JPS61101518A - Production of vinyl ester resin having air dryability - Google Patents

Abstract

PURPOSE:To obtain a vinyl ester resin excellent in corrosion inhibition and air dryability, by incorporating an allyl ether group in a specified product compound. CONSTITUTION:A product compound is obtained by reacting the epoxy groups of an epoxy resin with an unsaturated monobasic acid [e.g., (meth)acrylic acid] part of which may be replaced with a half-ester carboxylic acid obtained by reacting a polyallyl ether monoalcohol (e.g., glycerin diallyl ether) with a dibasic acid anhydride (e.g., maleic anhydride) at 80-150 deg.C in the presence of a polymerization inhibitor and an esterification catalyst and, if desired, effecting an addition reaction between the OH group in the reaction product and a dibasic acid anhydride to form a half-ester carboxylic acid. This product compound is reacted with allyl glycidyl ether or glycidyl (meth)acrylate to incorporate at least one allyl ether group per epoxymethacryl molecule in the product compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an air-drying vinyl ester resin.

[Prior art] Epoxy methacrylate resin, which is represented by a reaction product of epoxy resin and (meth)grilled acid, has excellent radiation curing properties, so it is used in the field of coating materials as one of the ultraviolet curable resins. At the same time, it dissolves reactive diluents such as styrene monomers, and is called vinyl ester resin, and is also widely used in the field of unsaturated polyester resins. The cured product is highly tough, hard, and has excellent adhesive properties, as well as excellent chemical and water resistance, so it is especially suitable for use as FR for corrosion resistance and anti-corrosion purposes.
In recent years, it has been widely used as a lining, paint, adhesive primer, and resin mortar by blending P, FRP lining, flake glass, and pigments as necessary.

[Problem that the invention seeks to solve]

The curing properties and workability of this resin are comparable to those of unsaturated polyester resin, but since the curing method relies on a radical reaction mechanism, the surface layer of the resin that comes into contact with air is similar to unsaturated polyester resin. It is difficult to cure sufficiently, and in some cases, only the surface layer may become sticky.

In order to prevent this drawback, it is common knowledge to mix paraffin wax into the resin and actively precipitate the wax during the curing process to block air and harden.

However, the precipitation of paraffin waxes depends on the solubility and melting point of the paraffin wax compound in the resin.
It is also complex and is governed by many factors such as the ambient temperature of use, the ambient atmospheric concentration of the reactive diluent monomer, the humidity, the time of curing and the amount of curing agent.

In the case of vinyl ester resins, which are often used for purposes such as corrosion resistance, they are often used at outdoor construction sites, and if they are not properly managed, the desired purpose may not be achieved. Furthermore, when blending paraffin wax, the surface becomes opaque and non-glossy due to wax precipitation during curing, and improvements in appearance are desired in applications where this is not desirable, such as painting and floor lining, where aesthetics are also important. Ta.

Among non-wax resins, unsaturated polyester resins have been invented for a long time, and their application to polyester paints for wood is widely known. Although ester resins appear to be non-tacky and dry, chemically non-wax types have not been successful to date.

The reason for this is that vinyl ester resins have stronger anaerobic properties than unsaturated polyester resins, and are more prone to gelation during production than unsaturated polyester resins and are difficult to produce.

The present invention provides a vinyl ester resin that is not significantly inferior when applied to the main corrosion-resistant and anti-corrosion uses of vinyl ester resins, does not require the troublesome management of the above-mentioned paraffin wax-containing resins, and has excellent gloss. It is something.

[Means for solving problems]

The present inventors have conducted extensive research into the synthesis of vinyl ester resins that can be produced and have effective drying properties.As a result, we have synthesized a polyvalent allyl ether monoalcohol equivalent to an epoxy acrylate resin via an ester group. The problem was solved by introducing more than 1, preferably 1.5 or more realyl ether groups per molecule of epoxy (meth)acrylic molecule.

That is, the present invention provides a half-ester carboxylic acid by reacting an epoxy group of an epoxy resin with an unsaturated monobasic acid, and a polyhydric allyl ether monoalcohol and a dibasic anhydride in place of a part of the unsaturated monobasic acid. A product compound obtained by adding and reacting in the presence of a polymerization inhibitor and an esterification catalyst,
Or furthermore, after adding a dibasic acid anhydride to the hydroxyl group in the product compound and oxidizing the half ester carboxylic acid, allyl glycidyl ether or glycidyl (meth)acrylate is reacted. This is a method for producing an air-drying vinyl ester resin characterized by containing more than one aryl ether group and four aryl ether groups.

[Effect]

That is, when the ratio of allyl ether groups per epoxy (meth)grill molecule is less than one, the desired drying cannot be achieved, and as a means of introducing allyl ether groups in a ratio greater than one, carbon An attempt was made to make epoxy (meth)glylate with an acid pendant and react it with allylglycyl ether, but the resin production was extremely unstable.

In this method, the ratio of allyl ether groups was limited to one at most, and the method of the present invention was extremely effective in achieving the desired drying.

The most typical method for introducing more than 1 allyl ether group, preferably 1.5 or more allyl ether groups into epoxy (meth)acrylic, which can be produced, is to use a polyvalent ether group such as trimethylolpropane diallyl ether, which is usually commercially available. Allyl ether monoalcohol equivalent is reacted with phthalic anhydride,
Make its half-esterified product. This is a method in which this compound is substituted for a portion of the (meth)grilic acid in the reaction between the epoxy resin and (meth)grilic acid.

Regarding the above reaction, in the case of a compound having three or more epoxy groups in the same molecule, such as a novolak epoxy resin, the reaction is as shown in the following schematic diagram (1).

Next, using a bisphenol type epoxy resin, which is a general-purpose epoxy resin, as described above, an unsaturated monobasic acid is added to the epoxy group of the epoxy resin, and a polyvalent allyl ether is added to the epoxy group of the epoxy resin, and a part of the unsaturated monobasic acid is replaced with polyvalent allyl ether. A half ester carboxylic acid produced by the reaction between a monoalcohol and a dibasic acid anhydride is added and reacted, an acid anhydride is added to the hydroxyl group of the epoxy acrylic compound of this reaction product, half ester carboxylic oxidation is measured, and allyl Allyl ether groups can be supplemented by reacting with glycidyl ether.

For example, when supplemented with glycysyl methacrylate, it is as shown in Schematic IIG-1.

When supplemented with allyl glycidyl ether, for example, 2 equivalents of epoxy group, 1.5 equivalents of unsaturated monobasic acid, 0.5 equivalents of trimethylolpropane diallyl ether acid pendant, 0.5 mol of dibasic acid, 0 allyl glycidyl ether.
．． When reacting with a chemical reaction ratio of 5 equivalents,
It is expected that the mixture compositions shown in diagram (■)-(1) to (4) will be obtained, but even with these mixtures, if the above conditions are satisfied in the proportions, the purpose can be achieved.

Q　　　　　0 The manufacturing method will be explained below.

In the above case via an ester group, a ring-opening addition reaction is carried out at a photochemical reaction rate between a monoalcohol containing a polyvalent allyl ether and a dibasic rIR anhydride.

The end of the reaction was determined by infrared spectroscopy at a wave number of 1760.18.
It can be traced and confirmed by the behavior of 20cm-1 and acid value.

After the reaction, this compound is reacted with the epoxy groups of the epoxy resin in a chemical equivalent amount to the epoxy groups excluding the epoxy groups consumed by meth)acrylic acid.

During the reaction, hydroquinone, benzoquinone,
0.001 to 0.1% by weight of a phenolic polymerization inhibitor such as methylhydroquinone and other known polymerization inhibitors, and amines such as triethylamine, dimethylbenzylamine, dimethylaniline, etc. as an esterification catalyst to facilitate the reaction. 0.005 to 3
Add the weighted view% and make it react. The reaction temperature is 80℃~15℃.
The reaction is carried out in the presence of air at 0°C, more preferably from 90°C to 130°C.
The reaction may be carried out by mixing styrenes, and the completion of the reaction can be determined by measuring the acid value.

The epoxy resins used in this production are diglycidyl ether, phenol novolac, gresol novolac, brominated novolac, and brominated talesol novolak obtained by reacting bisphenol compounds represented by bisphenol A and bisphenol F with epichlorohydrin and methylepichlorohydrin. Hydroquinone is a polyglycidyl ether obtained by the reaction of epichlorohydrin with a polynuclear phenolic resin represented by .

Polyglycidyl ethers obtained by reacting polyphenols represented by resorcin with epichlorohydrin, glycidyl ester ethers obtained by reacting benzoic acid with epichlorohydrin, dimer acid, phthalic acid, trimellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid Polyglycidyl ethers obtained by the reaction of organic polybasic acids such as exemplified by E.g. and epichlorohydrin, glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A, or glycidyl ethers obtained by the reaction of hydrogenated bisphenol A and epichlorohydrin, etc. These can be used alone or in combination.

The unsaturated monobasic acids used in the present invention include acrylic acid,
Methacrylic acid, crotonic acid, cinnamic acid, etc. are known, but methacrylic acid and acrylic acid are practically sufficient. Further, if necessary, dibasic acid anhydrides to be reacted with the carboxylic acid anhydride for half ester carboxylated epoxy acrylic and polyvalent allyl ether monoalcohol include phthalic acid, maleic acid, succinic acid, tetrahydrophthalic acid, Acid anhydrides such as methyltetrahydrophthalic acid and hexahydrophthalic acid or trimellitic anhydride can be used. The allyl ether compound that reacts with the half-ester carboxylic acid is allyl glycidyl ether. The (meth)grill compound is glycysyl (meth)acrylate. In addition, the polyvalent allyl ether monoalcohol source used includes glycerin diallyl ether, trimethylolpropane diallyl ether, trimethylolethane diallyl ether, pentaerythritol triallyl ether, etc. However, from the viewpoint of supply stability, trimethylolpropane diallyl ether is used. is sufficient.

The resulting resin is usually made of reactive diluent monomers such as styrene and vinyltoluene in consideration of workability.

It is used after being diluted with chlorstyrene, paramethylstyrene, tert-butylstyrene, etc.

For curing, organic peroxides such as methyl ethyl ketone peroxide, acetoacetate peroxide,
Acetylacetone peroxide.

Tertiary butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, cumene hydroperoxide, etc., and the curing accelerators include naphthenic acid or octoic acid, cobalt, manganese, iron, vanadium, etc., and commonly used curing systems. Just adopt it.

〔Example〕

The manufacturing method will be described in more detail with examples below, but the invention is not limited by the examples.

Example 1 Trimethylolpropane diallyl ether: 214g (
1 mol) and 148 g (1 mol) of phthalic anhydride were charged and heated at 100 to 130°C under a nitrogen gas atmosphere for 2.
The reaction was carried out for 5 hours to obtain a half ester carboxylic acid having an acid value of 155. In addition to the acid value, the end point of the reaction is determined by infrared spectroscopy at a wave number of 17.
This was confirmed by the disappearance of acid anhydride absorption at 60 cm-1 and 1820 cm''. This composite is referred to as compound (A).

Separately, novolac type epoxy resin manufactured by Dow Chemical Company, USA, trade name DEN-438: 179 g (1 equivalent), methacrylic acid: 60 g (0.7 equivalent), compound (A): 1
09g (0.3 equivalent), hydroquinone: 0.2g,
Benzylmethylamine: 1.7g, styrene monomer =
58g of the compound was heated to 110~12° while blowing air.
When the reaction is carried out at 0°C for 3 hours, the acid value becomes 10 or less and the reaction is completed. After the completion of the reaction, 74 g of styrene monomer was further added to obtain a resin having a viscosity of 3.5 poise/25°C. In this case, Dow Chemical DEN-438 is an approximately trifunctional epoxy containing 0.9 diallyl ether compounds, that is, approximately 1.8 allyl ethers per molecule of epoxy (meth)gril.

100 parts of this resin, 1.5 parts of MEKPO (methyl ethyl ketone peroxide), and 0.5 parts of cobalt naphthenate.
When the mixture was coated on a glass plate to a thickness of L20tLm, it gelatinized in about 15 minutes at 25°C and was dry to the touch and hardened in 2 hours. After 3 to 4 hours after gelation, the coating film showed no stickiness at all even in a rubbing test using an acetone solvent, and had excellent air drying properties.

Example 2 Trimethylolpropane diallyl ether: 214g
(1 mol), terahydrophthalic anhydride: 152g
(1 mol) and under nitrogen gas atmosphere 100~13
0'c 2,5 o'clock Vr reaction sasser rsl 1lff1
51 half-ester carboxylic acids were obtained. This composite is designated as compound (B).

Separately, Gresol novolac type epoxy resin manufactured by Ciba Geigy Japan, trade name Araldite ECN-1299: 2
10g (1 equivalent), methacrylic acid: 60g (0°7 equivalent), compound (B): 110 parts g (0.3g equivalent), methylhydroquinone 20.2g, triethylamine: 1.9g, styrene monomer = 63g. After charging and reacting at 100 to 120°C for 3 hours while blowing air, the acid value became 8. Styrene monomer after reaction:
190 g was added to obtain a resin with a viscosity of 7 poise/25°C.

In this case, Ciba's Araldite ECN-1299 is an epoxy with an average trifunctionality or more, and contains 0.9 or more diallyl ether compounds per molecule of epoxy (meth)grill, that is, about 1.8 or more allyl ethers. There is.

1.5 parts of MEKPO and 0.5 parts of cobalt naphthenate were mixed with 100 parts of this resin, and the mixture was temporarily coated on glass. It is dry to the touch in about 2 hours at 25℃, and after 3 hours it becomes acetic acid.
No stickiness was observed in the rubbing test with solvent.

Example 3 Epoxy resin manufactured by U.S. Shell Company, trade name Epicote-828
: 185g (1 equivalent), 51') UrrIl! :
60 g (0.7 eq.) of the compound in Example 2 (B
): Llog (0,3 equivalent), triethylamine X
1.8 g of hydroquinone and 0.2 g of hydroquinone were charged and reacted at 120 to 130° C. for 3 to 4 hours while blowing air, resulting in an acid value of 2.

Furthermore, add 23g of tetrahydrophthalic acid from 110~
After reacting at 120°C for 2 hours, the acid value became 24. In addition to the acid value, it was confirmed by infrared spectroscopy that the end point of the reaction was the disappearance of absorption of the acid anhydride.

Thereafter, 17 g of allyl glycidyl ether was further added and reacted at 5120 to 130°C for 2 hours, resulting in an acid value of 3. After the reaction was completed, 263 g of styrene monomer was added to obtain a resin with a viscosity of 7 boads/25°C. In this case, Shell's Epicote-828 is an epoxy with an average difunctionality, and the number of diallyl ether compounds per 1 molecule of epoxy (meth)acrylic is 0.6, that is, 1.2 as allyl ether, which is due to introduction from allyl glycidyl ether. Contained 0.13 allyl ethers, 1.3 or more in total. cumene hydroperoxide per 100 parts of this resin.
When 2 parts of cobalt naphthenate and 0.5 parts of cobalt naphthenate were mixed and applied to a thickness of 120 μm on a glass plate, the coating gelatinized in 40 minutes at 25°C, and no stickiness was observed in a rubbing test with an acetone solvent in 4 to 5 hours. I couldn't.

Comparative Example 1 Novolac type epoxy resin manufactured by Dow Chemical Co., USA, trade name DEN-438: 358 g (2000), methacrylic acid: 155 g (1,8 our company), the compound of Example 1 (
A): 72.4 g (0,'2 equivalent), hydroquinone: 0.2 g, trisdimethylaminophenol: 2
．． When 9 g of styrene monomer m and 90 g of styrene monomer m were charged and reacted at 110 to 120° C. for 3 hours while blowing air, the acid value became 8.

Then 225g of styrene monomer was added and the viscosity was 3.
A resin of 4 poise/25°C was obtained. In this case, DEN-438 manufactured by Dow Chemical Company (Example 1), this epoxy (
It contained 0.3 diallyl ether compounds per meth)acrylic molecule, that is, about 0.6 as allyl ether.

100 g of this resin was mixed with 1.5 g of MEKPO and 0.5 g of cobalt naphthenate, and the mixture was placed on a glass plate with a thickness of 120 μm.
When applied thickly, the coating gelatinized in about 20 minutes at 25°C. After several hours passed, a rubbing test with an acetone solvent was carried out, but stickiness remained and air dryability was insufficient.

Comparative Example 2 Epicote-828 similar to Example 3: 370 g (
2 equivalents), methacrylic acid: 146 g (1,7 equivalents), compound (B) in Example 2: 110 g (0,3
When 0.38 g of hydroquinone and 3.1 g of trisdimethylaminophenol were charged and reacted at 120 to 130°C for 3 hours while blowing air, the acid value became almost zero. Further, 46 g of tetrahydrophthalic anhydride was added and reacted at 100 to 120°C for 2 hours, resulting in an acid value of 1.25.

This end point was confirmed by acid value and infrared spectroscopic analysis as in Example 3. Further, 34 g of allyl glycidyl ether was charged and reacted at 120 to 130°C for 1.5 to 2.0 hours, resulting in an acid value of 4 and the reaction was completed.

After the completion of the reaction, 470 g of styrene monomer was added to obtain a resin having a 25°C viscosity of 5 poise/25°C. in this case.

Shell's Epicote-828 is an epoxy with an average bifunctionality, and contains 0.3 diallyl ether compounds per 1 molecule of epoxy (meth)gril, that is, about 0.6 as allyl ether, and further allyl ether introduced from allyl glycidyl ether. It contained about 0.3 and about 0.9 in total.

1.5 parts of MEKPO and 0.5 parts of cobalt naphthylate were mixed with 100 parts of this resin, and the mixture was coated on a glass plate and subjected to a rubbing test using an acetone solvent as in Comparative Example 1, but sticky residue remained and the mixture was air-dried. The gender was insufficient.

〔Effect of the invention〕

The resulting resin has excellent corrosion resistance, physical properties, and gloss, so it can be used as a material for FRP, FRP lining, etc., or as a surface finishing material by adding extender pigments such as talc, glass flake pigments, etc. as a coating material, gel coat. It can be widely used as a material for floor coating, resin mortar, adhesives, primers, and electric panels.

Claims (1)

[Claims] An unsaturated monobasic acid to the epoxy group of the epoxy resin,
A product obtained by adding a half-ester carboxylic acid produced by the reaction of a polyvalent allyl ether monoalcohol and a dibasic acid anhydride in place of a part of the unsaturated monobasic acid, and reacting the mixture in the presence of a polymerization inhibitor and an esterification catalyst. per 1 molecule ratio of epoxy (meth)acrylic in the compound, or the product compound obtained by adding dibasic acid anhydride to the hydroxyl group in the above-mentioned product compound and reacting with allyl glycidyl ether or glycidyl (meth)acrylate after half-ester carboxylic oxidation. A method for producing an air-drying vinyl ester resin, which comprises introducing more than one allyl ether group.