JP2601699C - - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a liquid curable resin composition, which is particularly suitable for coating optical fibers, has excellent ultraviolet resistance, and hardly generates hydrogen gas. The present invention relates to a water-soluble resin composition. [Related Art] In the production of optical fibers, resin coating is applied immediately after the hot-melt spinning of glass fibers for the purpose of protecting and reinforcing the optical fiber. As this resin coating, a structure is known in which a flexible primary coating layer is provided on the surface of an optical fiber and a secondary coating layer having higher rigidity is provided outside the primary coating layer. For these coating layers, materials that are excellent in ultraviolet resistance and generate a small amount of hydrogen gas are required. That is, the manufactured coated optical fiber may be stored under a fluorescent lamp, in which case it is exposed to ultraviolet light emitted from the fluorescent lamp for a long time. If the optical fiber is exposed to ultraviolet rays for a long time in the presence of oxygen, the primary coating layer of the optical fiber is photo-oxidized and deteriorated, whereby the degree of crosslinking is reduced and hydrogen gas is generated. In particular, hydrogen gas generated from the coating layer diffuses into the optical fiber and absorbs light, and also forms hydroxide with SiO ₂ or GeO ₂ as a main component of the optical fiber and a hydroxide. This increases the transmission loss of the optical fiber. [Problems to be Solved by the Invention] An object of the present invention is to provide a liquid curable resin composition having excellent ultraviolet resistance and generating less hydrogen gas. [Means for Solving the Problems] The present invention relates to (A) a polyether polyurethane having an ethylenically unsaturated group (hereinafter referred to as “(A
(B) monofunctional unsaturated compound and / or polyfunctional unsaturated compound (hereinafter, referred to as “component”).
(C) Photopolymerization initiator (hereinafter referred to as “(C) component”) (D) Formula (Wherein, R ¹ represents a hydrogen atom or a methyl group) (hereinafter, referred to as “(D) component”) and (E) an aliphatic amine (hereinafter, referred to as “(E) component”). The present invention provides a liquid curable resin composition characterized in that: As the component (A) used in the present invention, a polyether polyurethane having preferably 2 to 5, particularly preferably 2 to 3, ethylenically unsaturated groups such as a (meth) acryloyl group in a molecule is exemplified. be able to. The component (A) is obtained by, for example, reacting a diol having a polyoxyalkylene structure composed of an oxyalkylene group having 2 to 10 carbon atoms (hereinafter, simply referred to as “polyoxyalkylene structure”), a compound having an ethylenically unsaturated group, and diisocyanate. To be obtained. Here, as the diol having a polyoxyalkylene structure, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol, polydecamethylene glycol, polyalkylene oxide adduct diol of bisphenol A, Examples thereof include polyalkylene oxide adduct diols of tricyclodecane dimethanol, and polyether diols obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds. Here, examples of the ion-polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran,
-Methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl (
Cyclic ethers such as (meth) acrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate; . Further, the above ion-polymerizable cyclic compound, a cyclic imine such as ethyleneimine, p
Polyether diols obtained by ring-opening copolymerization of cyclic lactones such as propiolactone and glycolic lactide or cyclic siloxanes such as dimethylcyclopolysiloxane can also be used. The ionic polymerizable cyclic compound may be used in combination of two or more. Examples of the combination of two or more ionic polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, Examples include tetrahydrofuran and ethylene oxide, and propylene oxide and ethylene oxide. Also, at this time, the ring-opening copolymer of two or more ion-polymerizable cyclic compounds binds randomly or to a block. Preferred structures of the polyoxyalkylene structure are oxypropylene, oxytetramethylene and a 2- or 3-methyl-substituted tetramethyleneoxy structure. More preferably, a copolymer structure of oxypropylene and oxytetramethylene and oxytetramethylene and 2 -Or a 3-methyl-substituted tetramethyleneoxy copolymer structure. Further, a diol having a polyoxyalkylene structure is, for example, PTMG10
00 (Mitsubishi Kasei Kogyo), PTMG2000 (same), PPG1000 (Asahi Orin Co., Ltd.), PPG2000 (same), EXCENOL2020 (same), EXCE
NOL1020 (same as above), PEG1000 (Nippon Yushi Co., Ltd.), Unisafe DC11
00 (same), Unisafe DC1800 (same), Uniall DA-400, DA-
700, DB-400 (same), PPTG2000 (Hodogaya Chemical), PPTG1
000 (the same), PTG400 (the same), and PTGL2000 (the same). These diols having a polyoxyalkylene structure can be used alone or in combination of two or more. A diol having no polyoxyalkylene structure and / or a diamine can be used in combination with these diols having a polyoxyalkylene structure. Examples of the diol having no polyoxyalkylene structure include polyester diol, polycaprolactone diol, polycarbonate diol, alkylene diol, and alicyclic diol. Examples of the polyester diol include diols such as ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol, and phthalic acid, isophthalic acid, terephthalic acid, and maleic acid. And polyester diols obtained by reaction with polybasic acids such as fumaric acid, adipic acid and sebacic acid. Examples of polycaprolactone diol include ε-caprolactone and diols such as ethylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,4-butanediol. Polycaprolactone diol obtained by the reaction is mentioned.
N-980 (Nippon Polyurethane Co., Ltd.), DN-981 (same), DN-982 (same), DN-983 (same), PC-8000 (US PPG) and the like. Examples of the alkylene diol include ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol, and examples of the alicyclic diol include cyclohexyl diol and tricyclodecane dimethanol. As the diamine, for example, ethylene diamine, tetramethylene diamine,
Diamines such as hexamethylenediamine, para-phenylenediamine, and 4,4'-diaminodiphenylmethane; diamines containing a hetero atom; and polyether diamines. When these diols and / or diamines having no polyoxyalkylene structure are used in combination, the amount of the diol and / or diamine is usually 40 parts by weight or less based on 100 parts by weight of the diol having the polyoxyalkylene structure. As the diisocyanate, 2,4-tolylene diisocyanate, 2,2
6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-
Xylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene Diisocyanate, 4,4 '
-Biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like. Among these diisocyanates, 2,4-tolylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like are preferable. These diisocyanates may be used alone or in combination of two or more. Further, examples of the compound having an ethylenically unsaturated group include (meth) acrylic compounds having a hydroxyl group, a carboxyl group, an epoxy group or an acid halide group. Here, as the (meth) acrylic compound having a hydroxyl group, for example, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, Polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1,4-butanediol mono (Meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate,
1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerin di (meth) acrylate, (meth) acrylate represented by the following structural formula, alkyl glycidyl ether, aryl glycidyl ether, glycidyl (meth) ) Compounds obtained by an addition reaction between a glycidyl group-containing compound such as acrylate and (meth) acrylic acid. (Wherein R ³ is H or CH ₃ , and n is 1-5) Among the (meth) acrylic compounds having a hydroxyl group, preferred are 2-
Hydroxyethyl acrylate; The (meth) acrylic compound having a carboxyl group includes (meth) acrylic compounds.
Acrylic acid and the like can be mentioned, and as the (meth) acrylic compound having an epoxy group, glycidyl ether of (meth) acrylic acid and the like can be mentioned. Examples of the (meth) acrylic compound having an acid halide group include (meth) acrylic halides such as (meth) acrylic chloride and (meth) acrylic bromide. In the present invention, the component (A) preferably has a number average molecular weight of 1,000 to 7000, particularly preferably 1500 to 5,000. The proportion of the polyoxyalkylene structure in the component (A) is 50 to 9%.
8% by weight, preferably in the range of 60 to 93% by weight, especially 70 to 9% by weight.
A range of 0% by weight is most preferred. In the present invention, the proportion of the ethylenically unsaturated group in the component (A) is usually 0.5 to 10% by weight, preferably 1 to 8% by weight. Examples of the component (B) of the resin composition of the present invention include the following. Monofunctional unsaturated compound: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate,
2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methyltriethylene glycol (meth) Acrylate, diethylaminoethyl (meth) acrylate, 7-
(Meth) acrylic compounds such as amino-3,7-dimethyloctyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylphenol, acrylamide, vinyl acetate , Vinyl ether, styrene, isobornyl acrylate, isobornyl methacrylate, a compound represented by the following structural formula. Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkyl group having 1 to 8 carbon atoms or an alkylphenyl group having an alkyl group having 1 to 12 carbon atoms, and n is 1
~ 12) (Wherein, R ⁵ is as described above, R ⁶ is an alkylene group having 2 to ⁶ carbon atoms,
R ⁷ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and m is an integer of 3 to 16. ) (Wherein, R ⁵ is as described above, R ⁸ is an alkylene group having 2 to 7 carbon atoms,
p is 1 to 15) Wherein R ⁵ , R ⁸ and p are as described above, and R ⁹ is a hydrogen atom or a methyl group. Polyfunctional unsaturated compound: trimethylolpropane triacrylate, ethylene glycol diacrylate, tetraethylene glycol Diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane trioxyethylyl acrylate, tricyclodecane dimethanol diacrylate, triacrylate Cyclodecane dimethanol dimethacrylate, dicyclopentadiene diacrylate, tricyclodecanyl diacrylate, dicyclopentadiene dimethacrylate trimethylolpropane trioxypropyl alcohol Acrylate
Tris-2-hydroxyethyl isocyanurate tri (meth) acrylate, tris-2-hydroxyethyl isocyanurate di (meth) acrylate, an acrylate of an ethylene oxide adduct of bisphenol A, a compound represented by the following structural formula. (m is 1) Examples of commercially available products of the component (B) include “Viscoat 3700 (Osaka Organic Co., Ltd.)”, “Viscoat 700 (same as above)”, and “KAYARAD DCPA-20 (
Nippon Kayaku Co., Ltd.) "," -30 (the same) "," -60 (the same) "," -120 (the same)
The same). Among these (B) components, preferred are 2-ethylhexyl acrylate,
Cyclohexyl acrylate, phenoxyethyl acrylate, isobornyl acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, cyclopentenyl acrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, “KAYARAD DCPA-60”, “KA
YARAD DCPA-120 "and" VISCOAT 700 ". As the component (C) of the composition of the present invention, for example, 2,2-dimethoxyn-2-phenylacetophenone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,
4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, acetophenone diethyl ketal, benzoin ethyl ether, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2- Hydroxy-
2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2-isopropylthioxanthone, acylphosphine oxide-based compounds are exemplified. be able to. Here, examples of the acylphosphine oxide-based compound include trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, and the like. As the component (C), an acylphosphine oxide-based compound is preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide is particularly preferable. These components (C) can be used alone or in combination of two or more. If necessary, a sensitizer (photopolymerization accelerator) can be used in combination as long as the effects of the present invention are not impaired. . In the present invention, the component (E) has a function of imparting excellent ultraviolet resistance to the composition of the present invention in combination with the action of the component (D), and includes, for example, diethylamine, n-butylamine, An aliphatic amine such as di-n-butylamine can be used. Of these aliphatic amines, diethylamine is preferred. In the composition of the present invention, the component ratio of the components (A), (B), (C), (D) and (E) is usually 25 to 85% by weight, preferably 30 to 80% by weight of the component (A). weight%,
The component (B) is 10 to 70% by weight, preferably 15 to 60% by weight, and the component (C) is 0% by weight.
. 1 to 5% by weight, preferably 0.5 to 4% by weight, the component (D) is 0.05 to 5% by weight, preferably 0.05 to 1% by weight, and the component (E) is 0.01 to 3% by weight. %, Preferably 0.05 to 1% by weight. Further, the composition of the present invention may contain various additives such as a coloring agent, a storage stabilizer, a leveling agent, and an ultraviolet absorber in addition to the above components (A) to (E). Each is 10% by weight or less. The viscosity of the composition of the present invention thus prepared is usually from 1,000 to 20,000.
cp / 25 ° C., preferably 2000 to 10000 cp / 25 ° C.
The Young's modulus at 3 ° C. is usually 0.01 to 1 kg / mm ² for the primary coating material and 10 to 90 kg / mm ² for the secondary coating material. EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Example 1 (1) 51.61 2,4-toluene diisocyanate was placed in a reaction vessel equipped with a stirrer.
g, polypropylene glycol having a number average molecular weight of 3000 (PPG30, Asahi Glass Co., Ltd.)
00) 612.65 g, polymerization inhibitor 2,6-di-t-butyl-4-methylphenol 0.21 g and phenothiazine 0.07 g were charged and stirred. 0.14 g of a reaction catalyst dibutyltin dilaurate was added thereto and reacted while maintaining the temperature at 40 ° C. After the consumption of isocyanate groups reached 65%, 2-
22.94 g of hydroxyethyl acrylate was added and reacted at 50 to 60 ° C., and after confirming that the residual isocyanate group was 0.1% or less, the reaction was terminated, and the polyether having an ethylenically unsaturated group was added. A reaction solution containing polyurethane was obtained. (Hereinafter, this reaction solution is referred to as “(A) -1 component)”. (2) To 70 g of the component (A) -1 obtained in (1), (Wherein, n is 3) 19 g of a monofunctional unsaturated compound represented by the following formula, 6 g of vinylcaprolactam and 5 g of lauryl acrylate were blended to obtain a composition FI. (3) To 100 g of the composition FI obtained in (2), 1.5 g of trimethylbenzoyldiphenylphosphine oxide and 0.3 g of bis (2,2,6,6-tetramethylpiperidinyl-4-sebacate) And 0.5 g of diethylamine were blended to prepare Composition A. Example 2 3.0 g of 1-hydroxycyclohexylphenyl ketone, bis (2,2,6,6-tetramethylpiperidinyl-4-sebacate) were added to 100 g of the same composition FI as obtained in Example 1 (2). ) 0.3 g and 0.5 g of diethylamine,
Composition B was prepared. Example 3 (1) 145.3 2,4-Toluene diisocyanate was placed in a reaction vessel equipped with a stirrer.
0 g, polymerization inhibitor 2,6-di-tert. -Butyl-4-methylphenol 0.
15 g, phenothiazine 0.05 g, tricyclodecanediyl dimethylene diacrylate 112.7 g, and a reaction catalyst dibutyltin dilaurate 0.45 g were charged and reacted at 5 to 10 ° C. for 1 hour to give 2-hydroxyethyl acrylate 126.6.
g was added over 1.5 hours while maintaining the internal temperature at 5 to 15 ° C, followed by stirring for 15 hours. The internal temperature was kept at 15 to 35 ° C., and 70.40 g of ethylene oxide adduct of bisphenol A (NOF DA-400)
Was added in 1 hour and then stirred for 1.5 hours. Next, 225.0 g of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG2000, Sanyo Chemical Industries, Ltd.)
Was added in 1 hour while maintaining the internal temperature at 30 to 50 ° C., and then the reaction was performed while maintaining the internal temperature at 50 to 60 ° C., and it was confirmed that the residual isocyanate group was 0.1% or less. The reaction was terminated to obtain a polyether polyurethane having an ethylenically unsaturated group (hereinafter, this composition is referred to as "(A) -2 component"). (2) To 68.0 g of the component (A) -2 obtained in (1), 4.9 g of tricyclodecanediyl dimethylene diacrylate, 8.9 g of N-vinylpyrrolidone, 7.7 g of isobornyl acrylate, and polyester acrylate ( Viscort 700) 7.0 g
, 1-hydroxycyclohexyl phenyl ketone 3.0 g, bis (2,2,6,
6-tetramethylpiperidinyl-4-sebacate) 0.15 g, 2,2'-thiodiethylbis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 0.15 g, diethylamine 0 .15 g was prepared to give Composition C. Comparative Example 1 A composition D was prepared by mixing 3.0 g of 1-hydroxycyclohexyl phenyl ketone with 100 g of the same composition FI as obtained in Example 1 (2). Comparative Example 2 The same composition D as that obtained in Comparative Example 1 was further added to octadecyl-3- (3,5-di-
Composition E was prepared by mixing 0.3 g of (tert-butyl-4-hydroxyphenyl) propionate. Comparative Example 3 Bis (2,2,6,6-tetramethylpiperidinyl-4-sebacate) was removed from Composition C obtained in Example 3 (2) and blended to prepare Composition F. . Comparative Example 4 The composition A was prepared by removing diethylamine from the composition A obtained in Example 1 (3) and blending. Test Example Using compositions A to G obtained in Examples 1 to 3 and Comparative Examples 1 to 4, UV resistance,
Hydrogen gas generation and optical fiber tests were performed. 1. UV resistance test: Using a 75 micron thick applicator, apply the composition onto a 30 micron thick SUS plate, and irradiate with 0.5 J / cm ² (wavelength 350 nm) ultraviolet light to obtain a cured film. Then, after irradiating ultraviolet rays with a QUV weathering accelerator (manufactured by Q-panel), the following test was conducted. (1) Measurement of Extraction Residual Rate Soxhlet extraction (methyl ethyl ketone, 12 hours) was performed, and the extraction residual rate excluding decomposition products due to deterioration was determined from the weight before and after extraction. The results are shown in Table 1. 2. Test of hydrogen gas generation: A cured film obtained in the same manner as in the UV resistance test was cut into a size of 12 mm in length and 6 mm in width, precisely weighed, placed in a vial bottle of known capacity, and heated at 120 ° C. for one day. Thereafter, gas was collected from the headspace of the vial using a gas tight syringe and introduced into a gas chromatograph to quantify the amount of hydrogen gas. The quantification was performed by the absolute calibration curve method. Table 2 shows the results. 3. Test of optical fiber: The amount of hydrogen gas was quantified in the same manner as in the test of the amount of generated hydrogen gas for an optical fiber obtained by combining and drawing the compositions A to G as the primary and secondary coating materials. Next, ultraviolet rays were irradiated for 6 days, and during that time, the presence or absence of voids in the optical fiber was visually observed. The results are shown in Table-3. [Effects of the Invention] The liquid curable resin composition of the present invention is cured by various radiations, for example, X-rays, electron beams, ultraviolet rays, visible rays, and the like. It is suitable for a coating material of an optical fiber with less occurrence of cracks.

Claims (1)

Claims 1. (A) Polyether polyurethane having an ethylenically unsaturated group (B) Monofunctional unsaturated compound and / or polyfunctional unsaturated compound (C) Photopolymerization initiator (D) Formula (Wherein, R ¹ represents a hydrogen atom or a methyl group) and (E) an aliphatic amine.