JPH05306343A - Soft polyvinyl chloride resin water-proof sheet - Google Patents

Abstract

PURPOSE:To provide a resin water-proof sheet good in the flexibility, opacifying property and weather resistance and useful as a water-proof sheet for roofs, etc., by adding a plasticizer, glycine zinc salt, an organic phosphate ester and chlorination method titanium dioxide to a polyvinyl chloride resin. CONSTITUTION:100 pts.wt. of a polyvinyl chloride resin, 40-80 pts.wt. of a plasticizer such as dioctyl phthalate, 0.1-5.0 pts.wt. of glycine zinc salt as a stabilizer, 1.0-10.0 pts.wt. of an organic phosphate ester as a stabilization auxiliary, and 3.0-15.0 pts.wt. of chlorination method titanium dioxide as a filler are dry- blended with each other by the use of a Henschel mixer, etc., and subsequently molded by a conventional extrusion method into the objective soft polyvinyl chloride resin waterproof sheet added in the flexibility, good in the opacifying property, sheeting property, and weather resistance, not deteriorating its softness over a long period, reduced in the lowering of the mechanical strength, and free from the generation of sags, creases and cracks.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soft polyvinyl chloride resin waterproof sheet.

[0002]

2. Description of the Related Art In recent years, with the increase in the durability of houses, there is a tendency that the waterproof sheet stretched over the flat roof is required to have further improved durability.

Conventionally, as this type of waterproof sheet, a soft polyvinyl chloride resin-based waterproof sheet is most commonly used. The waterproof sheet is obtained by blending a polyvinyl chloride resin with a plasticizer. In addition to imparting flexibility, a stabilizer, a filler and the like are blended to impart hiding property, sheet formability, weather resistance and the like.

[0004]

A conventional soft polyvinyl chloride resin-based waterproof sheet contains a zinc-based stabilizer or a tin-based stabilizer, and the former zinc-based stabilizer, that is, barium-zinc-based stabilizer. In the case of an agent or a calcium-zinc-based stabilizer, the weather resistance is improved, but when heat-molded, the heat resistance during processing is inferior, and therefore there is a problem that the amount used must be limited. there were.

On the other hand, in the case of the tin-based stabilizer, there is no problem in heat resistance, but there is a problem in that the so-called bleeding phenomenon, which is caused by hydrolysis and is blown to the surface, easily occurs and the weather resistance is poor. It was

In any conventional soft polyvinyl chloride resin-based waterproof sheet, if it is used outdoors for a long period of time, the material will change over time, the flexibility will be impaired, and the mechanical strength will be remarkably high. There was a downward trend. Therefore, during long-term use, slack and wrinkles occur in the sheet due to repeated expansion and contraction due to temperature changes, local stress is generated, leading to cracks, and waterproofness is significantly impaired, In terms of durability, there was a problem that it was not sufficiently satisfactory.

As a result of earnest studies in view of the above points, the present inventors have found that a specific stabilizer for polyvinyl chloride resin is
It has been found that the heat resistance, the weather resistance and the waterproof durability at the time of sheet processing can be improved by adding a filler and a stabilizing aid in a predetermined ratio, and the present invention has been completed.

An object of the present invention is to solve the above-mentioned problems of the prior art and provide a soft polyvinyl chloride resin-based waterproof sheet having excellent heat resistance during sheet processing, weather resistance and waterproof durability. It is in.

[0009]

In order to achieve the above object, the present invention provides 100 parts by weight of polyvinyl chloride resin, 40 to 80 parts by weight of a plasticizer, and 0.1 to 0.1 parts of glycine zinc. 5.0 parts by weight of organic phosphate 1.
0 to 10.0 parts by weight and chlorine method titanium oxide 3.0 to 1
The gist is a soft polyvinyl chloride resin-based waterproof sheet characterized by comprising 5.0 parts by weight.

As the above polyvinyl chloride resin, a vinyl chloride monomer polymer or vinyl chloride and vinyl acetate,
A copolymer with ethylene, propylene or the like, or a mixture of two or more kinds of these polymers is used.

As the plasticizer to be blended with the polyvinyl chloride resin, for example, DOP (dioctyl phthalate), D
Phthalates such as BP (dibutyl phthalate), DIBP (diisobutyl phthalate), DHP (diheptyl phthalate), DOA (di-2-ethylhexyl adipate), DIDA (diisodecyl adipate), DOS (di-2-ethylhexyl) Sebasate) etc., aliphatic dibasic acid ester series, ethylene glycol benzoates, etc. aromatic carboxylic acid ester series, or TOTM (trioctyl trimellitate) etc. trimellitic acid ester series, etc. To use.

The zinc glycine acts as a stabilizer, and these are produced by the following two methods, for example.

First, an aqueous solution is prepared by dispersing and dissolving a predetermined amount of glycine in water. A concentrated aqueous solution of caustic soda is added to this dispersed aqueous solution and heated to 50 to 60 ° C. to form glycine sodium. Next, while slowly adding an aqueous solution of zinc sulfate to this aqueous solution, metathesis is promoted under stirring to generate zinc glycine. After that, ethanol was added to crystallize Glauber's salt, the mixture was separated by filtration, and the filtrate was dried,
A powder of zinc glycine is obtained.

Another method is to add zinc oxide to an aqueous solution of glycine with stirring, and to add 70 to 80 ° C.
After being held for several hours, it is dried to obtain zinc glycine powder.

The above-mentioned organic phosphate ester acts as a stabilizing aid, and examples thereof include tricresyl phosphate (TCP), trixylyl phosphate (TXP), tributyl phosphate (TBP) and tri-phosphate. 2-Ethylhexyl, 2-ethylhexyl phosphate diphenyl, etc. are mentioned.

The filler to be blended with the polyvinyl chloride resin is mainly for imparting the undercoat hiding property to the waterproof sheet. In the present invention, rutile type titanium oxide, especially chlorine method titanium oxide, is selectively used.

The reason why the chlorine method titanium oxide is selected as the filler and the other sulfuric acid method titanium oxide or calcium carbonate is not used as the filler is as follows.

That is, in the case of the sulfuric acid method titanium oxide, due to its manufacturing method, a slight amount of iron component is contained in the titanium oxide component, and iron oxide is generated by the oxidation reaction, which accelerates the deterioration of the polyvinyl chloride resin. It is not preferable because it causes deterioration of color tone and flexibility.

Calcium carbonate has only about one tenth of the surface concealing property of titanium oxide compared with titanium oxide, so that it is necessary to increase the amount used and elute by the acid component in the air. It is not preferable because it has the drawbacks described above and the weather resistance is poor.

On the other hand, the chlorine method titanium oxide has a high purity, contains very little iron component, can prevent the deterioration of the polyvinyl chloride resin over time, and has an excellent undercoat hiding property. Excellent weather resistance with no risk of elution by acid components in the air.

The mixing ratio of the above components is as follows: 100-80 parts by weight of polyvinyl chloride resin, 40-80 parts by weight, preferably 50-70 parts by weight of plasticizer, 0.1% by weight of glycine zinc.
1 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight,
Organic phosphate ester 1.0 to 10.0 parts by weight, preferably 3.0 to 7.0 parts by weight, chlorine method titanium oxide 3.0 to 1
The amount is 5.0 parts by weight, preferably 5.0 to 10.0 parts by weight.

Here, 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 will not have sufficient flexibility and will not comply with JIS A6009, which is the standard of the waterproof sheet. .. Further, if it exceeds 80 parts by weight, the elongation is large, again not conforming to JIS A6009, and even if it is added more, the effect of plasticizing the polyvinyl chloride resin cannot be obtained, and it is not economical.

Further, the stabilizer consisting of zinc glycine is 0.1
If it is less than parts by weight, the amount added is too small and the effect of improving heat resistance and weather resistance does not appear, which is not preferable. Also 5.
If it exceeds 0 parts by weight, it becomes so-called porous, and the weather resistance is deteriorated.
And if too much stabilizer is added, it is not economical.
Not preferable.

If the amount of the stabilizing aid made of an organic phosphate is less than 1.0 part by weight, the amount added is too small and the effect of improving weather resistance is not exhibited, which is not preferable. Again 1
If it exceeds 0.0 parts by weight, the weather resistance is improved, but the heat resistance and cold resistance are deteriorated, and further addition is not effective, and the addition amount becomes too large, which is not economical. , Not preferable.

Further, if the amount of the chlorine-based titanium oxide filler is less than 3.0 parts by weight, the hiding property of the underlying layer is poor and the surface layer is apt to discolor or crack over time, which is not preferable. In addition, the chlorine-based titanium oxide filler is 1
If it exceeds 5.0 parts by weight, the inside of the sheet becomes porous and the initial physical properties deteriorate, and the diffusion effect of the plasticizer and the stabilizer becomes large, and bleeding easily occurs, and the initial physical properties cannot be maintained for a long time. Therefore, it is not preferable.

As a method of compounding the material components constituting the above-mentioned soft polyvinyl chloride resin-based waterproof sheet, a generally known compounding means may be used, and the compounding sheeting method may be an ordinary roll or extrusion. All you have to do is a seating operation.

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

[0028]

In the soft polyvinyl chloride resin-based waterproof sheet of the present invention, by adding a plasticizer to the polyvinyl chloride resin, it is possible to impart sufficient flexibility to the waterproof sheet and, of course, glycine as a stabilizer. By adding zinc, the heat resistance and weather resistance of the waterproof sheet can be improved. Further, by adding an organic phosphoric acid ester as a stabilizing aid, weather resistance is improved and heat resistance and cold resistance are not deteriorated. Furthermore, by adding chlorinated titanium oxide as a filler, chlorinated titanium oxide has a high degree of purity and excellent underlayer hiding properties, and can prevent deterioration of the polyvinyl chloride resin over time, and The initial physical properties of the waterproof sheet can be maintained and the weather resistance can be improved. Therefore, the flexibility of the waterproof sheet is not impaired, the mechanical strength is not significantly reduced, and it is possible to maintain excellent waterproof performance for a long period of time without sagging, wrinkling, or cracking of the waterproof sheet. it can.

Since the waterproof sheet according to the present invention can be joined by using a solvent type adhesive such as tetrahydrofuran (THF), it has a very large joining force and can be immersed in hot water for a long time. Also, the joining strength does not decrease and the durability is excellent.

[0030]

EXAMPLES Next, Examples of the present invention will be described together with Comparative Examples. Examples 1 to 7 and Comparative Examples 1 to 13 100 parts by weight of a polyvinyl chloride monopolymer are each added with the components shown in Table 1. After blending in a ratio of 1 and dry blended with a Henschel mixer, various soft polyvinyl chloride resin-based waterproof sheets according to the present invention having a thickness of 1.3 mm were manufactured by an extrusion molding method according to a conventional method.

Here, the following materials were used as materials for the respective components in Examples and Comparative Examples.

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: zinc glycine, trade name NX-176 , Nissan Ferro Organic Chemicals Co., Ltd. Stabilizing Aid: Organic Phosphate Ester Tricresyl Phosphate (TCP), Daihachi Chemical Co., Ltd. Trixylyl Phosphate (TXP), Daihachi Chemical Co., Ltd. Filler: Chlorine Method Titanium oxide (Trade name CR-6 CR-6
0, manufactured by Ishihara Sangyo Co., Ltd.) Comparative stabilizer: General Ba-Zn liquid MARK AC-
167, Asahi Denka Kogyo Co., Ltd. (Stabilized mixture of organic acid Ba salt / organic acid Zn salt) General Ba-Zn powder Ba-St.Zn-St, manufactured by Katsuta Kako Co., Ltd. (Ba stearate, stearin) Stabilizer of powdered mixture of acid Zn) Dibutyltin maleate, trade name RC-40F, manufactured by Sankyo Machine Gosei Co., Ltd. Comparative filler: Sulfuric acid method titanium oxide (trade name Taipaque R
-670, manufactured by Ishihara Sangyo Co., Ltd.) In the above, Examples 1 to 7 are the soft polyvinyl chloride resin waterproof sheets according to the present invention.

In Comparative Examples 1 to 4, the stabilizer and the filler were
It is a waterproof sheet for comparison using a different type from that of the present invention.

Comparative Examples 5 and 6 are waterproof sheets for comparison in which the range of use of the plasticizer is different from that of the present invention.

Comparative Examples 7 and 8 are waterproof sheets for comparison in which the chlorine method titanium oxide as the filler is different from the use range of the present invention.

Comparative Examples 9 to 11 are waterproof sheets for comparison in which the organic phosphate ester is different from the use range of the present invention.

Comparative Examples 12 and 13 are waterproof sheets for comparison in which glycine zinc is different from the use range of the present invention.

Performance Comparison Test Next, initial physical properties (elongation rate) and heat resistance of the samples of various soft polyvinyl chloride resin-based waterproof sheets obtained based on the formulations in the above Examples and Comparative Examples were measured by the following test methods. , Weather resistance-residual elongation, and weather resistance-appearance state (surface deterioration state). The results obtained are summarized in the table below.

The initial physical properties are JIS A6009.
The initial elongation (%) was measured according to the above.

The heat resistance was measured using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.), and the time when the torque sharply increased was taken as the decomposition time (minutes).

The measurement conditions were as follows: filling amount: 75 g, rotation speed: 120 rpm, temperature: 200 ° C., and preheating time:
3 minutes.

Weather resistance-residual elongation (%) is
Using a long-life sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), the residual elongation rate (%) after 6000 hours had elapsed was measured under rainfall at regular intervals of 18 minutes / 2 hours. ..

The weather resistance-appearance state was observed by the EMMAQUA test (solar concentrating method, manufactured by DSET Co., Arizona, USA) for 10 months, and the surface state after the test was observed.

◯: No change, Δ: Slight cracks and discoloration were observed, ×: Large cracks and discoloration.

[0045]

[Table 1] As can be seen from the results in the above table, Example 1 of the present invention
The soft polyvinyl chloride resin-based waterproof sheets obtained in Nos. 7 to 7 are excellent in heat resistance during sheet processing, weather resistance and waterproof durability.

On the other hand, among the conventional waterproof sheets obtained in Comparative Examples, the waterproof sheet of Comparative Example 1 using general Ba-Zn (liquid) as a stabilizer has poor heat resistance and has a solar condensing property. In the weather resistance test of the method, cracks were generated and significant discoloration was observed.

Further, the waterproof sheet of Comparative Example 2 using general Ba-Zn (powder) as the stabilizer has poor heat resistance and has a small residual elongation in the weather resistance test by sunshine / W / M. At the same time, a crack was generated in the weathering test of the solar concentrating method, and a remarkable discoloration was observed.

Further, in the waterproof sheet of Comparative Example 3 using dibutyltin maleate as the stabilizer, the sunshine W
In the weather resistance test with M, the residual elongation was small, and in the weather resistance test of the solar concentrating system, cracks were generated and discoloration was observed.

In the waterproof sheet of Comparative Example 4 using sulfuric acid titanium oxide as the filler, the heat resistance and the residual elongation of the weather resistance test by sunshine. Slight cracks and discoloration were observed in the system weatherability test.

Next, in the waterproof sheet of Comparative Example 5 in which the range of use of the plasticizer was smaller than that of the present invention, sufficient flexibility was not obtained, and heat resistance, weather resistance and waterproof durability were all Was also inferior.

On the other hand, in the waterproof sheet of Comparative Example 6 in which the range of use of the plasticizer was larger than that of the present invention, the elongation was very large, and the residual elongation rate in the weather resistance test by sunshine / W / M was remarkable. Not only were they large, but a slight crack and discoloration were also observed in the solar concentrating weathering test.

Further, in the waterproof sheet of Comparative Example 7 in which the amount of chlorine-containing titanium oxide used as the filler was smaller than that of the invention, the hiding property of the base was poor, and discoloration or cracks were observed in the surface layer over time. It was liable to occur, and the weather resistance and waterproof durability were all inferior.

On the other hand, in the waterproof sheet of Comparative Example 8 in which the chlorine-containing titanium oxide was used in a wider range than that of the present invention, the initial elongation was small, the heat resistance was poor, and the solar condensing Slight cracks and discoloration were also observed in the weather resistance test of the system.

Further, in the waterproof sheets of Comparative Examples 9 and 10 in which the organic phosphoric acid ester as the stabilizing aid is not used or the range of use thereof is smaller than that of the present invention, the heat resistance is poor and the weather resistance and The waterproof durability was also poor.

On the other hand, in the waterproof sheet of Comparative Example 11 in which the use range of the organic phosphoric acid ester was larger than that of the present invention, the heat resistance was inferior and a slight crack was observed in the weather resistance test of the solar concentrating system. Occurrence and discoloration were observed.

Further, in the waterproof sheet of Comparative Example 12 in which the use range of the stabilizer glycine zinc was smaller than that of the present invention, both heat resistance and weather resistance were inferior.

On the other hand, the range of use of zinc glycine is
The waterproof sheet of Comparative Example 13 having a larger amount than that of the present invention became porous and the weather resistance was lowered.

[0058]

As described above, the soft polyvinyl chloride resin-based waterproof sheet according to the present invention has the polyvinyl chloride resin 1
00 parts by weight, plasticizer 40 to 80 parts by weight, glycine zinc 0.1 to 5.0 parts by weight, organic phosphate ester 1.0 to 10.0 parts by weight, and chlorine method titanium oxide. It is composed of 3.0 to 15.0 parts by weight, and by adding a plasticizer to the polyvinyl chloride resin, it is possible to impart sufficient flexibility to the waterproof sheet and, of course, glycine zinc as a stabilizer. The heat resistance and weather resistance of the waterproof sheet can be improved by adding it at a predetermined ratio. Further, by adding an organic phosphoric acid ester as a stabilizing aid in a predetermined ratio, weather resistance is improved and heat resistance and cold resistance are not deteriorated. Furthermore, by adding chlorinated titanium oxide as a filler at a predetermined ratio, chlorinated titanium oxide has a high purity and excellent underlayer hiding property and can prevent deterioration of the polyvinyl chloride resin over time. Thus, the initial physical properties of the waterproof sheet can be maintained for a long period of time, and the weather resistance can be improved. Therefore, the flexibility of the waterproof sheet is not impaired, the mechanical strength is not significantly reduced, and it is possible to maintain excellent waterproof performance for a long period of time without sagging, wrinkling, or cracking of the waterproof sheet. It has the effect of being able to.

The soft polyvinyl chloride resin-based waterproof sheet according to the present invention is, for example, tetrahydrofuran (TH
Since it can be bonded using a solvent type adhesive such as F), the bonding strength is very large, and the bonding strength does not decrease even after immersion in hot water for a long time, and the durability is excellent. It is a thing.

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Claims (1)

[Claims] 1. A polyvinyl chloride resin 100 parts by weight, a plasticizer 40 to 80 parts by weight, a glycine zinc 0.1 to 5.0 parts by weight, and an organic phosphate ester 1.0 to
10.0 parts by weight and chlorine method titanium oxide 3.0 to 15.0
A soft polyvinyl chloride resin-based waterproof sheet, characterized by comprising parts by weight.