JPH05186572A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which has an excellent curability, gives a cured article having a high elongation at normal temp., a sufficient flexibility to follow cracks occurring on a substrate, and an excellent resistance to wet heat at a high temp. and corrosion due to alkali in cement, and is best suited for a water-proof material, a flooring material, and a lining material. CONSTITUTION:The title compsn. comprises a polyester having a content of a terminal unsatd. monocarboxylic acid of 1-25mol% of the total content of the carboxylic acid and a content of an intramolecular unsatd. carboxylic acid of 8mol% or lower and an unsatd. monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester resin composition which is excellent in curability, has flexibility at room temperature, and has excellent high temperature wet heat resistance and alkali resistance and is suitable for use as a roof waterproofing material. Is.

[0002]

2. Description of the Related Art Conventional roof waterproofing materials include:
Asphalt, rubber sheet, vinyl chloride sheet, urethane resin, acrylic resin, unsaturated polyester resin, etc. are used. Asphalt has the characteristics that it can be applied even if there is some unevenness on the base, has a low water absorption rate, etc.It is also inexpensive and can secure a large thickness by the laminated structure, and it is used as a holding mortar construction method and various reinforcing materials. It is most widely used in new buildings because the combination can form a highly reliable waterproof layer. However, since the adhesive strength is small, phenomena such as peeling and floating occur, and because the mechanical strength is low, it is not possible to follow the movement of the base material due to building vibration, contraction crack of the base concrete, etc. Trouble is likely to occur. Also, in the repair work, since the melting pot is brought to the site to heat and melt the asphalt, there is no risk of odor or fire, and the construction becomes large scale.If it is applied directly on the presser mortar, it will swell. It is not possible to use it for walking when the repair specification is an exposed asphalt construction method, and the adhesive strength is very small for asphalt that has begun to deteriorate even on the old asphalt waterproof layer. This is a problem due to the inconvenience of having to completely remove the old waterproof layer.

In rubber sheets and PVC sheets, the physical properties and thickness of the waterproof layer are controlled by factory production, and troubles at the time of construction are eliminated and construction is quicker than other on-site manufacturing type waterproof materials. Due to such features, it has been widely used in recent years mainly for refurbishment. However, the smoothness of the base is strongly required, and there are drawbacks such that even small protrusions may be broken or peeled off, thermal contraction is large, and the edges are easily peeled off. Also, because the surface hardness is small,
It is not suitable for walking as it will be damaged even in light walking and lead to breakage.

A waterproof coating material such as urethane or acrylic resin can be applied in a complicated shape, has an excellent aesthetic appearance, and has a large elongation rate and can be covered by elongation even if a crack is generated in the base. Due to its strength, it is used regardless of whether it is new or renovated. However, these resins are slow to cure and it takes too long before the construction site can be used.
Since it has low mechanical strength such as pulling and tearing, it has severe defects such as severe deterioration of stretched parts and floating parts, and easy occurrence of defects such as peeling.

Further, a specific unsaturated polyester resin has relatively excellent performance, and is disclosed in, for example, JP-A-56-92917.
The unsaturated polyester resin disclosed in JP-A No. 10-29100 has excellent mechanical strength and has a large elongation at room temperature, and thus can be used as a roof waterproofing material. However, there are still problems with the above unsaturated polyester resin, and the present inventors have previously found that the amount of 1,2-alkenedicarboxylic acid in the unsaturated polyester is sufficient for imparting durable adhesion to a substrate and imparting flexibility at low temperatures. It was found that the trans 1,2-alkene dicarboxylic acid was present in the chain in an amount of 0.1 mol% or more and less than 1 mol% based on the total amount of the dicarboxylic acid, and 1,2-alkene dicarboxylic acid was present at the end. An unsaturated polyester resin composition comprising 100 parts by weight of an unsaturated polyester resin in which an alkenedicarboxylic acid is present in an amount of 1 mol or more and 25 mol% or less and 20 to 200 parts by weight of a vinyl-polymerizable monomer has been proposed (Japanese Patent Laid-Open Publication No. Sho. 63-120714). However, the types and methods of use of the polymerization initiator and the polymerization accelerator that can be used to cure the unsaturated polyester resin composition are limited, and a ketone peroxide such as methyl ethyl ketone peroxide is used as the polymerization initiator to accelerate the polymerization. Does not cure at all even when using metal salts such as cobalt naphthenate and zinc naphthenate commonly used as agents,
The curing is so slow that the sufficient mechanical strength is not reached. Further, when a diacyl peroxide such as benzoyl peroxide is used as a polymerization initiator and amines such as dimethylaniline are used, there is no significant decrease in curing as in the former case, but the amount of the polymerization initiator and amines used is However, there has been a problem that the weather resistance and water resistance of the cured product deteriorate. Furthermore, the physical properties of the cured unsaturated polyester resin composition change with time, and particularly when the temperature and humidity are high, unreacted components are leached out from the cured product, and mechanical properties tend to be remarkably deteriorated and hardened. In addition, there is a problem that when immersed in an alkaline solution, it undergoes alkali decomposition and its physical properties change greatly, such as a decrease in flexibility.

[0006]

Means for Solving the Problems As a result of various studies on the waterproof material, the present inventors have found that a specific unsaturated polyester resin has relatively excellent performance.
Therefore, the present inventors have made further studies to solve these drawbacks, and as a result, have reached the present invention.

That is, the terminal unsaturated acid content of the unsaturated polyester is 1 to 25 mol% based on all carboxylic acid compounds.
And the unsaturated acid is a monocarboxylic acid, and 8 mol%
An unsaturated polyester resin composition comprising an unsaturated polyester containing the following unsaturated acid in the chain and an unsaturated monomer is provided, wherein the hydroxy compound in the chain according to claim 1. Contains 80 mol% or more of a bisphenol A / alkylene oxide adduct (the number of added mols is from 2 to 20) based on all hydroxy compounds, and 80 mol% or more of the saturated dicarboxylic acid in the chain is an aliphatic acid. An unsaturated polyester resin composition characterized by the above is provided.

The unsaturated polyester resin used in the present invention comprises an unsaturated polyester compound and an unsaturated monomer copolymerizable with the compound, and has workability, flexibility, hardness, weather resistance, solvent resistance and dryness. The content of the unsaturated monomer is 20 to 80% by weight, preferably 30 to 7 depending on the intended use such as properties.
It is in the range of 0% by weight.

The unsaturated polyester compound used in the present invention can be obtained by condensation and addition reaction of a hydroxy compound and a carboxylic acid compound (including an acid anhydride and an alkyl ester compound of carboxylic acid). Among them, a dihydroxy component is particularly preferable. And those derived from dicarboxylic acid and monocarboxylic acid components are preferred. More preferably, it has 1 to 25 mol% of unsaturated monocarboxylic acid at the end with respect to all carboxylic acids, and does not contain an unsaturated bond in the chain of the unsaturated polyester compound, or contains it. The ratio of unsaturated carboxylic acid to total carboxylic acid is 8
It is preferably not more than mol%. If the amount of unsaturated monocarboxylic acid at the terminal is more than 25 mol%, the elongation of the cured product will be remarkably reduced, the rubber elasticity will be impaired, and it will become hard to follow the cracks in the base. The amount of unsaturated monocarboxylic acid at the terminal is 1 mol%
If it is less than the above range, the number of cross-linking points in the unsaturated polyester resin is reduced, gelation is deteriorated and curability is lowered. On the other hand, if the amount of unsaturated bonds in the chain is more than 8 mol%, the performance of the coating film becomes hard at low temperatures and the elongation is lost, resulting in brittleness.

The unsaturated polyester compound is preferably produced in two steps. In this case, the excess amount of the hydroxy compound component is esterified with the dicarboxylic acid component in the first step, and the unsaturated monocarboxylic acid is added in the second step. And the dicarboxylic acid component in the first step consists of alkene dicarboxylic acid in an amount of 8 mol% or less, and in the second step, the unsaturated monocarboxylic acid is converted to 1% of all carboxylic acid compounds. It is better to choose to form ˜25 mol%.

The hydroxy component is predominantly composed of dihydroxy compounds, but may also partially contain polyhydroxy compounds such as, for example, up to 20 mol% of triol compounds.

As the dihydroxy compound, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol,
Aliphatic dialcohols such as 1,4 butanediol and neopentyl glycol, alicyclic dihydroxy compounds such as 4,4-dihydroxydicyclohexylpropane, and aromatics such as alkylene oxide adducts of bisphenol A such as ethylene oxide or propylene oxide. A dihydroxy compound can be illustrated. Examples of the polyhydroxy compound include trimethylolpropane, glycerin, pentaerythritol and the like. Bisphenol A /
When the alkylene oxide adduct is less than 80 mol%, unreacted components are eluted from the cured product at high temperature and high humidity.
There are problems that the mechanical properties are remarkably deteriorated and it becomes hard, and that when it is immersed in an alkaline solution, it undergoes alkali decomposition and its flexibility is reduced. The dihydroxy compound of the bisphenol A / alkylene oxide adduct is an alkylene oxide adduct such as ethylene oxide or propylene oxide, and the number of addition moles thereof is preferably about 2 to 20 moles. More preferably, it is about 4 to 14 moles. If it is 2 moles or less, the cured product becomes hard, and if it is 20 moles or more, the OH concentration decreases during the reaction of the polyester resin. Results in slower water resistance and alkali resistance.

Examples of the saturated aliphatic acid in the dicarboxylic acid in the chain include succinic acid, adipic acid, azelaic acid and sebacic acid. Other saturated acids that can be used include phthalic acid, phthalic anhydride, isophthalic acid,
Examples thereof include terephthalic acid, 3,6-endomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorphthalic anhydride and the like. When the amount of the aliphatic acid in the saturated acid in the chain is less than 80 mol%, the performance of the coating film becomes hard at low temperature and the elongation is lost and the coating becomes brittle.

As the unsaturated acid in the chain used in the present invention, one or more of maleic anhydride, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid and chlorinated maleic acid are used. ..

The unsaturated monocarboxylic acid is used as the terminal unsaturated acid, because the free carboxylic acid produced when an unsaturated dicarboxylic acid or an unsaturated anhydride is used is used as a polymerization accelerator. This is because it reacts with a salt and significantly reduces the activity of the polymerization accelerator. After reacting with an unsaturated dicarboxylic acid or an unsaturated anhydride, the free carboxylic acid may be blocked. Examples of the blocking agent include monoalcohols such as methanol and ethanol, monophenyls such as phenylglycidyl ether and butylglycidyl ether. When an epoxy compound or dicyclopentadiene is reacted, the blocking agent must be added in excess to reduce the free carboxylic acid to the extent that it does not affect the polymerization accelerator. The blocking agent of the reaction is reactive,
Water resistance is reduced. Examples of unsaturated monocarboxylic acid compounds include (meth) acrylic acid, methacrylic acid, maleic anhydride and methyl alcohol, ethyl alcohol, and n.
-Propyl alcohol, isopropyl alcohol, n-
Saturated alcohols such as butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, sec-butylcarbinol, neopentyl alcohol, 2-pentanol, dicyclopentadiene and monoepoxy compounds. And an addition reaction product thereof with.

Examples of the unsaturated monomer used in the present invention include styrene, vinyltoluene and methyl (meth).
Acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl methacrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) Acrylate, stearyl (meth) acrylate, (methyl) glycidyl (meth) acrylate, dimethylaminoethyl (meth)
There are acrylate, diethylaminoethyl (meth) acrylate and the like, and they are used alone or in combination of two or more.

For the purpose of adjusting the viscosity, modifying the physical properties of the cured product, improving the curing speed, and storing stability, the resin composition is
A polymer compound, a plasticizer, a curing catalyst (crosslinking initiator, crosslinking initiation aid, etc.), an inhibitor, and a filler can be added if necessary. Polymers that can be used are those that are mixed in order to reduce the manufacturing cost or improve the coating performance or coating performance when used as a coating material, such as acrylic resin, polyester resin, polyurethane resin, styrene- Examples thereof include allyl alcohol copolymers. Examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, butyl phthalyl butyl glycolate, tricresyl phosphate, chlorinated paraffin, and the like. Bottom residue during petroleum refining such as asphalt and clean products such as coal tar. Can also be added in order to improve the performance of the coating film and to improve compatibility with the base. If necessary, for example, hydroquinone, parabenzoquinone, chloranyl, 2,3-dichloro-5,6-dicyanoparabenzoquinone, para-tert-butylcatechol, sec-tert-butyl-
1,4-hydroquinone, 2,5-di-tert-butyl-1,3-
Hydroquinone, copper naphthenate, 1,4-naphthoquinone,
Polymerization inhibitors such as hydroquinone monomethyl ether and hydroquinone monoethyl ether can be added to prevent gelation during production and storage and improve storage stability.

The curing catalyst added as necessary can be appropriately selected depending on the curing method. A polymerization initiator is not particularly required when high energy such as electron beam is used, but a known photosensitizer is required as a polymerization initiator when light or ultraviolet rays is used. Further, as a general polymerization initiator, an organic peroxide such as benzoyl peroxide, methyl ethyl ketone peroxide, ditertiary butyl peroxide, lauroyl peroxide, cumene hydroperoxide is suitable, and cobalt naphthenate is a polymerization accelerator. The metal soaps, tertiary amines such as dimethylaniline and dimethylparatoluidine, alcoholates such as sodium methylate, and lauryl mercaptan are suitable. Among them, benzoyl peroxide / tertiary amine, methyl ethyl ketone peroxide / cobalt naphthenate and the like can be generally used.

In addition to these components, various substances can be added for the purpose of improving the performance of the cured product. These additives include titanium white, carbon black, pigments such as red iron oxide, methyl alcohol, ethyl alcohol, toluene, xylene, methyl ethyl ketone, ethyl acetate, solvents such as mineral spirits, polyethylene, polypropylene, nylon, calcium carbonate, magnesium carbonate, Fillers such as barium sulfate, calcium sulfate, alumina, clay, kaolin, talc, diatomaceous earth, silica gel, mica powder, glass fiber powder, asbestos powder, silica stone powder, silica, bentonite, colloidal silicic acid, castor oil derivatives, etc. A thixotropic agent can be added.

As a coating method, an unsaturated polyester resin is mixed with a polymerization initiator and a polymerization accelerator, and if necessary, wax and other additives and an isocyanate compound are mixed, and a machine such as a construction tool such as a rubber spatula, a brush, a roller or a spray is used. It suffices to coat and cure by a usual coating means such as painting. The coating amount of these mixtures per time is usually 0.05 to 5.0 mm, preferably 0.3 to 3.0 mm. If the coating is thinner than 0.05 mm, pinholes are likely to occur in the coating, and if the coating is thicker than 5.0 mm, the cured product shrinks. Peeling may occur.

[0021]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the invention is not limited thereto. In the following, parts are based on weight, unless otherwise specified. The test results of the examples and comparative examples are summarized in the table. Example 1 In a four-necked flask equipped with a stirrer, a thermometer, a condenser equipped with a condenser, and a nitrogen introducing tube, 5825 g (10.6 mol) of propylene oxide 6 mol adduct of bisphenol A and 1418 g (9.7 mol of adipic acid) were added. ) And fumaric acid (35 g (0.3 mol)) and charged with nitrogen gas (215).
The esterification reaction was carried out at 0 ° C., and water was distilled off until the acid value reached 8.0. Next, 198 g (0.8 mol) of unsaturated monocarboxylic acid obtained by reacting 1 mol of maleic anhydride and 1 mol of dicyclopentadiene at a temperature of 150 ° C.,
After continuing the reaction and distilling off water until the acid value reached 8 or less, the reaction product was cooled to 100 ° C. and dissolved in 1300 g of styrene in which 150 mg of hydroquinone was dissolved to give a pale yellow unsaturated polyester resin composition. Obtained. To 100 parts of this unsaturated polyester resin, 0.2 part of paraffin wax having a melting point of 56 to 58 ° C. as a wax, 0.1 part of Disparlon OX-720 (manufactured by Kusumoto Kasei Kogyo Co., Ltd.) as an antifoaming agent, uniformly at room temperature under high speed stirring Mixed and dispersed in
Immediately before use, 2.0 parts of 55% methyl ethyl peroxide as a polymerization initiator and 0.5 parts of 6% cobalt naphthenate as a polymerization accelerator were further added. [Evaluation Method] (1) Room Temperature Gelation Time The room temperature gelation time was measured according to JIS K-6901. The gelation time was measured up to 3 hours, and when the gelation did not occur within 3 hours, it was indicated by x. 55 as a polymerization initiator
MEK blended with 2.0 parts of 6% methyl ethyl peroxide and 0.5 parts of 6% cobalt naphthenate as a polymerization accelerator.
In addition to the PO system, the BPO system containing 50 parts of benzoyl peroxide (3.0 parts) as a polymerization initiator and dimethylaniline (0.5 parts) as a polymerization accelerator was also measured. (2) Tensile test This composition was applied on a polyester film to a thickness of 3 mm, cured at 20 ° C. for 168 hours, and then removed from the polyester film to give a dumbbell No. 3 shape test piece described in JIS K-6301. Punching, JIS A-60
According to No. 21, a tensile test was performed at a test temperature of 20 ° C. and 0 ° C., and the tensile strength and the elongation rate were measured. (3) DuPont Impact Test This compound was applied on a polyester film, and one layer of glass mat # 380 was placed so as to have a thickness of 3 mm. After curing at 20 ° C for 168 hours, it is detached from the polyester film, a test piece of 10 cm square is cut, and a 500 gr steel ball is dropped from a height of 1 m using a DuPont impact tester, and the test temperature is set. The impact resistance at 20 ° C and 0 ° C was examined. The appearance was evaluated by observing the appearance. When there was no noticeable change in appearance, the sample was evaluated as ◯, the sample that was destroyed was evaluated as x, and the sample in which the hair crack was generated was evaluated as Δ. (4) Moisture and Heat Resistance Test A 3 cm × 7 cm test piece was cut out from the same sheet as in the tensile test, exposed to a saturated steam atmosphere at a temperature of 70 ° C. for 10 days, and the moist heat resistance was judged by appearance and finger touch. The case where the oily component was eluted from the cured product sheet was marked with x, and the case where no elution was observed was marked with o. (5) Alkali resistance test A test piece having the same dimensions as the wet heat resistance test was immersed in a 5% caustic soda aqueous solution at a temperature of 50 ° C for 168 hours, and the alkali resistance was judged from the appearance. ○, if there is no noticeable change in appearance
Those having abnormalities such as appearance change and hardness change were marked with x.

Examples 2 to 8 and Comparative Examples 1 to 4 Similar to Example 1, Examples 2 to 8 and Comparative Examples 1 to 4 show the raw materials and their addition amounts in Table 1, and the unsaturated polyester resin cured products. The properties of are listed in Table-2. still,
Propylene oxide is abbreviated as PO.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

[0027]

[Table 5]

[0028]

[Table 6]

[0029]

According to the unsaturated polyester resin composition of the present invention, the curability is excellent, the elongation at room temperature is large, the flexibility to follow the crack of the base is obtained, and the heat and humidity resistance at high temperature is high. It is intended to provide an unsaturated polyester resin composition capable of obtaining a cured unsaturated polyester resin optimal as a waterproofing material, flooring material and lining material having excellent corrosion resistance to cement alkali.

Claims (2)

[Claims] 1. An unsaturated polyester having a terminal unsaturated acid content of 1 to 25 mol% based on all carboxylic acid compounds,
An unsaturated polyester resin composition, wherein the unsaturated acid is a monocarboxylic acid, and is composed of an unsaturated polyester containing 8 mol% or less of an unsaturated acid in the chain and an unsaturated monomer. 2. The hydroxy compound in the chain according to claim 1, wherein the hydroxy compound in the chain contains a bisphenol A / alkylene oxide adduct (the number of added moles is 2 to 20) in an amount of 80 mol% or more based on all hydroxy compounds. An unsaturated polyester resin composition, wherein 80 mol% or more of the saturated dicarboxylic acid is an aliphatic acid.