JPS63120714A - Unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in low-temperature strength and suitable as a waterproof roofing material, by mixing a specified unsaturated polyester resin with a vinyl polymerizable monomer. CONSTITUTION:An excess of a glycol component is esterified with a dicarboxylic acid, and the product is reacted with a cis1,2-alkenecarboxylic anhydride to obtain an unsaturated polyester resin (A) which consists mainly of the dicarboxylic acid component and the diol component, in which 0.1mol%, based on the total dicarboxylic acid, trans1,2-alkenedicarboxylic acid is present in the main chain, 1-25mol% 1,2-alkenedicarboxylic acid is present on the terminals, and which has an acid value of 5-60 and a hydroxyl value of 0-30. 100pts.wt. component A is mixed with 20-200pts.wt. vinyl monomer (B) (e.g., styrene) and, optionally, a polymerization inhibitor (e.g., hydroquinone) and 0.2-0.8pt.wt. paraffin wax (C) of an m.p. of 45-65 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an unsaturated polyester resin composition suitable for applications such as rooftop waterproofing materials.

[Conventional technology and its problems]

Traditionally, rooftop waterproofing materials include asphalt, rubber sheets, PVC sheets, urethane resins, acrylic resins,
Unsaturated polyester resin etc. are used.

Asphalt has characteristics such as being able to be applied even if the base is slightly uneven, and having a low water absorption rate.As it is also inexpensive, it can have a large thickness due to its laminated structure, and it can be used in combination with holding mortar and various reinforcing materials. It is most widely used in new buildings because it can form a highly reliable waterproof layer. However, due to the low adhesive strength, phenomena such as peeling or floating may occur, and the waterproof layer may rupture due to the inability to follow the movement of the base material due to building vibrations or shrinkage cranks of the base concrete due to its low mechanical strength. Trouble can easily occur.

In addition, during renovation work, a melting pot is brought to the site to heat and melt the asphalt, which poses a risk of odor and fire, and also makes the construction work more extensive. The old asphalt waterproof layer has very little adhesion to asphalt that has begun to deteriorate, so the old waterproof layer must be completely removed. This is an inconvenience and a problem.

Rubber sheets and PVC sheets are produced in factories, so the physical properties and thickness of the waterproof layer are controlled, and compared to other waterproof materials that are manufactured on-site, problems during construction are eliminated and construction is quick. In recent years, it has become widely used mainly for repair purposes.

However, the smoothness of the base is strongly required, and there are drawbacks such as even small protrusions can cause breakage and discoloration, and the heat shrinkage rate is large and the edges tend to peel off. Furthermore, since the surface hardness is low, even light walking can cause damage and breakage, making it unsuitable for walking.

In addition, coating waterproof materials such as urethane and acrylic resin have advantages such as being able to be applied to complex shapes, having an excellent finished surface appearance, and having a high elongation rate so that even if cracks occur in the base, they can be covered by the elongation rate. Since then, it has been used in both new construction and renovations. However, these resins cure slowly, take too long to use the construction site, and are
Since the mechanical strength against tearing and the like is low, it has disadvantages such as severe deterioration in stretched and floating areas, which easily causes defects such as breakage and peeling.

As a result of various studies regarding rooftop waterproof materials, the present inventor found that a specific unsaturated polyester resin has relatively excellent performance. For example, the unsaturated polyester resin disclosed in JP-A No. 56-92917 has good mechanical strength and a large elongation rate at room temperature, and can also be used as a rooftop waterproofing material.

However, problems still remain with the above unsaturated polyester resins. One of them is the adhesion to the base. Particularly when used for renovation purposes, the durable adhesion is insufficient because the base has deteriorated. The second problem is a decrease in strength at low temperatures. In particular, at low temperatures below 0°C, the elongation rate drops dramatically, making it impossible to follow the movement of the base and even cracks. This property acts as a very large negative factor in cold regions, and directly leads to problems such as cracking and peeling of the waterproof layer.

It is an object of the present invention to provide an unsaturated polyester resin suitable as a rooftop waterproofing material for renovation.

Another object of the present invention is to provide an unsaturated polyester resin suitable as a rooftop waterproofing material that has excellent low-temperature strength and can be sufficiently used even in cold regions.

[Means to solve the problem]

The present invention has been achieved based on the discovery that the amount of 1,2-alkenedicarboxylic acid in the unsaturated polyester has an important meaning regarding the above-mentioned problems.

That is, the present invention provides a) a fII value of 5 to 60, a hydroxyl value of 0 to 30, and the molecule is mainly composed of a dicarboxylic acid component and a diol component, and in the chain, a trans-1,2-alkenedicarboxylic acid is a dicarboxylic acid component. 100 parts by weight of an unsaturated polyester resin having an amount of 0.1 mol % or more and less than 1 mol % based on the total amount of acids, and 1 mol % or more and 25 mol % or less of 1,2-alkenedicarboxylic acid at the terminal, b) vinyl This is an unsaturated polyester resin composition containing 20 to 200 parts by weight of a polymerizable monomer.

The unsaturated polyester resin used in the present invention 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 0.0% based on the total amount of dicarboxylic acid. 1 mol% or more and less than 1 mol%, preferably 0.2 to 0.9 mol%
, more preferably 0.3 to 0.9 mol% trans 1,
Contains 2-alkenedicarboxylic acid, 1-25 mol% of 1.2-alkenedicarboxylic acid is present at the terminal based on the total amount of carboxylic acid, and the acid value is 5-60, preferably 16-25%. 30, and the hydroxyl value is 0 to 30, preferably θ to 20.

Diol components include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, 114-cyclohexane dimetatool, 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-trimethylpentanedio-ru 1 Examples include .3 and 3-methylbentanediol.

In the chain, trans-1,2-alkenedicarboxylic acid is present in an amount of 0.1 mol % or more and less than 1 mol % based on the total amount of carboxylic acid. As the trans-1,2-alkenedicarboxylic acid, fumaric acid and mesaconic acid are preferred.

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

The trans-1,2-alkenedicarboxylic acid in the chain is 0.
If it is less than 1 mol% or the terminal 1.2-alkened dicarboxylic acid is less than 1 mol%, the temperature dependence of the elongation rate is very small and the elongation rate is large even at low temperatures, but the tensile strength and tear strength are decreased. However, the gelation time and curing time are extremely slow, and the cured state of the cured product surface is poor (because the adhesiveness remains indefinitely, the coating surface becomes easily stained and the aesthetic appearance is significantly impaired, and it is also prone to walking and objects). There are problems such as being easily damaged when dropped.Also, if the trans-1゜2-alkenedicarboxylic acid in the chain exceeds 1 mol% or the terminal 1,2-alkenedicarboxylic acid exceeds 25 mol%, the elongation The temperature dependence of the rate is strong and it is 0 compared to the state at 20℃.
The elongation rate in °C is extremely reduced.

The unsaturated polyester resin of the present invention contains dicarboxylic acids other than those mentioned above in the main chain and terminals.The other carboxylic acids contained in the main chain include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, or It is an alkenedicarboxylic acid that does not have any 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 carboxylic acids include tetrahydrophthalic acid, Endomethylenetetrahydrofucric acid, hexachlorendomethylenetetrahydrophthalic acid, and alkenedicarboxylic acids having no tra〉'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 mol%, based on the total amount of dicarboxylic acids. 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.

In order to increase mechanical strength, the unsaturated polyester resin of the present invention contains a small amount of trimethylolpropane, a polyhydric alcohol such as glycerin, trimellitic acid, 1,2.3
．． It may also contain polycarboxylic acids such as 4-butanetetracarboxylic acid, 1°2.4.5-benzenetetracarboxylic acid, and 1,4,5.8-naphthalenetetracarboxylic acid. The amount of polyhydric alcohol is 20 mol % or less based on the total amount of diol and polyhydric alcohol, and the amount of polyhydric carboxylic acid is 20 mol % or less based on the total amount of carboxylic acids. in this case,
Both high functionalities need to be compensated with monohydroxy compounds or monocarboxylic acids.

In addition, dichloropentagenyl units can be added to improve water resistance, air drying properties, and chemical resistance.
Dicyclopentadiene can also be formulated, for example by reaction with an alkenedicarboxylic acid.

The saturated polyester resin has an acid value of 5 to 60 and a hydroxyl 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, and the curing will be slow and it cannot be used as a rooftop waterproofing material.
There are problems such as increased viscosity and manufacturing inconvenience.

The unsaturated polyester resin of the present invention can be obtained by reacting the above-mentioned raw materials or derivatives thereof, such as acid anhydrides, lower alkyl esters, and the like, by a known method.

The unsaturated polyester resin is preferably produced in two steps, in which in the first step the excess amount of the glycol component is esterified with the dicarboxylic acid component and in the second step 1.
Rapid esterification is carried out using a 2-alkenedicarboxylic acid, in which the dicarboxylic acid component in the first step consists of 0.1 mol% or more and less than 1 mol% of trans-1,2-alkenedicarboxylic acid, or isomerized thereto, and rapid esterification in a second step is carried out with an alkenedicarboxylic acid or its derivative, in which this acid or derivative is present in an amount of 1 to 25 mol % of the total dicarboxylic acids. In fact, the first
The process is carried out at a reaction temperature of 190 to 220°C with an acid value of almost 1.
0 or less and a hydroxyl number of 15-6°, followed by a second step of reaction using cis-1,2-alkenedicarboxylic anhydride at 110-170°C of 0.5-4°.
Post-reaction takes place in hours. At such low reaction temperatures, little transesterification occurs; this esterification is preferably carried out in an inert atmosphere;
The water of reaction is removed, for example azeotropically. If the unsaturated polyester resin is boiled, it is cooled.

Unsaturated polyester resin 10 produced in this way
0 parts by weight of a vinyl polymerizable monomer, such as styrene,
Vinyl toluene, tert-butylstyrene, divinylbenzene, alkyl acrylate, alkyl methacrylate, chlorstyrene, bromstyrene, vinyl acetate, vinyl propionate, vinyl pivalate, allyl phthalate, diallyl phthalate, triallyl cyanurate, isocyanuric acid Diluted with 20-200 parts by weight, preferably 40-70 parts by weight of one or more vinyl compounds such as triallyl, 1.3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate and alkyl vinyl ether. If necessary, for example, hydroquinone, parabenzoquinone, chloranil, 2,3-dichloro-5,6
- dicyatubarabenzoquinone, para-tert-butylcatechol, 2-tert-butyl-II 4-hydroquinone, 2.
5-di-tert-butyl-1,3-hydroquinone, naphthene f
Polymerization inhibitors such as I&copper, 1,4-naphthoquinone, hydroquinone monomethyl ether and hydroquinone monoethyl ether are added to form an unsaturated polyester resin composition.

The unsaturated polyester resin composition of the present invention can be treated in the same way even when fillers, pigments, coloring agents and similar substances are added, and these additive layers may be added in an amount of 5 to 200 parts by weight per 100 parts by weight of the unsaturated polyester resin. Preferably, paraffin wax with a melting point of 45 to 65°C is added to 0.0 parts by weight.
It may be contained in an amount of about 2 to 0.8 parts by weight, and in this case, air drying properties are improved.

The unsaturated polyester resin compositions according to the invention can be cured using peroxide initiators in a conventional manner at low temperatures such as 0 to 20°C, e.g. when using a benzoyl peroxide/amine curing system. It can be cured in a short time even at high temperatures.

In this way, a rooftop waterproofing material made of unsaturated polyester that has a high elongation rate at low temperatures and high mechanical strength can be obtained.

These waterproof materials have good adhesion to various substrates, good ability to follow the substrate over a wide temperature range, and furthermore, have excellent weather resistance and mechanical strength. In addition, because of its low viscosity, it has excellent workability with brushes, rollers, etc., and is extremely advantageous as a rooftop waterproofing material.

〔Example〕

Next, the present invention will be explained in detail using Examples and Comparative Examples.

Example 1 At room temperature, 625 g (6,0 mol) of neopentyl glycol, 864 g (5,91 mol) of adipic acid and 3,5 g (0,03 mol) of fumaric acid were mixed with a stirrer, a thermometer, a Vigreau condenser and nitrogen 4 It was placed in a 2 liter capacity flask equipped with a man tube. The mixture was then gradually heated to esterify water at 215°C to an acid value of 6.
．． This was then cooled to 150° C. and 50.0 g (0.51 mol) of maleic anhydride was added. After reacting at 150°C for 2 hours, the reaction mixture was heated to 100°C.
Cooled to ℃. When this temperature is reached, styrene 8
92 g and 11 hg of hydroquinone were added. The mixture thus obtained has an acid number of 20.7, a hydroxyl number of 6.0 and a solids content of 57.5%, and a viscosity of 5.
Boise (BH type viscometer, 20°C).

50% benzoyl peroxide 3% and N,N-dimethyl-
0.3% paratoluidine was blended with the polyester resin, and the blend was heated to 2suwJ! in a 30cm square at 20°C.
J.

It was poured into a metal mold and cured for 168 hours.

Gelation time at 20°C was 25 minutes.

The physical properties of the cured sheet thus obtained were determined at +20°C and 0°C.
, at -20°C, and the results are shown in Table 2.

Note that the physical properties were measured by the following method.

Shore AtFkei ASTM D2440-68 tensile strength
JrSA6021 Elongation at break JISA6021 Tear strength JISA6021 Examples 2 to 5, Comparative Examples 1 to 3 An unsaturated polyester resin was synthesized according to Example 1 except for the diol component and dicarboxylic acid component based on Table 1. Furthermore, each resin was cured based on Example 1,
The gelation time and physical properties of the cured sheet were measured.

The results are shown in Table-2.

〔Effect of the invention〕

As is clear from the Examples and Comparative Examples, trans 1 in the chain
．． If the content of the 2-alkenedicarboxylic acid is less than 0.1 mol %, the gelation time becomes long and the tensile strength and tear strength of the cured product decrease. On the other hand, if it is 1 mol % or more, the elongation rate at low temperatures is extremely poor. On the other hand, within the scope of the present invention, all exhibit excellent physical properties.

Claims (1)

[Scope of Claims] a) The acid value is 5 to 60, the hydroxyl value is 0 to 30, and the molecule is mainly composed of a dicarboxylic acid component and a diol component, and a trans-1,2-alkenedicarboxylic acid is present in the chain. 100 parts by weight of an unsaturated polyester resin containing 0.1 mol % or more and less than 1 mol % based on the total amount of dicarboxylic acids, and 1 mol % or more and 25 mol % or less of 1,2-alkenedicarboxylic acid present at the terminal, b) An unsaturated polyester resin composition containing 20 to 200 parts by weight of a vinyl polymerizable monomer.