POLYMER, AND OXYGEN ABSORBENT AND RESIN COMPOSITION USING SAME

Abstract

A polymer comprising a structural unit derived from a compound (A) represented by formula (I):

##STR00001##

wherein X, Y, R.sup.1, R.sup.2, R.sup.7, R.sup.8, R.sup.3, R.sup.4, R.sup.5, R.sup.6, J, and n are as defined in the description,
provides a resin composition that has an excellent curability and sufficiently polymerizes for curing even in the presence of oxygen in an air atmosphere to form a cured product having excellent appearance.

Claims

1. A polymer comprising a structural unit derived from a compound (A) represented by 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 comprising an aliphatic hydrocarbon having 3 to 15 carbon atoms which has at least one substituent selected from the group consisting of a hydroxy group, a (meth)acryloyloxy group, a 4-vinylphenoxy group, and an alkenyloxy group having 2 to 6 carbon atoms; at least one selected from the at least one substituent is any one selected from the group consisting of a (meth)acryloyloxy group, a 4-vinylphenoxy group, and an alkenyloxy group having 2 to 6 carbon atoms; a carbon atom in the linking group may be replaced by an oxygen atom; and n represents an integer of 1 to 5; provided that Ys, R.sup.5′s, R.sup.6's, R.sup.7's, and R.sup.8's, if present, may represent different atoms or groups, respectively.

2. The polymer according to claim 1, wherein X is an oxygen atom.

3. The polymer according to claim 1, wherein R.sup.3 and R.sup.6 are hydrogen atoms.

4. The polymer according to claim 1, wherein R.sup.4 and R.sup.5 are each independently a hydrogen atom or a methyl group.

5. The polymer according to claim 1, wherein the compound (A) is a compound (A′) represented by 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 (meth)acryloyloxy group, a 4-vinylphenoxy group, and an alkenyloxy group having 2 to 6 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 polymer according to claim 5, wherein R.sup.9 is a hydrogen atom.

7. The polymer according to claim 5, wherein R.sup.10 is a (meth)acryloyloxy group.

8. The polymer according to claim 1, wherein the polymer comprises a structural unit derived from a monomer (B) other than the compound (A).

9. The polymer according to claim 8, wherein the monomer (B) is a monofunctional monomer (B1).

10. The polymer according to claim 9, wherein the monofunctional monomer (B1) is an alkyl (meth)acrylate.

11. An oxygen absorbent comprising the polymer according to claim 1.

12. The oxygen absorbent according to claim 11, wherein the oxygen absorbent comprises a transition metal salt in an amount of 0.001 to 10 mol % based on an amount of the vinyl group in the polymer.

13. A resin composition comprising the oxygen absorbent according to claim 11 and a polyfunctional monomer and/or a resin.

14. The resin composition according to claim 13, wherein the polyfunctional monomer is a polyvalent (meth)acrylic acid ester.

15. A cured product obtained by curing the resin composition according to claim 13.

Description

EXAMPLES

[0122] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Production Example 1: Synthesis of 1,3-bis(3-methyl-2-butenoxy)-2-methacryloyloxypropane

[0123] In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, 410.2 g of acetonitrile, 298.1 g (1.31 mol) of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane, and 218.3 g (2.16 mol) of triethylamine were charged under an air stream. While maintaining the internal temperature at 15° C. or lower, 166.9 g (1.60 mol) of methacrylic chloride containing 2200 ppm of p-methoxyphenol as a polymerization inhibitor was added dropwise with stirring, and the temperature was raised to 25° C. after the dropwise addition. The mixture was stirred at an internal temperature of 25° C. for 1.5 h. After adding 167.1 g of ion-exchanged water and 1.70 g of p-dimethylaminopyridine to the reaction solution, the mixture was stirred at 25° C. for 2 h. After confirming the decomposition of the by-produced methacrylic anhydride, the mixture was extracted three times with ethyl acetate. The organic layer was successively washed with a 2% by mass hydrochloric acid, a 3% by mass aqueous solution of sodium hydrogen carbonate, and a saturated brine, and then dried over sodium sulfate. The obtained organic layer was purified by distillation to obtain 300.0 g (1.012 mol; yield 77.6%) of 1,3-bis(3-methyl-2-butenoxy)-2-methacryloyloxypropane represented by formula (A−1). The measured results of 1.sub.H-NMR are shown below.

##STR00010##

[0124] 1.sub.H-NMR (400 MHz, CDCl.sub.3, TMS) δ: 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)

Production Example 2: Synthesis of 1,3-diallyloxy-2-methacryloyloxypropane

[0125] In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, 81.7 g of acetonitrile, 50.17 g of 1,3-diallyloxy-2-hydroxypropane (0.291 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 48.5 g (0.480 mol) of triethylamine, and 0.05 g of “Quino Power 40” (manufactured by Kawasaki Kasei Chemicals Ltd.) were charged under an air stream. While maintaining the internal temperature at 20° C. or lower, 37.0 g (0.354 mol) of methacrylic acid chloride containing 2000 ppm of p-methoxyphenol as a polymerization inhibitor was added dropwise with stirring, and the temperature was raised to 25° C. after the dropwise addition. The mixture was stirred at an internal temperature of 25° C. for 1.5 h. After adding 60.1 g of ion-exchanged water and 300 mg of p-dimethylaminopyridine to the reaction solution, the mixture was stirred at 25° C. for 2 h. After confirming the decomposition of the by-produced methacrylic anhydride, the mixture was extracted three times with ethyl acetate. The organic layer was successively washed with a 3% by mass hydrochloric acid, a 3% by mass aqueous solution of sodium hydrogen carbonate, and a saturated brine. The obtained organic layer was purified by distillation to obtain 79.9 g (0.333 mol; yield 57%) of 1,3-diallyloxy-2-methacryloyloxypropane represented by formula (E−1). The measured results of 1.sub.H-NMR are shown below.

##STR00011##

[0126] 1.sub.H-NMR (400 MHz, CDCl.sub.3, TMS) δ: 6.14 (d, J=1.6 Hz, 1H), 5.87 (ddt, J=17.2, 10.4, 5.6 Hz, 2H), 5.57 (t, J=1.6 Hz, 1H), 5.26 (dq, J=17.2, 1.6 Hz, 2H), 5.19 (quin, J =4.8 Hz, 2H), 5.17 (dq, J =10.4, 1.6 Hz, 1H), 4.05-3.95 (m, 4H), 3.65 (d, J=4.8 Hz, 4H), 1.95 (s, 3H)

Example 1: Synthesis of Polymer (P1)

[0127] Under a nitrogen stream, in a reactor equipped with a stirrer, a thermometer, and a reflux tube, 86.4 g of ion-exchanged water, 3.4 g of an aqueous solution of sodium dihydrogen phosphate, and 0.5 g of “ROHAGIT Smv” (dispersion stabilizer) (manufactured by Rohm Co., Ltd.) were charged, and the mixture was stirred. After adding 22.5 g (0.076 mol) of 1,3-bis(3-methyl-2-butenoxy)-2-methacryloyloxypropane obtained in Production Example 1, 0.014 g of AIBN (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 0.15 g of n-octylmercaptan (manufactured by FUJIFILM Wako Pure Chemical Corporation), the mixture was stirred for 6 h while maintaining the internal temperature at 70° C. Thereafter, the internal temperature was raised to 80° C., and the mixture was aged for one hour. The polymerization suspension was cooled and then dried under reduced pressure after removing the aqueous layer. The obtained polymer was washed with methanol to obtain a polymer (P1). The polymer (P1) had a number average molecular weight (Mn) of 18,500 and a weight average molecular weight (Mw) of 35,000.

Example 2: Synthesis of Polymer (P2)

[0128] Under a nitrogen stream, in a reactor equipped with a stirrer, a thermometer, and a reflux tube, 115.5 g of ion-exchanged water, 4.6 g of an aqueous solution of sodium dihydrogen phosphate, and 0.7 g of “ROHAGIT Smv” (dispersion stabilizer) (manufactured by Rohm Co., Ltd.) were charged, and the mixture was stirred. After adding 22.5 g (0.076 mol) of 1,3-bis(3-methyl-2- butenoxy)-2-methacryloyloxypropane obtained in Production Example 1, 7.6 g of methyl methacrylate (manufactured by Kuraray Co., Ltd.), 0.018 g of AIBN (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 0.20 g of n-octylmercaptan (manufactured by FUJIFILM Wako Pure Chemical Corporation), the mixture was stirred for 6 h while maintaining the internal temperature at 70° C. Thereafter, the internal temperature was raised to 80° C., and the mixture was aged for one hour. The polymerization suspension was cooled and then dried under reduced pressure after removing the aqueous layer. The obtained polymer was washed with methanol to obtain a polymer (P2). The polymer (P2) had a number average molecular weight (Mn) of 17,500 and a weight average molecular weight (Mw) of 38,900.

Comparative Example 1: Synthesis of Polymer (P3)

[0129] Under a nitrogen stream, in a reactor equipped with a stirrer, a thermometer, and a reflux tube, 115.0 g of ion-exchanged water, 4.5 g of an aqueous solution of sodium dihydrogen phosphate, and 0.7 g of “ROHAGIT Smv” (dispersion stabilizer) (manufactured by Rohm Co., Ltd.) were charged, and the mixture was stirred. After adding 30.0 g (0.125 mol) of 1,3-diallyloxy-2-methacryloyloxypropane obtained in Production Example 2, 0.018 g of AIBN (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 0.20 g of n-octylmercaptan (manufactured by FUJIFILM Wako Pure Chemical Corporation), the mixture was stirred for 4 h while maintaining the internal temperature at 70° C. Thereafter, the internal temperature was raised to 80° C., and the mixture was aged for one hour. The polymerization suspension was cooled and then dried under reduced pressure after removing the aqueous layer. The obtained polymer was washed with methanol to obtain a polymer (P3). The obtained polymer (P3) was insoluble in a solvent to make it impossible to determine the molecular weight.

Comparative Example 2: Synthesis of Polymer (P4)

[0130] Under a nitrogen stream, in a reactor equipped with a stirrer, a thermometer, and a reflux tube, 115.0 g of ion-exchanged water, 4.5 g of an aqueous solution of sodium dihydrogen phosphate, and 0.7 g of “ROHAGIT Smv” (dispersion stabilizer) (manufactured by Rohm Co., Ltd.) were charged, and the mixture was stirred. After adding 21.1 g (0.088 mol) of 1,3-diallyloxy-2-methacryloyloxypropane obtained in Production Example 2, 8.8 g of methyl methacrylate (manufactured by Kuraray Co., Ltd.), 0.018 g of AIBN (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 0.20 g of n-octylmercaptan (manufactured by FUJIFILM Wako Pure Chemical Corporation), the mixture was stirred for 6 h while maintaining the internal temperature at 70° C. Thereafter, the internal temperature was raised to 80° C., and the mixture was aged for one hour. The polymerization suspension was cooled and then dried under reduced pressure after removing the aqueous layer. The obtained polymer was washed with methanol to obtain a polymer (P4). The obtained polymer (P4) was insoluble in a solvent to make it impossible to determine the molecular weight.

Curability Test

[0131] The curability in an air atmosphere of the resin composition comprising each polymer synthesized above and a UV curable resin was evaluated by the appearance after curing and the thickness of the uncured portion. The smaller the thickness of the uncured portion, the more excellent the curability, because the polymerization inhibition by oxygen was effectively prevented and the polymerization for curing proceeded sufficiently even in the presence of oxygen.

[0132] A PET film (polyethylene terephthalate film having a thickness of 300 μm) having a hole with diameter of 4 cm was attached onto a PET film having no hole to prepare a cell.

[0133] Next, 100 parts by mass of 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Ltd.) and 3 parts by mass of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were mixed. To the resultant mixture, one part by mass of any one of the polymers (P1) to (P4) obtained in Examples and Comparative Examples was further mixed to obtain each curable resin composition.

[0134] Each of the obtained curable resin compositions was put into the cell and UV-cured under irradiation conditions of an illuminance of 78 mW/cm.sup.2 and an integrated light quantity of 99 mJ/cm.sup.2 in an air atmosphere.

[0135] The appearance of the cured product (coating film) was observed and evaluated as “A” when it was flat and “B” when it had significant defects. The surface of the cured product was wiped with a cotton impregnated with acetone to remove the uncured product. The weight change before and after wiping was measured, and the thickness of the uncured portion was calculated from the measured value and the specific gravity of the curable resin composition. The results are shown in Table 1. The results for a curable resin composition prepared without adding any of the polymers (P1) to (P4) are shown together as Comparative Example 3.

TABLE-US-00001 TABLE 1 Coating film Thickness of Polymer appearance uncured portion Example 1 P1 A 4.2 μm Example 2 P2 A 5.2 μm Comparative Example 1 P3 B (with unevenness) — Comparative Example 2 P4 B (with unevenness) — Comparative Example 3 — A 6.2 μm

[0136] As shown in Table 1, the curable resin composition comprising the polymer of Example 1 or 2 formed the coating film excellent in the appearance after curing and having the uncured portion with a small thickness, showing that these curable resin compositions were excellent in the curability because the polymerization inhibition by oxygen was effectively prevented and the polymerization for curing proceeded sufficiently even in the presence of oxygen. Therefore, when the curable resin composition is actually used as a UV coating material or a UV ink under the condition in the presence of oxygen, such as in an air atmosphere, it is expected to effectively prevent the decrease in curing rate and the occurrence of surface stickiness.

[0137] On the other hand, the curable resin composition comprising the polymer of Comparative Example 1 or 2 was inferior in the appearance of the coating film after curing and formed the uneven coating film without forming a flat coating film, showing that the curability was poor. In Comparative Example 3 in which no polymer was added, the thickness of the uncured portion after curing was thick and the curability was poor.