of the present invention. 1: Nylon tube, 2 one-component moisture-curing adhesive layer, 3: Organic fiber reinforcement layer, 4: Urethane adhesive layer, 5: Thermoplastic resin cover.

Claims (1)

[Claims] 1. In a resin hose that has a nylon tube, an organic fiber reinforcement layer, and a thermoplastic resin cover, the adhesive interface of the nylon tube has a ▲ mathematical formula, chemical formula, table, etc. in the molecule ▼ group (X indicates halogen). After treatment with an organic active halogen compound having an organic active halogen compound, or without treatment, polytetramethylene glycol having an average molecular weight of 700 to 1,800 and an isocyanate compound whose main component is 4,4'-diphenylmethane diisocyanate are subjected to equivalence of isocyanate groups/hydroxyl groups. A one-component moisture-curing adhesive made of a urethane prepolymer obtained by reacting the urethane prepolymer so that the A resin characterized in that the nylon tube and the organic fiber reinforcing layer are bonded by applying a one-component moisture-curing adhesive made of a urethane prepolymer modified with a short-chain diol so that the nylon tube is 0.5 or less. hose.