Alkylene oxide-modified dipentaerythritol (meth)acrylate and reactive composition containing same

Abstract

An alkylene oxide-modified polyfunctional (meth)acrylate is provided wherein the problems according to high crystallinity or high viscosity are improved, and the photosensitivity, etc. is enhanced. The compound has a structure represented by the following formula (I), provided that in the formula (I), R represents a substituent represented by the formula (II); AO represents one member or two or more members selected from alkylene oxide units represented by CH.sub.2CH.sub.2O, CH.sub.2CH(CH.sub.3)O, CH.sub.2CH.sub.2CH.sub.2CH.sub.2O and CH.sub.2CH(C.sub.2H.sub.5)O; l indicating the average polymerization degree of the added alkylene oxide is 0<l5; the average value of m is more than 0 and 6 or less; each of the average values of n and o is from 0 to 6, the total value of m, n and o is 6, and in the formula (II), R.sup.2 represents a hydrogen atom or a methyl group. ##STR00001##

Claims

1. A reactive composition containing an ethylene oxide-modified dipentaerythritol acrylate and a poly(ethylene oxide) acrylate, wherein said ethylene oxide-modified dipentaerythritol acrylate has a structure represented by formula (I) ##STR00004## wherein, R represents a substituent represented by the formula (II), wherein R.sup.2 represents a hydrogen atom, ##STR00005## AO represents CH.sub.2CH.sub.2O; l is average degree of polymerization of the added ethylene oxide and the average value is from 2 to 5; average value of m is from 2 to 5; n is 0; average value of o is from 1 to 4; the total value of m, n and o is 6; and wherein the content of said ethylene oxide-modified dipentaerythritol acrylate is 88.5% by mass or more and 98.9% by mass or less, and the content of the poly(ethylene oxide) acrylate is 1.1% by mass or more and 11.5% by mass or less, and wherein the ethylene oxide of the poly(ethylene oxide) acrylate has an average degree of polymerization of from 2 to 5.

Description

EXAMPLES

(1) Although the present invention is described in more detail below by referring to Examples, the present invention is not limited to the following Examples as long as it is included in the gist. In this connection, unless otherwise indicated, % is % by mass, and parts is on the mass basis.

(2) <Conditions of Liquid Chromatography Mass Spectrometry (Hereinafter, Simply Referred to as LC-MS Analysis)>

(3) The LC-MS analysis in Examples and Comparative Examples was performed under the following conditions.

(4) [LC Portion]

(5) 1100 Series manufactured by Agilent Technologies

(6) Column: Inertsil ODS-2 (4.6 mm 250 mm, 5 m), eluent: water 80.0%-30 min.fwdarw.0.0%, methanol 20.0%-30 min.fwdarw.100.0%, column temperature: 40 C., flow rate: 1 mL/min, injection amount: 5 L (200 ppm methanol solution), detector: UV, RI

(7) [MS Portion]

(8) JMS T100LP (manufactured by JEOL)

(9) Ring lens voltage: 10 V, ionization process: APCl+, temperature of solvent removal chamber: 350 C., needle voltage: 2,500 V, orifice 1 temperature: 80 C., orifice 1 voltage: 60 V, voltage between ion guide peaks: 1,000 V, orifice 2 voltage: 5 V.

(10) <Hydroxyl Value Measurement Conditions>

(11) Acetic acid and pyridine were mixed in a weight ratio of 1:9 and used as an acetylation reagent. A sample is weighed in a flask; added with the acetylation reagent; and heated at 80 C. for 2 hours. After the reaction, titration was performed with an aqueous 1 mol/l potassium hydroxide solution by using phenolphthalein as an indicator.

(12) <NMR Analysis>

(13) As for the results of NMR analysis, the attribution of each peak is indicated by the number ((1) to (3)) shown in the following formula.

(14) ##STR00003##

Example 1

(15) (Synthesis of Dipentaerythritol 2EO Adduct Acrylate)

(16) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 0.3 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated at 130 C., and 132 g (3 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of ethylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 140 C. or less. After the reaction, the pressure was reduced at 140 C. to 10 mmHg mercury column or less to remove excess ethylene oxide and an ethylene glycol polymer occurring as a by-product. Thereafter, the pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 2EO adduct was 982.

(17) Subsequently, 343 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH value: 982), 562 g (7.8 mol) of acrylic acid, 45 g of para-toluenesulfonic acid, 900 g of toluene and 0.9 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 112 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 594 g (yield: 89%) of dipentaerythritol 2EO adduct acrylate represented by the formula (I).

(18) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 2EO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(19) <Dipentaerythritol 2EO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(20) 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with ethylene oxide, from 68 to 73 ppm: derived from ethylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bonded acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(21) <Dipentaerythritol 2EO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(22) From 3.3 to 4.1 ppm (16H): derived from (1) and (3), from 3.6 to 4.4 ppm (8H): derived from ethylene oxide added to OH of (3), from 5.7 to 6.4 ppm (18H): derived from double bond of acrylic acid ester, and 7.3 ppm: derived from deuterated chloroform.

(23) <Dipentaerythritol 2EO Adduct Acrylate> (LC-MS Analysis)

(24) From 8.8 to 11.5 minutes: poly(ethylene oxide) diacrylate, from 14 to 16 minutes: dipentaerythritol ethylene oxide-modified monoacrylate, and from 16 to 20 minutes: dipentaerythritol ethylene oxide-modified hexaacrylate.

Example 2

(25) (Synthesis of Dipentaerythritol 3EO Adduct Acrylate)

(26) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 0.3 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated at 130 C., and 176 g (4 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of ethylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 140 C. or less. After the reaction, the pressure was reduced at 140 C. to 10 mmHg mercury column or less to remove excess ethylene oxide and an ethylene glycol polymer occurring as a by-product. Thereafter, the pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 3EO adduct was 897.

(27) Subsequently, 375 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH value: 897), 562 g (7.8 mol) of acrylic acid, 46 g of para-toluenesulfonic acid, 900 g of toluene and 0.9 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 112 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 615 g (yield: 88%) of dipentaerythritol 3EO adduct acrylate represented by the formula (I).

(28) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed, as a result, the compound obtained was revealed to be dipentaerythritol 3EO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(29) <Dipentaerythritol 3EO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(30) 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with ethylene oxide, from 68 to 73 ppm: derived from ethylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bonded acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(31) <Dipentaerythritol 3EO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(32) From 3.3 to 4.1 ppm (16H): derived from (1) and (3), from 3.6 to 4.4 ppm (12H): derived from ethylene oxide added to OH of (3), from 5.7 to 6.4 ppm (18H): derived from double bond of acrylic acid ester, and 7.3 ppm: derived from deuterated chloroform.

(33) <Dipentaerythritol 3EO Adduct Acrylate> (LC-MS Analysis)

(34) From 8.8 to 11.5 minutes: poly(ethylene oxide) diacrylate, from 14 to 16 minutes: dipentaerythritol ethylene oxide-modified monoacrylate, and from 16 to 20 minutes: dipentaerythritol ethylene oxide-modified hexaacrylate.

Example 3

(35) (Synthesis of Dipentaerythritol 3.5EO Adduct Acrylate)

(36) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 0.3 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated to 130 C., and 198 g (4.5 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of ethylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 140 C. or less. After the reaction, the pressure was reduced at 140 C. to 10 mmHg mercury column or less to remove excess ethylene oxide and an ethylene glycol polymer occurring as a by-product. Thereafter, the pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 3EO adduct was 819.

(37) Subsequently, 411 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH value: 819), 562 g (7.8 mol) of acrylic acid, 48 g of para-toluenesulfonic acid, 900 g of toluene and 0.9 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 646 g (yield: 88%) of dipentaerythritol 3.5EO adduct acrylate represented by the formula (I).

(38) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 3.5EO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(39) <Dipentaerythritol 3.5EO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(40) 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with ethylene oxide, from 68 to 73 ppm: derived from ethylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bonded acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(41) <Dipentaerythritol 3.5EO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(42) From 3.3 to 4.1 ppm (16H): derived from (1) and (3), from 3.6 to 4.4 ppm (14H): derived from ethylene oxide added to OH of (3), from 5.7 to 6.4 ppm (18H): derived from double bond of acrylic acid ester, and 7.3 ppm: derived from deuterated chloroform.

(43) <Dipentaerythritol 3.5EO Adduct Acrylate> (LC-MS Analysis)

(44) From 8.8 to 11.5 minutes: poly(ethylene oxide) diacrylate, from 14 to 16 minutes: dipentaerythritol ethylene oxide-modified monoacrylate, and from 16 to 20 minutes: dipentaerythritol ethylene oxide-modified hexaacrylate.

Example 4

(45) (Synthesis of Dipentaerythritol 4EO Adduct Acrylate)

(46) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 0.3 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated at 130 C., and 220 g (5 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of ethylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 140 C. or less. After the reaction, the pressure was reduced at 140 C. to 10 mmHg mercury column or less to remove excess ethylene oxide and an ethylene glycol polymer occurring as a by-product. Thereafter, the pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 4EO adduct was 765.

(47) Subsequently, 440 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH value: 765), 562 g (7.8 mol) of acrylic acid, 50 g of para-toluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 665 g (yield: 87%) of dipentaerythritol 4EO adduct acrylate represented by the formula (I).

(48) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 4EO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(49) <Dipentaerythritol 4EO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(50) 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with ethylene oxide, from 68 to 73 ppm: derived from ethylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bonded acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(51) <Dipentaerythritol 4EO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(52) From 3.3 to 4.1 ppm (16H): derived from (1) and (3), from 3.6 to 4.4 ppm (16H): derived from ethylene oxide added to OH of (3), from 5.7 to 6.4 ppm (18H): derived from double bond of acrylic acid ester, and 7.3 ppm: derived from deuterated chloroform.

(53) <Dipentaerythritol 4EO Adduct Acrylate> (LC-MS Analysis)

(54) From 8.8 to 11.5 minutes: poly(ethylene oxide) diacrylate, from 14 to 16 minutes: dipentaerythritol ethylene oxide-modified monoacrylate, and from 16 to 20 minutes: dipentaerythritol ethylene oxide-modified hexaacrylate.

Example 5

(55) Synthesis of Dipentaerythritol 5EO Adduct Acrylate

(56) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 36 g of distilled water and 0.3 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated at 130 C., and 264 g (6 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of ethylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 140 C. or less. After the reaction, the pressure was reduced at 140 C. to 10 mmHg mercury column or less to remove excess ethylene oxide and an ethylene glycol polymer occurring as a by-product. Thereafter, the pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 5EO adduct was 706.

(57) Subsequently, 477 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH value: 706), 562 g (7.8 mol) of acrylic acid, 52 g of para-toluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 697 g (yield: 87%) of dipentaerythritol 5EO adduct acrylate represented by the formula (I).

(58) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 5EO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(59) <Dipentaerythritol 5EO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(60) 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with ethylene oxide, from 68 to 73 ppm: derived from ethylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bonded acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(61) <Dipentaerythritol 5EO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(62) From 3.3 to 4.1 ppm (16H): derived from (1) and (3), from 3.6 to 4.4 ppm (20H): derived from ethylene oxide added to OH of (3), from 5.7 to 6.4 ppm (18H): derived from double bond of acrylic acid ester, and 7.3 ppm: derived from deuterated chloroform.

(63) <Dipentaerythritol 5EO Adduct Acrylate> (LC-MS Analysis)

(64) From 8.8 to 11.5 minutes: poly(ethylene oxide) diacrylate, from 14 to 16 minutes: dipentaerythritol ethylene oxide-modified monoacrylate, and from 16 to 20 minutes: dipentaerythritol ethylene oxide-modified hexaacrylate.

Example 6

(65) (Synthesis of Dipentaerythritol 6EO Adduct Acrylate)

(66) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 36 g of distilled water and 0.3 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated at 130 C., and 352 g (8 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of ethylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 140 C. or less. After the reaction, the pressure was reduced at 140 C. to 10 mmHg mercury column or less to remove excess ethylene oxide and an ethylene glycol polymer occurring as a by-product. Thereafter, the pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 6EO adduct was 646.

(67) Subsequently, 521 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH value: 646), 562 g (7.8 mol) of acrylic acid, 54 g of para-toluenesulfonic acid, 900 g of toluene and 1.1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 727 g (yield: 86%) of dipentaerythritol 6EO adduct acrylate represented by formula (I).

(68) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed, as a result, the compound obtained was revealed to be dipentaerythritol 6EO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(69) <Dipentaerythritol 6EO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(70) 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with ethylene oxide, from 68 to 73 ppm: derived from ethylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bonded acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(71) <Dipentaerythritol 6EO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(72) From 3.3 to 4.1 ppm (16H): derived from (1) and (3), from 3.6 to 4.4 ppm (24H): derived from ethylene oxide added to OH of (3), from 5.7 to 6.4 ppm (18H): derived from double bond of acrylic acid ester, and 7.3 ppm: derived from deuterated chloroform.

(73) <Dipentaerythritol 6EO Adduct Acrylate> (LC-MS Analysis)

(74) From 8.8 to 11.5 minutes: poly(ethylene oxide) diacrylate, from 14 to 16 minutes: dipentaerythritol ethylene oxide-modified monoacrylate, and from 16 to 20 minutes: dipentaerythritol ethylene oxide-modified hexaacrylate.

Example 7

(75) (Synthesis of Dipentaerythritol 4EO Adduct Acrylate with Decreased Amount of by-Product Poly(Ethylene Oxide) Acrylate)

(76) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 0.3 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated at 130 C., and 198 g (4.5 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of ethylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 140 C. or less. After the reaction, the pressure was reduced at 140 C. to 10 mmHg mercury column or less to remove excess ethylene oxide and an ethylene glycol polymer occurring as a by-product. Thereafter, the pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 4EO adduct was 765.

(77) Subsequently, 433 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH value: 778), 562 g (7.8 mol) of acrylic acid, 50 g of para-toluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 659 g (yield: 87%) of dipentaerythritol 4EO adduct acrylate represented by the formula (I).

(78) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 4EO adduct acrylate decreased in the amount of the by-product ethylene oxide derivative. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(79) <Dipentaerythritol 4EO Adduct Acrylate with Decreased By-Product Poly(Ethylene Oxide) Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(80) 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with ethylene oxide, from 68 to 73 ppm: derived from ethylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bonded acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(81) <Dipentaerythritol 4EO Adduct Acrylate with Decreased By-product Poly(Ethylene Oxide) Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(82) From 3.3 to 4.1 ppm (16H): derived from (1) and (3), from 3.6 to 4.4 ppm (24H): derived from ethylene oxide added to OH of (3), from 5.7 to 6.4 ppm (18H): derived from double bond of acrylic acid ester, and 7.3 ppm: derived from deuterated chloroform.

(83) <Dipentaerythritol 4EO Adduct Acrylate with Decreased By-Product Poly(Ethylene Oxide) Acrylate> (LC-MS Analysis)

(84) From 8.8 to 11.5 minutes: poly(ethylene oxide) diacrylate, from 14 to 16 minutes: dipentaerythritol ethylene oxide-modified monoacrylate, and from 16 to 20 minutes: dipentaerythritol ethylene oxide-modified hexaacrylate.

Example 8

(85) (Synthesis of Dipentaerythritol 4PO Adduct Acrylate)

(86) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 0.5 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated to 140 C., and 290 g (5 mol) of propylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of propylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 150 C. or less. After the reaction, the pressure was reduced at 150 C. to 10 mmHg mercury column or less to remove excess propylene oxide and an propylene glycol polymer occurring as a by-product. The pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 4PO adduct was 727.

(87) Subsequently, 463 g (1 mol) of the obtained propylene glycol-modified dipentaerythritol (OH value: 567), 562 g (7.8 mol) of acrylic acid, 58 g of para-toluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 669 g (yield: 85%) of dipentaerythritol 4PO adduct acrylate represented by the formula (I).

(88) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 4PO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(89) <Dipentaerythritol 4PO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(90) 20 ppm: derived from propylene oxide, 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with propylene oxide, from 65 to 80 ppm: derived from propylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bonded acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(91) <Dipentaerythritol 4PO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(92) 1.4 ppm (12H): derived from methyl group of propylene oxide added to OH of (3), from 3.2 to 4.5 ppm (28H): derived from (I), (3) and propylene oxide (excluding methyl group) added to (3), from 5.7 to 6.5 ppm (18H): derived from (3) and acrylic acid ester bound to propylene oxide added to (3), and 7.3 ppm: derived from deuterated chloroform.

(93) <Dipentaerythritol 4PO Adduct Acrylate> (LC-MS Analysis)

(94) From 14 to 15 minutes: dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, from 16.1 to 21.1: dipentaerythritol propylene oxide-modified hexaacrylate, and from 15 to 19.5 minutes: poly(propylene oxide) diacrylate.

Example 9

(95) (Synthesis of Dipentaerythritol 6PO Adduct Acrylate)

(96) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 0.5 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated at 140 C., and 406 g (7 mol) of propylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of propylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 150 C. or less. After the reaction, the pressure was reduced at 150 C. to 10 mmHg mercury column or less to remove excess propylene oxide and a propylene glycol polymer occurring as a by-product. The pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 6PO adduct was 567.

(97) Subsequently, 594 g (1 mol) of the obtained propylene glycol-modified dipentaerythritol (OH value: 567), 562 g (7.8 mol) of acrylic acid, 58 g of para-toluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 771 g (yield: 84%) of dipentaerythritol 6PO adduct acrylate represented by the formula (I).

(98) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 6PO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(99) <Dipentaerythritol 6PO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(100) 20 ppm: derived from propylene oxide, 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with propylene oxide, from 65 to 80 ppm: derived from propylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bound acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(101) <Dipentaerythritol 6PO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(102) 1.4 ppm (1811): derived from methyl group of propylene oxide added to OH of (3), from 3.2 to 4.3 ppm (34H): derived from (1), (3) and propylene oxide (excluding methyl group) added to (3), from 5.7 to 6.5 ppm (18H): derived from acrylic acid ester-bound to propylene oxide added to (3), and 7.3 ppm: derived from deuterated chloroform.

(103) <Dipentaerythritol 6PO Adduct Acrylate> (LC-MS Analysis)

(104) From 14 to 15 minutes: dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, from 16.1 to 23.2: dipentaerythritol propylene oxide-modified hexaacrylate, and from 15 to 20.1 minutes: poly(propylene oxide) diacrylate.

Example 10

(105) (Synthesis of Dipentaerythritol 4BO Adduct Acrylate)

(106) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 2 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated to 150 C., and 360 g (5 mol) of butylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of butylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 150 C. or less. After the reaction, the pressure was reduced at 150 C. to 10 mmHg mercury column or less to remove excess butylene oxide and a butylene glycol polymer occurring as a by-product. The pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 4BO adduct was 660.

(107) Subsequently, 510 g (1 mol) of the obtained butylene glycol-modified dipentaerythritol (OH value: 660), 562 g (7.8 mol) of acrylic acid, 51 g of para-toluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 701 g (yield: 84%) of dipentaerythritol 4BO adduct acrylate represented by the formula (I).

(108) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 4BO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(109) <Dipentaerythritol 4BO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(110) 29 ppm: derived from butylene oxide, 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with butylene oxide, 63 ppm: derived from butylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bound acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(111) <Dipentaerythritol 4BO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(112) From 1.1 to 1.6 ppm (20H): derived from ethyl group of butylene oxide, from 3.3 to 4.3 ppm (28H): derived from (1), (3) and butylene oxide (excluding ethyl group) added to (3), from 5.5 to 6.5 ppm (18H): derived from (3) and acrylic acid ester bound to butylene oxide added to (3), and 7.3 ppm: derived from deuterated chloroform.

(113) <Dipentaerythritol 4BO Adduct Acrylate> (LC-MS Analysis)

(114) From 17.0 to 22.1 minutes: poly(butylene oxide) diacrylate, from 16.3 to 23.0: dipentaerythritol butylene oxide-modified pentaacrylate, and from 17 to 24 minutes: dipentaerythritol butylene oxide-modified hexaacrylate.

Example 11

(115) (Synthesis of Dipentaerythritol 6BO Adduct Acrylate)

(116) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 2 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated to 150 C., and 504 g (7 mol) of butylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of butylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 150 C. or less. After the reaction, the pressure was reduced at 150 C. to 10 mmHg mercury column or less to remove excess butylene oxide and a butylene glycol polymer occurring as a by-product. The pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 6BO adduct was 518.

(117) Subsequently, 650 g (1 mol) of the obtained butylene glycol-modified dipentaerythritol (OH value: 518), 562 g (7.8 mol) of acrylic acid, 51 g of para-toluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 799 g (yield: 82%) of dipentaerythritol 4BO adduct acrylate represented by the formula (I).

(118) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 6BO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(119) <Dipentaerythritol 6BO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(120) 29 ppm: derived from butylene oxide, 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with butylene oxide, 63 ppm: derived from butylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bound acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(121) <Dipentaerythritol 6BO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(122) From 1.1 to 1.6 ppm (30H): derived from ethyl group of butylene oxide, from 3.3 to 4.3 ppm (34H): derived from (1), (3) and butylene oxide (excluding ethyl group) added to (3), from 5.5 to 6.5 ppm (18H): derived from acrylic acid ester-bound to butylene oxide added to (3), and 7.3 ppm: derived from deuterated chloroform.

(123) <Dipentaerythritol 6BO Adduct Acrylate> (LC-MS Analysis)

(124) From 17.0 to 22.1 minutes: poly(butylene oxide) diacrylate, from 16.3 to 23.0: dipentaerythritol butylene oxide-modified pentaacrylate, and from 17 to 24 minutes: dipentaerythritol butylene oxide-modified hexaacrylate.

Example 12

(125) (Synthesis of Dipentaerythritol 4EO Adduct Acrylate Increased in Amount of By-Product Poly(Ethylene Oxide) Acrylate)

(126) Into a 1 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 0.3 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated to 130 C., and 242 g (5.5 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of ethylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 140 C. or less. After the reaction, the pressure was reduced at 140 C. to 20 mmHg mercury column or less to remove excess ethylene oxide and an ethylene glycol polymer occurring as a by-product. Thereafter, the pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 4EO adduct was 775.

(127) Subsequently, 434 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH value: 775), 562 g (7.8 mol) of acrylic acid, 50 g of para-toluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 637 g (yield: 84%) of dipentaerythritol 4EO adduct acrylate represented by the formula (1).

(128) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 4EO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(129) <Dipentaerythritol 4EO Adduct Acrylate Increased in Amount of By-Product Poly(Ethylene Oxide) Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(130) 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with ethylene oxide, from 68 to 73 ppm: derived from ethylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bound acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(131) <Dipentaerythritol 4EO Adduct Acrylate Increased in Amount of By-Product Poly(Ethylene Oxide) Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(132) From 3.3 to 4.1 ppm (16H): derived from (1) and (3), from 3.6 to 4.4 ppm (16H): derived from ethylene oxide added to OH of (3), from 5.7 to 6.4 ppm (18H): derived from double bond of acrylic acid ester, and 7.3 ppm: derived from deuterated chloroform.

(133) <Dipentaerythritol 4EO Adduct Acrylate Increased in Amount of By-Product Poly(Ethylene Oxide) Acrylate> (LC-MS Analysis)

(134) From 8.8 to 11.5 minutes: poly(ethylene oxide) diacrylate, from 14 to 16 minutes: dipentaerythritol ethylene oxide-modified monoacrylate, and from 16 to 20 minutes: dipentaerythritol ethylene oxide-modified hexaacrylate.

Comparative Example 1

(135) (Synthesis of Dipentaerythritol 12EO Adduct Acrylate)

(136) Into a 2 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 0.3 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated at 130 C., and 572 g (13 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of ethylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 140 C. or less. After the reaction, the pressure was reduced at 140 C. to 10 mmHg mercury column or less to remove excess ethylene oxide and an ethylene glycol polymer occurring as a by-product. Thereafter, the pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 12EO adduct was 434.

(137) Subsequently, 776 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH value: 434), 562 g (7.8 mol) of acrylic acid, 50 g of para-toluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 902 g (yield: 82%) of dipentaerythritol 4EO adduct acrylate represented by the formula (I).

(138) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 12EO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(139) <Dipentaerythritol 12EO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(140) 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with ethylene oxide, from 68 to 73 ppm: derived from ethylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bound acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(141) <Dipentaerythritol 12EO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(142) From 3.3 to 4.1 ppm (16H): derived from (1) and (3), from 3.6 to 4.4 ppm (48H): derived from ethylene oxide added to OH of (3), from 5.7 to 6.4 ppm (18H): derived from double bond of acrylic acid ester, and 7.3 ppm: derived from deuterated chloroform.

(143) <Dipentaerythritol 12EO Adduct Acrylate> (LC-MS Analysis)

(144) From 8.8 to 12.1 minutes: poly(ethylene oxide) diacrylate, from 14 to 16 minutes: dipentaerythritol ethylene oxide-modified monoacrylate, and from 16 to 21 minutes: dipentaerythritol ethylene oxide-modified hexaacrylate.

Comparative Example 2

(145) (Synthesis of Dipentaerythritol 30EO Adduct Acrylate)

(146) Into a 2 L-volume autoclave equipped with a stirring device, 254 g (1.0 mol) of dipentaerythritol (produced by Koei Chemical Co., Ltd., OH value: 1,324), 127 g of toluene and 0.3 g of KOH were charged, and the contents were subjected to a temperature rise to 90 C. with stirring to form a slurry-like liquid. The liquid was then heated at 130 C., and 1,364 g (31 mol) of ethylene oxide was gradually introduced into the autoclave and reacted. Along with the introduction of ethylene oxide, the temperature in the autoclave was raised. Cooling was applied as needed to keep the reaction temperature at 140 C. or less. After the reaction, the pressure was reduced at 140 C. to 10 mmHg mercury column or less to remove excess ethylene oxide and an ethylene glycol polymer occurring as a by-product. Thereafter, the pH was adjusted to a value of 6 to 7 by performing neutralization with acetic acid. The OH value of the obtained dipentaerythritol 30EO adduct was 215.

(147) Subsequently, 1,290 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH value: 215), 562 g (7.8 mol) of acrylic acid, 50 g of para-toluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass-made four-neck flask, and a thermal reaction was performed with blowing air into the flask. The water produced by the reaction was removed out of the system by azeotroping with toluene as needed. The reaction temperature was from 100 to 110 C., and the amount of reaction water removed out of the system at the completion of reaction was 113 g. After the reaction, aqueous alkali washing and water washing were preformed to separate the upper-layer toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 1,258 g (yield: 78%) of dipentaerythritol 30EO adduct acrylate represented by the formula (I).

(148) With respect to this product, measurement of hydroxyl value and analyses by .sup.1H-NMR, .sup.13C-NMR, HPLC and LC-MS were performed. As a result, the compound obtained was revealed to be dipentaerythritol 30EO adduct acrylate. The results of NMR analysis and LC-MS analysis are shown below, and the attribution of peak of NMR is indicated by the above-described number.

(149) <Dipentaerythritol 30EO Adduct Acrylate> (.sup.13C-NMR Analysis (400 MHz), in CDCl3)

(150) 45 ppm: derived from (2), 60 ppm: derived from (3), from 61 to 63 ppm: derived from (3) added with ethylene oxide, from 67 to 74 ppm: derived from ethylene oxide added to (3), from 77 to 79 ppm: derived from deuterated chloroform, from 128 to 131 ppm: derived from ester-bonded acrylic acid, and from 165 to 167 ppm: ester bond moiety.

(151) <Dipentaerythritol 30EO Adduct Acrylate> (.sup.1H-NMR Analysis (400 MHz), in CDCl3)

(152) From 3.3 to 4.1 ppm (16H): derived from (1) and (3), from 3.6 to 4.4 ppm (120H): derived from ethylene oxide added to OH of (3), from 5.7 to 6.4 ppm (18H): derived from double bond of acrylic acid ester, and 7.3 ppm: derived from deuterated chloroform.

(153) <Dipentaerythritol 30EO Adduct Acrylate> (LC-MS Analysis)

(154) From 8.8 to 12.5 minutes: poly(ethylene oxide) diacrylate, and from 16 to 24 minutes: dipentaerythritol ethylene oxide-modified hexaacrylate.

Comparative Example 3

(155) (AO-unmodified Dipentaerythritol Acrylate)

(156) As a target for comparison with the AO-modified dipentaerythritol acrylate of the present invention, an AO-unmodified dipentaerythritol, KAYARAD DPHA (dipentaerythritol pentalhexaacrylate mixture, hereinafter simply referred to as DPHA), produced by Nippon Kayaku Co., Ltd. was used.

(157) The samples obtained in Examples and Comparative Examples above were evaluated by the following methods. The results are shown in Table 1.

(158) [Viscosity]

(159) The viscosity was measured in accordance with JIS K 5600-2-3.

(160) [Photosensitivity]

(161) A material obtained by adding and dissolving 50 parts by weight of the sample obtained in each of Examples 1 to 14 and Comparative Examples, 50 parts by weight of ethyl acetate, and irgacure 184 produced by BASF as a photopolymerization initiator in an amount of 3 parts by weight based on the solid matters was coated on a glass substrate by a spin coater to a dry thickness of 5 m and dried at 80 C. to remove the solvent. This uncured product was cured at an integrated illuminance of 200 mj in a nitrogen atmosphere by using a parallel light exposure system (SX-UID501H UVQ) manufactured by Ushio Inc. with blocking light through a step tablet (25 steps, manufactured by Riston), and the step number when the touch by a finger becomes tack-free is shown.

(162) [Polymerization Ratio]

(163) A sample prepared in the same manner as in the item of photosensitivity was coated on a steel plate to a dry thickness of 5 m and dried at 80 C. to remove the solvent. This test piece was cured at an integrated illuminance of 200 mj and 1,000 mj under the same conditions as in the item of photosensitivity. After measuring the test piece by ATR-IR method, the ester bond-derived peak near 1,740 cm.sup.1 and the double bond-derived peak near 810 cm.sup.1 were compared, and the correlation between the disappearance of peak near 810 cm.sup.1 and the integrated illuminance was confirmed to thereby ascertain the curability.

(164) [Adherence]

(165) A sample prepared in the same manner as in the item of photosensitivity was cured at an integrated illuminance of 200 mj/cm.sup.2 on ABS, acrylic resin and PC substrates by using a belt conveyer-type UV curing apparatus fitted with a metal halide lamp and after performing a cross-cut test specified in JIS-K5400, the number of remaining squares was taken as the adherence.

(166) [Pencil Hardness]

(167) A cured film was formed by the same technique as in the adherence test, and the film hardness on ABS, PC, PET and acrylic resin was measured in accordance with JIS K5600-5-4.

(168) [Abrasion Resistance]

(169) A cured film was formed on a PET substrate by the same technique as in the adherence test and subjected to the Taber abrasion test. The haze after a predetermined number of cycles using a CS-10F abrasion wheel loaded with 500 g was measured by a haze meter (Model HGM, manufactured by Suga Test Instruments Co., Ltd.), and a haze difference between before and after the test was determined.

(170) [Steel Wool Resistance]

(171) A cured film was formed on a PET substrate by the same technique as in the adherence test, and the state of coating film after polishing 100 times with #00 steel wool under a load of 3 kg was observed with an eye and evaluated according to the following criteria:

(172) A: no scratch, B: around 10 scratches could be confirmed on the test piece, and C: many scratches could be confirmed.

(173) [Curling Property]

(174) A 150 m-thick PET film cut into a square 6 cm on a side was used as the base material, and a cured film was formed thereon by the same technique as in the adherence test. Out of four corners of the film, one point was fixed to a flat surface and at this time, the heights of the remaining three points were measured. The average value thereof was taken as the curling property.

(175) [Contamination Resistance]

(176) A cured film was formed on a PET substrate by the same technique as in the adherence test. A permanent marker, a hair dye liquid or a shoe polish was coated as a contaminant on the cured film and the film was left standing still for 18 hours and wiped off with ethanol-impregnated cotton. The outer appearance was observed with an eye and evaluated according to the following criteria:

(177) A: no coloring, B: slightly colored, and C: deeply colored.

(178) [Acid Resistance]

(179) A cured film was formed by the same technique as in the adherence test, and one drop of an aqueous 0.1 mol/L hydrochloric acid solution was dropped on the test film, left standing still for 18 hours in a petri dish, and wiped off with tissue paper. Whether the film was changed or not was observed with an eye and evaluated according to the following criteria:

(180) A: no abnormality on the cured film, B: a slight change in gloss was observed, and C: an obvious abnormality such as whitening, cracking or floating was observed on the cured film.

(181) [Alkali Resistance]

(182) A cured film was formed by the same technique as in the adherence test, and one drop of an aqueous 2% sodium hydroxide solution was dropped on the test film, left standing still for 18 hours in a petri dish, and wiped off with tissue paper. Whether the film was changed or not was observed with an eye and evaluated according to the following criteria:

(183) A: no abnormality on the cured film, B: a slight change in gloss was observed,

(184) and C: an obvious abnormality such as whitening, cracking or floating was observed on the cured film.

(185) [Water Resistance]

(186) A cured film was formed by the same technique as in the adherence test, and the outer appearance when tap water was dropped thereon and after 18 hours, wiped off was observed with an eye and evaluated according to the following criteria:

(187) A: no abnormality on the cured film, B: a slight change in gloss was observed, and C: an obvious abnormality such as whitening, cracking or floating was observed on the cured film.

(188) [Chemical Resistance]

(189) A cured film was formed by the same technique as in the adherence test, and a commercially available bleach consisting of hypochlorite, sodium hydroxide, a surfactant (alkylamine oxide), etc. was dropped on the test film, left standing still for 18 hours in a petri dish, and wiped off with tissue paper. Whether the film was changed or not was observed with an eye and evaluated in the same manner as the water resistance.

(190) [Contact Angle]

(191) This was measured by a drop method. The height of apex and the radius of droplet were directly read, and the contact angle was determined according to =2 arctan (h/a). The contact angles after 0.2 seconds and after 5 seconds were measured.

(192) [Crystallinity]

(193) 20 ml of the sample was put into a 100-ml glass-made screw-top bottle and stored in a refrigerator at 0 C. for 3 months, and the presence or absence of crystallization was observed with an eye and evaluated according to the following criteria:

(194) A: liquid form, B: slurry form, and C: crystallized.

(195) TABLE-US-00001 TABLE 1 LC-MS Measurement Polymerization Ratio By-Product After Irradiation After Irradiation Poly(alkylene Viscosity Photosensitivity at 200 mj at 1000 mj Oxide) Sample m .Math. pa .Math. s/25 C. x/25 (%) (%) Acrylate Example 1 (dipentaerythritol 2EO adduct acrylate) 1700 7 73.3 86.4 3.0 Example 2 (dipentaerythritol 3EO adduct acrylate) 910 8 73.2 86.6 4.5 Example 3 (dipentaerythritol 3.5EO adduct acrylate) 770 9 79.5 91.3 3.5 Example 4 (dipentaerythritol 4EO adduct acrylate) 393 12 85.1 92.8 11.5 Example 5 (dipentaerythritol 5EO adduct acrylate) 635 11 84.2 92.1 3.6 Example 6 (dipentaerythritol 6EO adduct acrylate) 567 11 85.3 92.3 0.6 Example 7 (dipentaerythritol 4EO adduct acrylate 501 12 84.0 90.7 1.1 reduced in amount of by-product poly(ethylene oxide) acrylate) Example 8 (dipentaerythritol 4PO adduct acrylate) 1600 6 83.8 91.2 2.1 Example 9 (dipentaerythritol 6PO adduct acrylate) 1024 7 86.9 92.6 2.3 Example 10 (dipentaerythritol 4BO adduct acrylate) 2100 7 81.5 88.0 1.8 Example 11 (dipentaerythritol 6BO adduct acrylate) 1880 8 83.2 89.2 3.4 Example 12 (dipentaerythritol 4EO adduct acrylate 349 12 83.1 90.4 18.0 increased in amount of by-product poly(ethylene oxide) acrylate) Comparative Example 1 (dipentaerythritol 12EO adduct 570 12 87.4 91.2 4.4 acrylate) Comparative Example 2 (dipentaerythritol 30EO adduct 680 12 87.7 91.9 6.1 acrylate) Comparative Example 3 (AO-unmodified 7200 4 58.9 74.4 0.0 dipentaerythritol acrylate) Adherence Pencil Hardness Acrylic Acrylic Abrasion Steel Wool Sample ABS PC Plate ABS PC PET Plate Resistance Resistance Example 1 (dipentaerythritol 2EO adduct acrylate) 100/100 100/100 100/100 HB F 4H 5H 3.3 A Example 2 (dipentaerythritol 3EO adduct acrylate) 100/100 100/100 100/100 HB F 4H 5H 3.1 A Example 3 (dipentaerythritol 3.5EO adduct acrylate) 100/100 100/100 100/100 HB F 4H 4H 4.4 A Example 4 (dipentaerythritol 4EO adduct acrylate) 100/100 100/100 100/100 HB F 4H 4H 4.0 A Example 5 (dipentaerythritol 5EO adduct acrylate) 100/100 100/100 100/100 HB F 4H 4H 5.1 A Example 6 (dipentaerythritol 6EO adduct acrylate) 100/100 100/100 100/100 B HB 3H 3H 5.0 A Example 7 (dipentaerythritol 4EO adduct acrylate 100/100 100/100 100/100 HB F 4H 4H 3.8 A reduced in amount of by-product poly(ethylene oxide) acrylate) Example 8 (dipentaerythritol 4PO adduct acrylate) 100/100 100/100 100/100 B HB 2H 3H 5.9 B Example 9 (dipentaerythritol 6PO adduct acrylate) 100/100 100/100 100/100 B HB 2H 3H 6.6 B Example 10 (dipentaerythritol 4BO adduct acrylate) 100/100 100/100 100/100 2B B H 2H 6.3 B Example 11 (dipentaerythritol 6BO adduct acrylate) 100/100 100/100 100/100 2B B H 2H 7.2 B Example 12 (dipentaerythritol 4EO adduct acrylate 100/100 100/100 100/100 B HB 3H 3H 6.5 B increased in amount of by-product poly(ethylene oxide) acrylate) Comparative Example 1 (dipentaerythritol 12EO adduct acrylate) 100/100 100/100 100/100 2B B H H 8.8 B Comparative Example 2 (dipentaerythritol 30EO adduct acrylate) 100/100 100/100 100/100 3B 3B B B 16 C Comparative Example 3 (AO-unmodified dipentaerythritol 100/100 100/100 100/100 HB F 4H 5H 2.3 A acrylate) Contamination Resistance Curling Permanent Hair Dye Acid Alkali Sample Property Marker Liquid Shoe Polish Resistance Resistance Example 1 (dipentaerythritol 2EO adduct acrylate) 7.4 A A A A A Example 2 (dipentaerythritol 3EO adduct acrylate) 6.2 A A A A A Example 3 (dipentaerythritol 3.5EO adduct acrylate) 5.1 A A A A A Example 4 (dipentaerythritol 4EO adduct acrylate) 2.1 A A A A A Example 5 (dipentaerythritol 5EO adduct acrylate) 3.6 A A A A A Example 6 (dipentaerythritol 6EO adduct acrylate) 3.5 A A A A A Example 7 (dipentaerythritol 4EO adduct acrylate reduced in amount of 6.2 A A A A A by-product poly(ethylene oxide) acrylate) Example 8 (dipentaerythritol 4PO adduct acrylate) 5.9 A A A A A Example 9 (dipentaerythritol 6PO adduct acrylate) 5.3 B B B B B Example 10 (dipentaerythritol 4BO adduct acrylate) 6.2 A A A A A Example 11 (dipentaerythritol 6BO adduct acrylate) 5.4 B B B B B Example 12 (dipentaerythritol 4EO adduct acrylate increased in amount 2.3 B B B B B of by-product poly(ethylene oxide) acrylate) Comparative Example 1 (dipentaerythritol 12EO adduct acrylate) 2.0 B B B B B Comparative Example 2 (dipentaerythritol 30EO adduct acrylate) 1.3 B C A C C Comparative Example 3 (AO-unmodified dipentaerythritol acrylate) 8.2 A A A A A Chemical Contact Angle Sample Water Resistance Resistance After 0.2 sec After 5 sec Crystallinity Example 1 (dipentaerythritol 2EO adduct acrylate) A A 56.7 56.3 B Example 2 (dipentaerythritol 3EO adduct acrylate) A A 56.6 56.1 A Example 3 (dipentaerythritol 3.5EO adduct acrylate) A A 55.8 53.0 A Example 4 (dipentaerythritol 4EO adduct acrylate) A A 55.0 52.1 A Example 5 (dipentaerythritol 5EO adduct acrylate) A A 54.6 51.8 A Example 6 (dipentaerythritol 6EO adduct acrylate) A A 54.0 51.1 A Example 7 (dipentaerythritol 4EO adduct acrylate reduced in amount of A A 55.3 52.5 A by-product poly(ethylene oxide) acrylate) Example 8 (dipentaerythritol 4PO adduct acrylate) A A 57.1 55.4 A Example 9 (dipentaerythritol 6PO adduct acrylate) B B 56.3 54.2 A Example 10 (dipentaerythritol 4BO adduct acrylate) A A 57.9 56.5 A Example 11 (dipentaerythritol 6BO adduct acrylate) B B 58.7 57.0 B Example 12 (dipentaerythritol 4EO adduct acrylate increased in amount B B 54.0 51.1 A of by-product poly(ethylene oxide) acrylate) Comparative Example 1 (dipentaerythritol 12EO adduct acrylate) B B 39.5 19.7 A Comparative Example 2 (dipentaerythritol 30EO adduct acrylate) B C 35.6 17.9 A Comparative Example 3 (AO-unmodified dipentaerythritol acrylate) A A 57.0 56.7 C

(196) As seen from the results in Table 1, with respect to high viscosity that has been a conventional problem, the viscosity can be greatly reduced by AO modification of dipentaerythritol (meth)acrylate. In addition, since the viscosity is also changed by the amount of by-product poly(alkylene oxide) (meth)acrylate, the desired product viscosity can be obtained by controlling the amount of by-product poly(alkylene oxide) (meth)acrylate contained.

(197) As for photosensitivity, enhancement of the photosensitivity was confirmed in any of modifications with ethylene oxide, propylene oxide and butylene oxide. High photosensitivity was exhibited in the ethylene oxide modification, and highest photosensitivity was exhibited when the addition mol number is around 4.

(198) It is seen that the polymerization ratio is also greatly enhanced by AO modification, and among others, in the ethylene oxide modification, a highest polymerization ratio is exhibited when the addition mol number is around 4.

(199) As seen from the measurement results of the amount of by-product poly(alkylene oxide) (meth)acrylate by LC-MS analysis shown in Table 1, the amount of by-product poly(alkylene oxide) (meth)acrylate is increased, in order, in Examples 7, 4 and 12 and the viscosity is decreased in that order, which leads to an understanding that the viscosity can be controlled by controlling the amount of by-product poly(alkylene oxide) (meth)acrylate. In addition, it is seen that although a difference is not observed in the photosensitivity by a finger touch test, the polymerization ratio is increased by containing a certain amount of by-product poly(alkylene oxide) (meth)acrylate as in Example 4 and is decreased when the amount is too large as in Example 12. This is considered that since a by-product poly(alkylene oxide) (meth)acrylate interpolates between (meth)acryloyl groups of the alkylene oxide-modified dipentaerythritol (meth)acrylate, a closest-packed state is thereby created. Other physical properties of the cured film tend to be deteriorated as the amount of by-product poly(alkylene oxide) (meth)acrylate is increased, and it is understood that various physical properties can be adjusted by controlling the amount of by-product poly(alkylene oxide) (meth)acrylate.

(200) As confirmed from Table 1, the adherence is not decreased depending on the kind or addition mol number of alkylene oxide. The pencil hardness of the cured film is found to decrease in order of ethylene oxide, propylene oxide and butylene oxide and in the same structure, is decreased as the addition mol number is increased. This is attributable mainly to reduction in the crosslinking density and is also true for other evaluation items of abrasion resistance, steel wool resistance, contamination resistance, acid resistance, alkali resistance, water resistance and chemical resistance. As for the crystallinity, it is found that the crystallinity of the acrylate of dipentaerythritol can be reduced by alkylene oxide modification. However, in the modification with a linear skeleton having high crystallinity like butylene oxide of Example 12, reduction in the crystallinity is insufficient.

(201) Also, as understood from comparison among Examples 4, 7 and 12, the amount of by-product poly(alkylene oxide) (meth)acrylate is correlated with the contact angle of the cured film.

INDUSTRIAL APPLICABILITY

(202) As described in the above, the composition containing an alkylene oxide-modified dipentaerythritol (meth)acrylate compound represented by the formula (I) of the present invention, in which the AO addition mol number is optimized and the content of by-product alkylene oxide is controlled, exhibits excellent photosensitivity, low crystallinity and low viscosity leading to excellent dilutability and provides a cured product with low cure shrinkage and high hardness, so that a polymerizable resin composition where a (meth)acrylate of a polyfunctional alcohol represented by dipentaerythritol, pentaerythritol, ditrimethylolpropane, trimethylolpropane, pentaerythritol and the like has been blended can be more decreased in the viscosity and the physical properties of the cured product can be enhanced. Accordingly, this composition can be suitably used for applications, e.g., a resist resin composition such as dry film resist, color resist, black resist and semiconductor resist, a resin composition for medical use such as dental use, a resin composition for paint/coating, an ink composition for printing, a film coating, a black matrix, a photospacer etc.