JPH0664100A - Rubber/pvc laminate and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a rubber/PVC laminate and a method for manufacturing the same having excellent elasticity and productivity. CONSTITUTION:A rubber/PVC laminate 1 formed by connecting a PVC material 11 to a rubber material 12, and the material 11 contains triazinethiol 10. The thiol 10 contains 0.5-10% (by weight) to 100% of the rubber material. The material 11 is formed by laminating pastelike material on the material 12 while heating to vulcanize it from extrusion molding. The material 11 is laminated on the material 12 while heating to vulcanize it.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber / PVC laminate having excellent elasticity and productivity and a method for producing the same.

[0002]

2. Description of the Related Art Rubber / PVC laminates are used, for example, in weather seals (door trims) and weather strips for automobiles. The door trim has a main body made of a sponge-like rubber material, a mounting base made of a solid rubber material, and a design portion formed thereon (FIG. 2).
reference). The above-mentioned design section is a request for improving the design of automobiles,
Since it is the part that is more visible than the indoor side, it must have a good appearance.

The above-mentioned rubber material is generally excellent in elasticity and is less likely to cause compression set. PVC materials are generally glossy and have excellent decorating properties. It is strongly desired that the design section has a chromatic or black decorative property that is generally vivid and has depth and gloss. However, since the design section is constructed by joining the PVC material to the surface of the rubber material, the PVC material must be joined after extrusion molding of the rubber material.

Conventionally, the following two methods have been proposed as a method for joining a PVC material to the surface of a rubber material. First
In the method (1), after the rubber material is extruded or heated for vulcanization, a primer treatment is applied, an adhesive is further applied, and then the rubber material and the PVC material are joined. Above PV
As the C material, a general-purpose paste-like vinyl chloride resin having adhesiveness is used.

The second method is to paste-form PV on the extruded surface of the attachment base through an intermediate rubber adhesive layer.
C material is coated. Then, in a heating step for vulcanization of the extruded product, the pasty PVC material is heated to gel and the coating layer is decorated in multiple colors. As the intermediate rubber-based adhesive layer, for example, a blend polymer composed of nitrile rubber (NBR), ethylene propylene rubber (EPDM) and styrene polymer is used.

[0006]

However, the above-mentioned conventional technique has the following problems. That is, the first method requires two steps of primer treatment and application of an adhesive. In addition, these processes are complicated because they require extra equipment and a long working time. Therefore, productivity is poor and cost is high. On the other hand, in the second method, the intermediate rubber adhesive layer must be applied to the surface of the rubber material. Therefore, the coating operation is as complicated as the first method and requires extra equipment.

Further, the work of coating the above-mentioned pasty PVC material is also complicated. Therefore, productivity and decoratability may decrease. The present invention has been made in view of such conventional problems, and an object of the present invention is to provide a rubber / PVC laminate excellent in elasticity and productivity and a method for producing the same.

[0008]

The present invention relates to a rubber / PVC laminated body obtained by joining a rubber material and a PVC material, wherein the rubber material contains triazine thiol. On the body.

The triazine thiol has a substituent (R), a mercapto group (-SH) and a mercaptide group (-SM) as shown in FIG. Triazine thiol is generally a volatile liquid and exhibits weak acidity. Among the mercaptide groups (SM), examples of M include alkali metals such as sodium (Na) and potassium (K) or hydrogen (H). Examples of the substituent (R) include an alkyl group, a mercapto group, a vinyl group (-CH = C
H-), alkene group (ethylene hydrocarbon), morphonyl group, diethanolamine group and the like.

Examples of the rubber material include natural rubber (N
R), butyl rubber (IIR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), chloroprene rubber (CR), acrylic rubber (ACM), ethylene-propylene rubber (EPDM), etc. are used.

As the PVC material, for example, a polyvinyl chloride resin composed of soft (containing a plasticizer), foam, and hard (non-plasticizer) is used. As the PVC material, for example, a sheet-shaped, paste-shaped or powder-shaped material is used. In the above, the sheet-shaped polyvinyl chloride resin is molded by, for example, compression lamination molding or calendering.

The rubber / PVC laminate is used as:
For example, there are elastic materials such as door trims for automobiles and weather strips, decorative elastic members for furniture or construction, and mat materials. The triazine thiol is a rubber material 100
% To 0.5% is preferable. If it is less than 0.5%, a sufficient cross-linking reaction is not carried out between the PVC material and the rubber material, and a sufficient bonding force between the two cannot be obtained. On the other hand, even if it exceeds 10%, there is little effect corresponding to it.

As a method for producing the rubber / PVC laminate, a rubber / PV formed by joining a rubber material and a PVC material is used.
In producing the C laminate, a rubber material containing triazine thiol is extruded by a rubber extruder and then heated for vulcanization, and the surface of the rubber material is heated between the extrusion molding and the heating for vulcanization. A rubber / PVC laminate in which a PVC material is laminated and a crosslinking reaction between the rubber material and the PVC material and between the rubber material and the rubber material is performed by the triazine thiol using the heat of the vulcanization heating. There is a body manufacturing method.

Instead of laminating between the extrusion molding and the heating for vulcanization, a PVC material may be laminated on the surface of the rubber material containing triazine thiol during the heating for vulcanization. The triazine thiol is contained in the rubber material. Further, the rubber material may be contained only in the vicinity of the interface with the PVC material. Further, it may be contained in both the rubber material and the PVC material. The above-mentioned heating for vulcanization refers to a heat treatment in which a vulcanizing agent such as sulfur (S) or its compound is added to raw rubber and the mixture is heated at a temperature of about 200 ° C. to form a strong bond between rubber molecules. .

In the present invention, when the above-mentioned heating for vulcanization is carried out, the rubber material and PV
Crosslinking reaction between the C material (see FIG. 5) and the rubber material and the rubber material (see FIG. 6) is caused. Further, when the PVC material also contains triazine thiol, a crosslinking reaction between the PVC material and the PVC material also occurs. To perform the heating for vulcanization, for example, microwave heating, hot air heating or the like is used. This controls the heating time for vulcanization, temperature, and crosslinking reaction.

As a mode of laminating the above PVC material, as shown in Example 1, for example, in the vicinity of the extrusion molding port of a rubber extruder, a PVC material in the form of film, paste or compound is formed on the surface of the rubber material. There is a method of stacking. Examples of the method for laminating the compound-like material include a roll coating method and a spray coating method. In addition, the above PV
As a method for laminating the C material, as shown in Example 2, for example, there is a method in which a paste PVC material is pressure-fed by a pressure feeding device onto a rubber material during lamination between extrusion molding and heating for vulcanization. In addition, as a method for laminating the PVC material,
As shown in Example 3, there is a method in which a PVC material is composite-extruded on the surface of a rubber material during heating for vulcanization, for example. After the heating for vulcanization, a PVC material may be laminated on the rubber material and the cross-linking reaction may be carried out by utilizing the residual heat of the heating for vulcanization.

A rubber material containing the above triazine thiol and P
In the cross-linking reaction with the VC material, the chlorine group of the PVC material,
The hydrogen groups of the triazine thiol transferred to the PVC material side react with each other to dissociate hydrochloric acid. Then, triazinethiol binds to the dehydrochlorinated portion (see FIG. 5). Further, regarding the bond between the rubber material and the triazine thiol, the part where the double bond of the rubber material is dissociated and the part where Na of the triazine thiol is dissociated are combined. As a result, both are crosslinked and bonded.

In the cross-linking reaction between rubber materials, triazine thiol is bonded and cross-linked to the part where the unsaturated group (double bond) of the rubber material is dissociated (see FIG. 6).

When the PVC material also contains triazine thiol, the PVC materials are cross-linked.
In this case, the PVC material does not undergo thermal decomposition and discoloration during vulcanization of the rubber material, and various physical properties such as heat resistance are improved.

[0020]

FUNCTION AND EFFECT In the rubber / PVC laminate of the present invention, the rubber material contains triazine thiol. Therefore, a crosslinking reaction occurs between the rubber material and the PVC material via the triazine thiol. Therefore, the rubber material and the PVC material are firmly joined. Therefore, conventional rubber / PV
Unlike the C laminate, it is not necessary to newly bond it with an adhesive. This improves the productivity of the rubber / PVC laminate. Further, a crosslinking reaction also occurs between the molecules of the rubber material via the triazine thiol. As a result, the rubber materials are firmly joined together. Therefore, the intermolecular bonding force of the rubber material is strengthened, and the elasticity is further improved as compared with the conventional rubber material.

On the other hand, according to the method for producing a rubber / PVC laminate, since the triazine thiol compound is used, the rubber material and the PVC material are bonded in a short time by the crosslinking reaction. Therefore, the PVC material is less likely to be exposed to heating for a long time at the time of joining. Therefore, according to the present invention, it is possible to provide a rubber / PVC laminate excellent in elasticity and productivity and a method for producing the same.

[0022]

【Example】

Example 1 FIG. 1 shows a rubber / PVC laminate and a manufacturing method according to the present invention.
~ It demonstrates using FIG. Rubber / PVC laminate 1 of this example
Is a PVC material 11 and a rubber material 1 as shown in FIGS.
2 is joined and used as a door trim 3 for an automobile.

As shown in FIG. 1, the rubber material 12 includes
Contains triazine thiol 10. Also, PVC
The material 11 contains a coloring material 15. As shown in FIG. 4, the triazine thiol 10 has di propyl amine (DA) [-N (CH
₂ · CH═CH ₂ ) ₂ ], and one having sodium (Na) as the metal group M is used.

The above triazine thiol 10 is the rubber material 1
2% is contained with respect to 00%. PVC material 1
For example, 1 is a solid (soft) material that constitutes the design part of the door trim, and is a transparent and tough polyvinyl chloride resin paste that is excellent in flame retardancy. The PVC material 11 constitutes the design part 34 of the door trim 3.

The solid polyvinyl chloride resin extruded product contains a plasticizer. This improves the elasticity of the rubber / PVC laminate. In addition, the above PVC
The material 11 includes a coloring material 15 such as a yellow-green pigment.
Contains. Therefore, the PVC material 11 exhibits a chromatic color that is fresh and has depth and gloss, and the decorating property is improved.

An extruded product of ethylene / propylene rubber is used as the rubber material 12. The rubber material 12 is classified into two types: soft and sponge-like, and solid and hard. Above P
The interface 13 between the VC material 11 and the rubber material 12 is firmly joined by the crosslinking reaction of the triazine thiol 10, as shown in FIG.

As shown in FIGS. 2 and 3, the door trim 3 comprises a trim body 31, a mounting base 32, a core metal 33, and a design element 34. Mounting base 3 above
2 has a welt portion 321 and a seal lip portion 322. The mounting base 32 is made of solid rubber.
The trim body 31 is made of sponge rubber. The design item portion 34 contains the coloring material 15. The design element 34, the trim body 31, and the mounting base 32 contain the triazine thiol 10. The mounting base 32 is mounted on the mounting panel 35.

In producing the door trim 3,
First, as shown in FIGS. 2 and 7, the trim main body 31,
Attach the mounting base 32 to the core 3 using a crosshead extruder.
Insert 3 and extrude. In addition, FIG. 7 (FIG. 9,
As shown in FIG. 11), the core metal 33 is the rubber extruder 4
In front of 1, the core metal is fed into the rubber extruder 41 by the core feed roller 40. And the above door trim 3
And PVC material 11 are integrally joined by coextrusion molding. That is, as shown in FIG. 7 and FIG.
2 is laminated on the surface of the attachment base 32 (FIG. 2). As a result, the design section 34 (FIG. 2)
To form. After that, in the vulcanization step, the triazine thiol 10 causes the rubber materials 12, the PVC material 11 and the rubber material 12 to be separated from each other as shown in FIGS.
It binds by a crosslinking reaction. Then, as shown in FIG. 3, the design top portion 34 is bent into a predetermined shape.

Here, the manufacturing process of the rubber / PVC laminate 1 is, as shown in FIG. 7, a process of extruding the rubber material 12 using a rubber extruder 41 and a rubber / using a microwave heating device 42. A first vulcanization step of vulcanizing the PVC laminate 1, a second vulcanization step of vulcanizing the PVC laminate 1 using the hot air heating device 43, and a rubber vulcanization of the water cooling device 44.
It comprises a cooling step of cooling the PVC laminate 1 with water and a molding step of molding the PVC trim 1 into the door trim 3 using the molding machine 45.

Here, it should be noted that the rubber material 12 is
As shown in FIG. 7 and FIG. 8, the surface of the extruded product of No. 1 has a paste-like PVC immediately after the extrusion of the rubber material 12.
The material 11 is pressure-fed by the pressure-feeding device 5 to be laminated. As shown in FIGS. 7 and 8, the rubber material 12 continuously extruded from the extrusion port 410 of the rubber extruder 41,
The paste PVC material 11 continuously fed under pressure to the opening of the extrusion molding die 411 is integrally laminated immediately after the extrusion molding. As a result, as shown in FIG.
The rubber / PVC laminate 1 including the C material 1 and the rubber material can be manufactured.

The rubber material 12 contains the triazine thiol 10. Then, as shown in FIG.
By the microwave heating device 42 and the hot air heating device 43,
The crosslinking reaction is performed as described above using the heat of vulcanization heating. Here, as the crosslinking reaction, as shown in FIGS. 5 and 6, the bonding between the PVC material 11 and the rubber material 12 and the bonding between the rubber materials 12 simultaneously occur.

Then, as shown in FIG. 1, a strong bond between the PVC material 11 and the rubber material 12 occurs in the vicinity of the interface 13. Further, in the rubber material 12,
A cross-linking reaction occurs between them. As shown in Figure 7, then
The rubber / PVC laminate 1 is cooled and bent into a predetermined shape (FIG. 3) of the door trim 3. As a result, the rubber / PVC laminate 1 having a strong bonding force can be easily manufactured. Others are the same as the conventional one.

Next, the function and effect will be described. In the rubber / PVC laminate 1 of this example, the rubber material 12 contains the triazine thiol 10. Therefore, rubber material 1
2 and the PVC material are firmly joined. Therefore, it is not necessary to newly bond via an adhesive unlike the conventional case. This improves the productivity of the rubber / PVC laminate 1.

A crosslinking reaction also occurs between the molecules of the rubber material 12 via the triazine thiol 10. As a result, the rubber materials 12 are firmly joined together. Therefore, the intermolecular bonding force of the rubber material 12 is strengthened and the elasticity is improved. Further, the bonding between the rubber material 12 and PVC is performed in a short time by the above-mentioned crosslinking reaction. Therefore, the PVC material 11 is less likely to be exposed to heating for a long time at the time of joining.

When the PVC material 11 also contains triazine thiol, polyene is not produced by the cross-linking reaction between the PVC materials 11. The reason is PVC
This is because the zipper reaction due to the unstable heterogeneous structure due to the imperfect polymerization in the material 11 does not occur. This allows PV
The C material 11 does not cause thermal decomposition or discoloration during heating of the rubber material 12 for vulcanization.

Example 2 In this example, as shown in FIGS. 9 and 10, immediately after extrusion molding of the rubber material 12 in the above Example 1, a paste-like PVC was used.
Instead of laminating the material 11, the paste PVC material 11 is laminated on the rubber material 12 between the high-frequency heating device 42 of the first vulcanizing step and the hot air heating device 43 of the second vulcanizing step. It is a thing. In addition, triazine thiol 10 is shown in FIG.
As shown in 0, it is contained in 5% with respect to 100% of the rubber material.

As shown in FIG. 10, the rubber / PVC laminate 1A comprises an extruded rubber material 12 and a PVC material 11 laminated on the surface thereof. PVC material 11
Is a microwave heating device 4 as shown in FIGS.
The rubber material 12 sent out from the sheet 2 is laminated on the surface and joined. From the outlet opening 420, the rubber material 12 is
It is sent by the molding machine 45 onto the sending roll 46.

As shown in FIGS. 9 and 10, the PVC material 11 is made of a paste material and has a relatively low viscosity, so that it is sprayed onto the rubber material 12 by the spray nozzle 60. The spray nozzle 60 has a pressure feeding pipe 61 connected to the pressure feeding device 6 (FIG. 9). Others are the same as in the first embodiment. As described above, according to this example, PV is applied to the surface of the rubber material 12 sent from the high frequency heating device 42.
Since the C material 11 is laminated, the PVC material 11 is not exposed to heating for a long time. Therefore, thermal decomposition and discoloration of PVC are reduced. Therefore, it is possible to easily obtain the rubber / PVC laminate 1A which is excellent in productivity and elasticity, and has little PVC thermal decomposition and discoloration. Further, the same effect as that of the first embodiment can be obtained.

Example 3 In this example, as shown in FIGS. 11 and 12, instead of the PVC material 11 in the above Example 2, a PVC was used from the second extruder 7.
Sheet material of material 11 is extruded, and rubber material 12 is PVC
The material 11 is subjected to composite extrusion molding.

Triazine thiol 10 is contained in an amount of 4% based on 100% of the rubber material. Therefore, as in Example 1, a cross-linking reaction occurs between the PVC material 11 and the rubber material 12 (see FIG. 5). In the production of the rubber / PVC laminate 1B, as shown in FIG. 12, the rubber material 12 sent out by the microwave heating device 42, as in Example 2, was
PVC extruded from the extrusion molding port 70 of the second extruder 7.
The material 11 is laminated. The PVC material 11 contains a coloring material 15.

Then, as shown in FIG. 11, the PVC material 11 and the rubber material 12 are joined by being heated by the hot air heating device 43 to cause a crosslinking reaction by the triazine thiol 10. Others are the same as those in the second embodiment. Therefore, it is possible to obtain the rubber / PVC laminate 1B which is as excellent in productivity and elasticity as in Example 2 and has little PVC thermal decomposition and discoloration. Further, the same effect as that of the second embodiment can be obtained.

[Brief description of drawings]

FIG. 1 is a perspective view of a rubber / PVC laminate according to a first embodiment.

FIG. 2 is a perspective view showing a state before molding of a door trim using the rubber / PVC laminate in Example 1.

FIG. 3 is a perspective view showing a usage state of a door trim in the first embodiment.

FIG. 4 is an explanatory view showing the chemical formula of triazinethiol in Example 1.

5 is an explanatory view showing a co-crosslinking reaction between a PVC material and a rubber material in Example 1. FIG.

FIG. 6 is an explanatory diagram showing a crosslinking reaction between rubber materials in Example 1.

FIG. 7 is a manufacturing process diagram of the rubber / PVC laminate according to the first embodiment.

FIG. 8 is a partially cutaway perspective view in the vicinity of an extrusion molding port of a rubber extruder in Example 1.

FIG. 9 is a manufacturing process diagram of the rubber / PVC laminate in Example 2.

FIG. 10 shows PVC on the surface of the rubber material in Example 2.
The perspective view which shows the state which laminates a material.

FIG. 11 is a manufacturing process diagram of the rubber / PVC laminate according to the third embodiment.

FIG. 12 is a perspective view showing composite extrusion molding of a PVC material and a rubber material in Example 3.

[Explanation of symbols]

 1, 1A, 1B. ． ． Rubber / PVC laminate, 10. ． ． Triazine thiol, 11. ． ． PVC material, 12. ． ． Rubber material, 3. ． ． Door trim, 41. ． ． Rubber extruder, 42. ． ． Microwave heating device, 43. ． ． Hot air heating device, 44. ． ． Water cooling device, 45. ． ． Molding machine, 6. ． ． Pump,

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // B60R 13/06 B29K 21:00

Claims (4)

[Claims] 1. A rubber / PVC laminate formed by joining a rubber material and a PVC material, wherein the rubber material contains triazine thiol. 2. The triazine thiol according to claim 1, wherein the content of triazine thiol is 0.
Rubber / PV containing 5 to 10%
C laminate. 3. In producing a rubber / PVC laminate obtained by joining a rubber material and a PVC material, a rubber material containing triazine thiol is extruded by a rubber extruder and then heated for vulcanization. At the same time, a PVC material is laminated on the surface of the rubber material between the extrusion molding and the heating for vulcanization, and the heat of the vulcanization heating is used to form the rubber material and the PVC material and the rubber material and the rubber material by the triazine thiol. A method for producing a rubber / PVC laminate, which comprises causing a crosslinking reaction between the rubber and PVC. 4. When manufacturing a rubber / PVC laminate obtained by joining a rubber material and a PVC material, a rubber material containing triazinethiol is extruded by a rubber extruder and then heated for vulcanization. At the same time, a PVC material is laminated on the surface of the rubber material during the heating for vulcanization, and the heat of the heating for vulcanization is used to combine the rubber material with the PVC material and the rubber material with the triazine thiol. A method for producing a rubber / PVC laminate, which comprises causing a crosslinking reaction between the two.