JPH04106148A - Sheet material for waterproof lining - Google Patents

Abstract

PURPOSE:To prepare the title material excellent in weatherability, strengths, etc., by compounding a specific ethylene-vinyl chloride copolymer resin with a specified amt. of a plasticizer component comprising a high-mol.-wt. polyester plasticizer and/or a phthalic ester plasticizer having a somewhat high mol.wt. CONSTITUTION:100 pts.wt. ethylene-vinyl chloride copolymer resin having an average degree of polymn. of 1000-4000 and an ethylene unit content of 0.5--10wt.% is compounded with 30-90 pts.wt. plasticizer component comprising a polyester plasticizer having an average mol. wt. of 1000-8000 (e.g. a poly-1,6-- hexanediol adipate plasticizer) and/or a phthalic ester plasticizer having an average mol.wt. of 450 or higher to produce the title material. The material is suitable for the use in an indoor water reservoir, swimming pool, heat storage vessel, etc., as well as rooftop waterproofing.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is suitable for outdoor use because it has excellent durability with little weight change, dimensional change, flexibility change, etc. even under harsh conditions due to outdoor exposure. The present invention relates to a high-performance vinyl chloride resin composition for waterproof coatings that can be used not only for roof waterproofing work but also for indoor water tanks, swimming pools, heat storage tanks, etc.

(Prior Art) Conventionally, asphalt roofing, synthetic polymer roofing, etc. have been used for waterproofing general buildings and civil engineering structures. Roofing materials are mainly installed outdoors, so they have good weather resistance and heat resistance, and they have little expansion and contraction in a wide temperature range from low to high temperatures.They are also flexible even at low temperatures, and have good mechanical strength. It is required to have strength and elongation. Also, bondability between sheets is required during roofing.

Asphalt waterproofing has been the mainstream of waterproofing work for many years, but there are problems with the working environment due to the use of fire during construction, a large number of work steps, and large changes in physical properties due to changes in outside temperature. There are many other problems, such as difficulty in construction on slopes and slopes, and synthetic polymer roofing has been developed to overcome these drawbacks.

Vulcanized rubber-based, non-vulcanized rubber-based, polyvinyl chloride resin-based, etc. are mainly used for such synthetic polymer roofing.

(The invention will solve the problem B) However, although vulcanized rubber roofing has excellent mechanical strength, there are problems with bonding between sheets, and non-vulcanized rubber roofing can be constructed by relieving internal stress. Although it is relatively easy to follow the sheet and has excellent sheet followability, it has low mechanical strength and requires a protective layer in places where external forces such as walking are applied. In addition, although polyvinyl chloride resin roofing has excellent bonding properties and mechanical strength, it is generally exposed to outdoor exposure for long periods of time because small molecular weight plasticizers such as small molecular weight phthalate ester plasticizers are generally used. During this time, changes in weight and dimensions of the sheet occur due to the volatilization of the plasticizer, which causes the sheet to harden and break at weak points due to shrinkage, resulting in a loss of waterproof function.

Therefore, an object of the present invention is to solve the above-mentioned problems of a polyvinyl chloride resin waterproof sheet, which is stable even when used outdoors for a long period of time with little plasticizer migration, leaching, or volatilization. An object of the present invention is to provide a polyvinyl chloride resin waterproof sheet that has excellent properties, mechanical strength, and bondability.

(Means for Solving the Problems) As a result of intensive research to solve the above problems, the inventors of the present invention have achieved the objective by using a highly durable vinyl chloride resin for coating waterproofing materials. The invention was achieved.

That is, the present invention has an average molecular weight of 100 to 4000,
A polyester plasticizer having an average molecular weight of 1000 to 8000 and a large molecular weight having an average molecular weight of 450 or more to 10 parts by weight of an ethylene-vinyl chloride copolymer resin having an ethylene content of 0.5 to 10.0% by weight. This is a coated waterproof sheet material characterized by containing 30 to 90 parts by weight of a phthalate ester plasticizer, either alone or in combination.

The present invention will be explained below based on its configuration.

The ethylene-vinyl chloride copolymer resin (E-PVC') used in the coated waterproof sheet material of the present invention has an average degree of polymerization of 1.
000 to 4000. Average degree of polymerization is 1000
If it is lower, the mechanical strength will be lower, and the average degree of polymerization will be 40.
This is because if it is higher than 00, processability and economical efficiency will be lowered, which is not preferable. Also, the ethylene content is 0
．． It is required that the content be within the range of 5 to 10.0% by weight, and if it exceeds io, o% by weight, the mechanical strength will decrease, and the melting temperature and viscosity will decrease significantly, resulting in poor processability.
If the amount is less than 0.5% by weight, the internal plasticizing effect of ethylene cannot be obtained, and the processability of the resin with a high degree of polymerization is poor, as is the case with ordinary straight polyvinyl chloride resins.

The polyester plasticizer used in the present invention includes dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, bimerylic acid, superric acid, azelaic acid, sebacic acid, and phthalic acid, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 1,2-butanediol, 1.3-butanediol, ■, 4-butanediol,
2,3-butanediol, 2,2-dimethylpropane-
1,3-diol, 1,4-pentadiol, l,6-
It is a polyester plasticizer having an average molecular weight of 1000 to 8000 and arbitrarily synthesized from various glycols such as hexanediol, 2-methyl-2,4-pentadiol, diethylene glycol, and triethylene glycol. If the average molecular weight exceeds 8,000, the processability, cold resistance, and compatibility of the resulting material will be poor; if it is less than 1,000, migration, leaching, and volatilization will increase, resulting in poor durability under harsh conditions such as long-term outdoor exposure. In other words, the waterproof function deteriorates, which is undesirable.

Further, in the case of a large molecular weight phthalate ester plasticizer, it is preferable that the average molecular weight is 450 or more. If the average molecular weight is lower than this, migration, leaching, and volatilization of the plasticizer increase, resulting in a decrease in durability, that is, waterproof function.

The amount of the two types of plasticizers used is preferably 30 to 90 parts by weight per 100 parts by weight of E-PVC, and the plasticizers can be used alone or in combination.

If the amount is less than 30 parts by weight, the sheet will be hard and have little elongation, which will have poor workability and may cause problems due to stiffness under low temperature conditions. Moreover, if the amount is more than 90 parts by weight, the mechanical strength decreases, and the decrease in strength is significant especially at high temperatures such as in the summer, and there is a possibility that problems may occur due to the application of external force.

Furthermore, the coated tarpaulin sheet material of the present invention may optionally include:
Stabilizers, fillers, pigments, processing aids, etc. used in ordinary flexible polyvinyl chloride resin compositions can be used.

(Function) The coated waterproof sheet material of the present invention uses E-PVC as a haze polymer, and due to the internal plasticizing effect of the ethylene part in E-PVC, it has the same tensile strength as straight polyvinyl chloride resin with the same degree of polymerization. The amount of plasticizer used can range from 5 to 20 parts by weight to obtain the desired physical properties. Furthermore, since it uses a large molecular weight plasticizer such as a polyester plasticizer or a large molecular weight phthalate ester plasticizer, it can It has a higher mechanical strength than waterproof sheet materials, and hardening of the sheet occurs due to weight changes and dimensional changes due to migration, leaching, and volatilization of plasticizers under harsh conditions such as long-term outdoor exposure. It is stable, with no breakage at weak points due to shrinkage, and is particularly preferred as a coated waterproof sheet material.

The coated waterproof sheet material of the present invention has little migration, leaching, or volatilization of plasticizer, so it can be applied by directly contacting the asphalt waterproof layer or foamed styrene insulation board, and it can be applied using a general low molecular weight phthalate ester type. There is no need to use an insulating film or sheet like polyvinyl chloride waterproof sheet materials that use plasticizers, and materials and construction steps can be omitted.

In addition, the coated tarpaulin sheet material of the present invention does not harden or expand or contract even after many years of use, and its mechanical strength is stable, so the sheets can maintain their bonding properties over a long period of time, and are easy to repair and maintain. It is also very good.

(Example) The present invention will be explained below using the following examples and comparative examples.

Various polyester plasticizers and large molecular weight phthalate plasticizers (DUP: diundecyl phthalate is used here) are blended with E-PVC in the proportions shown in Table 1, either alone or in combination, and then mixed with a Hensche mixer. The compound was produced into a 1.5 mm thick sheet using a 1101 twin screw extruder in different directions.

For comparison, a general-purpose small molecular weight phthalate ester plasticizer (DOP di(2-ethylhexyl) phthalate was used here) was blended with E-PVC or straight polyvinyl chloride resin using the same manufacturing method as above. A sheet was prepared and its formulation is shown in Table 1.

E-PVC: Suspension-polymerized ethylene-vinyl chloride copolymer resin with an average degree of polymerization P = 1300 and an ethylene content of 4% General-purpose polyvinyl chloride: Suspension-polymerized polyvinyl chloride resin with an average degree of polymerization P = 1300 Polyester system A: Adipine Acid-1,6-hexanediol system Polyester plasticizer with an average molecular weight of 12,600 Polyester system B: Adipic acid-neopentyl glycol system Polyester plasticizer with an average molecular weight of 2,600 Polyester system C: Sebacic acid-1,6-hexanediol system Polyester plasticizer with an average molecular weight of 6000 Ultraviolet absorber: Tinuvin P (triazole ultraviolet absorber manufactured by Civer Geigy) Polyethylene wax: Low density polyethylene wax Pigment: 0.5 parts by weight of chlorine-method rutile type titanium oxide, 0.5 parts by weight of carbon black. 5 parts by weight Book 9 Calcium carbonate: Shiraika cc (manufactured by Shiraishi Kogyo Co., Ltd.)
The obtained sheet was subjected to a tensile test according to J I 5-A6008 (synthetic polymer roofing) to measure tensile strength, tensile elongation, and 100% modulus, and
Hardness was measured according to JIS-6301 (Vulcanized Rubber Test Method), and the results shown in Table 2 were obtained.

Next, a sample was taken from the same loft sheet as in the above test, and this was placed in the Super Long Life Weather manufactured by Suga Test Instruments Co., Ltd.
J using a meter (WEL-3UN-HCH-B)
I5-A1415 (accelerated exposure test method for plastic building materials) for 9000 hours,
A tensile test was conducted based on I5-A6008 to measure tensile strength and tensile elongation, and JIS-K
Hardness was measured based on 6301, and these values were expressed as a percentage of the normal state physical properties as the weather resistance retention rate, and the results shown in Table 3 were obtained.

Next, the sheet with the same loft as in the above test was JIS-63
Punch out the dumbbell shape No. 3 specified in 3.2 of 01, and heat it at a heating temperature of 80±2°C for a prescribed heating time.
S- was subjected to air heating aging treatment based on 6301, 6.3, and the amount of volatile form due to the heat aging treatment expressed as a percentage of the original test piece weight was defined as the volatilization loss ■. A tensile test was conducted based on S-A6008 to measure tensile strength and tensile elongation, and JIS-K63
The hardness was measured based on No. 01, and these values were expressed as a percentage of the untreated normal state physical property value, which was defined as the heat aging physical property retention rate (■), and the results shown in Table 4 were obtained.

Furthermore, a sheet with the same loft as in the above test was heated at a temperature of 125°C.
At a predetermined heating time, the volatilization loss H and heat aging physical property retention rate H were measured using a method similar to the above method, and the results shown in Table 5 were obtained.

However, the heat aging retention rate ■12 of Comparative Examples 1 and 2 in the table above
The value of 5°C x 30 days was impossible to measure because the sample had hardened too much due to heat aging.

(Effects of the Invention) As explained above, the flexible polyvinyl chloride composition as a coated waterproof sheet material of the present invention has good weather resistance, heat aging resistance, and volatilization loss in addition to room temperature physical properties, so it can be used outdoors for a long time. It is stable in dimensions and physical properties even under harsh conditions such as exposure, and has good mechanical strength and elongation in a wide temperature range from low to high temperatures, so it is not only useful for waterproofing roofs. It is effective for applications that require high performance such as indoor water tanks, swimming pools, and heat storage tanks, and especially as a coated waterproof sheet material that is exposed for long periods of time under harsh outdoor conditions.

hand Continued dispute Positive book Heisei November 29, 2018

Claims (1)

[Claims] 1. To 100 parts by weight of an ethylene-vinyl chloride copolymer resin with an average molecular weight of 1000 to 4000 and an ethylene content of 0.5 to 10.0% by weight, an average molecular weight of 1000 to 8
1. A coated waterproof sheet material, characterized in that 30 to 90 parts by weight of a polyester plasticizer of 0.000 and a large-molecular-weight phthalate plasticizer with an average molecular weight of 450 or more are added alone or in combination.