JPH0466247B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Fields] The unsaturated polyester resin composition of the present invention can be used in combination with glass fibers, carbon fibers, polyimide fibers, etc. as composite materials, FRP for corrugated plates, bathtubs, ships, vehicles, etc. It is useful as resin concrete and resin mortar for block manholes, flower boxes, washstands, tables, counters, surface finishing paints for wood and silica boards, decorative boards, buttons, cast products, etc. [Prior Art] Generally, unsaturated polyester resins are produced by combining polyhydric alcohol and unsaturated polybasic acid (anhydride) with saturated polybasic acid (anhydride), animal or vegetable oil, epoxy resin, or isocyanate. , is produced by dissolving an unsaturated polyester obtained by reacting it in the presence of a small amount (5% or less) of an allyl ether compound in a polymerizable monomer, but during curing, the resin surface is hardened by oxygen in the air. As a result, the surface never dries, allowing dirt and dust to adhere to it, and the original performance of the resin is not exhibited, resulting in poor water resistance and solvent resistance. To date, two approaches have been taken to remedy these shortcomings. One method is to dissolve and add paraffin waxes to a resin, and upon curing, the paraffin waxes are precipitated on the surface of the resin to cut off contact between air and the resin. However, with this method, the composition of the resin, the environmental temperature during use, the stability during storage (prevention of agglomeration and precipitation)
For these reasons, there are restrictions on the type and amount of paraffin wax used. For example, if the wax is used in a place exposed to direct sunlight or in a heating furnace (40°C or higher) at a temperature above room temperature, it may be difficult to uniformly float the wax on the resin surface during curing, and it may be difficult to float the wax evenly on the resin surface when stored at low temperatures. It is also difficult to prevent the separation of tsukusu. Other methods include using an air-drying resin containing an allyl ether compound or drying oil alone, and adding it to general unsaturated polyester to improve air-drying properties. However, this method has the disadvantage that adding a large amount is not economical, and adding a small amount causes partial curing failure and insufficient surface drying properties, so there is a limit to the amount used. [Problems to be Solved by the Invention] As mentioned above, the conventional methods have the drawback that the range of use thereof is limited in order to improve the drying properties of the resin surface, but the present invention solves these drawbacks. To provide an unsaturated polyester resin composition which exhibits good surface drying in a wide temperature range without restrictions on usage conditions, can be used at high temperatures, and has an improved molding cycle. [Means for Solving the Problems] The unsaturated polyester resin composition of the present invention comprises: (A) an organic compound containing an unsaturated polybasic acid or its anhydride (hereinafter referred to as unsaturated polyhydrochloric acids) as a first-stage reaction; Presence of polybasic acid or its anhydride (hereinafter referred to as organic polybasic acids) and polyhydric alcohol in an amount of 5 to 40% by weight (based on the total amount charged) of dicyclopentadiene or its derivatives (hereinafter referred to as dicyclopentadiene) After the above reaction, as a second stage reaction, 100 parts by weight of the carboxyl group-containing dicyclopentadiene-modified unsaturated polyester produced in the first stage reaction is reacted with 0.5 to 5 parts by weight of the hydroxyl group-containing allyl ether compound. It is characterized by consisting of the obtained unsaturated polyester, (B) a polymerizable monomer, and (C) 0.01 to 0.5 parts by weight of waxes (based on 100 parts by weight of (A) + (B)). The above problem was solved. [Function] By configuring the unsaturated polyester resin composition of the present invention as described above, the surface drying properties and water resistance of the resin can be ensured over a wide range. The use of the unsaturated polyester of the present invention produced by the method. The unsaturated polyester of the present invention is produced by synthesizing an unsaturated polyester modified with a small amount of dicyclopentadiene, such as 5 to 40% by weight, in the first stage reaction, and then in the second stage reaction, 0.5 to 5 parts by weight of dicyclopentadiene is synthesized. It is produced by reacting a small amount of hydroxyl group-containing allyl ether compound with a small amount of hydroxyl group-containing allyl ether compound, but only through this specific reaction method can surface dryness and water resistance at high temperatures (40°C or higher) be exhibited. At low temperatures (below 15℃), its drying properties are not fully demonstrated, but by incorporating a small amount of waxes and supplementing the surface drying properties through their interaction, the surface can be dried over a wide temperature range. This ensures durability and water resistance. Hereinafter, the unsaturated polyester resin composition of the present invention will be explained in detail. The organic polybasic acids used in the method of the present invention include unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid, and citric acid, which are generally used in the production of unsaturated alkyds, as well as maleic anhydride. It contains an anhydride of an unsaturated polybasic acid as an essential component, and contains saturated acids such as phthalic acid, terephthalic acid, and isophthalic acid as an optional component. Of course, organic polybasic acids may be used alone or in combination. In addition, examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 1,6-
Hexanediol, 1,6-cyclohexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol,
Sorbitol, hydrogenated bisphenol A, polybutane diene glycol, propylene oxide diadduct of bisphenol A, and the like are used alone or in combination. Further, as the dicyclopentadiene, dicyclopentadiene such as dicyclopentadiene, hydroxylated dicyclopentadiene, and methyldicyclopentadiene is preferably used as a reaction component in the first stage reaction. The ratio of reaction components in the first stage reaction is 30 to 70 KOH mg/g of organic polybasic acid and polyhydric alcohol.
It is preferable to adjust the acid value so that an unsaturated polyester having an acid value of . The polyhydric alcohol is preferably used in an equimolar amount with the organic polybasic acid, and the dicyclopentadiene is used in an amount of 5 to 40% by weight based on the total amount charged, preferably 0.1 to 0.4 mol per 1 mol of the organic polybasic acid. It's better. The second stage reaction of the present invention is carried out by reacting 0.5 to 5 parts by weight of a hydroxyl group-containing allyl ether compound with 100 parts by weight of the carboxyl group-containing dicyclopentadiene-modified unsaturated polyester produced in the first stage reaction. You can proceed. In the second stage reaction, organic polybasic acids are added if necessary. The amount used is 3 to 100 parts by weight of the unsaturated polyester produced in the first stage reaction.
20, preferably 5 to 15 parts by weight. Examples of the hydroxyl group-containing allyl ether compounds used in the present invention include mono- or diallyl ether of trimethylolpropane, pentaerythritol triallyl ether, mono- or diallyl ether of glycerin, mono- or diallyl ether of pentaerythritol, and allyl glycol. Can be mentioned. Furthermore, the general formula [However, R is hydrogen or an alkyl group, and n is an integer of 1 to 10] It is also possible to use an alkylene oxide adduct of allyl alcohol. As a typical example, a compound obtained by adding a mixture of ethylene oxide and propylene oxide to allyl alcohol and in which R includes a mixture of hydrogen and methyl groups is preferably used. Furthermore, it is necessary that a polymerization inhibitor be present in the polymerizable monomers added during the second stage reaction or after the completion of the reaction. As the polymerization inhibitor, pt-butylcatechol, 2,5-di-t-butylhydroquinone, mono-t-butylhydroquinone, 2,5
-Hydroquinones such as di-t-amylhydroquinone, p-benzoquinone, naphthoquinone, p-
Examples include quinones such as xyloquinone, 2,5-diphenyl-p-benzoquinone, and 2,5-diacetoxy-p-benzoquinone, and phenols such as di-t-butyl para-cresol and hydroquinone monomethyl ether. These polymerization inhibitors are
0.02 to 0.05 per 100 parts by weight of unsaturated polyester
Used in parts by weight. The unsaturated polyester obtained in this way can be made of common polymerizable monomers such as styrene, vinyltoluene, chlorostyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and tertiary butyl acrylate. , 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylate It is dissolved in tetrahydrofurfuryl acid, vinyl acetate, vinyl propionate, etc. to obtain an unsaturated polyester resin. There is no particular restriction on the ratio of unsaturated polyester to polymerizable monomer, but if the ratio of polymerizable monomer is 50
If it exceeds % by weight, air drying properties at high temperatures tend to be poor, which is not preferable. The waxes used in the present invention are blended in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the unsaturated polyester resin, and paraffin waxes are most preferably used. The unsaturated polyester resin composition of the present invention can be used in combination with fillers, reinforcing agents, mold release agents, colorants, curing agents, accelerators, stabilizers, etc., as necessary, to produce decorative boards, paints, cast products, etc. Can be widely used in FRP, molding materials, etc. [Examples] Examples will be described below to further specifically explain the present invention. Parts or % in the text mean parts by weight and % by weight. Example 1 Add ethylene glycol to the 3 four-necked flask.
282 g, diethylene glycol 260 g, phthalic anhydride 311 g, maleic anhydride 480 g, and dicyclopentadiene 370 g were added, and heated at 140 to 160 °C in a nitrogen stream.
After reacting dicyclopentadiene, the temperature was raised to 210°C, kept at 210°C, and when the acid value reached 35 to 40 KOHmg/g, it was cooled to 150°C, and 4 parts of trimethylolpropane diallyl ether was added to 100 parts of the above ester. Rise to 180℃ over 2 hours, maintain 180℃, 5-9 poise with 30% styrene/25℃, acid value 25-
The end point was 30. After the reaction is complete, add hydroquinone
A resin was prepared by adding 0.1 g of paraffin having a melting point of 52° C. to an unsaturated polyester dissolved in 0.01 part of styrene. Example 2 Add ethylene glycol to the 4-necked flask from 3.
282g, diethylene glycol 260g, phthalic anhydride 207g, maleic anhydride 549g, and dicyclopentadiene 370g were charged, and the temperature rose to 110℃ in a nitrogen stream, and then rose to 140℃ due to heat generation, and the temperature rose to 140-160℃.
After reacting dicyclopentadiene at ℃, the temperature was raised to 210℃, kept at 210℃, and when the acid value reached 50 to 55 KOHmg/g, it was cooled to 150℃, and trimethylolpropane diallyl ether was added to 100 parts of the above ester.
Add 2.5 parts and raise the temperature to 150-180℃ for 2 hours.
Maintain 180℃, 6-10 poise/25 with 30% styrene
℃ and an acid value of 30 KOHmg/g or less was defined as the end point. Add 0.1 part of paraffin at mp.52℃ to polyester resin dissolved in styrene to which 0.01 part of hydroquinone has been added.
The partially heated and melted resin was designated as B. Comparative Example 1 Propylene glycol in 3 four-necked flask
814g, phthalic anhydride 741g, maleic anhydride 441g
g, the temperature rose to 110℃ in a nitrogen stream, the temperature rose to 165℃ due to heat generation, and the temperature rose to 210℃ in 3 hours.
6-9 poise with 35% styrene/25℃, acid value 35-
The end point was 40KOHmg/g. After completion of the reaction, 0.1 part of paraffin was heated and dissolved in polyester dissolved in styrene to which 0.01 part of hydroquinone was added, and the resin was designated as C. Comparative Example 2 Add ethylene glycol to the 4-necked flask from 3.
Add 372.6g of diethylene glycol, 424.5g of diethylene glycol, 981g of maleic anhydride, and 428g of trimethylolpropane diallyl ether, and heat at 150 to 190℃ in a nitrogen stream.
The reaction ends with an acid value of 25 or less, and hydroquinone is
0.02 part was added. A resin dissolved in 30% styrene (based on ester) was designated as D. Comparative Example 3 A resin in which 10 parts of resin D was added to 100 parts of resin C was designated as E, and a resin in which 20 parts of resin D was added to 100 parts of resin C was designated as F.
And so. 100 parts each of resins A, B, C, D, E and F obtained in Examples 1 and 2 and Comparative Examples 1, 2 and 3,
Using a resin containing 0.5 part of cobalt naphthenate and 1 part of methyl ethyl ketone peroxide,
Three sheets of #450 chopped strand pine were stacked at room temperature, left overnight at various temperatures, then immersed in water for 20 hours, and the surface condition was observed. Those with a good hardened surface showed no change, while those with a poorly hardened surface were hydrolyzed and turned white (usually referred to as a whitening phenomenon). those results first
Shown in the table.

〔Effect of the invention〕

The unsaturated polyester resin composition of the present invention has a wide range of properties by using an unsaturated polyester obtained by reacting dicyclopentadiene in the first stage of a two-stage esterification reaction with a hydroxyl group-containing allyl ether compound in the second stage reaction. It has excellent surface drying properties in the temperature range of
Useful as raw materials for FRP, paints, decorative laminates, cast products, etc.

Claims (1)

[Scope of Claims] 1 (A) In the first stage reaction, an organic polybasic acid or anhydride containing an unsaturated polybasic acid or anhydride thereof and a polyhydric alcohol are reacted with dicyclopentadiene or a derivative thereof 5-40 After reacting in the presence of % by weight (based on the total amount charged), as a second stage reaction, the carboxyl group-containing dicyclopentadiene-modified unsaturated polyester produced in the first stage reaction is
An unsaturated polyester obtained by reacting 100 parts by weight with 0.5 to 5 parts by weight of a hydroxyl group-containing allyl ether compound, (B) a polymerizable monomer, and (C) 0.01 to 0.5 parts by weight of waxes ((A) + (based on 100 parts by weight of (B)).