Novel (meth)acrylate and resin composition comprising the same

DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a novel (meth)acrylate and a novel resin composition comprising it, which is particularly useful for coating an optical glass fiber for light transmission.
An optical glass fiber for light transmission is brittle, easily flawed and deficient in flexibility, so that it is easily broken by a weak external force because of such flaws. Therefore, an optical glass fiber has been clad with a resin immediately after the preparation. Epoxy or urethane resins have been used as such a resinous cladding material, but these resins have disadvantages in that the productivity is low, because curing requires a long time and that the transmission characteristics are lowered by lateral pressure because of their low flexibility.
The inventors of the present invention have investigated to overcome the above disadvantages. They have succeeded in synthesizing a novel (meth)acrylate which can be rapidly cured and therefore is useful as a vehicle for ultraviolet-curing printing inks or coating materials and in providing a novel ultraviolet-curing resin composition comprising such a novel (meth)acrylate which can be rapidly cured to give a coating film which is flexible and exhibits a low glass transition temperature and therefore is suitable for cladding an optical glass fiber for light transmission.
The present invention relates to (1) a (meth)acrylate represented by the general formula [I]: ##STR2## wherein R.sub.1 stands for a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R.sub.2 and R.sub.3 each stand for a hydrogen atom or a methyl group; the mean value of m is 1 to 10 and the mean value of n is 1 to 10,
and (2) a resin composition comprising (A) a compound represented by the general formula [I]: ##STR3## wherein R.sub.1 stands for a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R.sub.2 and R.sub.3 each stand for a hydrogen atom or a methyl group; the mean value of m is 1 to 10 and the mean value of n is 1 to 10,
(B) a polyurethane acrylate and (C) a photopolymerization initiator.
The novel compound represented by the general formula [I] can be prepared by esterifying a compound represented by the general formula [II]; ##STR4## wherein R.sub.1 stands for a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R.sub.2 and R.sub.3 each stand for a hydrogen atom or a methyl group; the mean value of m is 1 to 10 and the mean value of n is 1 to 10, with (meth)acrylic acid. The mean value of m in the general formula [I] is preferably 1 to 5, more preferably 1 to 3, while that of n is preferably 1 to 2. It is preferred that R.sub.1 is a hydrogen atom or an alkyl group having 1-10 carbon atoms. It is particularly preferred that R.sub.1 is a hydrogen atom or a nonyl or octyl group and that R.sub.3 is a hydrogen atom. A particular process for preparing the compound represented by the general formula [I] is as follows: A mixture of 1 mol of a compound represented by the general formula [II], 1.0 to 2.0 mol, preferably 1.1 to 1.5 mol of (meth)acrylic acid, 0.01 to 5% by weight based on the amount of (meth)acrylic acid of an esterification catalyst (for example, p-toluenesulfonic, sulfuric or methanesulfonic acid) and 0.01 to 5% by weight based on the amount of (meth)acrylic acid of a polymerization inhibitor (for example, methoquinone, phenothiazine or hydroquinone) is heated preferably to 70.degree. to 130.degree. C., dehydrated, washed with caustic solution and water successively and distilled to remove low-boiling substances, thus obtaining a compound represented by the general formula [I].
The compound represented by the general formula [II] to be used as a raw material for preparing the compound represented by the general formula [I] can be prepared by reacting .epsilon.-caprolactone with an adduct of phenol or its derivative with ethylene oxide or propylene oxide. Examples of the compounds represented by the general formula [II] include reaction products obtained by reacting .epsilon.-caprolactone with adducts of phenol or its derivatives, such as cresol, t-butylphenol, nonylphenol, octylphenol or dodecylphenol, with ethylene oxide or propylene oxide.
The polyurethane acrylate (B) to be used in the present invention has an average molecular weight of preferably at least 1000, more preferably 1000 to 10000. Examples of the polyurethane acrylate include polyurethane acrylates of polyetherpolyol having ether linkage in the molecule, polyurethane acrylates of polyesterpolyol having ester linkage in the molecule and polyurethane acrylates having ether and ester linkages in the molecule. Examples of the polyetherpolyol include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, adducts of 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane or bisphenol A with ethylene or propylene oxide. The polyesterpolyol can be prepared by reacting an alcohol component with an acid component. Examples of the alcohol component include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, adducts of 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane or bisphenol A with ethylene oxide, propylene oxide or .epsilon.-caprolactone. Examples of the acid component include dibasic acids such as adipic, sebacic, azelaic and dodecanedicarboxylic acids and anhydrides thereof. Additionally, products obtained by reacting the above alcohol component with the above acid component and .epsilon.-caprolactone simultaneously can be used as the polyesterpolyol. The polyurethane acrylate (B) can be prepared by reacting polyol such as polyetherpolyol, polyesterpolyol or the like with an organic diisocyanate and a hydroxyl group-containing polymerizable monomer until substantially no NCO group remains intact. Examples of the organic diisocyanate include aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate; cycloaliphatic diisocyanates such as isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2'-trimethylhexamethylene diisocyanate. Examples of the hydroxyl group-containing polymerizable monomer include (meth)acrylates such as .beta.-hydroxyethyl (meth)acrylate, .beta.-hydroxypropyl (meth)acrylate, .beta.-hydroxylauryl (meth)-acrylate and adducts of .beta.-hydroxyethyl (meth)acrylate with .epsilon.-caprolactone. The reaction between the NCO group and the OH group can be carried out in the absence of any catalyst, but may be carried out also in the presence of an ordinary catalyst, for example, tertiary amines such as triethylamine, organometallic compounds such as dibutyltin dilaurate or dibutyltin diacetate, or tin chloride. The amount of the polyurethane acrylate (B) used is preferably not more than 200 parts by weight, more preferably 30 to 200 parts by weight, most preferably 40 to 120 parts by weight per 100 parts by weight of the compound represented by the general formula [I]. The use of too much polyurethane acrylate (B) enhance the viscosity to result in difficult handling. The photopolymerization initiator (C) to be used in the present invention may be any known one, so long as it exhibits a good storage stability after compounding. Examples of the photopolymerization initiator include benzoin alkyl ethers such as benzoin ethyl ether, benzoin isobutyl ether and benzoin isopropyl ether; acetophenones such as 2,2-diethoxyacetophenone and 4'-phenoxy-2,2-dichloroacetophenone; propiophenones such as 2-hydroxyl-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone and 4'-dodecyl-2-hydroxy-2-methylpropiophenone; benzil dimethyl ketal; 1-hydroxycyclohexylphenyl ketone; anthraquinones such as 2-ethylanthraquinone and 2-chloroanthraquinone and thioxanthone photopolymerization initiators. These photopolymerization initiators (C) may be used alone or as a mixture of two or more of them. The amount of (C) is 0.1 to 10% by weight, preferably 1 to 6% by weight based on the amount of the resin composition. The ultraviolet-curing resin composition of the present invention may further contain, if necessary, a monofunctional unsaturated compound such as 2-hydroxyethyl (meth)-acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, adducts of .beta.-hydroxyethyl (meth)acrylate with .epsilon.-caprolactone (Placcel FA-1, FM-1; both are products of Daicel Ltd.), esters of (meth)acrylic acid with adducts of tetrahydrofurfuryl alcohol with .epsilon.-caprolactone (KAYARAD TC-110S, KAYARAD TC-120; both are products of Nippon Kayaku Co., Ltd.), phenoxyethyl (meth)acrylate of N-vinylpyrrolidone; or a difunctional unsaturated compound such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate. The amount of such a compound is preferably at most 50% by weight based on the total amount of (A), (B) and (C). The resin composition of the present invention may further contain, if necessary, modifier resins or various additives. Examples of the modifier resin include epoxy resins, polyurethanes, polybutadiene, polyether, polyamidimide, silicone resins and phenolic resins. Examples of the additive include organosilicon compounds, surfactants and polymerization inhibitors. Particularly, examples of the polymerization inhibitor include methylhydroquinone, methoquinone, hydroquinone and naphthoquinone and the amount of the inhibitor used is preferably at most 1% by weight based on the resin composition.
The resin composition of the present invention is useful particularly for cladding an optical glass fiber.
An optical glass fiber is preferably clad with the resin composition of the present invention, particularly by die coating method.
In cladding an optical glass fiber with the resin composition of the present invention, the thickness of the cladding film is preferably from 20 to 300.mu., though not necessarily limited.
The resin composition of the present invention can be easily cured by ultraviolet-light irradiation. The curing of the resin composition of the present invention by ultraviolet light irradiation can be carried out according to an ordinary method, for example, by the use of low-voltage or high-voltage mercury vapor lamp, xenon lamp or the like.
The resin composition of the present invention can be also used as ultraviolet-curing adhesive for laminated glass, fiber treatment agent or the like.

[EXAMPLE]
The present invention will be described by the following Examples in more detail. In Examples, all "parts" are by weight.
Synthetic examples of the compound (A) represented by the general formula [I].
SYNTHETIC EXAMPLE 1
706 parts of a reaction product between phenoxyethyl alcohol and .epsilon.-caprolactone, represented by the formula: ##STR5## 242.2 parts of acrylic acid, 7.3 parts of sulfuric acid, 2.0 parts of hydroquinone, 560 parts of benzene and 140 parts of cyclohexane were placed in a 2 l reactor fitted with a stirrer, a thermostat, a thermometer and a condenser. The content was heated under reflux, while the generated water was separated from the solvent by a separator and taken out of the system and the solvent was recycled to the reactor.
When 50.4 parts of water was generated, the reaction mixture was cooled. The reaction temperature was 80.degree. to 87.degree. C. The reaction mixture was dissolved in a mixture of 1040 parts of benzene and 260 parts of cyclohexane. The solution was neutralized with 20% aqueous causic soda, washed with 500 parts of a 20% aqueous solution of common salt three times and distilled under a reduced pressure to remove the solvent, thus obtaining 786 parts of a pale yellow liquid. This liquid had the following characteristics:
______________________________________specific gravity (25.degree. C.) 1.103viscosity (25.degree. C.) 38.4 CPSsaponification 365.9 mgKOH/gvalueacid value 0.03 mgKOH/grefractive index (20.degree. C.) 1.5026elemental analysis C (%) H (%) 66.51 7.21______________________________________
The obtained product was analyzed by high-resolution nuclear magnetic resonance (NMR). The results of the measurement of absorption frequency are as follows:
______________________________________No. Absorption frequency (Hz)______________________________________ 1 11740.7 2 11732.9 3 11246.0 4 11236.1 5 10728.2 6 8882.9 7 8833.3 8 8765.0 9 8701.110 8671.411 8199.812 7759.213 7757.014 5259.415 5227.516 5195.517 4456.318 4453.019 4351.720 4336.221 4259.122 4242.623 2306.924 2295.925 1915.826 1726.327 1723.028 1662.429 1656.9______________________________________
The above measurement was carried out by using tetramethylsilane as a standard and chloroform as a solvent. The measurement with respect to the coupling of H.sup.1 and C.sup.13 --H was carried out and the identification results of D coupling of C.sup.13 was finally shown. Among the above frequencies, Nos. 14, 15 and 16 correspond to the absorption peaks of the solvent.
SYNTHETIC EXAMPLE 2
794.6 parts of a compound represented by the formula: ##STR6## 187.7 parts of acrylic acid, 15 parts of p-toluenesulfonic acid, 1.4 parts of hydroquinone, 610 parts of benzene and 153 parts of cyclohexane were placed in the same reactor as the one used in Synthetic Example 1 to carry out the reaction in a similar manner as described in Synthetic Example 1 until 39.0 parts of water was generated. The reaction temperature was 80.degree. to 88.degree. C. The reaction mixture was dissolved in a mixture of 1120 parts of benzene and 280 parts of cyclohexane. The solution was neutralized, washed and distilled to remove the solvent according to the same procedure as the one described in Synthetic Example 1 to obtain 775 parts of a pale yellow liquid. This liquid had the following characteristics:
______________________________________specific gravity (25.degree. C.) 1.103viscosity (25.degree. C.) 202.0 CPSsaponification value 399.7 mgKOH/gacid value 0.02 mgKOH/grefractive index (20.degree. C.) 1.4951elemental analysis C (%) H (%) 65.78 7.64______________________________________
Results of NMR measurement
______________________________________No. Absorption frequency (Hz)______________________________________ 1 11738.4 2 11730.7 3 11244.9 4 11233.9 5 10728.2 6 8880.7 7 8832.2 8 8765.0 9 8702.210 8671.411 8198.712 8186.613 7757.014 5260.515 5228.616 5196.617 4682.218 4456.319 4453.020 4350.621 4336.222 4258.023 4242.624 4148.925 2305.826 2295.927 1915.828 1726.329 1723.030 1662.431 1656.9______________________________________
Among the above frequencies, Nos. 14, 15 and 16 correspond to the absorption peaks of the solvent.
SYNTHETIC EXAMPLE 3
600 parts of a compound represented by the formula: ##STR7## 99.5 parts of acrylic acid, 3.8 parts of sulfuric acid, 2 parts of hydroquinone and 400 parts of toluene were placed in the same reactor as the one used in Synthetic Example 1 to carry out the reaction in a similar manner as described in Synthetic Example 1 until 22.6 parts of water was generated. The reaction temperature was 105.degree. to 116.degree. C. The reaction mixture was dissolved in 1000 parts of toluene. The solution was neutralized, washed and distilled to remove the solvent according to the same procedure as the one described in Synthetic Example 1 to obtain 541 parts of a pale yellow liquid. This liquid had the following characteristics:
______________________________________specific gravity (25.degree. C.) 1.0080viscosity (25.degree. C.) 249 CPSsaponification value 208.6 mgKOH/gacid value 0.02 mgKOH/grefractive index (20.degree. C.) 1.4865elemental analysis C (%) H (%) 71.23 9.28______________________________________
Results of NMR measurement
______________________________________No. Absorption frequency (Hz)______________________________________ 1 11751.5 2 11717.4 3 11258.0 4 8843.1 5 8836.5 6 8736.2 7 8732.9 8 8714.2 9 8648.110 8632.711 8607.312 8588.613 7724.914 7719.415 7712.816 5267.017 5235.118 5203.119 5123.820 5066.521 4975.122 4872.623 4859.424 4743.725 4717.326 4363.627 4349.328 3526.429 2950.230 2816.931 2759.632 2735.433 2542.634 2429.135 2376.236 2336.537 2320.038 2260.539 2165.840 2141.541 2132.742 2094.243 2047.944 1989.545 1951.046 1928.947 1751.548 1740.549 1736.150 1675.551 1609.452 1557.753 1544.454 1492.755 1451.956 1360.457 1313.158 1265.759 1184.260 1143.461 1016.762 993.663 977.164 964.965 784.366 733.667 595.968 12.0______________________________________
Among the above frequencies, Nos. 16, 17 and 18 correspond to the absorption peaks of the solvent.
SYNTHETIC EXAMPLE 4
760 parts of a compound represented by the formula: ##STR8## 160 parts of acrylic acid, 4.7 parts of sulfuric acid, 1.2 parts of hydroquinone, 576 parts of benzene and 144 parts of cyclohexane were placed in the same reactor as the one used in Synthetic Example 1 to carry out the reaction in a similar manner as described in Synthetic Example 1 until 32.4 parts of water was generated. The reaction temperature was 81.degree. to 87.degree. C. The reaction mixture was dissolved in a mixture of 1482.4 L parts of benzene and 370.6 parts of cyclohexane. The solution was neutralized, washed and distilled to remove the solvent according to the same procedure as the one described in the Synthetic Example 1, thus obtaining 601.5 parts of a pale yellow liquid. This liquid had the following characteristics:
______________________________________specific gravity (25.degree. C.) 1.420viscosity (25.degree. C.) 193 CPSsaponification value 263.8 mgKOH/gacid value 0.02 mgKOH/grefractive index (20.degree. C.) 1.4919elemental analysis C (%) H (%) 70.93 8.90______________________________________
Results of NMR measurement
______________________________________No. Absorption frequency (Hz)______________________________________ 1 11743.8 2 11739.4 3 11250.3 4 11244.8 5 10587.1 6 8866.2 7 8838.7 8 8708.7 9 8692.210 8660.211 8642.612 8627.213 8601.814 8595.215 8583.116 7721.617 7715.018 7708.419 7702.820 5267.021 5235.122 5203.123 4798.824 4787.825 4784.526 4732.727 4690.828 4687.529 4683.130 4558.631 4357.032 4342.733 4316.334 4298.635 3522.036 3442.637 2945.838 2810.339 2755.240 2729.841 2537.042 2422.543 2369.644 2313.445 2305.746 2256.147 2160.348 2134.949 2125.050 2087.651 2075.452 2041.353 1985.154 1980.755 1944.356 1923.457 1827.658 1746.059 1733.960 1731.761 1670.062 1664.563 1602.864 1552.165 1540.066 1487.167 1476.168 1445.369 1354.970 1308.771 1204.072 1011.273 989.274 972.775 960.576 766.677 729.278 591.5______________________________________
Among the above frequencies, Nos. 20, 21 and 22 correspond to the absorption peaks of the solvent.
SYNTHETIC EXAMPLE 5
593 parts of a compound represented by the formula: ##STR9## 103.2 parts of methacrylic acid, 2.9 parts of sulfuric acid, 1.0 part of hydroquinone, 480 parts of benzene and 120 parts of cyclohexane were placed in the same reactor as the one used in Synthetic Example 1 to carry out the reaction in a similar manner as described in Synthetic Example 1 until 18 parts of water was generated. The reaction temperature was 80.degree. to 87.degree. C. The reaction mixture was dissolved in a mixture of 1140 parts of benzene and 285 parts of cyclohexane. The solution was neutralized, washed and distilled to remove the solvent according to the same procedure as the one described in Synthetic Example 1, thus obtaining 575 parts of a pale yellow wax. This wax had the following characteristics:
______________________________________saponification value 422.9 mgKOH/gacid value 0.02 mgKOH/gelemental analysis C (%) H (%) 65.38 8.25______________________________________
Results of NMR measurement
______________________________________No. Absorption frequency (Hz)______________________________________ 1 11738.4 2 11730.7 3 9236.5 4 8765.0 5 8523.7 6 8474.2 7 8198.7 8 7762.5 9 7757.010 5261.611 5229.712 5197.713 4457.414 4360.515 4337.316 4271.217 4242.618 2306.919 2297.020 1918.021 1731.822 1727.423 1724.124 1662.425 1658.026 1238.327 0.0______________________________________
Among the above frequencies, Nos. 10, 11 and 12 correspond to the absorption peaks of the solvent.
APPLIED EXAMPLES 1 TO 5
40 parts of an epoxy acrylate resin, obtained by esterifying Epikote 828 (an epoxy resin of bisphenoltype; a product of Shell Petrochemicals) with acrylic acid, and 5 parts of Darocur--1173 (a product of E. Merck Co., Ltd.) as a photopolymerization initiator were added to 60 parts of each of the novel (meth)acrylates obtained in Synthetic Examples 1 to 5. The resulting mixture was applied on a steel panel and cured by ultraviolet-light irradiation by the use of a high-voltage mercury vapor lamp (a product of Toshiba Corporation; 2 KW). The results are shown in Table 1.
TABLE 1______________________________________No. (Meth)acrylate Curing time.sup. .circle.1 (sec)______________________________________Applied obtained in Synth. 0.7Example 1 Ex. 1Applied obtained in Synth. 1.0Example 2 Ex. 2Applied obtained in Synth. 1.2Example 3 Ex. 3Applied obtained in Synth. 1.2Example 4 Ex. 4Applied obtained in Synth. 4.2Example 5 Ex. 5______________________________________
SYNTHETIC EXAMPLES OF POLYURETHANE ACRYLATE (B)
SYNTHETIC EXAMPLE 6
964.47 parts of polypropylene glycol (molecular weight: about 3000, OH value; 34.9 mgKOH/g) and 150.16 parts of 4,4'-diphenylmethane diisocyanate were placed in a 2 l reactor fitted with a stirrer, a thermostat, a thermometer and a condenser to carry out the reaction at 75.degree. C. for 10 hours. The reaction mixture was cooled to 60.degree. C. 74.56 parts of 2-hydroxyethyl acrylate, 0.59 part of methoquinone and 0.24 parts of di-n-butyltin dilaurate were added to the reaction mixture. The resulting mixture was heated to carry out the reaction at 75.degree. to 80.degree. C., until the amount of free isocyanate group reached about 0.1% or below, thus obtaining an adduct of an adduct of polypropylene glycol with 4,4'-diphenylmethane diisocyanate with hydroxyethyl acrylate. This adduct had the following characteristics:
______________________________________viscosity (60.degree. C.) 137.5 Prefractive index (20.degree. C.) 1.4800______________________________________
SYNTHETIC EXAMPLE 7
787.36 parts of polytetramethylene glycol (molecular weight: about 2000, OH value: 57) was placed in the same reactor as the one used in Synthetic Example 6, followed by heating to 60.degree. C. 104.4 parts of tolylene diisocyanate was dropwise added to the reactor, followed by heating to carry out the reaction at 80.degree. C. for 10 hours. The reaction mixture was cooled to 60.degree. C. 45.02 parts of 2-hydroxyethyl acrylate, 0.46 part of methoquinone and 0.18 part of di-n-butyltin dilaurate were added to the reaction mixture, followed by heating to carry out the reaction at 80.degree. C. An adduct of an adduct of polytetramethylene glycol with tolylene diisocyanate with hydroxyethyl acrylate was obtained as a product. This product had the following characteristics:
______________________________________viscosity (60.degree. C.) 460 Prefractive index (20.degree. C.) 1.4850______________________________________
SYNTHETIC EXAMPLE 8
253.1 parts of polypropylene glycol (molecular weight: about 2000, OH value: 56.1), 251.3 parts of polyesterpolyol obtained by reacting neopentyl glycol and adipic acid with .epsilon.-caprolactone (Placcel L-220AL, molecular weight: about 2000, OH value: 575, a product of Daicel Ltd.) and 84.7 parts of isophorone diisocyanate were placed in the same reactor as the one used in Synthetic Example 6, followed by heating to carry out the reaction at 75.degree. C. for 10 hours. The reaction mixture was cooled to 60.degree. C. 91.4 parts of .epsilon.-caprolactone-.beta.-hydroxyethyl acrylate (Placcel FA-2; a product of Daicel Ltd.), 0.3 part of methoquinone and 0.12 part of di-n-butyltin dilaurate were added to the reaction mixture. The resulting mixture was heated to carry out the reaction at 75.degree. to 80.degree. C. The resulting product had the following characteristics:
______________________________________viscosity (60.degree. C.) 110 Prefractive index (20.degree. C.) 1.4721______________________________________
EXAMPLES OF ULTRAVIOLET-CURING RESIN COMPOSITION
EXAMPLE 1
30 parts of a polymerizable monomer obtained in Synthetic Example 1, 30 parts of a polymerizable monomer obtained in Synthetic Example 2, 40 parts of polyurethane acrylate obtained in Synthetic Example 6, 5 parts of 1-hydroxycyclohexyl phenyl ketone and 0.01 part of methylhydroquinone were mixed to prepare a resin composition A. The characteristics of the composition A are shown in Table 2.
EXAMPLE 2
60 parts of a polymerizable monomer obtained in Synthetic Example 2, 40 parts of polyurethane acrylate obtained in Synthetic Example 8, 5 parts of 4'-dodecyl-2-hydroxy-2-methylpropiophenone (Darocur-953, a product of E. Merck Co., Ltd.) and 0.01 part of methylhydroquinone were mixed to prepare a resin composition B. The characteristics of the composition B are shown in Table 2.
EXAMPLE 3
10 parts of a polymerizable monomer obtained in Synthetic Example 1, 50 parts of a polymerizable monomer obtained in Synthetic Example 3, 10 parts of .epsilon.-caprolactone-.beta.-hydroxyethyl acrylate (Placcel FA-2, a product of Daicel Ltd.), 30 parts of polyurethane acrylate obtained in Synthetic Example 7, 5 parts of 1-hydroxycyclohexyl phenyl ketone (Irgacure 154; a product of Ciba-Geigy) and 0.01 part of methylhydroquinone were mixed to prepare a resin composition C. The characteristics of the composition C are shown in Table 2.
EXAMPLE 4
60 parts of a polymerizable monomer obtained in Synthetic Example 4, 10 parts of phenoxyethyl acrylate, 30 parts of polyurethane acrylate obtained in Synthetic Example 8, 5 parts of Darocure-953 and 0.01 part of methylhydroquinone were mixed to prepare a resin composition D. The characteristics of the composition D are shown in Table 2.
COMPARATIVE EXAMPLE
5 parts of 2-ethyl-4-methylimidazole was dissolved in 100 parts of epoxy resin Epikote 828 (a product of Shell Chemical) to prepare a resin composition E. The characteristics of the composition E are shown in Table 2.
TABLE 2______________________________________ Resin composition A B C D E______________________________________Viscosity 1600 3800 4400 4800 15000(CPS/25.degree. C.)Curing time -- -- -- -- 59(sec/150.degree. C.)Curing time 0.2 0.2 0.2 0.2 --(sec/mercury tape)80 w/cmHardness 49 42 43 43 .gtoreq.100(Shore A)Glass transition -40 -46 -46 -43 115temperature (.degree.C.)______________________________________
The measurement of curing time in the above Table 2;
With respect to the compositions A, B, C and D, the composition was applied on a glass plate and irradiated with a high-voltage mercury vapor lamp (input 80 W/cm, lamp output 2 kW) which was placed in parallel with the conveyor and at a height of 8 cm from the conveyor (conveyor speed; 50 cm/min) to measure the irradiation time required for the coating film to become dry in a nitrogen atmosphere. With respect to the composition E, the time required for the coating film to gel by heating at 150.degree. C. was measured.
The measurement of Shore hardness A;
With respect to the compositions A, B, C and D, a sheet of a thickness of 250 .mu.m was prepared by irradiation with a high-voltage mercury vapor lamp (input 80 W/cm, lamp output 2 kW) which was placed in parallel with the conveyor and at a height of 8 cm from the conveyor (conveyor speed; 50 m/min). The measurement was carried out with this sheet. With respect to the composition E, the composition was cured by heating at 150.degree. C. for 15 minutes to prepare a plate of a thickness of 2 mm. The measurement was carried out with this plate. The measurement was carried out according to JIS-Z 2246.
The measurement of glass transition temperature;
Sheets and a plate were prepared according to the same procedure as the one described in "The measurement of Shore hardness A". These sheets and plate were measured for glass transition temperature by the use of a viscoelastic spectrometer (made by Iwamoto Manufacturing Co., Ltd.)
EXAMPLE 5
Optical glass fibers drawn to a diameter of 125 .mu.m at a rate of 5 m/second were immediately coated with the Compositions A, B, C and D respectively and each coatings was cured by irradiation of ultraviolet light (high-voltage mercury vapour lamp, lamp output: 2 KW). In each case, no increase in transmission loss was observed even at -40.degree. C.
The novel (meth)acrylate of the present invention is useful as a vehicle for coating or ink composition and can be cured by irradiation with ultraviolet ray or raidation, or by heating.
The resin composition of the present invention exhibits a low viscosity and a high curing speed and can give a coating film which is flexible, low water absorption rate and has a low glass transition temperature, so that it is suitable for coating an optical glass fiber for light transmission. A coating film obtained by using the resin composition of the present invention shows excellent adhesion properties to an optical glass fiber.
Further, the resin composition of the present invention have very low levels of skin toxicity and is free from strong odors.

Number	Date	Country
55-160747	Dec 1980	JPX
1242980	Aug 1971	GBX

Novel (meth)acrylate and resin composition comprising the same

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (1)

US Referenced Citations (1)

Foreign Referenced Citations (2)

Non-Patent Literature Citations (1)