JPS63137837A - Waterproof coating material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a soft unsaturated polyester resin coating material having waterproof performance that can be used for civil engineering and architectural structures.

[Conventional technology and its problems]

As coating materials with waterproof performance that have been conventionally used for architectural structures, coating film waterproofing materials that are coated with liquid resins such as urethane rubber resins, acrylic rubber resins, and rubber asphalt resins and then cured are well known. It is being

These coating film waterproofing materials are mainly used for renovation purposes in the field of architectural waterproofing, but they generally harden slowly, taking time from the start of construction to restoration, and although they have a high elongation rate, they have low tensile strength and tear strength. It has the disadvantage that its mechanical properties in a stretched state, ie, a state in which tension is applied, are extremely reduced and it eventually breaks. Therefore, if conventional coating film waterproofing materials are used directly on building structures, there may be expansion or contraction due to temperature changes, there may be severe vibrations due to the use of the building due to the machinery used, location conditions, etc., or there may be problems caused by The problem is that the coating film waterproofing material cannot follow the movement of the building structure, such as when there is a conflict between the foundations, and it eventually breaks. In addition, even if the high elongation rate of these coating film waterproofing materials is lost, the risk of simultaneous rupture with base cracks and creep rupture can be reduced, so woven glass fiber fabrics, vinylon fiber fabrics, polyester fiber woven fabrics, etc. Construction methods using reinforcing materials and specifications have been used, but ensuring uniform film thickness and cracking resistance of the base are still insufficient.

Fiber reinforced plastic (FRP) is well known as a typical covering lining material using reinforcing materials.

According to "Plus Materials Course 10" (Nikkan Kogyo Shimbun), the resins used in FRP include epoxy resin, unsaturated polyester resin, phenol resin, and polyimide resin, and the reinforcing materials include glass fiber, boron fiber, Metal fibers, carbon fibers, etc. are known, and unsaturated polyester resin/glass fiber accounts for the majority.

These resins are usually hard and have extremely high tensile strength, etc., but have almost no elongation, so they cannot follow the movement of the base when used to cover rooftops, balconies, kitchens, etc. for the purpose of waterproofing architectural structures. In order to impart rootability to the resin, methods such as making it flexible with additives such as plasticizers have been used, but this is not yet sufficient, and furthermore, when used as FRP in combination with reinforcing materials such as glass fiber, Although the strength is improved, the elongation rate is impaired, and it cannot follow the movement of buildings, making it impossible to use in fields that require waterproof performance.

Therefore, it is desired to develop a waterproof coating material that does not have pores of 1 nm in conventional coating materials, has fast curing properties, and has base crack resistance with an unbalanced coating.

[Means to solve the problem]

The present inventors have conducted various studies to solve these problems, and have identified a two-component coating material of soft unsaturated polyester resin and organic synthetic fiber nonwoven fabric that is effective in fields that require waterproof performance. We have discovered that this is the case and have completed the present invention.

That is, the present invention consists of two components: (a) a cured product of a soft unsaturated polyester resin with a tensile bond of 100 kg4/cm or more, and (b) an organic synthetic fiber nonwoven fabric with a water retention index of 5 to 20; The weight ratio used for a) is 2 to 10%
The present invention provides waterproof coating materials for architectural structures.

The unsaturated polyester resin (a) of the present invention is a soft unsaturated polyester resin that can be cured at room temperature and has a tensile area of 100 kgf/cm or more, and can be obtained as a mixture of a soft unsaturated polyester and a vinyl monomer. (In this specification, the unsaturated polyester polymer itself is referred to as unsaturated polyester, and the mixture of unsaturated polyester and vinyl monomer is referred to as unsaturated polyester resin for distinction.) Soft unsaturated polyester is Preferably, it is as follows. That is, it is mainly composed of a diol component and a dicarboxylic acid component, and the dicarboxylic acid group in the chain (excluding the terminal dicarboxylic acid group) is 8 mol % or less, preferably 0.
Contains 1 to 8 mol% of trans-1,2-alkenedicarboxylic acid, and 1 to 25 mol% of 1.2-alkenedicarboxylic acid exists at the terminal based on the total amount of carboxylic acid, and the acid value is 5 to 60, preferably 16 to
30, hydroquine number O-30, preferably O-20.

Diol components include ethylene glycol, pukopylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, 1.4-chlorohexanedimethanol, 1.6
-hexanediol, 1,5-bentanediol, 1.
4-butanediol, 1,3-butanediol, 1,2
-butanediol, pinacol, 2゜2-bis[4-(
2-Hydroxy-propoxy)-phenyl]propane and other adducts of bisphenol A with several molecules of propylene oxide or ethylene oxide, neopentyl glycol monoester of hydroxypivalic acid, 2.2.4-
Examples include trimethylpentanediol-1.3 and 3-methylbentanediol.

In the chain, trans-1,2-alkenedicarboxylic acid is present in an amount of 8 mol% or less based on the total amount of carboxylic acid, preferably 0,1
It is present in mol% or more and 8 mol% or less. trans-1,2-
As the alkenedicarboxylic acid, fumaric acid and mesaconic acid are preferred.

Furthermore, 1 to 25 mol % of 1,2-alkenedicarboxylic acid is present at the terminal, based on the total amount of carboxylic acid. 1.2
- As the alkenedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, and citraconic acid are preferred.

When the trans-1,2-alkenedicarboxylic acid in ii′i is less than 0.1 mol% or the terminal 1,2-alkenedicarboxylic acid is less than 1 mol%, the temperature dependence of the elongation rate is very small; Although it has a large elongation rate even at low temperatures, the tensile strength and tear strength are reduced, and the gelation time and curing time are extremely slow, resulting in poor hardening of the surface of the cured product and tackiness remaining indefinitely. There are problems such as the product becoming more prone to breakage, resulting in a noticeable deterioration of its aesthetic appearance, and being more likely to be damaged when walking or dropping something. Also, trans-1,2-alkenedicarboxylic acid in the chain is 8 mol%
or when the content of the terminal 1,2-alkenedicarboxylic acid exceeds 25 mol %, the temperature dependence of the elongation rate is strong and the elongation rate at 0°C is extremely lower than that at 20°C.

The soft unsaturated polyester contains dicarboxylic acids other than those mentioned above in the main chain and at the ends. Other carboxylic acids contained in the main chain are aliphatic dicarboxylic acids, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, or alkenedicarboxylic acids having no trans 1,2-configuration. Aliphatic dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, and dimer fatty acids; aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, and phthalic acid; and alicyclic dicarboxylic acids include tetrahydrophthalic acid and endo. Examples of methylenetetrahydrophthalic acid, hexachloroendomethylenetetrahydrophthalic acid, and alkenedicarboxylic acids having no trans 1,2-configuration include itaconic acid, maleic acid, and citraconic acid. Preferably, the alkenedicarboxylic acid having no trans 1,2-configuration is present in an amount of 0 to 10 mole percent relative to the dicarboxylic acid. However, with regard to cis-alkenedicarboxylic acids, they may be completely or mostly converted to trans compounds by isomerization during production, and the isomerized portion should be included in trans-1,2-alkenedicarboxylic acids. .

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

Soft unsaturated polyesters contain small amounts of trimethylolpropane, polyhydric alcohols such as glycerin, trimellitic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,4.5-butanetetracarboxylic acid, etc. to increase mechanical strength. -Hensentetracarboxylic acid, L4.5.8-Naphthalenetetracarboxylic acid. The amount of polyhydric alcohol is 20 mol % or less based on the total of diol and polyhydric alcohol, and the amount of polyhydric carboxylic acid is 20 mol % or less based on the total group of carboxylic acids. In this case, both high functionalities have to be compensated with monohydroxy compounds or monocarboxylic acids.

Additionally, dichloropentadienyl units can be incorporated to improve water resistance, air drying properties, and chemical resistance, and synchlopentadiene can also be incorporated by reaction with alkenedicarboxylic acids. I can do that.

The soft unsaturated polyester has an acid value of 5 to 60 and a human quinol value of 30 or less. If the acid value is less than 5 or more than 60, or the hydroxyl value exceeds 30, the mechanical strength will decrease, curing will be slow and it cannot be used as a rooftop waterproofing material, and the viscosity will increase! l! There are problems such as structural inconveniences.

The above-mentioned soft unsaturated polyester can be obtained by reacting the above-mentioned raw materials or their derivatives, such as acid anhydrides, lower alkyl esters, and similar substances, by a known method.

Preferably, the soft unsaturated polyester is produced in two steps. In this case, in the first step, the excess amount of the glycol component is esterified with the dicarboxylic acid component, and in the second step, 1.
Esterification is carried out quickly using 2-flukenedicarboxylic acid. At that time, the dicarboxylic acid component in the first step was 8 mol%
consisting of or isomerized to a trans-1,2-alkenedicarboxylic acid, and the rapid esterification in the second step is carried out using an alkenedicarboxylic acid or a derivative thereof; The acid or derivative is selected in such an amount that it forms 1 to 25 mole percent of the total dicarboxylic acids. Actually, the first step is 190~
The reaction is carried out at a reaction temperature of 220°C until the acid number is almost below 1O and the hydroxyl number is 15-60, and then in the second step, the reaction is carried out using cis-1,2-flukenedicarboxylic anhydride at 110-170"C. The post-reaction takes place in 0.5 to 4 hours.At such a low reaction temperature, almost no transesterification reaction occurs.This esterification is
Preference is given to carrying out in an inert atmosphere, and the water of reaction is removed, for example azeotropically. If the unsaturated polyester is boiled, it is cooled.

Vesicles thus produced 141 Polyester 10
0 parts are replaced by a vinyl polymerizable monomer, such as styrene,
Vinyl toluene, tert-butylstyrene, divinylhensen, alkyl acrylate, alkyl methacrylate, chlorstyrene, bromustyrene, vinyl acetate, vinyl propionate, vinyl pivalate, allyl phthalate, diallyl phthalate, triallyl cyanurate, isocyanuric acid. one or more vinyl compounds such as triallyl acid, 1.3-butanediol dimethacrylate, L4-butanediol dimethacrylate and alkyl vinyl ether2
Dilute with 0 to 200 parts by weight, preferably 40 to 150 parts by weight, and optionally 2 such as hydroquinone, barahenzoquinone, chloranil, 2,3-dichloro-5,6
- dicyatzoquinone, para-tert-butylcatechol, 2-tert-butyl-1,4-hydroquinone, 2.
5-di-tert-butyl-1,3. Hydroquinone, naphthenic acid and a polymerization inhibitor such as 1,4-naphthoquinone, hydroquinone monomethyl ether and hydroquinone monoethyl ether are added to obtain the soft unsaturated polyester resin (a).

The soft unsaturated polyester resin (a) of the present invention has a tensile product range of 100 kgf/cm or more, preferably a tensile product of 200 kgf/cm or more and an elongation rate of 50% or more. Tensile load 100kgf/
If it is less than cm, the toughness of the cured unsaturated polyester resin will be poor, and even if appropriate reinforcing materials are used, the building structure will not move.
In other words, there is a disadvantage that it cannot follow the movement of the construction base and cannot exhibit sufficient waterproof performance.

Note that the tensile product is a value measured by the following method. That is, a soft unsaturated polyester resin is formed into a film with a thickness of approximately 2.5 mm by a conventional method using a peroxide initiator or the like.
Cured into a sheet to a thickness of 5 mm. Curing of the sheet-shaped cured material is for 72 hours or more, and after curing JIS K63
01 (Test method for vulcanized rubber) using a Danher shape No. 3 to punch out and use it as a test piece for measuring tensile precision. The tensile product (kgf/cm 2 ) is calculated by the following formula using the tensile strength (Jf/cffl) and the distance between the gauge lines at break (cm). The tensile strength and distance between gauge lines at break are measured using J.
Based on "3. Tensile test" of IS K6301.

Tensile product (kgf/cm ) = T11
) here T8 + tensile strength kgf/c+fl) L
: Distance between marked lines at break (cm) Lo, Distance between marked lines (cm) The organic synthetic fiber nonwoven fabric with a water retention index of 5 to 20 used in the present invention (b) is a material such as nylon, vinylon, etc. ,
Examples include polyethylene, polypropylene, polyvinyl chloride, and polyester, with nylon, vinylon, and polyester fiber nonwoven fabrics being preferred.

Furthermore, the water retention index according to the present invention refers to a Teflon plate, a polyethylene plate, or a polypropylene plate installed at an angle of 45 degrees (water retention support plate base), and the organic synthetic fiber nonwoven fabric (
Approximately 20cm
) divided by the weight (gr) of the organic synthetic fiber nonwoven fabric was defined 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 to 20. If the water retention index is less than 5, it will have little effect as a reinforcing material, and if the water retention index exceeds 20, it will absorb the soft unsaturated polyester resin (a), causing air pockets etc. to occur due to lack of resin in the organic synthetic fiber. Both have the disadvantage that it is difficult to ensure a uniform thickness. Further, the organic synthetic fiber nonwoven fabric used in the present invention may be a nonwoven fabric that is uniform over the entire surface or may have holes formed in a portion thereof, as long as the water retention index is within the range of 5 to 20. If holes are provided, impregnating properties will be improved. The diameter of the holes is typically 1-30+ nm.

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 reinforcement (t) cannot be obtained, and there is a problem in the foundation crack resistance against movement of the building. If it is used in excess of 10%, the soft unsaturated polyester of (a) Most of the resin is impregnated into the organic synthetic fiber non-IN cloth, resulting in problems such as poor adhesion between the waterproof layer and the base surface, and blisters (air pockets).

The synthetic fiber nonwoven fabric is used in one or more layers.

The waterproof covering material of the present invention may include fillers, face f4,
May contain colorant and 11 packs. For these mice, 5 to 5 parts by weight per 100 parts by weight of unsaturated polyester resin.
200 parts of acetic acid is desirable. Further, about 0.2 to 0.8 parts by weight of paraffin wax having a melting point of 40 to 70°C may be contained, and in this case, air drying properties are improved.

In order to construct the waterproof covering material of the present invention, for example, a normal paint film waterproofing material (such as L-IP, a construction method containing full-surface reinforcing material described in JASS 8) may be used. The soft unsaturated polyester resin can be cured using peroxide initiation in a conventional manner.

For example, when using a hendiyl peroxide/amine curing system,
It can be cured in a short time even at temperatures as low as 0 to 20"C.Specifically, the soft unsaturated polyester resin mixed with a curing agent system is applied to the construction base surface, and the synthetic fiber nonwoven fabric is cured. It is sufficient to use a construction method in which a soft unsaturated polyester resin is charged, and then a soft unsaturated polyester resin is applied, and the impregnated and integrally cured. The amount is preferably 1.0 to 4.5 kg per square meter.Also, using (a) and part) used in the present invention, form a sheet-like product in advance, and then mold the sheet into the same resin (a). ) may be used.Furthermore, if necessary, application of a primer treatment agent, top coat, etc. may be applied to improve adhesion to various substrates, and there is no problem in terms of aesthetics.

〔Example〕

The present invention will be explained in detail below using examples.

Example 1 Neopentyl glycol 110 was placed in a flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a Vigreux collection tube.
4g (10,6 mol), adipic acid 1418g (9
, 7 mol) 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 number reached 6. Next, add this to 1
Cooled to 50 °C Maleic anhydride 78 g (0.8 mol)
was added, and after reacting at 150°C for 2 hours, the reaction product was
Cooled to 00°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>.

After curing for 72 hours using 50% 0% hendiyl peroxide amount % and 0.3 weight % N,N-dimethyl-paratoluidine based on the unsaturated polyester resin <A>,
As a result of measuring the physical properties of the cured sheet according to JIS A6021, the tensile strength was 120 kg4/c+fl, and the elongation rate was 27.
0χ and tensile product 650 kgf/cm.

In addition, a polypropylene lower plate was installed at a 45-degree angle as a temporary water-retaining finger holder, and a polyester nonwoven fabric (Toyobo spunbond @t cut into 20cm x 25co+ and weighing 4.8g) was immersed in water for 1 minute. After that, the weight of the polyester nonwoven fabric after being left for 1 minute on a water retention finger board stand was 56.4 g, and the water retention index of the polyester nonwoven fabric was 12. This nonwoven fabric is referred to as nonwoven fabric <I>.

Waterproof coatings were formed using these unsaturated polyester resins and polyester nonwoven fabrics, and their adhesive strength and cyclic fatigue properties were measured.

To form the waterproof covering material, mix the same curing agent system as above into the unsaturated polyester resin, apply 1 kg/application (undercoat) immediately, apply this polyester nonwoven fabric, and impregnate it.
Furthermore, 1 kg/n of the resin? l Cloth Shitaku intermediate coating). After the applied resin has hardened (approximately 2 hours), the resin is further diluted with 0.8
kg/n (top coated to make waterproof covering material. Unsaturated polyester resin (a1
The total weight was 2.8 kg, and the weight ratio ((b)/(a)) of (b) to (a) was 3.7%.

The method for evaluating adhesive strength is to form the waterproof covering material using a flat plate as the base material specified in JIS^5304 r Concrete Plate for Sidewalks, and after hardening and curing for 72 hours or more,
An iron acuntiment having an adhesion area of 4 cm x 4 m was attached, a cut was made around the acuntiment to the base surface, the acuntiment was pulled, and the tensile strength was determined using the following formula.

A P = Maximum number of layers (kgf) A: Adhesive area (16cm) The adhesive strength of the waterproof covering material was 21kgf/cIA, and the cyclic fatigue characteristics were determined according to the "Standard Specifications for Construction Works/Commentary - Based on JASS 8 Waterproofing J (Architectural Institute of Japan), 120mm x 40 using asbestos cement board (8mw thickness) specified in JIS A3403 as the base material.
It was used as 0 mm. A cut was made from the back side of the base material in the center, the waterproof coating was formed on the surface, and before the test, the cut portion was broken to create a crack in the base material, and a specimen was used for repeated fatigue properties.

Evaluation of cyclic fatigue properties is based on the base crack width Omm.
The test was repeated 300 times under the conditions of 7 IJ and 130 seconds, and then a visual inspection was conducted.

No abnormality was found in the waterproof coating material in a 300 round repeated fatigue property test for cracking the base.

Example 2 The diol component was added to 711 g of dipropylene glycol (5,
3 mol) and 552 g (5,
3 mol), and the dicarboxylic acid component was 70 mol of adipic acid.
9g (4.85 mol), isophthal fJ2806g (4
, 85 mol), 35 g (0.3 mol) of fumaric acid and 78 g (0.8 mol) of maleic anhydride D were used, and an unsaturated polyester resin with a solid content of 59% was synthesized in the same manner as in Example-1. <B> was obtained. The physical properties of the cured product cured in the same manner as in Example-1 were a tensile strength of 67 kgf/l:J, an elongation rate of 250 χ, and a tensile area of 335 kgf/cm.

In addition, the water retention index of the polyester nonwoven fabric (manufactured by Toyobo Spunbond TL,!3) was measured in the same manner as in Example-1, and the water retention index was 8 and the weight per square meter was 92 g.

The formation of the waterproof covering material was the same as in Example-1, but the top coat was 1.0 kg/bo, the total amount of the resin <B> was 3 kg for the nonwoven fabric <11>92 g, and the weight ratio of the nonwoven fabric was It was 3.1%.

Adhesive strength measured in the same way as Actual Example-1 was 22kgf/C
rA, and no abnormality was observed in the repeated fatigue property test.

Example 3 Neopentyl glycol 1104g (1
0.6 mol), and the dicarboxylic acid component is adipic acid 134
4g (9,2 mol), fumaric acid 12g (0,1 mol)
The reaction was carried out in the same manner as in Example 1 except that 196 g (2.0 mol) of maleic anhydride was used, and styrene 800e and 150 mg of hydroquinone were added to obtain an unsaturated polyester resin <C> having a solid content of 67%. Ta.

The physical properties of the cured product cured in the same manner as in Example-1 were tensile strength of 48 kgf/cd, elongation rate of 150χ, and tensile area of 145.
kg/cm.

In addition, polyester nonwoven fabric <m><Toyobo Spunpond 9 grade) had a water retention index similar to Example-1! As a result, the water retention index was 16 and the weight per square meter was 160g.
Met.

The method of forming the waterproof covering material was the same as in Example-1, but the base coat, intermediate coat, and top coat were each 1.5 kg/+4, for a total of 4.5 kg/nf, and the weight ratio of the nonwoven fabric used was 3.
It was 6%.

Adhesive strength measured in the same manner as Example-1 was 24 kgf/c
ml, and no abnormality was observed in the repeated fatigue property test.

Comparative Example 1 403g of dipropylene glycol (3
,00 mol), triethylene glycol 300g (2,00 mol),
0 mol) and neopentyl glycol 583 g (5,6
mole), and the dicarbonate component is phthalic anhydride 11
10 g (7.5 mol), fumaric acid 232 g (2.0 mol) and maleic anhydride 147 g (1.5 mol) were synthesized in the same manner as in Example-1, and had a solid content of 60%. An unsaturated polyester resin <D> was obtained. The physical properties of the cured product cured in the same manner as in Example 1 are as follows: tensile strength: 122
kg+/c+l! , elongation rate 35% and tension 1 to 85k
gf/cm.

The formation of the organic synthetic fiber nonwoven fabric and the waterproof covering material was the same as in Actual Example 1 (when the physical properties were measured, the adhesive strength was 2.
Although it was 6 kgf/effl, it fractured in two cyclic fatigue tests.

Examples 4-'7, Comparison i: ;If 2-7 The unsaturated polyester resin A> synthesized in Example 1 was used, and the organic synthetic fiber (N) was used as the nonwoven fabric used in Examples 1-3. The water retention index of the other samples was measured in the same manner as in Example 1 and used. A waterproof covering material was formed by using the same method as in Example 1, using a different weight ratio of the nonwoven fabric, and the adhesive strength and repeatability and fatigue properties were tested. The results are shown in Table-1.

Claims (1)

[Claims] Consists of two components: (a) a cured product of a soft unsaturated polyester resin with a tensile product of 100 kgf/cm or more, and (b) an organic synthetic fiber nonwoven fabric with a water retention index of 5 to 20, and the use of (b) for (a) A waterproof covering material for architectural structures having a weight percentage of 2 to 10%.