COMPOUND CONTAINING UNSATURATED DOUBLE BOND, OXYGEN ABSORBER COMPRISING SAME, AND RESIN COMPOSITION

Abstract

Provided is an unsaturated double bond-containing compound capable of sufficiently advancing a crosslinking reaction or a curing reaction when used for a coating material or the like and having oxygen absorption performance. The present invention also provides an oxygen absorbent containing the unsaturated double bond-containing compound and a resin composition containing the same. Provided are an unsaturated double bond-containing compound represented by general formula (I), an oxygen absorbent containing the same, and a resin composition.

Claims

1. An unsaturated double bond-containing compound represented by the following general formula (I): ##STR00012## wherein: X and Y each independently represent a chalcogen atom; R.sup.1, R.sup.2, R.sup.7, and R.sup.8 each independently represent any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; R.sup.3, R.sup.4, R.sup.5, and R.sup.6 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group; J represents a linking group composed of an aliphatic hydrocarbon having 3 to 15 carbon atoms, wherein any carbon atom of the linking group is optionally substituted with an oxygen atom, and wherein the linking group optionally has at least one substituent selected from the group consisting of a hydroxy group, a (meth)acryloyloxy group, a styryloxy group, and an alkenyloxy group having 2 to 5 carbon atoms; n is an arbitrary integer of 1 to 5; and when a plurality of Y, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are present, they may be are each optionally different atoms or groups.

2. The unsaturated double bond-containing compound according to claim 1, wherein X in the general formula (I) is an oxygen atom.

3. The unsaturated double bond-containing compound according to claim 1, wherein R.sup.3 and R.sup.6 in the general formula (I) are a hydrogen atom.

4. The unsaturated double bond-containing compound according to claim 1, wherein R.sup.4 and R.sup.5 in the general formula (I) are each independently a hydrogen atom or a methyl group.

5. The unsaturated double bond-containing compound according to claim 1, which is represented by the following general formula (II): ##STR00013## wherein: R.sup.9 represents a hydrogen atom or a methyl group; R.sup.10 represents any one selected from the group consisting of a hydroxy group, a (meth)acryloyloxy group, a styryloxy group, and an alkenyloxy group having 2 to 5 carbon atoms; and R.sup.11, R.sup.12, R.sup.13, and R.sup.14 each independently represent any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group.

6. The unsaturated double bond-containing compound according to claim 5, wherein R.sup.9 in the general formula (II) is a hydrogen atom.

7. An oxygen absorbent comprising the unsaturated double bond-containing compound according to claim 1.

8. The oxygen absorbent according to claim 7, comprising 0.001 to 10 mol % of a transition metal salt with respect to the vinyl group in the unsaturated double bond-containing compound.

9. A resin composition, comprising the oxygen absorbent according to claim 7, and a resin.

10. The resin composition according to claim 9, wherein the resin is an active energy ray-curable resin.

Description

EXAMPLES

[0078] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Measurement of physical properties in Examples and Comparative Examples was carried out by the following methods.

[Method of Measuring Oxygen Absorption Amount (20 C.)]

[0079] 100 mg of the oxygen absorbent obtained in Examples or Comparative Examples was accurately weighed and put into a sample bottle having a capacity of 20 mL. Thereafter, in order to adjust the humidity in the sample bottle, a vial containing 0.5 mL of ion-exchanged water was put into the sample bottle, and the opening of the sample bottle was closed with a rubber cap sealed with a polytetrafluoroethylene resin and an aluminum seal.

[0080] The sample bottle was allowed to stand in a constant temperature bath at 20 C., and after 1 day, 5 days, and 15 days, the residual oxygen amount in the sample bottle was measured using a residual oxygen meter (Pack Master RO-103, manufactured by Iijima Electronics Corporation).

[0081] As a control, the residual oxygen amount was measured under the same conditions as in Examples and Comparative Examples, except that the oxygen absorbent obtained in Examples and Comparative Examples was not added, and the difference (oxygen absorption amount) between the measurement values obtained in Examples and Comparative Examples and the measurement value obtained for the control was determined, and the oxygen absorption amount per 1g of the oxygen absorbent was calculated to be the oxygen absorption amount (20 C.) [mL/g] of the oxygen absorbent. The same test was performed three times, and the average value was adopted.

[Method of Measuring Oxygen Absorption Amount (60 C.)]

[0082] In the measurement of the oxygen absorption amount (20 C.), the oxygen absorption amount (60 C.) [mL/g] (the average value of three tests) of the oxygen absorbent was measured in the same manner except that the temperature of the constant temperature bath was changed from 20 C. to 60 C.

Example 1

[0083] Synthesis of 1,3 -bis(3-methyl-2 -butenoxy)-2-hydroxypropane

##STR00009##

[0084] In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, 61.8 g (0.717 mol) of 3-methyl-2-buten-1-ol and 36.84 g (0.657 mol) of potassium hydroxide were charged under a nitrogen stream. While maintaining the internal temperature at 10 C. or lower, 19.34 g (0.209 mol) of epichlorohydrin was added dropwise with stirring, and the temperature was raised to 50 C. after completion of the dropwise addition. The mixture was stirred at an internal temperature of 50 C. for 6 hours and then cooled to 25 C. The reaction solution was neutralized with a 4M hydrochloric acid aqueous solution, and the upper layer was washed with 310 mL of ion-exchanged water. The obtained organic layer was purified by distillation to obtain 28.77 g (0.126 mol; yield 60.3%) of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane represented by the above general formula (A-1). The results of .sup.1H-NMR measurement are shown below.

[0085] .sup.1H-NMR (400 MHz, CDCl.sub.3, TMS) : 5.34 (tsept, J=6.8, 1.6 Hz, 2H), 4.00 (d, J=6.8 Hz, 4H), 3.94 (dhex, J=4.4, 1.6 Hz, 1H), 3.49 (dd, J=9.6, 6.4 Hz, 2H), 3.43 (dd, J=9.6, 4.8 Hz, 2H), 2.84 (d, J=4.0 Hz, 1H), 1.74 (s, 6H), 1.67 (s, 6H)

Example 2

[0086] Synthesis of 1,3 -bis(3-methyl-2-butenoxy)-2-methacryloyloxypropane

##STR00010##

[0087] In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, 16.1 g of acetonitrile, 11.43 g (0.050 mol) of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane, and 8.41 g (0.083 mol) of triethylamine were charged under an air stream. While maintaining the internal temperature at 15 C. or lower, 6.30 g of methacrylic acid chloride (0.060 mol, containing 2200 ppm of p-methoxyphenol as a polymerization inhibitor) was added dropwise with stirring, and the temperature was raised to 25 C. after completion of the dropwise addition. The mixture was stirred at an internal temperature of 25 C. for 1.5 hours. To the reaction mixture were added 7.07 g of ion-exchanged water and 61 mg of p-dimethylaminopyridine, and the mixture was stirred at 25 C. for 2 hours to confirm decomposition of methacrylic anhydride as a by-product, followed by extraction with ethyl acetate three times. The organic layer was washed with a 2% by mass hydrochloric acid aqueous solution, a 3% by mass sodium hydrogen carbonate aqueous solution, and a saturated saline solution, and dried over sodium sulfate. The obtained organic layer was purified by distillation to obtain 7.70 g (0.026 mol; yield 52%) of 1,3-bis(3-methyl-2-butenoxy)-2-methacryloyloxypropane represented by the above general formula (A-2). The results of .sup.1H-NMR measurement are shown below.

[0088] .sup.1H-NMR (400 MHz, CDCl.sub.3, TMS) : 6.14 (s, 1H), 5.56 (quin, J=1.6 Hz, 1H), 5.32 (tquin, J=4.0, 1.6 Hz, 2H), 5. 18 (quin, J=5.2 Hz, 1H), 3.99 (dq, J=14.8, 3.2 Hz, 4H), 3.62 (d, J=5.2 Hz, 4H), 1.95 (d, J=1.6 Hz, 3H), 1.74 (s, 6H), 1.66 (s, 6H)

Example 3

[0089] In a glass sample bottle, 5.00 g (21.9 mmol) of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane produced in Example 1, and 34 mg (0.048 mmol; 0.11 mol % based on vinyl groups in 1,3-bis (3-methyl-2-butenoxy)-2-hydroxypropane) of cobalt (II) stearate (manufactured by FUJIFILM Wako Pure Chemical Corporation; purity: 90% by mass) were added and stirred well to obtain an oxygen absorbent. The evaluation results are shown in Table 1.

Example 4

[0090] An oxygen absorbent was obtained in the same manner as in Example 3, except that cobalt (II) stearate was not added. The evaluation results are shown in Table 1.

Comparative Example 1

[0091] An oxygen absorbent was obtained in the same manner as in Example 3, except that 5.00 g of a compound (E-1) represented by the following formula (manufactured by Tokyo Chemical Industry Co., Ltd.; purity: 99%; 29.0 mmol) was used instead of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane produced in Example 1, and the amount of cobalt (II) stearate was changed from 34 mg to 44 mg (64 mmol; 0.11 mol % based on the vinyl groups in the compound (E-1)). The evaluation results are shown in Table 1.

##STR00011##

Comparative Example 2

[0092] An oxygen absorbent was obtained in the same manner as in Example 4, except that in Example 4, 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane was changed to the compound (E-1) (manufactured by Tokyo Chemical Industry Co., Ltd.; purity: 99%) represented by the above formula. The evaluation results are shown in Table 1.

TABLE-US-00001 TABLE 1 After 1 After 5 After day days 15 days Oxygen Example 3 6.9 44.6 44.9 absorption 4 2.6 2.6 6.4 amount Comparative 1 2.5 29.0 32.2 (20 C.) Example 2 0.6 0.5 1.4 [mL/g] Oxygen Example 3 >49 >49 >49 absorption 4 27.6 >49 >49 amount Comparative 1 40.0 >49 >49 (60 C.) Example 2 5.8 42.5 >49 [mL/g]

[0093] As shown in Table 1, it is understood that the unsaturated double bond-containing compound of the present invention has excellent oxygen absorption ability even at room temperature. Further, it is surprisingly found that oxygen can be absorbed without using a transition metal salt, and a crosslinking reaction or a curing reaction of the resin composition can be sufficiently developed.

[Effect of Preventing Polymerization Inhibition of UV Curable Resin]

[0094] A test for confirming the effect of the UV-curable resin on prevention of polymerization inhibition by oxygen was conducted by the following method.

[0095] A PET film (polyethylene terephthalate film; thickness: 125 m) having a hole with a diameter of 3 cm was stuck on the PET film having no hole to prepare a cell.

[0096] Next, 100 parts by mass of 1,9-diacryloylnonane (manufactured by Osaka Organic Chemical Industry Ltd.) and 3 parts by mass of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were mixed, and 1 part by mass of the unsaturated double bond-containing compound produced in Examples was further added and mixed to obtain a UV-curable composition. This was placed in the cell, and UV curing was performed under the irradiation conditions of an illuminance of 150 W/cm.sup.2 and an integrated light amount of 300 mJ/cm.sup.2. Then, the surface of the cured product was wiped with acetone-impregnated cotton, the weight change before and after the wiping was measured, and the thickness of the resin portion which was an uncured portion was calculated from the measured value and the specific gravity of the UV-curable composition.

Example 5

[0097] As the unsaturated double bond-containing compound of Examples in the above-mentioned polymerization inhibition prevention effect test of the UV-curable resin, 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane produced in Example 1 was used. The results are shown in Table 2.

Example 6

[0098] A test was carried out in the same manner as in Example 5, except that 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane in Example 5 was changed to 1,3-bis(3-methyl-2-butenoxy)-2-methacryloyloxypropane produced in Example 2. The results are shown in Table 2.

Comparative Example 3

[0099] The test was carried out in the same manner as in Example 5, except that the unsaturated double bond-containing compound produced in Example 1 was not added. The results are shown in Table 2.

TABLE-US-00002 TABLE 2 Thickness of Uncured portion (m) Example 5 4.0 Example 6 2.3 Comparative Example 3 7.1

[0100] As shown in Table 2, the unsaturated double bond-containing compound of the present invention has a large effect of preventing polymerization inhibition of the active energy ray-curable resin by oxygen, and by adding the unsaturated double bond-containing compound of the present invention, good curability can be imparted to a UV coating material, a UV ink or the like even in the presence of air or in an environment where oxygen may be present.

INDUSTRIAL APPLICABILITY

[0101] The oxygen absorbent of the present invention can be suitably used as an oxygen absorbent for suppressing an adverse effect of oxygen in a crosslinking reaction or a curing reaction of a resin including a curing process involving a radical polymerization reaction of an unsaturated polyester resin, a vinyl ester resin, a (meth)acrylic resin, or a urethane (meth)acrylate resin. In addition, by mixing in a resin or coating on the surface, oxygen barrier performance can be improved in a resin such as polyvinyl alcohol, a partially or completely saponified ethylene-vinyl acetate copolymer, or the like in which oxygen barrier properties are required.