JPH06106684A - Production of rubber/pvc laminate - Google Patents

Abstract

PURPOSE:To obtain a rubber/PVC laminate excellent in decorativeness and productivity without generating the running, thermal decomposition and discoloration of PVC by adding triazine thiol to at least one of a PVC material and a rubber material and using the PVC material as paste. CONSTITUTION:Triazine thiol is preliminarily added to at least one of a PVC material 11 and a rubber material 12. The rubber material 12 is subjected to extrusion molding by a rubber extruder and the extrudate is vulcanized under heating while the paste of the PVC material 11 is laminated to the surface of the rubber material 12 in the vicinity of the cap of the rubber extruder 41 and the crosslinking reaction between both materials is performed by triazine thiol using vulcanizing heat. The paste of the PVC material 11 is pref. set to a high viscosity state of 5000-20000cps. By this method, a rubber/PVC laminate excellent in decorativeness and productivity is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a rubber / PVC laminate which is free from sagging, thermal decomposition and discoloration of PVC (polyvinyl chloride), and which is excellent in decorativeness and productivity.

[0002]

2. Description of the Related Art Rubber / PVC laminates are used, for example, in door moldings, weather seals (door trims), weather strips, etc. for automobiles. The door trim has a main body made of a sponge-like rubber material, a mounting base portion made of a solid rubber material, and a design top portion formed thereon. The above design top is a request for improvement of the design of the automobile,
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 top of the design has a chromatic or black decorative property that is generally bright and has depth and gloss. However, since the design top is formed by joining the PVC material to the surface of the rubber material, the PVC material must be joined after the 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 operation of coating the above-mentioned pasty PVC material is also complicated, and the PVC material may sag, or the PVC may be thermally decomposed and discolored during heating for vulcanization. Therefore, the decorativeness may be reduced. The PVC material has a property of easily causing thermal decomposition and discoloration of PVC when heated at about 180 ° C. for about 5 minutes. The present invention has been made in view of such conventional problems, and PV
An object of the present invention is to provide a method for producing a rubber / PVC laminate, which does not cause sagging of C, thermal decomposition and discoloration, and is excellent in decorativeness and productivity.

[0008]

According to the present invention, in producing a rubber / PVC laminate formed by joining a rubber material and a PVC material, at least one of the rubber material and the PVC material contains triazinethiol in advance. The rubber material is extruded by a rubber extruder and then heated for vulcanization, and a paste of PVC material is laminated on the surface of the rubber material in the vicinity of the die of the rubber extruder to heat the vulcanization heat. A method for producing a rubber / PVC laminate is characterized in that the triazine thiol is used to cause a crosslinking reaction between a rubber material and a PVC material.

What is most noticeable in the present invention is P
At least one of the VC material and the rubber material contains triazine thiol, and the PVC material is a paste. As shown in FIG. 2, the triazinethiol has a substituent (R) and a mercapto group (-S).
H) and a mercaptide group (-SM). 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 = CH-), an alkene group (ethylene hydrocarbon), a morphonyl group, and a diethanolamine group.

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 paste compound (plastisol) composed of soft (containing a plasticizer) and hard (non-plasticizer) is used. Also,
The PVC material is made into a highly viscous paste by adding a thickener. That is, a thickening agent is added to the PVC material to make it into a high-viscosity paste. Then, this paste is laminated on the surface of the rubber material.

The high viscosity state is, for example, 5000 to
The state of 20000 cps is preferable. When the viscosity of the above paste is less than 5000 cps, sagging occurs during heating, and the handling and workability of the PVC material deteriorates.
On the other hand, when it exceeds 20000 cps, it becomes a gel state or a solidified state, and the handling and workability of the PVC material deteriorates.

As a method for laminating the above-mentioned paste on the surface of the rubber material, a PVC material is pressure-fed by a paste pressure-feeding device in the vicinity of the die of the rubber extruder, and the PVC material is extruded and molded on the surface of the rubber material. There is a method of coating. Applications of the rubber / PVC laminate include elastic sealing materials such as door moldings, door trims, weather strips for automobiles, decorative elastic members for furniture or construction, mat materials and the like.

The above triazine thiol is a rubber material or P
It is preferable that the content of the VC material is 0.5 to 10% with respect to 100%. 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.

The triazine thiol is a rubber material or P
Either one of the VC materials or both the PVC material and the rubber material is contained. 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, during the heating for vulcanization, the rubber material and P are mixed with the triazine thiol in the PVC material.
VC material (see FIG. 3), PVC material and PVC material (see FIG. 4)
A cross-linking reaction between Further, when triazine thiol is also contained in the rubber material, a crosslinking reaction between the rubber material and the rubber material also occurs (see FIG. 5). To perform the heating for vulcanization, for example, microwave heating, hot air heating or the like is used. As a result, the heating time for vulcanization, temperature,
Control the crosslinking reaction.

In the crosslinking reaction between the PVC material and the rubber material by the above triazine thiol, the chlorine group of the PVC material and the hydrogen group of the triazine thiol react to dissociate hydrochloric acid. Then, triazinethiol binds to the dehydrochlorinated portion (see FIG. 3). 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, the two are crosslinked and bonded.

Further, in the cross-linking reaction between the PVC material and the PVC material, triazine thiol is bonded to the portion where the unsaturated group (double bond) of the PVC material is dissociated and cross-linked (FIG. 4).
reference). In addition, when the rubber material also contains triazine thiol, the rubber materials are cross-linked (FIG. 5).

[0020]

In the method for producing a rubber / PVC laminate of the present invention, at least one of the rubber material and the PVC material contains triazine thiol. Therefore, a crosslinking reaction occurs between molecules of the rubber material and the PVC material via the triazine thiol. Therefore, the molecules of the rubber material and the PVC material are firmly bonded to each other, and thermal decomposition and discoloration of the PVC do not occur unlike the conventional rubber / PVC laminate. In addition, polyene is not produced in the cross-linking reaction of PVC material. The reason is that the zipper reaction due to the unstable heterogeneous structure due to the imperfect polymerization in the PVC material does not occur.

Therefore, the decorating property and heat resistance of the PVC material are improved. Here, the term "decorative effect" means that a coloring material such as a pigment or a dye is added to a PVC material to give a vivid, deep or glossy chromatic or achromatic color (black, gray, etc.) to exert a decorative effect. Refers to the nature of Moreover, since the PVC material is excellent in bonding strength and heat resistance, weather resistance and durability are improved.

In the heating process for vulcanization,
Through the triazine thiol, the rubber material and PVC
A co-crosslinking reaction occurs between molecules with the material. As a result, the rubber material, the PVC material, and the materials are firmly joined together. Therefore, unlike the conventional example, when joining the rubber material and the PVC material, it is not necessary to apply an adhesive for joining the both. This improves the productivity of the rubber / PVC laminate.

The PVC material is a paste in a highly viscous state, which is laminated on the surface of the rubber material. Therefore, the PVC material can be easily laminated, and the handling and workability of the PVC material is improved. In addition, unlike the conventional general-purpose paste PVC material, the PVC material does not sag when laminated. Moreover, the paste of PVC material can be easily coated and laminated on the surface of an extruded product having a complicated shape having an irregular cross section or the like. Therefore, according to the present invention, it is possible to provide a method for producing a rubber / PVC laminate, which is free from sagging, thermal decomposition and discoloration of PVC, and is excellent in decorativeness and productivity.

[0024]

【Example】

Example 1 FIG. 1 to FIG.
This will be described with reference to FIG. As shown in FIG. 1, the rubber / PVC laminate 1 produced by the method of this example is made of PVC material 1
1 and the rubber material 12 are joined together. The layered body is firmly bonded at its interface 13 by a crosslinking reaction.

As shown in FIG. 1, the PVC material 11 and the rubber material 12 contain triazine thiol 10. Further, the PVC material 11 contains a coloring material 15. As shown in FIG. 2, the triazine thiol 10 has a dipropyl amine (D
A) [—N (CH ₂ .CH═CH ₂ ) ₂ ], which has sodium (Na) as the metal group M, is used.

The triazine thiol 10 is contained in an amount of 3% based on 100% by weight of the PVC material (hereinafter the same). Also, triazine thiol 10 is 100% rubber material
In contrast, 2% is contained. As shown in FIGS. 1 and 7, the triazine thiol 10 is contained in both the PVC material 11 and the rubber material 12, respectively.

The PVC material 11 contains a plasticizer. This improves the elasticity of the rubber / PVC laminate. Further, the PVC material 11 contains a coloring material 15 such as a yellow-green pigment. Therefore, PV
The C material 11 exhibits a fresh, deep and glossy chromatic color, and the decorating property is improved. As the rubber material 12, ethylene
An extruded product of propylene rubber is used. Also, rubber material 1
There are two types of soft (soft) sponge (foam) and solid (hard).

The manufacturing process of the rubber / PVC laminate 1 is, as shown in FIG. 6, a process of extruding the rubber material 12 using the rubber extruder 41, a process of laminating the PVC material 11, and a micro process. First vulcanization step of vulcanizing the rubber / PVC laminate 1 using the wave heating device 42, second vulcanization step of further vulcanizing the rubber / PVC laminate 1 using the hot air heating device 43, and water cooling A cooling step of cooling the rubber / PVC laminate 1 with water using the device 44.

Here, it should be noted that the rubber material 12 is
As shown in FIGS. 6 and 7, on the surface of the extruded product of FIG.
That is, the paste of the C material 11 is pressure-fed and supplied, and the paste is coated on the surface of the rubber material 12 to be laminated. That is, as shown in FIGS. 6 and 7, the rubber material 1 continuously extruded from the extrusion port 410 of the rubber extruder 41.
The paste of the PVC material 11 is continuously supplied to the surface of No. 2 to the die 411 of the rubber extruder 41, and is integrally pressure-bonded.

The PVC material 11 and the rubber material 12 contain the triazine thiol 10. Then, as shown in FIG. 6, by the microwave heating device 42 and the hot air heating device 43, the crosslinking reaction is carried out as described above using the heat of heating for vulcanization. Here, as the crosslinking reaction, as shown in FIGS. 3 to 5, the PVC material 11 and the rubber material 12 are used.
And the PVC materials 11 and the rubber materials 12 are simultaneously bonded. Others are the same as the conventional one.

Next, the function and effect will be described. In the method for manufacturing the rubber / PVC laminate 1 of this example, the rubber material 1
2, Both PVC materials 11 contain triazine thiol 10. Therefore, with respect to the PVC material 11, first, as shown in FIG. 4, a crosslinking reaction occurs between the molecules of the PVC material 11 via the triazine thiol 10. As a result, the molecules of the PVC material 11 are strongly bonded to each other, and the conventional P
It does not cause thermal decomposition and discoloration unlike VC materials.

Further, as shown in FIG. 4, polyene is not produced in the cross-linking reaction between the PVC materials 11. The reason is that the zipper reaction due to the unstable different structure due to the imperfect polymerization in the PVC material 11 does not occur. Therefore, the decorating property and heat resistance of the PVC material 11 are improved.
Here, the decorating property means, for example, when a coloring material 15 such as a yellow-green pigment is added to the PVC material 11, it is colored in a vivid, deep or glossy chromatic color, that is, a vivid yellow-green color, and decoration It is a property to which sex is added. Also,
Since PVC material 11 has excellent bonding strength and heat resistance,
Improves weather resistance and durability.

Further, as shown in FIG. 3, the PVC material 11 and the rubber material 12 are intervened via the triazine thiol 10.
A cross-linking reaction also occurs between the molecules. As a result, the PVC material 11 and the rubber material 12 are firmly joined. Therefore, unlike the conventional example, it is not necessary to apply an adhesive when joining the PVC material 11 and the rubber material 12. This improves the productivity of the rubber / PVC laminate 1. Also, PVC
The material 11 is a high-viscosity paste, which is laminated on the surface of the rubber material 12. Therefore, PV at the time of stacking
The handling property and workability of the C material 11 are improved. Further, unlike conventional general-purpose paste PVC materials, there is no sagging during lamination.

Example 2 In this example, as shown in FIGS. 8 and 9, a paste of a PVC material 11 forming a PVC material design top 21 was laminated on a rubber material 12 in order to manufacture a door molding 2 for an automobile. To do. Moreover, the triazine thiol 10 is contained only in the PVC material 11. The triazine thiol 10 is contained in 5% with respect to 100% of PVC material.

The door molding 2 is, as shown in FIG.
PVC material top 21 and rubber molding 22
And consists of. The molding body 22 has a mounting recess groove 220.
And a welt portion 222 and a seal lip portion 223. The mounting recessed groove 220 has a protrusion 224.

The molding body 22 is made of a solid rubber material. The PVC material design top 21 is made of a coloring material 15
Contains. Further, as shown in FIG. 9, the rubber extruder 41 has a die 5 near the extrusion port. Base 5
Has a paste inflow port 51, a paste outflow port 52, a paste coater section 53, and a rubber material extrusion port 54.
In the figure, reference numeral 50 is a base body, and 55 is a mounting nut.

In manufacturing the door molding 2,
As shown in FIG. 9, the rubber extruder 41 is used. First, the rubber material 12 is extruded from the rubber material extrusion port 54. Next, the paste of the PVC material 11 is laminated on the surface from the paste outlet 52, and then heating for vulcanization is performed.

Here, the PVC material 11 containing the triazine thiol 10 is a paste in a high viscosity state of about 10,000 cps. Then, the paste flowing out from the paste outlet 52 is easily laminated on the rubber material 12. Then, a film of the PVC material 11 is formed on the surface of the rubber material 12. Others are the same as in the first embodiment. According to this example, a door molding for an automobile can be easily obtained. Further, the same effect as that of the first 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 an explanatory view showing a chemical formula of triazinethiol in Example 1.

FIG. 3 is an explanatory view showing a co-crosslinking reaction between a PVC material and a rubber material in Example 1.

FIG. 4 is an explanatory diagram showing a cross-linking reaction between PVC materials in Example 1.

5 is an explanatory view showing a crosslinking reaction between rubber materials in Example 1. FIG.

FIG. 6 is a manufacturing process diagram of the rubber / PVC laminate according to the first embodiment.

FIG. 7 is a schematic view of the vicinity of an extrusion molding port of a rubber extruder in Example 1.

FIG. 8 is a front view of a mouthpiece attached to a rubber extruder according to a second embodiment.

FIG. 9 is a perspective view showing a state in which a paste of PVC material is laminated on the surface of a rubber material in the second embodiment.

[Explanation of symbols]

 1. ． ． Rubber / PVC laminate, 10. ． ． Triazine thiol, 11. ． ． PVC material, 12. ． ． Rubber material, 2. ． ． Door mall, 4. ． ． Pressure feeding device, 41. ． ． Rubber extruder, 42. ． ． Microwave heating device, 43. ． ． Hot air heating device, 44. ． ． Water cooling device, 5. ． ． Clasp,

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location B32B 25/08 27/18 Z 6122-4F 27/30 101 8115-4F // B29K 21:00 27 : 06 105: 24 B29L 9:00 4F

Claims (3)

[Claims] 1. When manufacturing a rubber / PVC laminate obtained by joining a rubber material and a PVC material, the above rubber material and PV
At least one of material C contains triazine thiol in advance, the rubber material is extruded by a rubber extruder, then heated for vulcanization, and at the same time, the PVC material is attached to the surface of the rubber material near the mouth of the rubber extruder. 2. A method for producing a rubber / PVC laminate, which comprises laminating the paste of claim 1 and performing a crosslinking reaction between the rubber material and the PVC material with the triazine thiol using the heat of the vulcanization heating. 2. The triazine thiol according to claim 1, wherein the rubber material or PVC material is 100% (weight ratio, hereinafter the same).
0.5 to 10% is contained in the rubber / PVC laminate. 3. The method for manufacturing a rubber / PVC laminate according to claim 1, wherein the PVC material paste is 5000 to 20000 cps.