JPH06179860A - Adhesive polymer composition and technique of bonding fibrous material or the like - Google Patents

Abstract

PURPOSE:To obtain an adhesive polymer composition which can give a tight bonding force to a fibrous material or a like polymeric material by adding a specified amount of a specified blocked diisocyanate to a polymeric material. CONSTITUTION:The composition is prepared by adding 0.5-5 pts.wt. blocked isocyanate obtained by blocking the NCO groups with a substance having a functional group (e.g. a compound of the formula) and desirably kneading the mixture at a temperature lower than the dissociation temperature of the blocked diisocyanate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive polymer composition having excellent adhesiveness to fiber materials and other polymer materials, and polymer materials and fiber materials using the adhesive polymer composition. The present invention relates to a method for adhering polymer materials to each other.

[0002]

2. Description of the Related Art Conventionally, a polymer material such as rubber or synthetic resin is combined with a fiber material such as cloth or cord,
BACKGROUND ART Different kinds of polymer materials are combined and used as a composite material. In order to secure the strength of these composite materials, it is required that the polymer material and the fiber material or another polymer material are firmly bonded.

In order to bond a polymeric material and a fiber material, it is generally necessary to apply various adhesive surface treatments such as applying an adhesive or RFL treatment to the fiber material. Has been done. In addition, when different kinds of polymer materials are bonded to each other, an adhesive having adhesiveness to both polymer materials is used, but there is often no suitable adhesive, The surface of the polymer material is often subjected to various surface treatments in order to enhance the adhesiveness thereof.

[0004]

However, in these surface treatments, the treatment process is complicated and the adhesiveness cannot be sufficiently improved.

Further, after the surface treatment of the fiber material or the polymer material, strict control is required. Depending on the storage environment after the surface treatment, the surface treatment agent is deteriorated or the surface of the fiber material or the polymer material is changed. In many cases, the treatment agent was peeled off and sufficient adhesiveness could not be secured.

[0006] The present invention has been made in view of the above circumstances, and by providing an adhesive property to a polymer composition,
It is intended to impart strong adhesiveness to fiber materials and other polymer materials without requiring special management.

[0007]

In the adhesive polymer composition of the present invention, the blocked diisocyanate blocked with a substance having an isocyanate group having a functional group is added in an amount of 0.5 to 100 parts by weight of the polymer material. It is characterized by adding 5 parts by weight.

The first method for producing this adhesive polymer composition is as follows: 0.5 to 5 parts by weight of blocked diisocyanate blocked with a substance having an isocyanate group as a functional group, based on 100 parts by weight of the polymer material. Partly added and kneading at a temperature lower than the dissociation temperature of the blocked diisocyanate.

The invention of the masterbatch of the adhesive polymer composition is such that 10 to 50% by weight of blocked diisocyanate blocked with a substance having an isocyanate group as a functional group is added to the polymer material to dissociate the blocked diisocyanate. It is characterized in that it is kneaded at a temperature lower than the temperature.

Further, a second method for producing an adhesive polymer composition is to use a polymer material in which the master batch based on a polymer material which is the same as or different from the polymer material is used as an all polymer material. Block diisocyanate is added in an amount of 0.5 to 5 parts by weight with respect to 100 parts by weight,
The kneading is performed at a temperature lower than the dissociation temperature of the blocked diisocyanate.

Further, the invention of the adhesive polymer molding material comprises a pellet of a polymer material and a pellet of a masterbatch according to claim 3, which is based on a polymer material which is the same as or different from the polymer material. The block diisocyanate is mixed in an amount of 0.5 to 5 parts by weight with respect to 100 parts by weight of the material.

In the invention of the method for adhering a polymer material and a fiber material, 0.5 to 5 parts by weight of a blocked diisocyanate blocked with a substance having an isocyanate group as a functional group is added to 100 parts by weight of the polymer material. The adhesive polymer composition thus obtained is bonded to a fiber material and heated to a temperature higher than the dissociation temperature of the blocked diisocyanate.

The invention of a method for adhering a polymer material to another polymer material is based on 100 parts by weight of the polymer material, and 0.5 to 5 parts by weight of blocked diisocyanate in which an isocyanate group is blocked with a substance having a functional group. It is characterized in that the adhesive polymer composition added in part is joined to another polymer material and heated to a temperature higher than the dissociation temperature of the blocked diisocyanate.

Suitable polymer materials in the present invention are thermoplastic resins such as polyurethane elastomer, nylon, polyester, and natural or synthetic rubber.
Materials with low polarity such as polyolefins are unsuitable.

As the polymer material used as the base of the masterbatch, the above-mentioned materials can be used, but a polyurethane elastomer excellent in miscibility with different polymer materials is suitable.

The blocked diisocyanate used in the present invention is a diisocyanate having two isocyanate groups in which the isocyanate group is blocked with a substance having a functional group to lose the reactivity. When heated to a temperature, it dissociates to generate an isocyanate group and has a property of recovering high reactivity.

As the blocked diisocyanate used in the present invention,

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7] And so on.

The dissociation temperatures of these blocked diisocyanates are as follows. Chemical 1 Approx. 180 ° C Chemical 2 Approximately 140 ° C Chemical 3 Approximately 130 ° C Chemical 4 Approximately 180 ° C Chemical 5 Approximately 140 ° C Chemical 6 Approximately 140 ° C Chemical 7

There are various other blocked diisocyanates having an isocyanate group blocked with a functional group, but the above-mentioned ones are preferable because the dissociation temperature is close to the processing temperature of the polymer material and easy to use.

In the adhesive polymer composition of the present invention, the addition amount of the block diisocyanate is 100
It should be 0.5-5% by weight with respect to parts by weight. In particular, it is preferable to be 1 to 3% by weight.

The amount of the blocked diisocyanate added is 0.
If it is less than 5% by weight, the adhesiveness to the fiber material and the polymer material is poor, and if the addition amount exceeds 5% by weight, not only does it not contribute to the improvement of the adhesiveness, but also a large amount of expensive blocked diisocyanate is used. It is an economy.

When the block diisocyanate is added to the adhesive polymer composition, the block diisocyanate can be directly kneaded into the polymer material, but in order to make the dispersion of the block diisocyanate in the polymer material uniform, a large amount of the block diisocyanate is previously prepared. It is preferable to prepare a masterbatch kneaded in, and mix the masterbatch with a polymer material so that the amount of the blocked diisocyanate with respect to the whole polymer material becomes a predetermined amount.

The amount of the blocked diisocyanate to be added to the masterbatch is preferably about 10 to 50% by weight of the blocked diisocyanate with respect to the polymer material.

In order to produce the adhesive polymer composition of the present invention, a block diisocyanate or a masterbatch is kneaded into the polymer material. It should be kneaded at a temperature below the dissociation temperature.

Therefore, the blocked diisocyanate should be selected so that its dissociation temperature is higher than the melting point of the polymer material. That is, when the block diisocyanate is added to the polymer material, it is necessary to heat the polymer material above its melting point and knead it in a molten state, but the block diisocyanate does not dissociate due to the heat during the kneading, It is necessary to knead into the polymer material while the isocyanate group remains blocked.

When the dissociation temperature of the block diisocyanate is exceeded in the production process of the adhesive polymer composition, the block diisocyanate in the polymer material is dissociated, the blocking of the isocyanate group is released, and the reactivity is exhibited. And reacts with water in the air and loses its reactivity. Therefore, even if an attempt is made to adhere to a fiber material or another polymer material in a later step, the isocyanate group does not contribute to the adhesion and the adhesiveness is lost.

Next, in order to adhere the adhesive polymer composition of the present invention to a fiber material or another polymer material, the adhesive polymer composition is bonded to the fiber material, and the adhesive polymer composition is bonded to the block diisocyanate at a dissociation temperature or higher. Heat to the temperature of.

The fibers that can be bonded according to the present invention can be applied to polyester fibers, polyamide fibers, acrylic fibers, vinylon, etc., but the effect is small for fibers having no polarity such as polyolefin fibers.

The form of the fiber material includes woven cloth, knit,
Various forms such as non-woven fabrics and filamentous materials such as cords can be used.

As the other polymer material which can be adhered by the present invention, synthetic resins such as polyurethane elastomer, nylon and polyester, and natural or synthetic rubber are suitable as well as the base material of the adhesive polymer composition. Is. Also in this case, the polyolefin resin is unsuitable.

As a method for joining the adhesive polymer composition to a fiber material or another polymer material, the sheet-like adhesive polymer composition can be superposed on a woven cloth or the like and joined. Alternatively, the fibrous material or the like may be passed through a head of an extruder, and the adhesive polymer composition may be extruded on the surface of the head to bond the composition.

When the above masterbatch is used, the masterbatch can be kneaded into a polymer material to form an adhesive polymer composition, which can be used for joining with a fiber material or another polymer material. However, as another method of use, the master batch may be formed into pellets, which may be mixed with pellets of a polymer material to form an adhesive polymer molding material.

In the adhesive polymer molding material, the individual pellet particles in the material do not yet constitute the adhesive polymer composition, but by subjecting this to molding such as extrusion molding, The master batch and the polymer material are melted and kneaded uniformly in the machine to form an adhesive polymer composition therein, and at the same time, they are bonded to the fiber material and other polymer materials.

When the adhesive polymer composition and the fiber material are bonded to each other, the block diisocyanate is dissociated by heating to a temperature higher than the dissociation temperature of the block diisocyanate, and the block of the isocyanate group is eliminated. As a result, reactivity is exhibited and the polymer material and the fiber material react with polar groups.

[0035]

In the adhesive polymer composition of the present invention, a blocked diisocyanate is contained, and the isocyanate group in the blocked diisocyanate is blocked by a substance having a functional group. Therefore, the blocked diisocyanate itself is not reactive. I don't have it. Therefore, the adhesiveness is not lost even if the adhesive polymer composition is stored for a long period of time.

When the adhesive polymer composition is bonded to a fiber material or another polymer material and heated to a temperature not lower than the dissociation temperature of the blocked diisocyanate, the bond between the isocyanate group and the functional group in the blocked diisocyanate is bonded. It is dissociated and the block is released to produce an isocyanate group.

Isocyanate groups are extremely reactive,
Since it reacts with many polar groups, it reacts with the polar groups that the polymer material and the fiber material have, and the polymer material and the fiber material are chemically bonded, so that the adhesive strength is improved.

[0038]

According to the present invention, therefore, the polymer material can be bonded to the fiber material or other polymer material extremely firmly, and the time before bonding can be increased as in the conventional surface treatment of the fiber material. The adhesiveness does not decrease with the passage of
The adhesiveness can be maintained for a long period of time.

Further, the present invention can be used in combination with other adhesion improving means such as surface treatment on a fiber material. And thereby, the adhesiveness improving effect by the present invention and the adhesiveness improving effect by the surface treatment etc. are both expressed,
Further, the adhesiveness can be greatly improved.

[0040]

[Embodiment] Polyurethane elastomer (Takeda Badishe, trade name Elastollan ET-370, melting point 135 ° C)
To 80% by weight, 20% by weight of the blocked diisocyanate of Chemical Formula 1 (manufactured by Meisei Chemical Co., Ltd., trade name DMS-3X, dissociation temperature 180 ° C.) is added, and the mixture is kneaded at a temperature of 180 ° C. or lower to form a masterbatch. Got

Next, a polyurethane elastomer, a nylon elastomer and a polyester elastomer are used as a polymer material, and the master batch is added thereto so that the content of the blocked diisocyanate is 2% by weight. 1
The mixture was kneaded at a temperature of 80 ° C. or lower to obtain an adhesive polymer composition.

The polymer materials are as follows. Polyurethane elastomer: Mobilon P-30, manufactured by Nisshinbo Industries
(Melting point approx. 170 ° C) Nylon elastomer: Toray Co., Ltd., Pevax 2533 (melting point
148 ℃) Polyester elastomer: Toyobo Co., Ltd., Pelplan P-
30B (melting point 160 ℃)

This adhesive polymer composition was laminated on a polyester woven fabric and a nylon woven fabric as a fiber material, and heat-pressed to bond them.

The structure of the woven fabric as the fiber material is as follows. Polyester woven warp: 1000d Polyester yarn 50 / inch Weft: 1000d Polyester yarn 28 / inch Organization: Plain weave Nylon woven Warp: 840d Nylon thread 38 / inch Weft: 840d Nylon thread 35 / inch Organization : Plain weave

Further, the above adhesive polymer composition was laminated on a sheet of polyurethane elastomer, nylon elastomer and polyester elastomer, which was another polymer material, and was heated and pressed for adhesion. As the other polymer material, one of the same kind as that described as the polymer material serving as the base of the adhesive polymer composition was used.

The conditions of the heating press at the time of bonding are as follows. Pressing temperature: 185 ° C Pressing pressure: 18.6 kg / cm ₂ Pressing time: After heating for 5 minutes, water cooling down to 50 ° C or less

For comparison, each polymeric material was blended with a polyurethane elastomer to which no blocked isocyanate was added, and this was laminated on the same fiber material and other polymeric material as above, and heat-pressed and bonded under the same conditions. .

The adhesive force between the polymer material and the fiber material was measured for each sample. The test results are shown in Table 1.

[Table 1]

As can be understood from the results shown in Table 1, the polymeric material to which the blocked diisocyanate is added has a high adhesive force to the fiber material and other polymeric materials, and the high adhesiveness of the present invention is high. The molecular composition has excellent adhesion to fiber materials and other polymeric materials.

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Claims (7)

[Claims] 1. A high adhesion property, characterized in that 0.5 to 5 parts by weight of a blocked diisocyanate in which an isocyanate group is blocked by a substance having a functional group is added to 100 parts by weight of a polymer material. Molecular composition 2. 0.5 to 5 parts by weight of a blocked diisocyanate in which an isocyanate group is blocked by a substance having a functional group is added to 100 parts by weight of a polymer material and kneaded at a temperature lower than the dissociation temperature of the blocked diisocyanate. A method for producing an adhesive polymer composition, characterized in that 3. A polymer material, to which 10 to 50% by weight of blocked diisocyanate whose isocyanate group is blocked by a substance having a functional group is added and kneaded at a temperature lower than the dissociation temperature of the blocked diisocyanate. The masterbatch of the adhesive polymer composition 4. The masterbatch according to claim 3, which is based on a polymer material which is the same as or different from the polymer material, is used for the polymer material, and 0.5 parts of the block diisocyanate is added to 100 parts by weight of the whole polymer material. To 5 parts by weight, and kneading at a temperature lower than the dissociation temperature of the blocked diisocyanate, a method for producing an adhesive polymer composition, 5. A pellet of a polymer material and a polymer material which is the same as or different from the polymer material.
Of the masterbatch pellets of 100
Block diisocyanate is 0.5 to 5 parts by weight
Adhesive polymer molding material characterized by being mixed so as to be part by weight 6. An adhesive polymer composition obtained by adding 0.5 to 5 parts by weight of a blocked diisocyanate blocked with a substance having an isocyanate group having a functional group to 100 parts by weight of a polymer material as a fiber material. Bonding and heating to a temperature higher than the dissociation temperature of the blocked diisocyanate, a method for adhering a polymer material and a fiber material 7. An adhesive polymer composition obtained by adding 0.5 to 5 parts by weight of a blocked diisocyanate in which an isocyanate group is blocked by a substance having a functional group to 100 parts by weight of a polymer material. A method for adhering a polymeric material to another polymeric material, characterized by bonding to a molecular material and heating to a temperature higher than the dissociation temperature of the blocked diisocyanate.