JP3138622B2 - Coating waterproof sheet material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly durable coated waterproof sheet material which can be used for outdoor roof waterproofing work, indoor water storage tanks, pools, heat storage tanks and the like.

[0002]

2. Description of the Related Art Since a roofing material is mainly installed outdoors, it must be able to withstand various severe conditions. In other words, weather resistance, heat resistance,
It is required that mechanical strength, flexibility, expansion and shrinkage in a wide temperature range be small, and that the bonding property between sheets be reliable.

At present, asphalt waterproofing is generally used most often as a waterproofing method. However, asphalt waterproofing involves work environment problems and a large number of working steps due to a thermal method, heat and cold resistance, weather resistance, and substrate followability. And so on. A synthetic polymer roofing material has been developed to solve these problems. Such synthetic polymer roofing materials include vulcanized rubber, non-vulcanized rubber and vinyl chloride.

[0004]

The vulcanized rubber system has good heat resistance, cold resistance, and substrate followability, but has poor reliability in joining sheets and often causes water leakage accidents. . Non-vulcanized rubber type has relatively easy workability due to relaxation of internal stress, and has good sheet base followability and bondability, but has low mechanical strength and is protected in places where external force such as walking is applied. A layer is required, and in this case, there are problems such as an increase in the number of construction steps.

[0005] The roofing of the polyvinyl chloride resin is
Despite excellent bondability and mechanical strength, low-molecular-weight phthalate plasticizers are generally used, so during long-term outdoor exposure, sheet weight changes and dimensional changes due to loss of plasticizer volatilization. This causes a problem that the weak point is broken due to the curing and shrinkage of the sheet due to these causes, and the waterproof function is impaired. In addition, even when using a high molecular weight phthalate ester to improve such a problem, although the reduction of the waterproof function caused by the volatilization of the plasticizer can be improved to some extent, when renovating the existing exposed waterproof layer, If the renovation waterproofing sheet immediately comes into contact with the existing waterproofing layer, it will not be possible to improve the waterproofing function, such as hardening, shrinkage, or breaking of weak points due to migration and loss of the plasticizer. An insulating layer must be interposed between the sheet layer, and there remain problems such as chronic shortage of waste disposal sites in recent years, environmental problems, and an increase in man-hours.

When a part of the high-molecular-weight phthalate-based plasticizer is replaced with a polyester-based plasticizer in order to improve the transferability of the plasticizer in the waterproof sheet containing the high-molecular-weight phthalate-based plasticizer, the chloride is added. The cold-resistant property generally referred to as a vinyl-based waterproof sheet, that is, the flexibility in a low-temperature atmosphere is reduced.

Accordingly, an object of the present invention is to solve the above-mentioned problems and to provide a vinyl chloride resin coating waterproofing material which hardens and shrinks the sheet by volatilization and migration of a plasticizer.

[0008]

The coated waterproof sheet material of the present invention is obtained by adding 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 1000 to 4000 and an acrylic or methacrylic group to a vinyl chloride resin having an average degree of polymerization of 1000 to 4000. The graft polymer obtained by grafting a compound having
30 to 90 parts by weight of a plasticizer is added to the system in which the parts by weight are added, and the plasticizer has an average molecular weight of 450 to 56.
0 high molecular weight phthalate plasticizer. The plasticizer may be the high-molecular-weight phthalate-based plasticizer or a combined plasticizer of the high-molecular-weight phthalate-based plasticizer and a polyester-based plasticizer having an average molecular weight of 1,000 to 8,000. preferable.

The vinyl chloride resin used in the waterproof sheet of the present invention has an average degree of polymerization of 1,000 to 4,000. If the average degree of polymerization is lower than 1000, the mechanical strength of the material is reduced, and if the average degree of polymerization is higher than 4000, the workability of the material and the associated economic efficiency are reduced.

The graft copolymer used in the present invention is a copolymer obtained by grafting a compound having an acryl group or a methacryl group onto a vinyl chloride resin having an average degree of polymerization of 1,000 to 4,000. As such a compound, one or more kinds of ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and the like are used. The vinyl chloride resin as a base polymer has an average degree of polymerization of 100 due to mechanical strength, processability, and the like.
Desirably, it is 0 to 4000. The graft copolymer is obtained by grafting 2 to 30 parts by weight of a compound having an acryl group or a methacryl group to 100 parts by weight of a vinyl chloride resin. In addition, vinyl chloride resin 1
The graft copolymer compound was added in an amount of 10 to 100 parts by weight.
It is preferable to mix 60 parts by weight. When this is less than 10 parts by weight, when a polyester plasticizer is used in combination,
When low-temperature characteristics cannot be improved, and when a high-molecular-weight phthalate-based plasticizer is blended alone as a plasticizer,
Inability to improve plasticizer migration. On the other hand, if it exceeds 60 parts by weight, the workability of the final sheet deteriorates.

The phthalate plasticizer used in the present invention has an average molecular weight of 450 to 560. If it is less than 450, the leaching and volatilization of the plasticizer increases, and the durability under severe conditions such as long-term outdoor exposure, that is, the waterproof function is reduced.

The polyester plasticizer used in the present invention includes succinic acid, glutaric acid, adipic acid, bimerylic acid,
Dicarboxylic acids such as suberic acid, azelaic acid, sebacic acid and phthalic acid and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-
2-ethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,2-dimethylpropane-1,3- Diol, 1,4-pentanediol, 1,6-hexanediol, 2-methyl-2,4-
A polyester plasticizer having an average molecular weight of 1,000 to 8,000, which is arbitrarily synthesized from various glycols such as pentanediol, diethylene glycol, and triethylene glycol. When its average molecular weight exceeds 8000,
The workability, cold resistance and compatibility of the resulting material are poor, and 100
When it is less than 0, migration, leaching, and volatilization of the plasticizer increase,
This is because the durability under severe conditions such as long-term outdoor exposure, that is, the waterproof function is reduced.

Further, in the case of using the phthalate ester plasticizer and the polyester plasticizer alone and in the case of using the polyester plasticizer in combination, the total amount of the plasticizer is 30 to 90. Desirably, parts by weight are used. If less than 30 parts by weight,
The sheet becomes hard and has little elongation, which may cause stiffening and hindrance. If the amount is more than 90 parts by weight, the mechanical strength is reduced, and the strength is remarkably reduced particularly at a high temperature such as in a summertime, and there is a possibility that an external force is applied to cause trouble.

Further, the coated waterproof sheet material of the present invention may use, if necessary, stabilizers, fillers, pigments, processing aids and the like which are used in ordinary flexible polyvinyl chloride resin compositions.

[0015]

The present invention will be described below with reference to the following examples and comparative examples. (Preparation method of waterproof sheet) A compound was prepared using a Henschel mixer at the compounding ratio shown in Table 1, and the compound was 1.5 mm in a 110 mm co-directional twin screw extruder.
It was extruded into a thick sheet.

[0016]

[Table 1]

The components shown in Table 1 are as follows. * 1: Vinyl chloride resin--Suspension polymerized vinyl chloride resin with average degree of polymerization bar P = 1300 * 2: Polyester plasticizer A--Adipic acid-1,6-
Hexanediol-based, polyester plasticizer having an average molecular weight of 1200 * 3: Polyester-based plasticizer B--adipic acid-1,6-
Hexanediol-based, polyester-based plasticizer having an average molecular weight of 2600 * 4: Graft copolymer C--average degree of polymerization bar P = 130
A copolymer obtained by grafting 15 parts by weight of ethyl acrylate and 5 parts by weight of methyl methacrylate to 100 parts by weight of a suspension-polymerized vinyl chloride resin of No. 0 * 5: Graft copolymer D--average degree of polymerization bar P = 130
A copolymer obtained by grafting 10 parts by weight of butyl acrylate and 10 parts by weight of methyl methacrylate to 100 parts by weight of a suspension-polymerized vinyl chloride resin of No. 0 * 6: UV absorber--Tinuvin P (a triazole type manufactured by Ciba-Geigy Corporation) * 7: Polyethylene wax--low density polyethylene wax * 8: Pigment--chlorine method rutile type titanium oxide 0.5 part by weight, carbon black 0.5 part by weight * 9: Calcium carbonate--white gloss flower CC (Manufactured by Shiraishi Industry Co., Ltd.)

For each of the obtained sheets, JIS-A6
Tensile strength and tensile elongation were measured according to the vinyl chloride resin system of 008 (synthetic polymer roofing) homogeneous sheet, and the results shown in Table 2 were obtained.

[0019]

[Table 2]

As can be seen from Table 2, in Examples 1 to 6, although part or most of the phthalate ester plasticizer DUP was replaced with a polyester plasticizer or a graft copolymer, Compared with the polyester-based plasticizer alone of Comparative Example 1, the low-temperature properties are significantly improved.

Next, sheets of the same lot as the above test are
Punched into a dumbbell-shaped No. 3 shape specified in 3.2 of JIS-K6301, and air-aged based on 6.3 of JIS-K6301 at a heating temperature of 120 ± 2 ° C for a predetermined heating time. The volatile weight loss due to the aging treatment was expressed as a percentage of the weight of the original test piece as the volatilization loss, and the tensile strength and tensile elongation were measured by performing a tensile test of physical properties in normal condition based on JIS-A6008, The values shown in percentage of the normal physical property values in Table 2 were regarded as the heat aging retention rates, and the results shown in Table 3 were obtained.

[0022]

[Table 3]

However, in the above table, the value of the retention of heat-aged properties of Comparative Example 4 at 120 ° C. × 30 days was such that the sheet was too brittle due to excessive hardening due to heat aging of the sample, and the measurement was impossible. As can be seen from Table 3, in comparison with Comparative Examples 3 and 4 using a low molecular weight phthalate ester plasticizer, other examples using a polyester plasticizer, a high molecular weight phthalate ester plasticizer and a graft copolymer were used. In the formulation examples, good results were obtained because the low molecular weight volatile component was small in the 120 ° C. volatilization loss and the heat aging physical property retention.

Next, as shown in FIG. 1, sheets of the same lot as in the above test were cut into 11 cm squares, and this was used as a sample sheet (2), which was placed on a 2 mm thick prototype semi-rigid sheet (3). Then, an 11 cm square iron plate (1) having a thickness of 1 mm was placed on the sample sheet (2) as a weight so that the sample sheet (2) was always completely in contact with the semi-rigid sheet (3). In this state, 80 ± 2 ° C., heating days 30, 60, 9
The weight loss of the sample sheet (2) at 0 and 180 days was measured, and these values, expressed as a percentage with respect to the weight of the sample sheet (2) before exposure, were expressed as a transfer heat weight loss (I). did. In addition, the sample sheet (2) exposed for 180 days was subjected to a tensile test of normal physical properties based on JIS-A6008, and the value obtained at this time was taken as a transition heat aging physical property (I).

Further, as shown in FIG. 2, an 11 cm square sample sheet (2) obtained from
11 cm square iron plate (1) is placed as a weight, and in this state, heating days 30, 60, 90, 1
The weight loss of the sample sheet (2) during 80 days was measured, and these values, expressed as a percentage with respect to the weight of the sample sheet (2) before exposure, were defined as the thermal weight loss rate (II). The sample sheet (2) exposed for 180 days was subjected to a tensile test of normal physical properties in accordance with JIS-A6008.
Based on the normal physical properties (III) obtained in Table 2, the transfer weight loss rate and the transfer physical property retention rate were defined as follows, and the results shown in Table 4 were obtained.

[0026]

(Equation 1)

The composition of the trial semi-rigid sheet is as follows.
When a general vinyl chloride waterproof sheet is exposed outdoors for a long period of time and the plasticizer is in a state where about half of the plasticizer has volatilized, the modified sheet is assumed to be in contact with immediately, and the following is assumed. Prototype semi-hard sheet compounding Vinyl chloride resin 100 phr Diisononyl phthalate (DINP) (molecular weight 418) 30 Epoxidized soybean oil 5 Ba-Zn composite metal soap 3 Ultraviolet absorber 0.1 Polyethylene wax 0.1 Pigment 1 Calcium carbonate 10 ────────────────────────────── 149.2 However, all of the above compounded materials are the same as the compounded materials used in Table 1. The same was used.

[0028]

[Table 4]

As can be seen from Table 4, Comparative Example 2 using only a phthalate plasticizer regardless of the molecular weight.
In Examples 4 to 4, the change rates of the transfer weight loss rate and the transfer property retention rate were large, while the change rates of Examples 1 to 6 were small, and a part of the phthalate ester plasticizer was replaced with a polyester plasticizer and a graft. It was demonstrated that the migration was greatly improved by replacing the copolymer.

[0030]

As described above, the coated waterproof sheet material of the present invention has excellent mechanical strength and can suppress migration, leaching, volatilization, etc. of the plasticizer even when used under severe conditions for a long period of time. It is a vinyl chloride roofing material having good physical properties at low temperatures.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1: Transfer heat weight loss rate (I) and transfer heat aging properties (I)
FIG. 5 is a view showing a sample sheet used for measurement of the sample.

FIG. 2 is a view showing a sample sheet used for measuring a heat loss rate (II) and a heat aging physical property (II).

[Explanation of symbols]

 1 Iron plate 2 Sample sheet 3 Prototype semi-rigid sheet

Claims (3)

(57) [Claims] 1. 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 1000 to 4000 and an average degree of polymerization of 1000 to 40.
Graft copolymer obtained by grafting a compound having an acryl group or a methacryl group onto a vinyl chloride resin
A plasticizer is added in an amount of 30 to 90 parts by weight to a system in which 0 to 60 parts by weight is added, and the plasticizer has an average molecular weight of 45.
A coated waterproof sheet material comprising a high-molecular-weight phthalate plasticizer of 0 to 560. 2. The coated waterproof sheet material according to claim 1, wherein the plasticizer is the high molecular weight phthalate plasticizer. 3. The coating according to claim 1, wherein the plasticizer is a combined plasticizer of the high molecular weight phthalate ester plasticizer and a polyester plasticizer having an average molecular weight of 1,000 to 8,000. Tarpaulin material.