JPS582830B2 - Synthetic resin sheet for covering roofs of automobiles, etc. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel synthetic resin sheet for covering roofs of automobiles, etc.

Conventionally, the roofs of automobiles, especially passenger cars, have been mainly made of iron plates with baking paint applied to the surface, but there are also other types of roofs that have PVC leather pasted instead of painting. It is used.

Vinyl chloride leather for roof coverings is called top leather, and cars covered with this leather are especially called leather top leather.

Since this top leather is literally attached to the top of a car, that is, the roof, it must withstand extremely harsh conditions.

In other words, excellent weather resistance is required due to constant exposure to the sun, rain, and snow, and there is no change in quality or size such as shrinkage due to the intense heat of summer, and detergents used during car cleaning and maintenance. In particular, chemical resistance against waxes, cleaners, etc. is required.

In this regard, conventional roof coverings do not meet these performance requirements, but may cause discoloration and shrinkage due to thermal deterioration, shrinkage and peeling, surface whitening and minute cracks due to weather deterioration due to sunlight exposure, rain, snow, etc. Cleaners, waxes, detergents, etc. caused hardening, whitening, and cracking, which deteriorated the aesthetic appearance within a short period of time and required replacement.

In view of these current circumstances, the present invention has developed a synthetic resin sheet for covering the roofs of tractors, etc., which does not have any of these drawbacks.An example of its implementation will be explained with reference to the drawings.The back amplifier layer 1 is made of vinyl chloride. This is a soft vinyl chloride resin layer based on a composition in which resin is the main component and 30 parts or more of an acrylic rubber modifier is added to 100 parts of the main component.

Examples of acrylic rubber modifiers include Kanesu FM manufactured by Kanebuchi Chemical Industry Co., Ltd. and Kureha HIA-12 manufactured by Kureha Chemical Industry Co., Ltd.
5. HIA-28, Mitsubishi Rayon ■Metablen W-
300, Pararoid KM-3 manufactured by Rohm and Harness Co., Ltd.
23B, Paraloid KM-350, Hitachi Chemical's Pitacs 4000, etc., and these are mainly processing aids,
Although it is used in the range of 5 to 10 parts for impact modification (particularly with weather resistance), in the present invention, such a modifier is used as a component of the soft vinyl chloride formulation, and moreover, it is added in an amount of 30 parts or more. It shows excellent application as a synthetic resin sheet for roof covering in a range of quantities.

In that case, any type of plasticizer used for softening was effective.

For example, when a monomolecular weight plasticizer such as di-isodecyl phthalate is used, if the amount of acrylic rubber modifier is about 25 parts, the improvement of the volatilization loss and the residual elongation after the entrapment exposure test will be reduced. No significant improvement effect was observed, but when the amount added was 30 parts or more, a significant improvement effect was seen on these properties.
Ru.

This improvement effect is extremely remarkable even when a high molecular weight plasticizer is used.

In the synthetic resin sheet for roof covering of the present invention, a transparent synthetic resin thin film 3 is laminated on the surface of the backup layer 10 having such characteristics with or without an adhesive 2 interposed therebetween.

The transparent synthetic resin thin film 3 not only protects the backup layer 1 (maintains physical properties, etc.), but also prevents the adhesion and accumulation of dust and smoke, or makes it less noticeable, and has a structure that has not been seen in conventional top leather. It has become.

This transparent synthetic resin thin film 3 is a fluorine-based synthetic resin film,
Acrylic films and soft vinyl chloride films are suitable.

The technical requirements for selecting these films were that the film itself should have ■ excellent weather resistance, ■ good weather resistance, and ■ suppression of exudation and volatilization of components contained in the backup layer such as plasticizer. Good adhesion with backup layer■
Easy to handle.

It has various performances such as.

In this respect, all of the above three types of films satisfy these various properties and are suitable for use in the present invention.

Examples of fluorine-based synthetic resin films include DuPont's Tedlar film (polymerized vinyl), Asahi Glass Co., Ltd.'s Afflex film (47-ethylene ethylene copolymer), and Daikin Industries' Neoflon film (polymerized ethylene copolymer). Copolymers of ethylene and 67-propylene) and Daiflon film (37-chloroethylene resin) are suitable.
As the acrylic film, Sunduren film manufactured by Kanekabuchi Chemical Co., Ltd. and Acryprene film manufactured by Mitsubishi Rayon Co., Ltd. are suitable.

The thickness of the film is 0.0125 to 0.0 in all cases.
A diameter of about 5m/m is good.

Although all of these films are commercially available, there are no examples of their use in synthetic resin sheets for covering the roofs of vehicles as in the present invention.

Furthermore, in the case of soft vinyl chloride resin films, there are no commercially available products suitable for the use of the present invention, and they are manufactured using original designs.

In this case, the following points must be kept in mind: ■ In order to maintain the durability of the film itself, the plasticizer is mainly a high molecular weight plasticizer. ■ As an ultraviolet absorber, it has excellent ultraviolet absorption performance. In addition to the fact that it is durable, point 02 is also important: it has excellent durability when placed in a high-temperature environment for a long time, that is, it has excellent heat resistance.

As the high molecular weight plasticizer, Adeka Sizer PN-150, -220, -250, -260 manufactured by Adeka Argus Co., Ltd.
, -270, -350, -400, -650, -800
With molecular weight is suitable.

In addition, as a UV absorber, nickel dibutyl dithiocarbanote (manufactured by Inunai Shinko Co., Ltd.: Nocrac NBC
), 2,6-di-t-butyl-p-cresol (same, N
ocrac 2Q0), 4,4'-thiobis(3-methyl-6-t-butylphenol) (Nocra
c 300), 2,2'-methylenebis(4-methyl-6-t-butylphenol) (Nocrac
NS-6), 2(2'-hydroxy-3', 5'-di-t-butylphenol)-5-chlorobenzotriazole (Tinuvin327, manufactured by Ciba Geigy Japan)
), 2-hydroxy-4-methoxy penzophenone (
Sumisorb 110) manufactured by Sumitomo Chemical Co., Ltd. 2-Hydroxy-4-n-octylbenzophenone (Sum
isorbl30), 4-t-butyl phenyl salicylate (T-B-S manufactured by Inu Nippon Ink Chemical Co., Ltd.), 2.2
'-Dihydroxy-4-methoxybenzophenone (Cgasorb UV-24 manufactured by American Cyanamid)
, etc. are used, but penzophenone-based ones are particularly suitable in terms of both ultraviolet absorption performance and heat resistance.

In the case of a soft vinyl chloride resin film, it is necessary to make it relatively thick, and the thickness is about 0.1 to 0.20%.

When such a film 3 is laminated on the backup layer 1, a thermocompression bonding method and an adhesive method are used. However, in the case of acrylic film and soft vinyl chloride resin film, they are of a heat activated type, so the film 3 and Lamination is performed by heating both the bank-up layers 10 and pressing them between pressing rolls, but in the case of the fluorine-based film 3, since it does not have such thermocompression bonding properties, adhesive 2 is used to bond them.

The adhesive 2 used in this case is an acrylic or urethane adhesive, and a heat-activated adhesive is suitable.

That is, after coating the adhesive 2 on the backup layer 1, it is heated and dried to completely volatilize the solvent, and then
This is heated again (if the heating continues, the heated state remains) to activate the adhesive layer, and the adhesive layer is suitably pressed and laminated between the same pressing rolls as above.

The synthetic resin sheet for roof covering of the present invention can be used in a three-layer or two-layer structure consisting of a transparent synthetic resin film (adhesive layer) and a back-up layer as described above, but it can also be used in the form of a three-layer or two-layer structure consisting of a transparent synthetic resin film (adhesive layer) and a back-up layer. , and a backing material 4 such as gold cloth or stockinette cloth is laminated for the purpose of ease of handling, prevention of unnecessary stretching (which causes shrinkage after construction), and prevention of shrinkage during long-term use. There is also.

In this case, when manufacturing the bank-up layer 1 by rolling, a method is used in which the bank-up layer 1 is crimped and laminated with a base fabric that has been glued in advance.

The presence of such a base fabric is effective when considering the lamination of the transparent film 3 or the application of the adhesive 2 and the lamination of the film 3 in a later process.

Usually, such a synthetic resin sheet for roof covering is coated with a pressure-sensitive adhesive on its two back sides, that is, on the back side of the backup layer 1, either directly or through a nonwoven fabric as a cushioning material, and through a backing material 4 to prevent spreading and shrinkage. The product is coated with release paper and sent to automobile manufacturing lines, and then sold at gas stations and auto parts stores in the city.

Since this pressure-sensitive adhesive is mainly composed of alkivinyl ether resin and other rubber components, and is mixed with a large amount of plasticizer and adhesive, the influence of this pressure-sensitive adhesive layer on the back-up layer cannot be overlooked.

If the quality design of the backup layer is poor, the backup layer will swell or shrink due to the influence of the adhesive layer, but the synthetic resin sheet for roof covering of the present invention will not cause such problems. There is no need to worry.

In addition, the surfaces of these synthetic resin sheets for roof covering, that is, the three sides of the transparent synthetic resin thin film, may optionally be provided with various concave and convex patterns in order to enhance the decorativeness, but in this case, 0.0
Since an extremely thin film with a thickness of 125 to 0.05 m/m is used or a soft vinyl chloride resin film is used, squeezing is easy. Since it is laminated without any inclusions, it will not bubble or swell due to heating during squeezing.

Next, specific embodiments of the present invention will be explained in detail with reference to Examples.

Examples 1 to 7 According to the formulation shown in Table 1, using a heating roll at 165°C,
The sheet has a thickness of 0.45 m/m.

After heating this sheet in a heating gear oven at 120° C. for 14 days, the volatilization loss and elongation rate are measured.

As a result, in Examples 1 to 5, the volatilization loss was 70 to 80 g/m.
In contrast, in Examples 6 and 7 in which the amount of the acrylic rubber modifier was 30 parts or more, the amount was 50 g/m2 or less, showing extremely excellent volatility resistance.

Also, in terms of elongation, when the acrylic rubber modifier is 20 parts or less as in Examples 1 to 5, the elongation rate is only 60% or less, but in Examples 6 and 7, the elongation is as high as 180 to 200%. The rate was shown.

The results are shown in the lower column of Table 10 and FIG.

Examples 8 to 12 Using the formulations shown in Table 2, sheeting was performed in the same manner as in Examples 1 to 7, and the same tests were conducted, resulting in the measurement results shown in the lower column of Table 20.

According to this, in the case of a combination of an acrylic rubber modifier and a polyester plasticizer, Example 8 does not contain the modifier amount.
In Example 9 and IO in which 30 parts and 40 parts of the modifier were added, there was not much difference in the volatilization loss, but there was a significant difference in elongation rate.

A similar tendency is observed when a polymer such as an EVA-based permanent plasticizer is used, and the elongation rate is different between Example 11 where the acrylic rubber modifier is 20 parts and Example 12 where the acrylic rubber modifier is 30 parts. The difference was more than double.

Example 13 A backup layer was prepared according to the formulation of Example 10, and each film shown in Table 3 was laminated on the surface thereof under the specified conditions, and then each test shown in Table 3 was conducted.

As shown in Example 1-13, (1) As for the backup layer, no matter what kind of plasticizer or the like, if it contains 30 parts or more of an acrylic rubber modifier, the volatilization loss and the roughness rate after heating are 20. This performance is significantly improved compared to the 40 parts and 50 parts, but this performance gradually increases as seen between 20 and 30 parts.

■ This tendency is also seen when a transparent synthetic resin thin film is applied.

(2) As the transparent synthetic resin thin film, a soft vinyl chloride film containing acrylic, fluorine, and an ultraviolet absorber and in which 90% or more of the plasticizer is a high molecular weight plasticizer is suitable.

I understand that.

These sheets are extremely suitable for use as roof covering sheets for automobiles, and the results of actual vehicle tests were consistent with the overall evaluation results.

[Brief explanation of drawings]

The drawings show an example of the implementation of the synthetic resin sheet for covering roofs of automobiles, etc. of the present invention. Fig. 1 is a cross-sectional view, and Fig. 2 shows the volatilization loss and residual amount with respect to the amount of acrylic rubber modifier added to the backup layer. This is a table showing the roughness ratio, and in the figure, 1 is a backup layer, 2 is an adhesive, 3 is a transparent synthetic resin thin film, and 4 is a backing material.

Claims (1)

[Claims] 1. The backup layer is a soft vinyl chloride resin containing 30 parts or more of an acrylic rubber modifier based on 100 parts of the soft vinyl chloride resin, and the surface of the backup layer is coated with or without an adhesive. A synthetic resin sheet for covering the roofs of automobiles, etc., which is made by laminating a transparent synthetic resin thin film on top. 2. A synthetic resin sheet for covering roofs of automobiles, etc., as set forth in claim 1, wherein the transparent synthetic resin thin film is a fluorine-based synthetic resin film. 3. A synthetic resin sheet for covering the roof of an automobile or the like as set forth in claim 1, wherein the transparent synthetic resin thin film is an acrylic resin film. 4. A synthetic resin for roof coverings of automobiles, etc. as set forth in claim 1, wherein the transparent synthetic resin thin film is a soft vinyl chloride resin film in which 90% or more of the plasticizer contained is a high molecular weight plasticizer. sheet.