JPH0655436B2 - Waterproof covering - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a water-repellent, soft unsaturated polyester resin coating material that can be used in civil engineering and construction structures.

[Conventional technology and its problems]

Well-known coating waterproof materials that have been applied to liquid resins such as urethane rubber-based resins, acrylic rubber-based resins, and rubber asphalt-based resins and cured as coating materials with waterproof performance that have been conventionally used in building structures. Has been.

These coating film-preventing materials are mainly used for renovation in the field of building waterproofing, but generally hard to cure, it takes time from the start of construction to restoration, and the elongation is large, but the tensile strength and tear strength are small, There is a drawback that mechanical properties in a pulled state, that is, a state in which a tension is applied are extremely deteriorated and eventually break. Therefore, when a conventional waterproof membrane is used directly on a building structure, if there is expansion or contraction due to temperature changes, if there is severe vibration during use of the building due to the machinery used, location conditions, etc. There is a problem in that the waterproof membrane can follow the movement of the building structure when there is a conflict with the ground and the like, and the membrane waterproof material breaks. In addition, it is possible to reduce the risk of simultaneous rupture with base cracks and creep rupture even if the large elongation ratio of these coating film-preventing materials is impaired, and reinforcement of glass fiber woven fabric, vinylon fiber woven fabric, polyester fiber nonwoven fabric, etc. Although a construction method using materials is used, it is still insufficient in securing a uniform film thickness and resistance to ground cracking.

Fiber reinforced plastics (FRP) is well known as a typical covering lining material using a reinforcing material.
According to "Plastic Materials Lecture 10 (Nikkan Kogyo Shimbun)", epoxy resins, unsaturated polyester resins, phenol resins and polyimide resins are used as resins for FRP, and glass fiber, boron fiber, and Metal fibers, carbon fibers, and the like are known, and quantitatively, unsaturated polyester resin / glass fibers are the majority. These resins are usually hard and have extremely high tensile strength, etc., but have almost no elongation, so that they cannot follow the ground movement in coating applications such as rooftops, balconies, and corridors for waterproofing in building structures. In order to impart flexibility to the resin, means such as softening with an additive such as a plasticizer is also used, but it is not sufficient yet, and when used as an FRP combined with a reinforcing material such as glass fiber. Although the strength is improved, the elongation rate is hindered, it cannot follow the movement of the building, and it cannot be used in a field requiring waterproof performance.

Therefore, there has been a demand for the appearance of a waterproof coating material which is not easily obtained by the conventional coating material, and which has a fast curing property and has a well-balanced base crack resistance and the like.

[Means for solving problems]

The present inventors have conducted various studies to solve these problems and are effective in a field in which a coating material composed of two components, a specified soft unsaturated polyester resin and an organic synthetic fiber nonwoven fabric, requires waterproof performance. Therefore, the present invention has been completed.

That is, the present invention comprises (a) a cured product of a soft unsaturated polyester resin having a tensile product of 100 kgf / cm or more, and (b) an organic synthetic fiber nonwoven fabric having a water retention index of 5 to 20 as a reinforcing material contained therein. It is composed of components, and the weight ratio of (b) to (a) used is 2 to 10% (a waterproof coating material for building structures is provided.

The unsaturated polyester resin of (a) of the present invention is a soft unsaturated polyester resin having a tensile product of 100 kgf / cm or more that can be cured at room temperature, and can be obtained as a mixture of a soft unsaturated polyester and a vinyl monomer. (In the present specification, the unsaturated polyester polymer itself is referred to as an unsaturated polyester, and a mixture of an unsaturated polyester and a vinyl monomer is referred to as an unsaturated polyester resin to distinguish them.) The soft unsaturated polyester is The following is preferable. That is, it is mainly composed of a diol component and a dicarboxylic acid component, and the dicarboxylic acid group (excluding the terminal dicarboxylic acid group) in the chain is 8 mol% or less, preferably 0.1 mol% based on the total amount of the dicarboxylic acid.
Contains not less than 8 mol% of trans 1,2-alkene dicarboxylic acid and 1 at the end based on the total amount of carboxylic acid.
~ 25 mol% of 1,2-alkenedicarboxylic acid is present and has an acid value of 5-60, preferably 16-30, hydroxyl value 0-
30, preferably 0-20.

Examples of diol components include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,5-pentanediol, 1,4- Butanediol, 1,3-butanediol, 1,2-butanediol, pinacol, 2,2-bis [4- (2-hydroxy-propoxy) -phenyl] propane and bisphenol A and several molecules of propylene oxide or ethylene oxide Other adducts with, neopentyl glycol monoester of hydroxypivalic acid, 2,2,4-trimethylpentanediol-1,3 and 3-
Methyl pentanediol etc. can be illustrated.

In the chain, trans-1,2-alkene dicarboxylic acid is 8 mol% or less, preferably 0.1 mol% based on the total amount of carboxylic acid.
The amount is 8 mol% or less. As the trans-1,2-alkene dicarboxylic acid, fumaric acid and mesaconic acid are preferable.

In addition, 1 to 25 mol% based on the total amount of carboxylic acid at the terminal
1,2-alkene dicarboxylic acids are present. As the 1,2-alkene dicarboxylic acid, maleic acid, fumaric acid, mesaconic acid and citraconic acid are preferable.

When the trans 1,2-alkene dicarboxylic acid in the chain is less than 0.1 mol% or the terminal 1,2-alkenedicarboxylic acid is less than 1 mol%, the temperature dependence of elongation is very small and large even at low temperature. Although it has elongation, the tensile strength and tear strength are lowered, and the gelation time and curing time are extremely delayed, and the cured state of the cured product surface is poor and the tackiness remains forever, so the coating material surface becomes easily soiled. There are problems that the aesthetic appearance is significantly impaired, and that it is easily damaged when walking or dropping an object. When the trans 1,2-alkenedicarboxylic acid in the chain exceeds 8 mol% or the terminal 1,2-alkenedicarboxylic acid exceeds 25 mol%, the temperature dependence of the elongation is large and the elongation is higher than that at 20 ° C. The elongation at 0 ° C is extremely reduced.

The soft unsaturated polyester contains a dicarboxylic acid other than the above in the main chain and the terminal. Other carboxylic acids contained in the main chain are aliphatic carboxylic acids, aromatic dicarboxylic acids, alicyclic dicarboxylic acids or alkene dicarboxylic acids having no trans 1,2-configuration. Aliphatic dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dimeric fatty acids, aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, phthalic acid, and alicyclic dicarboxylic acids such as tetrahydrophthalic acid and endo. Examples of methylenetetrahydrophthalic acid, hexachloroendomethylenetetrahydrophthalic acid, and alkenedicarboxylic acid having no trans 1,2-configuration include itaconic acid, maleic acid, and citraconic acid. Preferably, the alkene dicarboxylic acid having no trans 1,2-configuration is present in an amount of 0 to 10 mol% based on the total dicarboxylic acid. However,
Alkenedicarboxylic acids may be converted to the trans compound during production either wholly or mostly by isomerization, and the isomerized moieties should be included in the trans 1,2-alkenedicarboxylic acid.

Examples of the other carboxylic acid contained in the terminal include the above-mentioned aliphatic dicarboxylic acid, aromatic dicarboxylic acid and alicyclic dicarboxylic acid.

Soft unsaturated polyester is a small amount of trimethylolpropane, polyhydric alcohols such as glycerin and trimellitic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,4, to increase mechanical strength. 5-benzenetetracarboxylic acid, 1,
It may contain a polyvalent carboxylic acid such as 4,5,8-naphthalenetetracarboxylic acid. The amount of polyhydric alcohol is 20 mol% or less with respect to the total of diol and polyhydric alcohol, and the amount of polyhydric carboxylic acid is 20 mol% or less with respect to the total amount of carboxylic acid. In this case, the high functionality of both needs to be compensated with a monohydroxy compound or monocarboxylic acid.

Further, in order to improve water resistance, air drying property, and chemical resistance, dichloropentadienyl units can be blended,
Dicyclopentadiene can also be incorporated, for example by reaction with an alkene dicarboxylic acid.

The acid value of the soft unsaturated polyester is 5 to 60 and the hydroxyl value is 30 or less. Acid value less than 5 or more than 60,
Alternatively, when the hydroxyl value exceeds 30, there are problems that mechanical strength is lowered, curing is slow and it cannot be used as a roof waterproofing material, and viscosity becomes high, which causes inconvenience in manufacturing.

The above-mentioned soft unsaturated polyester can be obtained by reacting the above-mentioned raw material or its derivative such as an acid anhydride, a lower alkyl ester and the like by a known method.

The soft unsaturated polyester is preferably produced in two steps. In this case, the excess amount of the glycol component is esterified with the dicarboxylic acid component in the first step, and 1,2-
Rapid esterification is carried out with alkenedicarboxylic acids. The dicarboxylic acid component of the first step then consists of or is isomerized to 8 mol% or less of the trans-1,2-alkenedicarboxylic acid, and the rapid esterification in the second step is It is carried out with the derivative and in this second step the acid or derivative is chosen in such an amount that it forms 1 to 25 mol% of the total dicarboxylic acid. Actually, in the first step, at an reaction temperature of 190 to 220 ° C, an acid value of 10 or less and a hydroxyl value of 15 to
It is reacted until it reaches 60, and then in the second step cis-1,2-
With alkene dicarboxylic acid anhydride at 110-170 ℃
The post-reaction is carried out in 0.5 to 4 hours. Almost no transesterification reaction occurs at such a low reaction temperature. This esterification is preferably carried out in an inert atmosphere and the water of reaction is azeotropically eliminated, for example. If the unsaturated polyester has boiled, cool it.

100 parts by weight of the unsaturated polyester produced in this manner is used as a vinyl polymerizable monomer, for example, styrene, vinyltoluene, tert-butylstyrene, divinylbenzene, alkyl acrylate, alkyl methacrylate, chlorostyrene, bromstyrene. , Vinyl acetate, vinyl propionate, vinyl pivalate, allyl phthalate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, 1,3 butanediol dimethacrylate, 1,4-butanediol dimethacrylate and alkyl vinyl ether. 20 to 200 parts by weight, preferably 40 to 150 parts by weight, of one or more vinyl compounds and, if necessary, for example hydroquinone, parabenzoquinone, chloranil, 2,3-dichloro-5,6 -Dicyano-parabenzoquinone, para-tert-butylcatechol , 2-tert-butyl-1,4-
Hydroquinone, 2,5-di-tert-butyl-1,3-hydroquinone,
A polymerization inhibitor such as copper naphthenate, 1,4-naphthoquinone, hydroquinone monomethyl ether and hydroquinone monoethyl ether is added to obtain the soft unsaturated polyester resin (a).

The tensile product range of the soft unsaturated polyester resin of (a) of the present invention is 100 kgf / cm or more, preferably the tensile product 200 kgf / cm
A soft polyester resin having a cm or more and an elongation of 50% or more. If the tensile product is less than 100 kgf / cm, the toughness of the unsaturated polyester resin that has been cured is poor, and even if a suitable reinforcing material is used, the movement of the building structure, that is, the movement of the construction base, cannot be followed and the waterproof performance is fully demonstrated. There is an inconvenience that you cannot do it.

The tensile product is a value measured by the following method. That is, the thickness of the soft unsaturated polyester resin after film formation is about 2.5 by the usual method using a peroxide initiator or the like.
It is cured into a sheet so that it becomes mm. Curing of the sheet-shaped cured product is 72 hours or more, and after curing, it is punched out using a dumbbell-shaped No. 3 type specified in JIS K6301 (vulcanized rubber test method) to obtain a tensile product measurement test piece. Tensile product (kgf / cm) is calculated by the following formula using the tensile strength (kgf / cm ² ) and the distance between marked lines at break (cm). The tensile strength and the distance between marked lines at break are measured according to JIS K6301 "3. Tensile test".

Tensile product _{(kgf / cm) = T B} × (L-L O) Here _{T B:} tensile strength (kgf / cm ²⁾ L: distance between marked lines at break (cm) _{L O:} between marked lines Distance (cm) The organic synthetic fiber nonwoven fabric having a water retention index of 5 to 20 of (b) used in the present invention is nylon, vinylon, polyethylene, polypropylene, polyvinyl chloride, polyester, etc. in terms of material, and nylon, vinylon Polyester fiber non-woven fabric is preferred. The water retention index according to the present invention means that a flat plate such as a Teflon plate, a polyethylene plate or a polypropylene plate is installed at an angle of 45 degrees (water support plate), and the organic synthetic fiber nonwoven fabric (about 20 cm x 25 cm) is immersed in water. After soaking it for 1 minute to allow it to absorb water, leave it on the water-retaining support plate and hold it for 1 minute (g
The value obtained by dividing r) by the weight (gr) of the organic synthetic fiber nonwoven fabric was taken as the water retention index of the organic synthetic fiber nonwoven fabric. The organic synthetic fiber nonwoven fabric (b) used in the present invention has a water retention index of 5
Those of ~ 20 are suitable. When the water retention index is less than 5, the effect as a reinforcing material is small, and when the water retention index exceeds 20, the soft unsaturated polyester resin (a) is absorbed, and air shortage occurs in the organic synthetic fiber due to lack of resin. It is easy and it is difficult to secure a uniform thickness for both. Further, even if the organic synthetic fiber nonwoven fabric used in the present invention is a uniform nonwoven fabric having a water retention index of 5 to 20,
A hole may be provided in a part. When the holes are provided, the impregnation property is improved. The diameter of the holes is usually 1 to 30 mm.

The proportion of the organic synthetic fiber nonwoven fabric (b) used is 2 to 10% by weight based on the soft unsaturated polyester resin (a).
If it is less than 2%, the effect as a reinforcing material cannot be obtained, and there is an inconvenience in resistance to base cracks against movement of buildings.
%, The soft unsaturated polyester resin of (a) is almost impregnated in the organic synthetic fiber nonwoven fabric, resulting in poor adhesion between the waterproof layer and the construction base surface, blisters (air pool), etc. Cause problems.

The organic synthetic fiber nonwoven fabric is used by laminating one or more layers.

The waterproof coating of the present invention may optionally contain fillers, pigments, colorants and the like. The amount of these is preferably 5 to 200 parts by weight based on 100 parts by weight of the unsaturated polyester resin. Further, paraffin wax having a melting point of 40 to 70 ° C. may be contained in an amount of 0.2 to 0.8 parts by weight, in which case the air-drying property is improved.

In order to apply the waterproof coating material of the present invention, for example, a general coating film waterproof material (construction method with full-faced reinforcing material described in JASS 8
L-UF, etc.) should be installed. The soft unsaturated polyester resin can be cured with a peroxide initiator in a conventional manner. For example, when a benzoyl peroxide / amine curing system is used, it can be cured in a short time even at a low temperature such as 0 to 20 ° C. Specifically, a construction in which the soft unsaturated polyester resin mixed with a curing agent system is applied to the construction base surface, the organic synthetic fiber non-woven fabric is charged, and further the soft unsaturated polyester resin is applied and impregnated and integrally cured. The total amount of the soft unsaturated polyester resin used is preferably 1.0 to 4.5 kg per 1 square meter in consideration of reliability and economical efficiency as a waterproof layer. Also,
A method may also be used in which (a) and (b) used in the present invention are used as a sheet-shaped molded product in advance, and the sheet is attached to the construction base surface with the same resin (a). Further, if necessary, the application of a primer for the surface treatment agent, the top coat, etc. may improve the adhesion to various substrates and may be aesthetically acceptable.

〔Example〕

 The present invention will be described in detail below with reference to examples.

Example 1 In a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a Vigreux agglomeration tube, 1104 g of neobenthyl glycol was added.
(10.6 mol), 1418 g (9.7 mol) of adipic acid, and 35 g (0.3 mol) of fumaric acid were charged, heated under a nitrogen atmosphere, esterified at 215 ° C, and water was distilled off until the acid value reached 6. did. Then cool it to 150 ° C. Maleic anhydride 7
8 g (0.8 mol) was added, and after reacting at 150 ° C for 2 hours, the reaction product was cooled to 100 ° C. After reaching 100 ° C., 1300 g of styrene and 150 mg of hydroquinone were added.

The mixture thus obtained had a solids content of 57%. This is referred to as unsaturated polyester resin <A>.

50% benzoyl peroxide 3% by weight and N, N-dimethyl-paratoluidine based on unsaturated polyester resin <A>
After curing and curing for 72 hours using 0.3% by weight, JIS A602
The physical properties of the cured product sheet were measured according to 1.
It was 120 kg / cm ² , elongation 270% and tensile product 650 kg / cm.

Also, a polypropylene flat plate was installed at a 45 ° angle as a water retention indicator board, and a polyester non-woven fabric (manufactured by Toyobo Spunbond Co., Ltd.) was cut into 20 cm x 25 cm (weight 4.8 g) and immersed in water for 1 minute. After that, the weight after standing for 1 minute on the water retention indicator board was 56.4 g, and this nonwoven fabric having a water retention index of 12 was designated as nonwoven fabric <I>.

A waterproof coating material was formed using these unsaturated polyester resin and polyester non-woven fabric, and the adhesive strength and cyclic fatigue properties were measured.

The formation of a waterproof coating material is carried out by mixing the unsaturated polyester resin with a curing agent system similar to the above, applying 1 kg / m ² (undercoat) and immediately impregnating this polyester nonwoven fabric and further impregnating the resin with 1 kg / m 2. ² applied (intermediate coating). After the applied resin was cured (about 2 hours), the resin was further overcoated with 0.8 kg / m ² to give a waterproof coating material. The waterproof coating material was converted into per square meter of rice, and the total amount of the unsaturated polyester resin (a) was 2.8 kg per 103 g of the organic synthetic fiber nonwoven fabric (b), and the weight ratio (() of (b) to (a) was used. b) / (a)) was 3.7%.

The adhesive strength evaluation method is JIS A5304 "Pavement concrete plate for sidewalks". The waterproof coating material is formed using a flat plate as a base material, and after curing and curing for 72 hours or more, 4 cm x 4 cm.
An iron attachment having an adhesion area of 1 was attached, the periphery of the attachment was cut to the surface of the base, the attachment was pulled, and the tensile strength was calculated by the following formula.

Here, F: adhesive strength (kgf / cm ² ) P: maximum load (kgf) A: adhesive area (16 cm ² ) The adhesive strength of the waterproof coating material was 21 kgf / cm ² . or,
For cyclic fatigue characteristics, refer to “Standard specifications for construction work / Commentary-JASS
8 Waterproofing work ”(Architectural Institute of Japan) and asbestos cement board (8 mm thickness) specified in JIS A 5403 is used as the base material 1
It was used as 20 mm x 400 mm. A notch was made in the central part of the base material from the back side in advance, the waterproof coating material was formed on the surface, and the notch was broken before the test to form a crack in the base, and a test piece for repeated fatigue properties was prepared.

Cyclic fatigue properties are evaluated by the crack width of the base from 0 mm to 3 m.
After repeating 300 times under the conditions of m and a repeating cycle of 30 seconds, the appearance was inspected.

No abnormalities were observed in the waterproof coating material under repeated cracking fatigue test of 300 times under repeated cracks.

Example 2 711 g (5.3 mol) of dipropylene glycol and 552 g (5.3 mol) of neopentyl glycol were used as diol components.
In addition, the dicarboxylic acid component is adipic acid 709 g (4.85 mol), isophthalic acid 806 g (4.85 mol), fumaric acid 35 g (0.35 mol).
Mol) and 78 g (0.8 mol) of maleic anhydride were synthesized in the same manner as in Example-1 to obtain an unsaturated polyester resin <B> having a solid content of 59%. The physical properties of the cured product cured in the same manner as in Example-1 were a tensile strength of 67 kgf / cm ² , elongation of 250%, and tensile product of 335 kgf / cm.

In addition, polyester non-woven fabric <II> (Toyobo Spunbond
The water retention index was measured in the same manner as in Example 1 to find that the water retention index was 8 and the weight per square meter was 92 g.

The formation of the waterproof coating is the same as in Example-1, but the top coat is applied.
And 1.0 kg / m ^2, the nonwoven fabric <II> 92 g total of the resin <B> to the 3kg, and the use proportion by weight of the nonwoven fabric was 3.1%.

The adhesive strength measured in the same manner as in Example-1 was 22 kgf / cm ² , and no abnormality was found in the repeated fatigue property test.

Example 3 1104 g (10.6 mol) of neopentyl glycol as a diol component and 1344 g (9.2 mol) of adipic acid, 12 g (0.1 mol) of fumaric acid and 196 g of maleic anhydride as a dicarboxylic acid component.
The reaction was performed in the same manner as in Example-1 except that the amount was 2.0 mol, 800 g of styrene and 150 mg of hydroquinone were added, and an unsaturated polyester resin <C> having a solid content of 67% was obtained.

The physical properties of the cured product cured in the same manner as in Example-1 have tensile strength of 4
8 kgf / cm ² , elongation rate 150%, and tensile product 145 kg / cm 2.

In addition, polyester non-woven fabric <III> (Toyobo Spunbond
The water retention index was measured in the same manner as in Example-1. As a result, the water retention index was 16 and the weight per square meter was 160 g.

The method for forming the waterproof coating is the same as in Example-1, except that the undercoat, middle coat, and top coat each have a weight of 1.5 kg / m ² , and a total of 4.5 kg / m.
^It became ² , and the weight ratio of the non-woven fabric used was 3.6%.

The adhesive strength measured in the same manner as in Example-1 was 24 kgf / cm ² , and no abnormality was found in the repeated fatigue property test.

Comparative Example 1 The diol component was dipropylene glycol 403 g (3.0 mol), triethylene glycol 300 g (2.0 mol) and neopentyl glycol 583 g (5.6 mol), and the dicarboxylic acid component was phthalic anhydride 1110 g (7.5 mol). Fumaric acid 232
An unsaturated polyester resin <D> having a solid content of 60% was obtained by the same synthesis as in Example 1 except that g (2.0 mol) and maleic anhydride 147 g (1.5 mol) were used. Example-1
The cured product has the same tensile strength of 122 kgf / c.
The m ^{2 was} 35%, the elongation was 35%, and the tensile product was 85 kgf / cm.

Examples of formation of organic synthetic fiber nonwoven fabric and waterproof coating material
When the physical properties were measured in the same manner as -1, the adhesive strength was 26kgf.
Although it was / cm ² , it broke in the repeated fatigue property test.

Examples 4 to 7, Comparative Examples 2 to 7 The unsaturated polyester resin <A> synthesized in Example 1 was used, the organic synthetic fiber nonwoven fabric used was the nonwoven fabric used in Examples 1 to 3, and other than that. As for the product, the water retention index was measured and used in the same manner as in Example 1. A waterproof coating material is formed according to Example 1 so that the weight ratio of the non-woven fabrics is different,
The bond strength and cyclic fatigue properties were tested. Table of results
Shown in 1.

(Effects of the invention) The waterproof coating material of the present invention has a large adhesive strength with the base surface and is excellent in repeated cracking fatigue resistance of the base material, so that it follows the movement of the base material of a building well, and even when tension is applied, it breaks. Hateful. Further, the waterproof coating material maintains the quick-curing property, and the work during construction is easily performed.

Claims (1)

[Claims] 1. A cured product of a soft unsaturated polyester resin having a tensile strength of 100 kgf / cm or more, and (b) a water retention index of 5 to 5 as a reinforcing material contained therein.
It consists of two components of 20 organic synthetic fiber nonwoven fabrics, (b)
The water-proof coating material for a building structure, wherein the used weight ratio to (a) is 2 to 10%.