JPH0647627B2 - Soft polyvinyl chloride resin waterproof sheet - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a soft polyvinyl chloride resin-based waterproof sheet which is stretched in a heat storage tank for cooling and heating of a building and has excellent hot water resistance and durability.

2. Description of the Related Art In recent years, as a waterproof sheet for a heat storage tank of this kind, one having excellent hot water resistance and durability has been demanded, and cooling and heating can be performed in a limited space of the heat storage tank as the building becomes taller. When carrying out, the heat storage tank temperature tended to be high.

Conventionally, as a waterproof material used for waterproofing a heat storage tank or the like, a sheet-type waterproof material such as ethylene / propylene rubber (EPDM), butyl rubber (IIR) or soft polyvinyl chloride resin (PVC), asphalt, mortar And other coating-type waterproof materials have been known.

However, none of these conventional waterproof materials sufficiently satisfies both hot water resistance and durability.

That is, first, the conventional ethylene-propylene rubber (EP
A waterproof sheet made of DM) and butyl rubber (IIR) has good hot water resistance, but since it is bonded using an adhesive, if it is immersed in hot water for a long time, the bonding strength will decrease and the durability will increase. There was a problem that it was inferior to.

Further, in the case of a conventional waterproof sheet made of soft polyvinyl chloride resin, the plasticizer and the stabilizer are eluted due to the long-term hot water immersion, whereby the flexibility of the waterproof sheet is impaired, and the mechanical strength of the waterproof sheet is reduced. A drop was seen. In addition, the sheet absorbs water and swells when immersed in hot water.
There has been a problem that slack and wrinkles are generated and a stress is locally generated in the sheet, and if this is for a long time, the sheet is cracked and the waterproof performance is impaired.

Further, the waterproof film made of asphalt and mortar is inferior in hot water resistance, and has a problem that cracking occurs when it is immersed in hot water for a long time and the waterproof performance is impaired.

And the above problems became more serious as the temperature of the heat storage tank increased with the rise of the building.

It is an object of the present invention to solve the above-mentioned problems of the prior art and to provide a soft polyvinyl chloride resin-based waterproof sheet that satisfies hot water resistance and durability at the same time.

Means for Solving the Problems In order to achieve the above object, the present invention provides a waterproof sheet made of a soft polyvinyl chloride resin in which a polyvinyl chloride resin is mixed with a plasticizer, a stabilizer, and a filler. In the above, the gist is a soft polyvinyl chloride resin-based waterproof sheet characterized in that the stabilizer comprises an organic acid barium salt and an organic acid zinc salt, and the filler comprises titanium oxide.

As the polyvinyl chloride resin, a vinyl chloride monopolymer, a copolymer of vinyl chloride and vinyl acetate, ethylene, propylene, or the like, or a mixture of two or more of these polymers is used. .

Examples of the plasticizer to be added to the polyvinyl chloride resin include phthalate ester systems such as DOP (dioctyl phthalate), DBP (dibutyl phthalate), DIBP (diisobutyl phthalate), DHP (diheptyl phthalate), and DOA (diethyl phthalate). 2-ethylhexyl adipate), DIDA (diisodecyl adipate), D
Aliphatic dibasic acid ester such as OS (di-2-ethylhexyl sebacate), aromatic carboxylic acid ester such as ethylene glycol benzoate, or TOTM (trioctyl trimellitate) Use a trimellitic acid ester type.

As the stabilizer, a mixture of an organic acid barium salt and an organic acid zinc salt is used, and the mixture may be liquid or powder.

Further, as the filler, titanium oxide is used for the purpose of hiding the undercoat by coloring, and particularly, titanium oxide having a low water-swelling property.

Here, the mixing ratio of the above components is 1% polyvinyl chloride resin.
40 to 80 parts by weight, preferably 50 to 70 parts by weight, and 0.5 to 3 parts by weight of a stabilizer comprising a mixture of an organic acid barium salt and an organic acid zinc salt, based on 00 parts by weight.
It is preferably 1 to 2 parts by weight, and the filler made of titanium oxide is 0.5 to 5 parts by weight, preferably 1.5 to 3 parts by weight.

If the plasticizer is less than 40 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin, the waterproof sheet is not sufficiently soft and the handling is troublesome. If it exceeds 80 parts by weight,
If it is added more than that, not only the effect of plasticizing the polyvinyl chloride resin cannot be obtained, but also the amount of the plasticizer added is too large, which is not economical, which is not preferable.

If the amount of the stabilizer comprising a mixture of organic acid barium salt and organic acid zinc salt is less than 0.5 parts by weight, the thermal stability is poor and separation and sheeting are not possible, which is not preferable. On the other hand, if it exceeds 3 parts by weight, not only is there no effect even if it is added more, but the amount of stabilizer added is too large and it is not economical, so this is not preferable.

Further, if the filler made of titanium oxide is less than 0.5 part by weight, the hiding property of the base is not good, which is not preferable.
On the other hand, if it exceeds 5 parts by weight, swelling due to hygroscopicity becomes large, which causes slack and wrinkles, which is not preferable.

As a method for compounding the material components that form the soft polyvinyl chloride resin-based waterproof sheet, generally known compounding means may be used, and the compounding sheeting method may also be a normal roll or extrusion sheeting operation. It's good.

The soft polyvinyl chloride resin-based waterproof sheet according to the present invention may, of course, be added with an ultraviolet absorber, a coloring agent, a lubricant or the like which is usually added to the soft polyvinyl chloride resin.

Effect According to the soft polyvinyl chloride resin-based waterproof sheet of the present invention, since the polyvinyl chloride resin containing the plasticizer is blended with a mixture of the organic acid barium salt and the organic acid zinc salt, the waterproof sheet Even when immersed in hot water for a long period of time, the plasticizer and the stabilizer are less likely to be eluted, so that the flexibility of the waterproof sheet is not impaired, the mechanical strength is not significantly reduced, and it has excellent hot water resistance.

In addition, since titanium oxide is blended as a filler, and titanium oxide has a very low water-absorption swelling property compared to other fillers, it is possible to suppress the water-absorption swelling of the waterproof sheet due to immersion in hot water as much as possible. In addition, excellent waterproof performance can be maintained for a long time without causing slack, wrinkles, or cracks.

Moreover, since the waterproof sheet of the present invention can be joined by using a solvent-type adhesive such as tetrahydrofuran (THF), the joining strength is very large, and the joining strength can be maintained even after immersion in hot water for a long time. It does not deteriorate and has excellent durability.

Examples Next, examples of the present invention will be described together with comparative examples.

Examples 1 to 10 Polyvinyl chloride resin powder, a plasticizer made of DOP (dioctyl phthalate), and a liquid or powdered stabilizer made of a mixture of an organic acid barium salt and an organic acid zinc salt,
A filler made of titanium oxide was added in various proportions shown in the table below for the purpose of concealing the base by coloring, and the mixture was molded into a sheet having a thickness of 0.5 mm by an ordinary roll-sheeting operation. Then, various soft polyvinyl chloride resin-based waterproof sheets according to the present invention were manufactured.

Here, the following materials were used as materials for each component.

Polyvinyl chloride resin powder: trade name Summit SX-7GL, manufactured by Sumitomo Chemical Co., Ltd.,
Polymerization degree 700.

Plasticizer: DOP (dioctyl phthalate), manufactured by Toho Rika Co., Ltd.

Stabilizer: Organic acid barium salt + organic acid zinc salt mixed solution type stabilizer,
Product name MARK AC-167, manufactured by Adeka Argus Chemical Co., Ltd.

Powder type stabilizer consisting of organic acid barium salt (barium stearate) manufactured by Katsuta Kako Co., Ltd.

Powder type stabilizer consisting of zinc salt of organic acid (Zinc stearate) manufactured by Katsuta Kako Co., Ltd.

Filler: Rutile titanium oxide (trade name R-650, manufactured by Sakai Chemical Co., Ltd.).

Comparative Examples 1 to 10 Next, for comparison, the same polyvinyl chloride resin powder as in Example 1 above, a plasticizer made of DOP (dioctyl phthalate), and a filler made of titanium oxide are used, but as a stabilizer. , A conventional organotin-based stabilizer (dibutyltin maleate, trade name RC-40F, manufactured by Sankyo Kisei Co., Ltd.) (Comparative Example 1), or a conventional organolead-based stabilizer (dibasic lead phosphite, A soft polyvinyl chloride resin-based sheet was manufactured in the same manner as in the example by using the product name L-FOS, manufactured by Katsuta Kako Co., Ltd. (Comparative Example 2).

For comparison, the same polyvinyl chloride resin powder, plasticizer, and liquid or powder stabilizer as in Example 1 above were used, but conventional calcium carbonate, zinc oxide (Z
nO), barium sulfate, and clay were used to produce various conventional soft polyvinyl chloride resin-based sheets in the same manner as in Examples (Comparative Examples 3 to 10).

Performance comparison test Next, regarding the samples of various soft polyvinyl chloride resin-based waterproof sheets obtained in the above Examples and Comparative Examples,
In order to evaluate hot water resistance and durability, these sheet samples were immersed in hot water at 90 ° C. in a constant temperature bath for 5 months, and then,
Each sample piece was tested for elongation reduction rate, elution rate, water absorption rate, and wrinkle generation, and the obtained results are summarized in the table below.

Here, the elongation reduction rate is obtained by measuring the elongation amount (mm) at break with respect to the distance between marked lines of 20 mm, calculating the elongation rate by the following formula, and setting the ratio with the elongation rate of the original sample as the elongation reduction rate. .

In the formula, L _B : distance between marked lines at break (mm) L _O : distance between marked lines (20 mm)

In addition, the elution rate was measured by measuring the weight of each sample piece taken out of the thermostatic bath after being immersed in hot water for one day in an oven at 80 ° C, and measuring its weight. The rate (%) was used.

The water absorption rate was determined as the water absorption rate (%) by immersing the sample piece in hot water for 5 months, taking out each sample piece from the constant temperature bath, measuring the weight, and determining the ratio with the weight before immersion.

Regarding the occurrence of wrinkles on the waterproof sheet, each sheet sample piece was attached to a PVC steel plate frame with a tension of 1% so as not to cause wrinkles and attached using a tetrahydrofuran (THF) solvent-type adhesive. After immersing in hot water for 5 months, each framed sheet sample piece was taken out from the thermostat and the surface condition was visually observed to determine whether wrinkles were generated.

Here, ◯: No wrinkle was generated, Δ: Slight wrinkle was observed, ×: Significant wrinkle was observed.

As can be seen from the results in the above table, the soft polyvinyl chloride resin-based waterproof sheets obtained in the examples of the present invention contain a mixture of organic acid barium salt and organic acid zinc salt as a stabilizer, Even when the waterproof sheet is immersed in hot water for a long period of time, the plasticizer and the stabilizer are very little eluted. Therefore, the flexibility of the waterproof sheet is not impaired,
In addition, the mechanical strength did not decrease so much and it had excellent hot water resistance.

Further, in the waterproof sheet obtained in the examples of the present invention, since titanium oxide having a very low water swelling property is blended as a filler, it is possible to suppress the water swelling of the waterproof sheet due to the immersion in hot water as much as possible. It was possible to maintain excellent waterproof performance for a long time without causing slack, wrinkles, or cracks in the waterproof sheet.

The waterproof sheets obtained in the examples of the present invention can be bonded using, for example, a solvent-type adhesive, so that the bonding strength is very large and the bonding strength is high even after hot water immersion for a long time. It does not deteriorate and has excellent durability.

On the other hand, among the conventional waterproof sheets obtained by the comparative example, the filler made of titanium oxide is the same as the example, but when the conventional organic tin-based stabilizer is used as the stabilizer (Comparative Example 1 (3) has good heat resistance, but has a drawback of being eluted because it is prone to hydrolysis.

When a conventional organic lead-based stabilizer was used as the stabilizer (Comparative Example 2), the elution resistance with hot water was good, but there was a drawback that water absorption was likely to occur.

As the stabilizer, a liquid or powdery stabilizer comprising the same mixture of organic acid barium salt and organic acid zinc salt as in the above-mentioned examples is used, but conventional calcium carbonate, zinc white, barium sulfate is used as a filler. Alternatively, when clay is used (Comparative Examples 3 to 10), there is a drawback that water swelling is likely to occur.

As described above, according to the conventional waterproof sheet, neither hot water resistance nor durability can be sufficiently satisfied at the same time, and the quality is poor.

EFFECTS OF THE INVENTION In the soft polyvinyl chloride resin-based waterproof sheet according to the present invention, as described above, a polyvinyl chloride resin containing a plasticizer is blended with a mixture of an organic acid barium salt and an organic acid zinc salt as a stabilizer. Therefore, even if the waterproof sheet is soaked in hot water for a long time, the plasticizer and the stabilizer are not eluted so much, the flexibility of the waterproof sheet is not impaired, the mechanical strength is not deteriorated, and it has excellent hot water resistance. ing.

Further, according to the present invention, titanium oxide is blended as a filler, and titanium oxide has very little water-swelling swelling property as compared with other fillers, so that water-swelling swelling of the waterproof sheet due to hot water immersion is suppressed as much as possible. You can do it on the tarpaulin,
Excellent waterproof performance can be maintained for a long period of time without sagging, wrinkling, or cracking. Moreover, since the waterproof sheet of the present invention can be joined by using, for example, a solvent-type adhesive, the joining strength is very large, and the joining strength does not decrease even after hot water immersion for a long time, and the durability is improved. It has the effect of being excellent.

Claims (1)

[Claims] 1. A polyvinyl chloride resin, a plasticizer, a stabilizer,
And a waterproof sheet made of a soft polyvinyl chloride resin in which a filler is blended, wherein the stabilizer is made of an organic acid barium salt and an organic acid zinc salt, and the filler is made of titanium oxide. A soft polyvinyl chloride resin-based waterproof sheet.