JPH0477010B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is directed to a novel ultraviolet resin composition,
In particular, the present invention relates to a novel ultraviolet curable resin composition for coating optical glass fibers for light transmission. Optical glass fibers used for light transmission are
Since it is brittle, easily scratched, and has poor flexibility, it is easily destroyed by even the slightest external force due to such scratches. Therefore, conventionally, optical glass fibers have been coated with a resin on their surfaces immediately after being manufactured from glass rods. Conventionally, epoxy resins, urethane resins, etc. have been used as such resin coating materials, but they require a long time to cure, resulting in poor productivity and lack of flexibility.
The disadvantage is that the transmission characteristics are impaired by lateral pressure. In order to solve the above problems, the present invention proposes a novel ultraviolet ray that has a fast curing speed, the resulting resin coating is flexible, and has a low glass transition temperature, and is suitable for coating optical glass fibers for light transmission. The purpose is to provide a curable resin composition. That is, the present invention is based on the general formula [] (In the formula, R ₁ to _{R 6} are H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ ,
C ₄ H ₉ or

[Formula] R ₇ is H or CH ₃ : The average value of m is a number from 1 to 10, preferably a number from 1 to 5, and n represents 0 or 1. ), a polyurethane acrylate (B), and a photopolymerization initiator (C). A compound represented by the general formula [] is a compound represented by the general formula [] (In the formula, R ₁ to _{R 6} are H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ ,
C ₄ H ₉ or

[Formula] The average value of m is a number from 1 to 10, preferably a number from 1 to 5, and n is 0 or 1.
shows. ) can be obtained by ester reacting two raw materials: a compound represented by (meth)acrylic acid and (meth)acrylic acid. A specific method for producing the compound represented by the general formula [] is as follows, as described in Japanese Patent Application No. 184375/1983. General formula above []
1 mol of the compound represented by, 1.2 mol of acrylic acid,
By adding an esterification catalyst (e.g. para-toluenesulfonic acid) and hydroquinone, heating at 70°C to 130°C, dehydration, neutralization washing, and water washing to remove low boiling point substances, a compound represented by the general formula [] is obtained. The general formula [] as a raw material for producing the compound of the general formula [] is a condensate of 1,2-alkoxydiol and 1,3-alkyldiol derivative, 2,2-dimethyl-3-oxypropanal, and epsilon. It can be obtained by reaction with caprolactone. Specific examples of 1,2-alkylene diol and 1,3-alkylene diol derivatives include ethylene glycol, propylene glycol, neopentyl glycol, hexylene glycol, 1,3-
butanediol, etc. In the present invention, polyurethane acrylate (B) is used, and its average molecular weight is usually 3,000 or more, preferably about 3,000 to 10,000. Examples of such polyurethane acrylate include polyurethane acrylate of polyether polyol having an ether group in the molecule, polyurethane acrylate of polyester polyol having an ester group, or polyurethane acrylate having both an ether group and an ester group in the molecule. I can do it. Examples of polyether polyols include polypropylene glycol, polyethylene glycol, polytetramethylene glycol and 1,
3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol,
2,2-bis(4-hydroxycyclohexyl)
A compound in which ethylene oxide or propylene oxide is added to propane, bisphenol A, etc. can be used. Polyester polyol can be obtained by reacting an alcohol component and an acid component. For example, polypropylene glycol, polyethylene glycol, polytetramethylene glycol and 1,3-butylene glycol, 1,4-butylene glycol, 1,6-
Hexanediol, neopentyl glycol, cyclohexanedimethanol, 2,2-bis(4-
Compounds in which ethylene oxide, propylene oxide is added to hydroxycyclohexyl) propane, bisphenol A, etc., and compounds in which epsilon caprolactone is added are used as alcohol components, and as acid components, adipic acid, sebacic acid, azelaic acid, Dibasic acids such as dodecanedicarboxylic acid and their anhydrides can be used. A compound obtained by simultaneously reacting the above-mentioned alcohol component, acid component, and epsilon caprolactone can also be used as the polyester polyol. Polyurethane acrylate using these polyether polyols and polyester polyols
To obtain (B), polyurethane acrylate (B) is obtained by reacting an organic isocyanate and a polymerization monomer having a hydroxyl group to the hydroxyl group of the polyol until it substantially contains no NCO group. Obtainable. Typical organic diisocyanates include aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate;
There are alicyclic diisocyanates such as isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2'-trimethylhexamethylene diisocyanate, and polymerizable monomers having a hydroxyl group include: (Meth)acrylates with hydroxyl groups such as β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, β-hydroxylauryl (meth)acrylate, and epsilon caprolactone-β-hydroxyethyl (meth)acrylate adduct. etc. The reaction between the NCO group and the OH group proceeds even without a catalyst, but for example, tertiary amines such as triethylamine, organometallic compounds such as dibutyltin dilaurylate and dibutyltin diacetate,
Alternatively, conventional catalysts such as tin chlorides and the like may be used. The proportion of polyurethane acrylate (B) to be used is preferably 200 parts by weight or less per 100 parts by weight of the compound represented by the general formula []; if too much is added, the viscosity becomes high and it becomes difficult to handle. Photopolymerization initiator used in the present invention
(C) may be any known photopolymerization initiator, but it is required to have good storage stability after blending. Examples of such photopolymerization initiators include benzoin alkyl ethers such as benzoin ethyl ether, benzoin isobutyl ether, and benzoin isopropyl ether;
-diethoxyacetophenone, 4'-phenoxy-
Acetophenones such as 2,2-dichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-
2-methylpropiophenone, 4'-dodecyl 2-
Propiophenones such as hydroxy-2-methylpropiophenone, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone and anthraquinones such as 2-ethylanthraquinone and 2-chloroanthraquinone, others,
Examples include thioxanthone photopolymerization initiators. These photopolymerization initiators (C) may be used alone or in a mixture of two or more in any proportion. The amount used is usually 0.1 to 10% by weight of the resin composition. The ultraviolet curable resin composition of the present invention may further contain a polymerizable monomer, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene, if necessary. Glycol mono (meth)
Acrylate, polybutylene glycol mono(meth)acrylate, ε-caprolactone-β-hydroxyethyl(meth)acrylate adduct (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-1, Plaxel FM-1, etc.), tetrahydrofuryl alcohol. (Meth)acrylate of ε-caprolactone adduct (manufactured by Nippon Kayaku Co., Ltd., KAYARAD TC-
110S, KAYARAD TC-120, etc.), monofunctional unsaturated compounds such as phenoxyethyl (meth)acrylate, and N-vinylpyrrolidone, and difunctional unsaturated compounds such as polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate. etc. can be used in addition. Furthermore, if desired, it may contain a modifying resin and various additives, and examples of the modifying resin include epoxy resin,
polyurethane, polybutadiene, polyether,
Examples include polyamideimide, silicone resin, and phenol resin. Examples of the additives include organosilicon compounds, surfactants, and polymerization inhibitors. The composition of the present invention has a low viscosity, a fast curing speed, a flexible resin coating, and a low glass transition point, and is suitable for coating optical glass fibers for light transmission. Hereinafter, the present invention will be specifically explained with reference to Examples. Note that parts in the examples are parts by weight. General formula []
Production example of compound (A) shown by Production example 1 A compound having the following configuration in two reactors equipped with a stirrer, a temperature control device, a thermometer, and a condenser.
624.5 copies 129.8 parts of acrylic acid, p-toluenesulfonic acid
15 parts, hydroquinone 1.0 parts, benzene 700 parts, and cyclohexane 175 parts are charged and heated, and the produced water is distilled and condensed together with the solvent, and only the water is removed from the system in a separator, and the solvent is returned to the reactor. It was cooled when 27 parts of water had been produced. The reaction temperature was 81-87°C.
Add 840 parts of benzene and cyclohexane to the reaction mixture.
Dissolve in 210 parts, neutralize with 20% caustic soda aqueous solution, and wash three times with 300 parts of 20% saline. The solvent was distilled off under reduced pressure to obtain 646.5 parts of liquid. This thing is
It has the following properties. Specific gravity (25℃) 1.052 Viscosity (25℃) 261.5 CPS Saponification value 355.9 mgKOH/g Acid value 0.02 mgKOH/g Refractive index (20℃) 1.4600 Production example 2 Stirrer, temperature control device, thermometer, condenser and Into two reactors equipped with separators, 411.2 parts of a compound having the following structure 112.5 parts of acrylic acid, p-toluenesulfonic acid
13 parts of hydroquinone, 1.0 part of hydroquinone, 400 parts of benzene, and 100 parts of cyclohexane are charged and heated. The produced water is distilled together with the solvent, condensed, and only water is removed from the system using a separator. The solvent is returned to the reactor. Cooling occurred when 23.4 parts of water had been produced. The reaction temperature was 79-88°C. The reaction mixture is dissolved in 504 parts of benzene and 126 parts of cyclohexane, neutralized with 20% aqueous NaOH, and washed three times with 200 parts of 20% aqueous NaCl. The solvent was distilled off under reduced pressure to obtain 406.8 parts of liquid. This thing is
It has the following properties. Specific gravity (25℃) 1.0175 Viscosity (25℃) 68.6 CPS Saponification value 301.9 mgKOH/g Acid value 0.06 mgKOH/g Refractive index (20℃) 1.4560 Production example 3 In the same reactor as Production example 1, the following structure was added. 603.5 parts of a compound with 129.8 parts of acrylic acid, p=toluenesulfonic acid
15 parts, 0.5 parts of phenothiazine, 420 parts of benzene, and 105 parts of cyclohexane were charged, and the reaction was carried out in the same manner as in Production Example 1 until the produced water became 27 parts. Then, neutralization, washing, and solvent removal were performed to obtain 606.3 parts of liquid. Ta. This material has the following properties. Specific gravity (25℃) 1.0580 Viscosity (25℃) 170.4 CPS Saponification value 367.9 mgKOH/g Acid value 0.04 mgKOH/g Refractive index (20℃) 1.4650 Production example 4 In the same reactor as Production example 1, the following structure was added. 402.3 parts of a compound with 129.8 parts of acrylic acid, p-toluenesulfonic acid
15 parts of hydroquinone, 1.0 parts of hydroquinone, 424 parts of benzene, and 106 parts of cyclohexane, and the reaction was carried out in the same manner as in Production Example 1 until the amount of water produced was 27 parts. The reaction temperature was 82-88°C. Benzene reaction mixture
Dissolved in 880 parts and 220 parts of cyclohexane, 20%
After neutralizing with NaOH aqueous solution, wash three times with 300 parts of 20% NaCl water. The solvent was distilled off to obtain 573.1 parts of liquid. This material has the following properties. Specific gravity (25℃) 1.0605 Viscosity (25℃) 127.1 CPS Saponification value 366.5 mgKOH/g Acid value 0.03 mgKOH/g Refractive index (20℃) 1.4620 Production example 5 In the same reactor as Production example 1, the following structure was added. 752.2 parts of a compound with 167.6 parts of acrylic acid, p-toluenesulfonic acid
19.4 parts, hydroquinone 1.3 parts, benzene 620 parts,
155 parts of cyclohexane was charged, and the reaction was carried out in the same manner as in Production Example 1 until the amount of water produced was 34.9 parts, followed by neutralization, washing, and solvent removal to obtain 694 parts of liquid.
This material has the following properties. Specific gravity (25℃) 1.050 Viscosity (25℃) 110 CPS Saponification value 377.1 mgKOH/g Acid value 0.01 mgKOH/g Refractive index (20℃) 1.4645 Production example of polyurethane acrylate (B) Production example 6 Stirrer, temperature control 964.47 parts of polypropylene glycol (molecular weight approximately 3000, OH value 34.9 mgKOH/g) was added to two reactors equipped with an apparatus, thermometer, and condenser.
4,4′ diphenylmethane diisocyanate 150.16
After raising the temperature, the reaction solution was cooled to 60°C, and 74.56 parts of 2-hydroxyethyl acrylate, 0.59 parts of methoquinone, and 0.24 parts of di-n-butyltin dilaurate were added, and after raising the temperature, , the reaction was carried out at 75-80°C. The reaction was continued until completion as indicated by less than about 0.1% free isocyanate groups. A hydroxyethyl acrylate adduct of polypropylene glycol with 4,4'-diphenylmethane diisocyanate was obtained as a reaction product. This material has the following properties. Viscosity (60℃) 137.5 P Refractive index (20℃) 1.4800 Production example 7 In the same reactor as production example 6, polytetramethylene glycol (molecular weight approximately 2000, OH value 57) 787.36
Then, the liquid temperature was raised to 60°C, and 104.4 parts of tolylene diisocyanate was added dropwise. After the dropwise addition was completed, the temperature was raised and the reaction was carried out at 80°C for 10 hours. After cooling to 60°C, 45.02 parts of 2-hydroxyethyl acrylate,
0.46 part of methoquinone and 0.18 part of di-n-butyltin dilaurate were charged, and after raising the temperature, the reaction was carried out at 80°C. A hydroxyethyl acrylate adduct of polytetramethylene glycol with tolylene diisocyanate was obtained as a reaction product. This material has the following properties. Viscosity (60°C) 460 P Refractive index (20°C) 1.4850 Production example 8 In the same reactor as Production example 6, 253.1 parts of polypropylene glycol (molecular weight approximately 2000, OH value 56.1),
Polyester polyol (manufactured by Daicel Chemical Industries, Ltd., Plaxel L-) is a reaction product of neopentyl glycol, adipic acid, and ε-caprolactone.
220AL, molecular weight approximately 2000, OH value 57.5) and 84.7 parts of isophorone diisocyanate were charged, and after raising the temperature, the reaction was carried out at 75°C for 10 hours.Then, the reaction solution was cooled to 60°C, and ε-caprolactone-β-hydroxyethyl 91.4 parts of acrylate (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-2), 0.3 parts of methoquinone, and 0.12 parts of di-n-butyltin dilaurate were charged, and after raising the temperature, the reaction was carried out at 75 to 80°C. The product has the following properties. Viscosity (60°C) 110 P Refractive index (20°C) 1.4721 Production example 9 In the same reactor as Production example 6, 253.1 parts of polypropylene glycol (molecular weight approximately 2000, OH value 56.1),
Polyester polyol (manufactured by Daicel Chemical Industries, Ltd., Plaxel L-) is a reaction product of neopentyl glycol, adipic acid, and ε-caprolactone.
220AL, molecular weight approximately 2000, OH value 57.5) 251.7 parts,
4,4'-diphenylmethane diisocyanate
After charging 95.01 parts and raising the temperature, react at 75℃ for 10 hours.
Next, the reaction solution was cooled to 60°C, 25.0 parts of 2-hydroxyethyl acrylate, 0.3 parts of methoquinone, and 0.12 parts of di-n-butyltin dilaurate were added, and after raising the temperature, the reaction was carried out at 75 to 80°C. The product has the following properties. Viscosity (60℃) 1160 P Refractive index (20℃) 1.4940 Example 1 30 parts of the polymerizable monomer obtained in Production Example 1, Production Example 2
A resin composition A was prepared by mixing 30 parts of the polymerizable monomer obtained in Example 6, 40 parts of the polyurethane acrylate obtained in Production Example 6, 5 parts of 1-hydroxycyclohexyl phenyl ketone, and 0.01 part of methylhydroquinone. Its characteristics are shown in Table 1. Example 2 50 parts of the polymerizable monomer obtained in Production Example 3, Production Example 8
50 parts of polyurethane acrylate and 1-
Resin composition B was prepared by mixing 5 parts of hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy, Irgikyure 184) and 0.01 part of methylhydroquinone. Its characteristics are shown in Table 1. Example 3 10 parts of the polymerizable monomer obtained in Production Example 2, Production Example 4
50 parts of the polymerizable monomer obtained in Example 7, 10 parts of ε-caprolactone-β-hydroxyethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-2), 30 parts of the polyurethane acrylate obtained in Production Example 7, and 1-hydroxy Resin composition C was prepared by mixing 5 parts of cyclohexyl phenyl ketone and 0.01 part of methylhydroquinone. Its characteristics are shown in Table 1. Example 4 60 parts of the polymerizable monomer obtained in Production Example 5, phenoxyethyl acrylate (manufactured by Nippon Kayaku Co., Ltd.,
KAYARAD R-561) 10 parts, 30 parts of polyurethane acrylate obtained in Production Example 9, 5 parts of 4'-dodecyl-2-hydroxy-2-methylpropiophenone (Darukiur 953, manufactured by Merck & Co., Ltd.), methylhydroquinone 0.01 part was mixed to prepare resin composition D. Its characteristics are shown in Table 1. Comparative example: Epoxy resin Epicoat 828 (manufactured by Shell Oil Co., Ltd.)
2-ethyl-4-methylimidazole 5 to 100 parts
A resin composition E was prepared by dissolving the following parts. Its characteristics are shown in Table 1.

[Table] In Table 1 above, measurement of curing time;
Compositions B, C, and D were applied to glass by irradiating them with a high-pressure mercury lamp (input 80 W/cm, lamp output 2 KW) at a position 8 cm below the parallel light source (conveyor speed 50 m/min). The number of seconds of irradiation in _N2 gas until the tack on the surface of the film disappears. Regarding E, it is the time it takes to heat cure at 150℃ and gel. Measurement of [Shore hardness A]: Compositions A, B, C, and D were irradiated with a high-pressure mercury lamp (input 80 W/cm, lamp output 2 KW) at a position 8 cm below the parallel light source (conveyor speed A sheet with a speed of 50 m/min) and a thickness of 250 μm was prepared and used for measurement. Regarding E, a plate-shaped body having a thickness of 2 mm was prepared by heating and curing at 150° C. for 15 minutes, and this was used for measurement. Measurement of [Glass Transition Point]: A test plate was prepared under the same conditions as those used for the measurement of Shore hardness A above. This was used for measurement.

Claims (1)

[Claims] 1. General formula [] (In the formula, R ₁ to _{R 6} are H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ ,
C ₄ H ₉ or [Formula] R ₇ is H or CH ₃ ; the average value of m is a number from 1 to 10, and n represents 0 or 1. ), a polyurethane acrylate (B), and a photopolymerization initiator (C).