KR102005740B1 - Radically polymerizable compound - Google Patents

Abstract

The present invention provides a radically polymerizable compound having a radically polymerizable unsaturated group and an alkyl group having 14 or more carbon atoms. The radically polymerizable compound can impart excellent surface dryness and storage stability when added to the radical polymerizable resin composition.
The above-mentioned air drying component excipient and radical polymerizable unsaturated group can be obtained by reacting a cyclic unsaturated aliphatic polybasic acid and a derivative thereof, a compound having an allyl ether group having an? -Positioned hydrogen, an alcohol decomposing compound obtained by transesterification of a polyhydric alcohol and a drying oil, A compound having a chloropentadienyl group as a raw material, and the alkyl group is obtained by using an alcohol and / or a carboxylic acid having 14 or more carbon atoms as a raw material. .

Description

[0001] RADICALLY POLYMERIZABLE COMPOUND [0002]

The present invention relates to a radical polymerizable compound capable of imparting excellent surface drying properties and storage stability when added to a radical polymerizable resin composition.

Radical polymerizable resin compositions are widely used in civil engineering, construction, railroad, road, and the like. The radically polymerizable resin composition generally includes a radically polymerizable resin having a radically polymerizable unsaturated group and a monomer. In addition, when used in the above-mentioned applications, curing agents, curing accelerators, petroleum waxes, and the like are often blended for the purpose of accelerating the curing time at the time of installation in the field (see, for example, Patent Documents 1 to 2 ).

Since the petroleum wax tends to be segregated on the surface of the coating film, the purpose of keeping the radical generated by the hardening agent from the oxygen inhibition present on the surface of the coating film contributes greatly to the surface drying property of the coating film. However, when the petroleum wax is used, desired surface dryness can be obtained. However, there is a problem that when stored in a radical polymerizable resin composition, stored as a gel or agglomerate with time. Further, when a small amount of the petroleum wax is added, the storage stability is improved, but the desired surface dryness can not be obtained.

As described above, a material that can impart surface dryness and storage stability has been desired.

Japanese Patent Application Laid-Open No. 2007-84601 Japanese Patent Application Laid-Open No. 2008-106169

A problem to be solved by the present invention is to provide a radical polymerizing compound capable of imparting excellent surface drying properties and storage stability when added to a radical polymerizable resin composition.

The inventors of the present invention, while studying to solve the above problems, focused on a combination of an air drying component and a wax-like component, and proceeded to conduct intensive studies.

As a result, it has been found that the above problems can be solved by a compound having an air drying imparting group and an alkyl group having 14 or more carbon atoms, and having a radically polymerizable unsaturated group polymerizable with a radically polymerizable resin, and has completed the present invention .

That is, the present invention provides a radically polymerizable compound having an air drying moiety, a radically polymerizable unsaturated group and an alkyl group having 14 or more carbon atoms.

The radically polymerizable compound of the present invention can impart excellent surface drying and storage stability to a radical polymerizable resin composition even in a small amount. In addition, even when added to a radical polymerizable resin composition, there is no adverse effect on tensile properties such as tensile strength.

The radically polymerizable compound of the present invention has a radically polymerizable unsaturated group and an alkyl group having 14 or more carbon atoms.

As the radically polymerizable compound, it is preferable to use one obtained by reacting a compound having an air drying moiety and a radically polymerizable unsaturated group with an alcohol having an alkyl group of 14 or more carbon atoms and / or a carboxylic acid.

From the viewpoint of surface drying properties, the compound having an air drying moiety excited and a radically polymerizable unsaturated group is preferably a compound having a cyclic unsaturated aliphatic polybasic acid and a derivative thereof, a compound having an allyl ether group having an? -Position hydrogen, an esterified product of a polyhydric alcohol and a drying oil, And a compound having a dicyclopentadienyl group having a dicyclohexyl group. Of these compounds, a cyclic unsaturated aliphatic polybasic acid and derivatives thereof, a compound having an allyl ether group having an? -Position hydrogen atom, and a compound having a dicyclopentadienyl group having a hydroxyl group are preferable from the standpoint that the surface drying property and the storage stability can be further improved. Is preferably used.

Examples of the cyclic unsaturated aliphatic polybasic acid and its derivatives include tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, alpha -terpinene-maleic anhydride adduct, trans-piperylene-maleic anhydride Adducts and the like can be used. These compounds may be used alone or in combination of two or more. Of these, methyltetrahydrophthalic anhydride is preferably used because it can further improve surface dryness and storage stability.

Examples of the compound having an allyl ether group having? -Position hydrogen include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, Glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, trimethylolpropane monoallyl ether, trimethylol Allyl ether compounds of polyhydric alcohols such as propane diallyl ether, glycerin monoallyl ether, glycerine diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether and pentaerythritol triallyl ether; And allyl ether compounds having an oxirane ring such as allyl glycidyl ether. These compounds may be used alone or in combination of two or more. Of these, pentaerythritol triallyl ether is preferably used because it can further improve surface dryness and storage stability.

Examples of the polyhydric alcohol used in the production of the esterified product include trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and trishydroxymethylaminomethane; And tetravalent alcohols such as pentaerythritol. These alcohols may be used alone or in combination of two or more.

Examples of the drying oil used in the production of the ester compound include flaxseed oil, soybean oil, cottonseed oil, peanut oil, palm oil and the like. These drying oils may be used alone or in combination of two or more.

As the compound having a dicyclopentadienyl group having a hydroxyl group, for example, dicyclopentenyloxymethanol, dicyclopentenyloxyethanol, dicyclopentenyloxypropanol, and the like can be used. These compounds may be used alone or in combination of two or more. Of these, dicyclopentenyloxyethanol is preferably used because it can further improve surface dryness and storage stability.

Examples of the alcohol having an alkyl group of 14 or more carbon atoms include oleyl alcohol, stearyl alcohol, 2-octyldodecanol, xyl alcohol, cetanol, 2-decyltetradecanol, behenyl alcohol, Can be used. These alcohols may be used alone or in combination of two or more. Among these, it is preferable to use those having a linear alkyl group, and more preferably those having a carbon number in the range of 18 to 22, from the viewpoint of further improving the surface dryness and storage stability.

Examples of the carboxylic acid having an alkyl group of 14 or more carbon atoms include saturated fatty acids such as palmitic acid, stearic acid, and behenic acid; Unsaturated fatty acids such as oleic acid, palmitoleic acid, linoleic acid, ricinoleic acid and linolenic acid; (Meth) acrylic acid, and the like. These carboxylic acids may be used alone or in combination of two or more. Among them, those having a carbon atom number of 18 to 30 are more preferably used in that the surface dryness and the storage stability can be further improved.

The known esterification reaction can be used for the reaction of the compound having an air drying moiety and the radically polymerizable unsaturated group with an alcohol and / or a carboxylic acid having an alkyl group having 14 or more carbon atoms, for example, at 130 ° C To 190 占 폚 for 3 hours to 15 hours.

Examples of the combination of the compound having an air drying moiety excited and a radically polymerizable unsaturated group with an alcohol and / or a carboxylic acid having an alkyl group having 14 or more carbon atoms include a compound having an air drying moiety and a radically polymerizable unsaturated group A combination of a compound having a carboxyl group and an alcohol having an alkyl group of 14 or more carbon atoms; A combination of a carboxylic acid having a hydroxyl group as a compound having an air drying moiety and a radically polymerizable unsaturated group and a carboxylic acid having an alkyl group having 14 or more carbon atoms; Having a carboxyl group as a compound having an air drying moiety and a radically polymerizable unsaturated group and having a hydroxyl group as a compound having an air drying moiety excited and a radically polymerizable unsaturated group is subjected to an esterification reaction and then an alkyl group having not less than 14 carbon atoms And a combination of reacting with an alcohol having a hydroxyl group.

In the esterification reaction, a polymerization inhibitor may be added as needed.

As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, methylhydroquinone and the like can be used. These polymerization inhibitors may be used alone or in combination of two or more.

The number average molecular weight of the radically polymerizable compound of the present invention obtained by the above method is preferably in a range of 350 to 900, more preferably in a range of 390 to 800 in view of being able to further improve surface dryness and storage stability , And more preferably in the range of 400 to 750. The number average molecular weight of the radically polymerizable compound indicates a value measured by gel permeation chromatography (GPC) under the following conditions.

Measurement apparatus: A high-speed GPC apparatus ("HLC-8220GPC" manufactured by Toso Kagaku Co., Ltd.)

Column: The following columns manufactured by Tosoh Corporation were connected in series and used.

"TSK gel gel 5000" (7.8 mm ID × 30 cm) × 1

"TSK gel G4000" (7.8 mm ID × 30 cm) × 1

"TSK Gel G3000" (7.8 mm ID × 30 cm) × 1

"TSK Gel G2000" (7.8 mm ID × 30 cm) × 1

Detector: RI (differential refractometer)

Column temperature: 40 DEG C

Eluent: tetrahydrofuran (THF)

Flow rate: 1.0 mL / min

Injection amount: 100 mu L (tetrahydrofuran solution with 0.4 mass% of sample concentration)

Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)

Quot; TSK gel standard polystyrene A-500 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene A-1000 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene A-2500 " manufactured by Toso Kabushiki Kaisha

&Quot; TSK gel standard polystyrene A-5000 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene F-1 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene F-2 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene F-4 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene F-10 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene F-20 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene F-40 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene F-80 " manufactured by Toso Kabushiki Kaisha

&Quot; TSK gel standard polystyrene F-128 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene F-288 " manufactured by Toso Kabushiki Kaisha

Quot; TSK gel standard polystyrene F-550 " manufactured by Toso Kabushiki Kaisha

The radically polymerizable compound of the present invention can impart excellent surface drying properties and storage stability when added to a radically polymerizable resin composition. As the radically polymerizable resin, for example, unsaturated polyester, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate and the like can be used.

The radically polymerizable resin composition contains the radically polymerizable compound and the radically polymerizable resin as essential components, but may contain other additives as required.

As the other additives, for example, a curing agent, a curing accelerator, a petroleum wax, a polymerization inhibitor, an antioxidant, a thixotropic property-imparting agent, and a light stabilizer can be used.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples.

[Example 1] Synthesis of radically polymerizable compound (1)

To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet and a reflux condenser, 332 parts by mass of methyltetrahydrophthalic anhydride was added, and 512 parts by mass of pentaerythritol triallyl ether was added to suppress heat generation And reacted at 180 DEG C for 3 hours. It was confirmed that the acid value became almost the same as the theoretical value, 540 parts by mass of stearyl alcohol was added, and the reaction was further performed for 8 hours. When the acid value became 3 mgKOH / g or less, 0.1 part by mass of hydroquinone was added to obtain a radically polymerizable compound (1) having a number average molecular weight of 632.

[Example 2] Synthesis of radically polymerizable compound (2)

To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser, 332 parts by mass of methyltetrahydrophthalic anhydride was added, 388 parts by mass of dicyclopentenyloxyethanol was added, And reacted at 180 DEG C for 3 hours. It was confirmed that the acid value became almost the same as the theoretical value, 540 parts by mass of stearyl alcohol was added, and the reaction was further performed for 8 hours. At the time when the acid value became 3 mgKOH / g or less, 0.1 part by mass of hydroquinone was added to obtain a radically polymerizable compound (2) having a number average molecular weight of 568.

[Example 3] Synthesis of radically polymerizable compound (3)

To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser, 332 parts by mass of methyltetrahydrophthalic anhydride was added and 540 parts by mass of stearyl alcohol was added. And reacted for 3 hours. It was confirmed that the acid value became almost the same as the theoretical value, and 0.1 part by mass of hydroquinone was added to obtain a radically polymerizable compound (3) having a number average molecular weight of 436.

[Comparative Example 1] Synthesis of radically polymerizable compound (4)

To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet and a reflux condenser, 332 parts by mass of methyltetrahydrophthalic anhydride was added, and 512 parts by mass of pentaerythritol triallyl ether was added to suppress heat generation And reacted at 180 DEG C for 3 hours. It was confirmed that the acid value became almost the same as the theoretical value, and 0.1 part by mass of hydroquinone was added to obtain a radically polymerizable compound (4) having a number average molecular weight of 380.4.

[Synthesis Example 1] Synthesis of urethane methacrylate

500 parts by mass of polytetramethylene glycol having a number average molecular weight of 1,000 and 174 parts by mass of tolylene diisocyanate were fed into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet and a reflux condenser, And reacted for 4 hours. Then, it was cooled to 50 占 폚. 0.07 parts by mass of hydroquinone and 131 parts by mass of 2-hydroxyethyl methacrylate were added under an air stream, and the reaction was carried out at 90 DEG C for 5 hours. It was confirmed that the NCO% became 0.1 mass% or less, and 0.07 mass part of tert-butyl catechol was added to obtain urethane methacrylate having a number average molecular weight of 1,584.

[Synthesis Example 2] Synthesis of epoxy methacrylate

A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser was charged with 1,850 parts by mass of a reaction product of bisphenol A and epichlorohydrin ("Epiclon 850" manufactured by DIC Corporation) 860 parts by mass of hydroquinone, 1.36 parts by mass of hydroquinone and 10.8 parts by mass of triethylamine were charged and heated to 120 DEG C and reacted for 10 hours to obtain an epoxy methacrylate having an acid value of 3.5 mgKOH / g.

[Production of Radical Polymerizable Resin Composition]

The urethane methacrylate or epoxymethacrylate, dicyclopentenyloxy methacrylate or phenoxyethyl methacrylate, the radical polymerizable compound and the paraffin wax having a melting point of 54 캜 were compounded as shown in Tables 1 and 2 , 2 parts by mass of a 40% by mass suspension of benzoyl peroxide (manufactured by Nippon Kayaku Co., Ltd.), 1 part by mass of the above toluidine compound isopropanol solution ("RP-191" manufactured by DIC Co.) And 0.5 part by mass of cobalt octoate were mixed to obtain a radical polymerizable resin composition.

[Evaluation method of surface dryness]

The evaluation of the surface dryness was evaluated from the values of [TF] / [GT] based on [Tack free time (TF)] and [Gel time (GT)] shown below.

Further, from the values of [TF] / [GT], the following evaluation was made.

2 " is "

2 ≤ 2.5 ≤

If it is 2.5 or more and less than 3, "? &Quot;

3 ", " x "

[Tack free time (TF)]

The radically polymerizable resin composition was applied on a glass plate to a thickness of 0.25 mm using an applicator under an environment of 25 캜, and this was used as a test piece. After the application, the surface of the coated film was pressed with a cotton pad, and the time (minute) until the cotton surface was not left on the surface of the coated film by the adhesion was measured to obtain a tack free time (TF).

[Gel Time (GT)]

50 parts by mass of the radically polymerizable resin composition was taken in a 100 ml beaker and placed in a high temperature water bath at 25 占 폚 to give gel time (minutes) until gelation.

[Evaluation method of storage stability]

500 parts by mass of the radical polymerizable resin composition was placed in a 1-kg can, covered with a cover, and allowed to stand at 60 캜 for 3 weeks. Thereafter, the radically polymerizable resin composition in the can was checked and evaluated as "? &Quot; when fluidity was maintained, and " x " when gelation or aggregation was visually confirmed.

It was found that Examples 1 to 6 of the radical curable compounds of the present invention can impart excellent surface drying properties and storage stability even in small amounts when added to the radical polymerizable resin composition.

On the other hand, in Comparative Example 1, as the radically polymerizable compound, 3 parts by mass of an air drying component-excited and radically polymerizable unsaturated group-containing compound having no more than 14 carbon atoms was used, Could know.

In Comparative Example 2, the same radically polymerizable compound as Comparative Example 1 was added in a larger amount than in Comparative Example 1, and it was found that the surface dryability was slightly improved but the storage stability was poor.

Comparative Example 3 was poor in surface dryness in the form of not using a radical polymerizing compound.

In Comparative Example 4, the blending amount of paraffin wax was increased in Comparative Example 3, and the surface dryness was slightly improved, but the storage stability was poor.

Claims (5)

A compound containing a cyclic unsaturated aliphatic polybasic acid and a derivative thereof, a compound containing an allyl ether group having an? -Position hydrogen, an alcohol decomposing compound obtained by an ester exchange reaction between a polyhydric alcohol and a drying oil, and a dicyclopentadienyl group having a hydroxyl group And a radically polymerizable compound containing at least one compound selected from the group consisting of a compound having a number of carbon atoms of not less than 14 and an alcohol and / or a carboxylic acid as essential raw materials. The radically polymerizable compound according to claim 1, wherein the radically polymerizable compound has a number average molecular weight of from 350 to 900. A radically polymerizable resin composition comprising the radical polymerizing compound according to any one of claims 1 to 3. delete delete