JPS5817239B2 - Adhesive resin molded products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive resin molded article for covering and fixing articles.

More specifically, the present invention relates to an adhesive resin molded article comprising an adhesive thermoplastic resin, an epoxy resin, and a curing agent for epoxy resin.

Conventionally, for the purpose of covering and fixing articles, liquid or powder thermosetting adhesives, or adhesive thermoplastic resin molded articles conforming to the shape of the article have been used.

Specifically, various epoxy resins are commonly used for the former, and these are materials that exhibit excellent fixing performance after curing and are excellent in both heat resistance and chemical resistance.

However, if the places to cover and fix the article are limited (which is always limited in actual use), it is difficult to cover and fix only the necessary parts due to the free-flowing nature of these materials. Control is difficult due to rice paddies or shortages.

In order to facilitate this control, various methods have been considered, particularly for powdered thermosetting materials, to form them into shapes that match the articles to be coated and fixed.

For example, a method of placing powder material in a closed mold and applying pressure to give a cohesive force between powder particles to form a regular shape, or
This method involves heating and melting a powder material, pouring it into a mold in an unhardened state, and cooling it to form a regular shape.

However, these shaped products are composed of uncured thermosetting materials, that is, monomers or oligomers, and are essentially brittle materials.

Therefore, the shaped material tends to break, and therefore, although it is theoretically possible, in practice there are significant restrictions on the shapes that can be shaped.

For example, it is not possible to create large objects.

Also, it is not possible to make it into a thin shape.

Furthermore, even within these limits, it is necessary to take great care when handling it, and it has the disadvantage that it can easily break due to even the slightest impact.

Furthermore, unlike the thermosetting resins mentioned above, the latter type of adhesive thermoplastic resin can be easily shaped to match the shape of the article, and since it is a polymeric material, even shaped articles can have sufficient strength for practical use. have.

Therefore, it is easy to cover and fix only the necessary parts of the article.

However, since it is a thermoplastic resin, it has the disadvantage that when the area where the coating is fixed is heated, it melts and rapidly loses its coating fixing function.

Furthermore, chemical resistance and solvent resistance are also not sufficient.

The inventors of the present invention have arrived at the present invention as a result of extensive research and consideration of the above-mentioned drawbacks.

That is, in the present invention, 20 to 300 parts by weight of an epoxy resin having a softening point in the range of 60 to 180°C and an appropriate amount of a curing agent for the epoxy resin are substantially uncured, based on 100 parts by weight of the adhesive thermoplastic resin. The present invention relates to an adhesive resin molded article that is uniformly dispersed in a continuous phase of the thermoplastic resin in a state in which the adhesive resin molded article can be melted and cured by heating means to cover and fix the article.

The adhesive resin molded article of the present invention comprises a shape-retentive adhesive thermoplastic resin component (first resin component), an epoxy resin component that essentially heats and hardens (second resin component), and an appropriate amount of epoxy resin curing. The shape of the product can be freely provided according to the shape of the three-dimensional article to be coated and fixed, such as a tube, a branched tube, a cup, or a semicircular donut.

This is because the adhesive resin molded article of the present invention has a form in which the second resin component and the curing agent component are substantially uniformly dispersed in an uncured state within the continuous phase of the first resin component. This is due to the fact that the first resin component has shape retention properties, and the essential brittleness of the second resin component is improved.

In addition, this adhesive resin molded product hardens by heating.
Due to dimensional crosslinking, compared to the case of the first resin component alone,
It has the characteristic of improving heat resistance and other physical properties.

In order to manufacture this adhesive resin molded article, any method can be used that allows the second resin component and the curing agent component to be substantially uniformly dispersed in an uncured state within the continuous phase of the first resin component. For example, the above-mentioned component mixture may be powder-coated on a mold that has been subjected to mold release treatment, cooled after melting, and molded by molding. A molded product can be obtained by pouring a mixture of each component into a mold while partially melting it and cooling it. Alternatively, if the shape is simple, it can be shaped by extrusion molding and then cutting with a cutter or the like.

As mentioned above, the first resin component used in the present invention is an important component in shaping the adhesive resin molded product, and includes ethyne-vinyl acetate copolymer, ethylene-acetic acid copolymer, and ethylene-vinyl acetate copolymer for ordinary hot melt adhesives. Shape-retentive thermoplastic resins such as derivatives from vinyl copolymers, polyolefins and their derivatives, nylon, and polyester are used.

On the other hand, in carrying out the present invention, it is important to use a bisphenol type, novolac type, etc. epoxy resin having a softening point in the range of 60 to 180°C as the second resin component that hardens by heating.

When using an epoxy resin with a softening point of 60°C or less, stickiness occurs on the surface of the adhesive resin molded product, and when these molded products are stacked, fusion of the molded products can be seen, making it difficult to work during use. Sexuality becomes worse.

In some cases, it becomes impossible to separate and cannot be used.

This is considered to be caused by the plasticization phenomenon caused by the addition of the low-melting-point low-molecular-weight material to the first resin component and the blooming phenomenon of the low-melting point material.

On the other hand, when using an epoxy resin with a softening point of 180°C or higher, in order to heat and melt it and harden it, the temperature must be 180°C.
In actual use, it is necessary to raise the temperature to a higher temperature than
There are restrictions on the material to be adhered, such as the fact that it cannot withstand temperatures higher than this or it cannot be used.

Therefore, the softening temperature of the second resin component is preferably in the range of 60 to 180°C.

Further, the amount of the second resin component is preferably in the range of 20 to 300 parts by weight based on 100 parts by weight of the first resin component.

If the amount of the second resin component is less than 20 parts by weight, the effect of three-dimensional crosslinking due to curing of the second resin component will not be seen, and the effect of improving the heat resistance of the molded product after heating will not be seen (
Become.

Furthermore, if the second resin component exceeds 300 parts by weight, the adhesive resin molded product may become uncured (uncured), resulting in a loss of shape retention.

Further, as the epoxy resin curing agent for curing the second resin component, what is generally called a latent curing agent is preferable in carrying out the present invention.

That is, in order for an adhesive resin molded article to be stored for a long period of time, it must be stable at room temperature and exhibit activity at high temperatures.

As such a nitrogen-containing compound, a nitrogen-containing compound is preferably used that is stable at room temperature but decomposes at high temperatures to produce at least one active hydrogen-containing amine.

Typical decomposable curing agents include monourea, polyurea, hydrazide, thiourea, etc., and preferred specific examples include 3-barachlorophenyl-1. Agemethylurea, 2,4-bis(N.

Examples include N-dimethylcarpamidonotluene and dianediamide, and one or more of these may be used in combination.

In this invention, in addition to the nitrogen-containing compounds mentioned above, various imidazoles, imidacillins, etc. can be used as curing agents.

Although some of these curing agents impose some restrictions on the pot life of the resin composition, they can be used satisfactorily when long-term deep stability is not particularly required.

Specific examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-ethylimidazole, 2-inpropylimidazole, 2. 4-dimethylimidazole, 2
-Phenyl-4-methylimidazole, 2-methylimidacillin, 2-ethyl-4-methylimidacillin, 2-
Phenylimidacillin, 2-undecylimidacillin,
Examples include 2-heptadecyl imidacilline, 2-ethylimidacilline, 2-inpropylimidazole, 2,4-dimethylimidacillin, 2-phenyl-4-methylimidacillin.

The usage ratio of the curing agent for epoxy resin in the present invention varies depending on the types of the first resin component and the second resin component and their blending ratio, but it is usually 0.00 to 0.00000000000000000000000000 with respect to the total amount of resin components.
It may be used in a proportion of 1 to 10% by weight.

In this invention, in addition to the above-mentioned components, various compounding agents can be added as necessary.

For example, in order to further improve heat resistance, phenyl-β
- Stabilizers and anti-aging agents such as naphthylamine, diphenyl-paraphenylenediamine, di-tert-butyl-4-methylphenol, paraphenylphenol, calcium stearate, dilaurylthiodipropionate, and to accelerate or completely cure the epoxy resin. A curing accelerator can be added to improve shrinkage resistance, and clay, talc, calcium carbonate, silica, barium carbonate, etc. can be added to improve shrinkage resistance and give hardness.

Next, this invention will be explained in more detail using Example 1pl.

Note that parts hereinafter refer to parts by weight.

Implementation row 1 Ethylene vinyl acetate copolymer with a softening point of 120°C (Evaflex 15 manufactured by Mitsui Polychemical Co., Ltd.) was used as the first resin component.
0) Softening point 75 as the second resin component for 100 parts
~85°C epoxy resin (Epicor manufactured by Shell Chemical Co., Ltd.) 1
002) 100 parts and 3 parts of dicyandiamide as a curing agent for epoxy resin, 3-parachlorophenyl-1,1
, -dimethylnirealo moiety were blended and mixed on a mixing roll at 120°C to obtain a resin composition.

This resin composition is made into pellets using a normal pellet machine, extruded using an extruder to obtain an uncured pipe-shaped molded product, and then cut with a cutter to form a hollow molded product 1 in the shape shown in Fig. 1. I got it.

This molded article can be used to cover and simultaneously fix a plurality of conductor wires to a substrate.

For example, a plurality of dedicated enameled wire terminals from each element on a printed circuit board are bundled and passed through a hollow part of a molded product.
When this was held in an open state at 150°C for 30 minutes and taken out, the speed collecting part of the enameled wire terminal was covered with the molded product.
Moreover, it was possible to firmly adhere it to the printed circuit board.

In addition, the melting behavior of the above molded product at 10120°C was
As a result of measurement using a plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), curve A shown in FIG. 2 was obtained.

The vertical axis in Figure 2 shows the torque (&y・cm),
A phenomenon is observed in which the torque increases from point b and saturates at point C.

This is considered to be an effect of gelation and subsequent curing of the epoxy resin, which is the second resin component.

On the other hand, when a hollow molded product (comparison row) obtained using an extruder using only the first resin component of this formulation is similarly measured, curve B in FIG. 2 is obtained, and the torque as shown in curve A is obtained. No increase is seen.

The torque value at that time is also much lower than the saturation value in curve A.

The above is the result of this implementation, by making Qin harden,
The melt viscosity during heating is much higher than Comparison No. 11 (,
This shows that it has excellent mechanical properties when heated.

Example 2 Ionomer resin with a softening point of 99°C (
For 100 parts of Suichirin 1652) manufactured by Mitsui Polychemical Co., Ltd., an epoxy resin (Epicor manufactured by Shell Chemical Co., Ltd.) 1004) 23 with a softening point of 95 to 105°C was added as the second resin component.
3 parts were mixed using a mixing roll at 120°C, and the resulting resin composition was pulverized using an ordinary hammer mill to obtain 333 parts of a powdered resin composition.

Powdered epoxy curing agent (Shikoku Kasei KK)
A powder resin composition was obtained by adding 16.5 parts of Ebicure 2MZ) and performing tri-blending.

This powder resin composition was powder-coated using a conventional electrostatic coating method on a cup-shaped mold with a diameter of 10 mm and a depth of 15 mm, which had been surface-treated with a fluororesin, and heated in an oven at 150° C. for 5 minutes. After melting the coating powder and cooling it, it is released from the mold.
A cup-shaped molded product 2 shown in FIG. 3 was obtained.

This molded product was able to firmly cover and fix the cable connection part by covering the parallel twisted part of the cable connection part 0 and heating it at 150 degrees centigrade for 30 minutes.

When this fixed article was left in an oven at 120° C., it was found that the fixing purpose was sufficiently achieved without any trouble such as flow due to melting of the fixed resin.

On the other hand, using a cup-shaped molded product obtained in the same manner as in this example using only the first resin component of this formulation, it was placed over the aforementioned cable connection part, fixed under the same conditions, and left in an oven at 120°C. As a result, stickiness of the resin due to melting of the adhesive resin was observed, and as time passed, the adhesive resin flowed and lost its adhesive function.

Example 3 100 parts of an adhesive polyolefin (Atmer N5100, manufactured by Mitsui Petrochemicals) with a softening point of 120°C as the first resin component, and an epoxy resin (Araldite manufactured by Ciba Geigy) with a softening point of 78 to 81°C as the second resin component. ECN-1
280) and 2 parts of a powdered epoxy curing agent (Ebicure 2MZ manufactured by Shikoku Kasei Co., Ltd.) were dry mixed,
A powdered resin composition is obtained.

This composition was powder coated using the mold of Example 2 in the same manner as in Example 2 to produce a cup-shaped molded product.

Next, the cup-shaped molded product was placed over the cable connection portion and heated in the same manner as in Example 2, and the twisted portion of the bare cable wires was firmly fixed.

Even if this fixed article is left in an atmosphere of 120℃,
There were no problems such as flow due to melting of the fixed resin (and the heat resistance of the connection part was also good.

[Brief explanation of drawings]

1 and 3 are perspective views showing rows of adhesive resin molded products of the present invention, and FIG. 2 is a graph showing the melting behavior of the adhesive resin molded products at 120°C, where curve A is a graph showing the melting behavior of the adhesive resin molded products in Example 1. The graph of the blow molded product 1 obtained in Example 1 and curve B are the graphs of the blow molded product of the comparative example described in Example 1. 1...Hollow molded product, 2...Cup-shaped molded product.

Claims (1)

[Claims] 1 100 parts by weight of adhesive thermoplastic resin, 20 to 30 parts of epoxy resin with a softening point in the range of 60 to 180°C
A molded article in which 0 parts by weight or an appropriate amount of a curing agent for an epoxy resin is uniformly dispersed in a continuous phase of the thermoplastic resin in a substantially uncured state, and the article is melted and hardened by heating means to cover and fix the article. Adhesive resin molded product.