JP3220221B2 - Liquid curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent curability, durability, etc., good adhesion to various substrates,
Liquid curable resin compositions useful as coating materials such as wood, ceramics, glass, paper, etc., optical molding materials, three-dimensional three-dimensional molding materials, printing plate materials, etc. More specifically, they have very low Young's modulus at room temperature. Further, the present invention relates to a liquid curable resin composition which is a resin composition exhibiting appropriate adhesion to glass fiber, excellent in durability, and capable of being cured at high speed, and suitable as an optical fiber coating material.

[0002]

2. Description of the Related Art Generally, an optical fiber is provided with a soft primary coating layer on the surface of the optical fiber immediately after the hot-melt spinning of the glass fiber for the purpose of protecting and reinforcing the optical fiber, and a secondary coating layer on the outside thereof. The resin coating of the provided structure is applied. Regarding the coating material for forming this coating, (1) it is liquid at room temperature and has high workability;
(2) fast curing and good productivity; (3) excellent flexibility; (4) little change in physical properties with a wide range of temperature changes; (5) heat resistance and hydrolysis resistance (6) excellent long-term reliability with little change in physical properties over time, (7) excellent resistance to chemicals such as acids and alkalis, (8) hygroscopicity and water absorption Are required, and (9) excellent light resistance is required.

[0003] In response to these requirements, various radiation-curable liquid coating materials have been developed, for example, a tetrahydrofuran-ethylene oxide ring-opening copolymer (Japanese Patent Application Laid-Open No. 61-1986).
No.-86450), a urethane acrylate containing a tetrahydrofuran-propylene oxide ring-opening copolymer (JP-A-60-181170) or a tetrahydrofuran-alkyltetrahydrofuran copolymer (JP-A-1-115964). .

[0004] However, the use of these polyether copolymers still has disadvantages that must be solved. That is, urethane acrylates using these polyether-based copolymers have drawbacks in either ultraviolet resistance, heat resistance, light yellowing resistance, heat yellowing or flexibility, and these are required for optical fiber coating materials. There was no one that could sufficiently satisfy the above characteristics.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an optical fiber having low viscosity at room temperature, good workability when coating the optical fiber, good photocurability, and high-speed production of the optical fiber. The cured product is rich in flexibility, UV resistance,
To provide a liquid curable resin composition having good heat resistance, light yellowing resistance, heat yellowing resistance, oil resistance, a small amount of hydrogen gas, exhibiting appropriate adhesion to optical fibers, and suitable as an optical fiber coating material. It is in.

[0006]

That is, the present invention provides: (I) the following (A), (B) and (C) (A) Formulas (1), (2) and (3) Polyether polyol compound containing a group as a structural unit

Embedded image (B) Polyisocyanate compound (C) Urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate compound
(II) Reactive diluent consisting of monofunctional compound 5-6%
0%; (III) polymerization initiator 0.1 to 10%; and (IV) other additives. The present invention provides a liquid curable resin composition for coating an optical fiber.

[0007]

Embedded image

(B) Polyisocyanate compound (C) A liquid curable resin composition characterized by containing a urethane (meth) acrylate obtained by reacting a (meth) acrylate compound containing a hydroxyl group. .

The polyether polyol compound used in the present invention (hereinafter abbreviated as "polyol compound (A)")
Needs to contain the structural units represented by the formulas (1), (2) and (3). The polymerization mode of these constituent units is not particularly limited, and may be any of random polymerization, block polymerization, and graft polymerization.

Such a polyol compound (A) includes, for example, 1,2-alkylene oxides having 4 or more carbon atoms such as ethylene oxide, 1,2-butylene oxide and 1,2-hexene oxide, polytetramethylene glycol, bisphenol It can be produced by subjecting one or more selected from A and bisphenol F to ring-opening polymerization by a known method.

The proportion of the structural unit of the formula (1) contained in the polyol compound (A) is preferably from 5 to 50% by weight (hereinafter simply referred to as "%"), particularly preferably from 10 to 45%. preferable. If it is less than 5%, the improvement in oil resistance after curing of the obtained composition is small, and if it exceeds 50%, the water resistance and flexibility after curing of the obtained composition tend to decrease.
Further, the proportion of the structural unit of the formula (2) is preferably from 10 to 90%, and particularly preferably from 20 to 80%. Further, the ratio of the structural unit of (3) is preferably from 5 to 85%, and particularly preferably from 10 to 70%. In the structure of the formula (2) in the (meth) acrylate (A), R preferably has 2 to 12 carbon atoms, and more preferably 2 to 4 carbon atoms.

The molecular weight of the polyol compound (A) is usually from 200 to 10,000 as a number average molecular weight, and from 500 to 8
000 is preferred. If it is less than 200, the Young's modulus at room temperature and low temperature after curing of the obtained composition increases, and transmission loss due to lateral pressure increases when applied to an optical fiber. If it exceeds 10,000, the viscosity of the obtained composition increases, When the composition is coated, the coatability tends to decrease.

The polyol compound (A) is not limited as long as it contains the groups represented by the above formulas (1), (2) and (3) as constituent units within a range that does not impair the effects of the present invention. And other structural units other than these structural units. Such other structural units include, for example, -CH ₂ CH ₂ C
H ₂ O— and —CH ₂ CH (CH ₃ ) O—.

Further, a polyol compound other than the polyol compound (A) can be used in combination. Examples of such a polyol compound include polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols that do not have the groups represented by the formulas (1), (2) and (3) as constituent units.
Other polyols are exemplified.

Examples of the polyether polyol having no groups represented by the formulas (1), (2) and (3) as constituent units include, for example, polyethylene glycol,
Examples thereof include 2-polypropylene glycol, 1,3-polypropylene glycol, 1,2-polybutylene glycol, polyisobutylene glycol, a propylene oxide-tetrahydrofuran copolymer, and a methyltetrahydrofuran-tetrahydrofuran copolymer.

Examples of the polyester polyol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, Polyhydric alcohols such as 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipine Acid, polyester polyol obtained by reacting with a polybasic acid such as sebacic acid,
Kuraray P-2010, P
MIPA, PKA-A, PKA-A2, PNA-200
0 and the like.

As the polycarbonate polyol, for example, 1,6-hexane polycarbonate, and as commercial products, DN-980 and DN-9 manufactured by Nippon Polyurethane Co., Ltd.
81, DN-982, DN-983, manufactured by PPG, USA
PC-8000 and the like.

The polycaprolactone polyol includes, for example, ε-caprolactone, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6 -Hexanediol, neopentyl glycol, 1,4-cyclohexane dimethanol, polycaprolactone diol obtained by reacting with a divalent diol such as 1,4-butanediol, as commercial products, Daicel's Plaxel 205, 205A
L, 212, 212AL, 220, 220AL and the like.

Other polyols include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, bisphenol A, ethylene oxide and / or propylene oxide addition diol, bisphenol F, ethylene oxide and / or propylene oxide addition diol, hydrogenated bisphenol A ethylene oxide and / or propylene oxide addition diol, hydrogenated bisphenol F
Ethylene oxide and / or propylene oxide addition diol, dimethylolated dicyclopentadiene, tricyclodecane dimethanol, hydroxy-terminated poly-β-methyl-δ-valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol And polydimethylsiloxane terminal diols, and polydimethylsiloxane carbitol-modified polyol. The molecular weight of these polyol compounds is usually 200 to 100 in number average molecular weight.
00, preferably 500-8000.

Examples of the polyisocyanate compound (B) used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3
-Xylylene diisocyanate, 1,4-xylylene 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, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, Bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-
Examples thereof include phenyl diisocyanate, 2,2-bis (4'-isocyanic acid) propane, and lysine diisocyanate, and particularly preferred are 2,4-tolylene diisocyanate, isophorone diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate.

The hydroxyl group-containing (meth) acrylate compound (C) used in the present invention includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, -Hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexane Diol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate, the following formula _{(4) CH 2 = C (} R 1) -COOCH 2 CH 2 - (OC = OCH 2 CH 2 CH 2 CH 2 CH 2) n -OH (4) [ In the formula, R ¹ represents a hydrogen atom or a methyl group;
To 15, preferably 1 to 4. And glycidyl group-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether and glycidyl (meth) acrylate, and compounds obtained by addition reaction of (meth) acrylic acid. be able to. Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like are particularly preferable.

The urethane (meth) acrylate used in the present invention is produced by reacting the above polyol compound (A), polyisocyanate compound (B) and hydroxyl group-containing (meth) acrylate compound (C). Specifically, the reaction is carried out by reacting the isocyanate group of the polyisocyanate compound (B) with the hydroxyl group of the polyol compound (A) and the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (C). This reaction is performed, for example, by the following method.

(1) A method in which a polyol compound (A), a polyisocyanate compound (B), and a hydroxyl group-containing (meth) acrylate compound (C) are charged at once and reacted. (2) The polyol compound (A) and the polyisocyanate compound (B) are reacted, and then the hydroxyl group-containing (meth)
A method of reacting an acrylate compound (C). (3) A method in which the polyisocyanate compound (B) and the hydroxyl group-containing (meth) acrylate compound (C) are reacted, and then the polyol compound (A) is reacted. (4) The polyisocyanate compound (B) and the hydroxyl group-containing (meth) acrylate compound (C) are reacted, then the polyol compound (A) is reacted, and finally, the hydroxyl group-containing (meth) acrylate compound (C) is further reacted. Method.

The proportion of each of the polyol compound (A), the polyisocyanate compound (B) and the hydroxyl group-containing (meth) acrylate compound (C) is such that the ratio of the hydroxyl group contained in the polyol compound (A) is 1 equivalent to the hydroxyl group. It is preferable that the isocyanate group contained in the isocyanate compound (B) be 1.1 to 3 equivalents, and the hydroxyl group of the (meth) acrylate compound (C) having a hydroxyl group be 0.1 to 1.5 equivalents.

In the above reaction, a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, triethylenediamine or 2-methyltriethylenediamine is usually used as the reactant. 0.0 to 100 parts by weight of total amount
Use 1 to 1 part by weight. The reaction temperature is usually 10 to
The temperature is 90 ° C., preferably at 30 to 80 ° C.

The urethane (meth) thus obtained
The content of the acrylate in the composition of the present invention is preferably 5 to 93%. However, in order to maintain coatability when coating an optical fiber, flexibility of a coating material after curing, long-term reliability, and the like. Is more preferably 20 to 87%.

The molecular weight of the urethane (meth) acrylate of the present invention is usually from 700 to 20,000, preferably from 1,000 to 10,000 (number average molecular weight). In the liquid curable resin composition of the present invention, other than urethane (meth) acrylate, as necessary, other radiation-curable compounds, reactive diluents and other compounds may be used as long as the effects of the present composition are not impaired. Additives can be added.

Other radiation-curable compounds include:
Examples thereof include urethane (meth) acrylates other than the urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, and polysiloxane having a (meth) acryloyloxy group. These may be added alone or in combination of two or more.

Examples of the reactive diluent include monofunctional compounds. Examples of the monofunctional compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl ( Meth) acrylate, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate,
Isobutyl (meth) acrylate, t-butyl (meth)
Acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) Acrylate, decyl (meth) acrylate,
Isodecyl (meth) acrylate, undecyl (meth)
Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate , Dicyclopentadiene (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, diacetone (meth) ) Acrylamide, isobutoxymethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate,
N, N-diethyl (meth) acrylamide, N, N'-
Dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, vinyl ethers such as 2-ethylhexyl vinyl ether, maleic esters, fumaric esters, and the following formulas (5) to The compound represented by (7) can be mentioned.

[0030]

Embedded image

Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ⁵ represents a hydrogen atom or 1 to 12 carbon atoms.
Preferably represents an alkyl group of 1 to 9, m is 0 to 12,
Preferably a number of 1 to 8 is shown. ]

[0032]

Embedded image

[0033] wherein, R ³ is as defined above, R ⁶
Represents an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, and p represents a number of 1 to 8, preferably 1 to 4. ]

[0034]

Embedded image

Wherein R ³ , R ⁶ and p are as described above, and R ⁷ represents a hydrogen atom or a methyl group. ]

[0036] These commercial products include Aronix M-111, M-113, M-114 and M-117.
(Toa Gosei Chemical Industry Co., Ltd.), KAYARAD TC
110S, R629, R644 (all manufactured by Nippon Kayaku Co., Ltd.),
VISCOAT 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

[0037]

The reactive diluent can be used properly depending on the required performance of the cured product of the composition. When flexibility, particularly flexibility at low temperature, is required, among the reactive diluents, (meth) acrylate compounds having a homopolymer having a glass transition point of -10 ° C or lower are preferred. Specific examples of preferred (meth) acrylate compounds include commercially available products such as Aronix M-10.
2, M-111, M-113, M-114, M-117
(Toa Gosei Chemical Industry Co., Ltd.), KAYARAD TC
110S, R629, R644 (all manufactured by Nippon Kayaku Co., Ltd.) and the like.

When the adhesiveness and curability are required, N-vinylpyrrolidone,
N-vinylcaprolactam is preferred.

These reactive diluents are preferably present in the composition according to the invention in a proportion of from 5 to 60%, particularly preferably from 10 to 4%.
0% can be blended.

The composition of the present invention is cured by heat and / or radiation. Here, radiation means infrared, visible and ultraviolet rays, X-rays, electron beams, α-rays, β-rays,
It means ionizing radiation such as gamma rays.

When the composition of the present invention is cured by heat, a radical polymerization initiator is usually used. Examples of the radical polymerization initiator include peroxides and azo compounds. Benzoyl peroxide, t-butyl-oxybenzoate, azobisisobutyronitrile and the like.

When the composition of the present invention is photocured, a photopolymerization initiator and, if necessary, a photosensitizer are further used. Examples of such a photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone,
2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene,
Anthraquinone, triphenylamine, carbazole,
3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-
Diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, commercially available as IRGA manufactured by Ciba-Geigy
CURE 184, 651, 500, 907, 369, C
G24-61, Lucirin LR872 manufactured by BASF
8, Merck Darocur 1116, 1173, U
Ubecryl P36 manufactured by CB may be mentioned. As the photosensitizer, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Isoamyl 4-dimethylaminobenzoate, commercially available as Ubecryl P102, 103, 104, 1
05 and the like. These polymerization initiators and photosensitizers are used alone or in combination of two or more. When the composition of the present invention is cured by using both heat and ultraviolet light, the above-mentioned radical polymerization initiator can be used in combination.

These polymerization initiators are contained in the composition in an amount of 0.1%.
It is preferable to mix 10% to 10%.

The composition of the present invention may further comprise epoxy resin, polyamide, polyamideimide,
Polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene / styrene block copolymer, styrene /
Ethylene / butene / styrene block copolymer, styrene / isoprene / styrene block copolymer, petroleum resin, xylene resin, ketone resin, fluorine-based oligomer,
Silicone-based oligomers, polysulfide-based oligomers and the like can also be blended.

The composition of the present invention may further contain various additives other than those described above, for example, an antioxidant, a coloring agent, an ultraviolet absorber,
Requires light stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, fillers, anti-aging agents, wetting improvers, coating surface improvers, etc. Can be blended according to Here, commercially available antioxidants include Irganox 1010, 1
035, 1076, 1222 (all manufactured by Ciba Geigy)
And the like. Commercially available ultraviolet absorbers include Tin
uvin P234, 320, 326, 327, 32
8, 213 (all manufactured by Ciba Geigy), Sumisor
b 110, 130, and 200 (all manufactured by Sumitomo Chemical Co., Ltd.) and the like.
n292, 144, 622LD (all manufactured by Ciba-Geigy), Sanol LS770 (manufactured by Sankyo Chemical Industries, Ltd.), and the like. Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, as commercial products, SH6062, 60
30 (manufactured by Toray Silicone Co., Ltd.), KBE903, 60
3, 403 (Shin-Etsu Chemical Co., Ltd.) and the like.

The liquid curable resin composition of the present invention can be produced by mixing the above-mentioned components by a conventional method. The viscosity of the liquid curable resin composition of the present invention thus obtained is usually from 200 to 20,000 cp / 25 ° C, preferably from 2,000 to 10,000 cp / 25 ° C. When the composition of the present invention is used as an optical fiber primary coating material, the cured Young's modulus is 0.05 to 0.5 kg / mm ² ,
In particular, it is preferable to be 0.06 to 0.13 kg / mm ^2, and the Young's modulus of such a cured product at −40 to 60 ° C. is usually 0.01 to 10 kg / mm ² .

[0048]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the following, parts mean parts by weight.

Urethane acrylate synthesis example 1 A reaction vessel equipped with a stirrer was charged with 170.0 g of isophorone diisocyanate, 1 g of dibutyltin dilaurate and 0.3 g of 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor. . Next, 59.2 g of hydroxyethyl acrylate was added while controlling the temperature to 20 ° C. or lower. After the addition, stirring was further continued at 10 to 20 ° C. for 1 hour, and then a copolymerized diol of ethylene oxide having a number average molecular weight of 2000 and 1,2-butylene oxide and polytetramethylene glycol (ethylene oxide: 1,2-butylene) (Oxide: polytetramethylene glycol = 1: 5: 4 (weight ratio)) 1020.8 g
Was added while maintaining the temperature at 40-50 ° C. Then
After continuing stirring at 50 to 60 ° C. for 5 hours, the reaction was terminated, and a urethane acrylate [A-1] having a number average molecular weight of 4,900 was obtained.

Urethane acrylate synthesis example 2 In a reaction vessel equipped with a stirrer, a copolymer of 168.2 g of isophorone diisocyanate, ethylene oxide having a number average molecular weight of 2052, 1,2-butylene oxide and bisphenol A (ethylene oxide: 1, 1044.6 g of 2-butylene oxide: bisphenol A = 1: 7: 1 (weight ratio) and 2,6-
0.3 g of di-t-butyl-methylphenol was charged.
After cooling to 15 ° C. in an ice water bath, 1 g of dibutyltin dilaurate was added to start the reaction,
The reaction was carried out for 2 hours while maintaining at ４０40 ° C. Then, 47.2 g of hydroxyethyl acrylate was added, and
After stirring at 60 ° C. for 5 hours, the reaction was terminated, and the number average molecular weight was 6140 urethane acrylate [A-2].
I got

Urethane acrylate synthesis example 3 In a reaction vessel equipped with a stirrer, 100 g of Aronix M-113 (trade name, manufactured by Toagosei Chemical Industry Co., Ltd.), 153.3 g of isophorone diisocyanate, 1 g of dibutyltin dilaurate, and 2,6- 0.3 g of di-t-butyl-methylphenol was charged. A copolymerized diol of ethylene oxide having a number average molecular weight of 2040, 1,2-butylene oxide and hydrogenated bisphenol A (ethylene oxide: 1,2-butylene oxide:
Hydrogenated bisphenol A = 47.1: 41.2: 11.8
(Weight ratio)) 10566 g was added while maintaining the temperature at 40 to 50 ° C., and reacted for 2 hours. Next, 40.1 g of hydroxyethyl acrylate was added, and 50-60 ° C.
After continuing the stirring for 5 hours, the reaction was terminated to obtain a urethane acrylate [A-3] having a number average molecular weight of 7,240.

Urethane acrylate synthesis example 4 A reaction vessel equipped with a stirrer was charged with 331.1 g of isophorone diisocyanate, 1 g of dibutyltin dilaurate and 0.3 g of 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor. . Next, 173.0 g of hydroxyethyl acrylate was added while controlling the temperature to 20 ° C. or lower. After the addition, stirring was further continued at 10 to 20 ° C for 1 hour, and then 745.8 g of polytetramethylene glycol having a number average molecular weight of 1,000 was added while maintaining the temperature at 40 to 50 ° C. Then, after continuing stirring at 50 to 60 ° C. for 5 hours, the reaction was terminated, and the number average molecular weight was reduced to 16
80 urethane acrylate [A-4] was obtained.

Urethane Acrylate Comparative Synthesis Example 1 A reaction vessel equipped with a stirrer was charged with 170.0 g of isophorone diisocyanate, 1 g of dibutyltin dilaurate and 0.3 g of 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor. It is. Next, 59.2 g of hydroxyethyl acrylate was added while controlling the temperature to 20 ° C or lower. After the addition, stirring was further continued at 10 to 20 ° C. for 1 hour, and then tetrahydrofuran-propylene oxide copolymerized diol having a number average molecular weight of 2000 (tetrahydrofuran: propylene oxide = 3: 7 (weight ratio), manufactured by Hodogaya Chemical Co., Ltd.) Name PPTG2000) 1
020.8 g was added while maintaining the temperature at 40-50 ° C. Next, after continuing stirring at 50 to 60 ° C. for 5 hours,
The reaction was terminated to obtain urethane acrylate [B-1] having a number average molecular weight of 4,900.

Urethane Acrylate Comparative Synthesis Example 2 In a reaction vessel equipped with a stirrer, 130.3 g of 2,4-tolylene diisocyanate, 1 g of dibutyltin dilaurate and 0.2 g of 2,6-di-tert-butyl-methylphenol as a polymerization inhibitor were added. 3 g were charged. This has a number average molecular weight of 20
1070.0 g of polytetramethylene glycol (trade name: PTG2000, manufactured by Hodogaya Chemical Industry Co., Ltd.) at a temperature of 4
The reaction was added for 2 hours while maintaining the temperature at 0 to 50 ° C. Next, 49.6 g of hydroxyethyl acrylate was added, and stirring was continued at 50 to 60 ° C. for 5 hours. Then, the reaction was terminated, and a urethane acrylate [B-2] having a number average molecular weight of 5,840 was obtained.

Example 1 In a reaction vessel equipped with a stirrer, urethane acrylate [A
-1], and Aronix M-1 as a reaction diluent
13, 30 parts of KAYARAD TC110S (manufactured by Nippon Kayaku), 5 parts of vinylpyrrolidone, 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 0.3 part of Irganox 1035 (manufactured by Ciba Geigy), Sumisorb1 as an ultraviolet absorber
10 (manufactured by Sumitomo Chemical Co., Ltd.), 0.1 part of diethylamine as a photosensitizer, and 1 part of a silane coupling agent (manufactured by Toray Silicone Co., trade name: SH6062)
Stir and mix at 0-60 ° C, viscosity 3700 cp / 25 ° C
Was obtained.

Example 2 In a reaction vessel equipped with a stirrer, urethane acrylate [A
-2], 25 parts of Aronix M-113, 12 parts of isobornyl acrylate, 5 parts of N-vinylcaprolactam, 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Irganox1
035 (manufactured by Ciba Geigy), 0.1 part of diethylamine and 1 part of SH6062 were stirred and mixed at 50 to 60 ° C to obtain a transparent liquid composition having a viscosity of 3000 cp / 25 ° C.

Example 3 In a reaction vessel equipped with a stirrer, urethane acrylate [A
-3], 60.5 parts, Aronix M-113 37
Parts, vinylpyrrolidone 5 parts, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 1.5 parts,
Irganox 1035 (manufactured by Ciba-Geigy) 0.3
Part, 0.1 part of diethylamine and 1 part of SH6062 are stirred and mixed at 50 to 60 ° C., and the viscosity is 5000 cp / 2.
A transparent liquid composition at 5 ° C. was obtained.

Example 4 In a reaction vessel equipped with a stirrer, urethane acrylate [A
-4], 60 parts of tricyclodecane dimethanol diacrylate, 10 parts of isobornyl acrylate and 10 parts of N-vinylcaprolactam, 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Irganox 10350 3 parts 50 ~
The mixture was stirred and mixed at 60 ° C to obtain a transparent liquid composition having a viscosity of 2000 cp / 25 ° C.

Comparative Example 1 A transparent liquid composition having a viscosity of 3000 cp / 25 ° C. was prepared in the same manner as in Example 1 except that 55 parts of urethane acrylate [B-1] was used instead of urethane acrylate [A-1]. Obtained.

Comparative Example 2 A transparent liquid composition having a viscosity of 11,000 cp / 25 ° C. was prepared in the same manner as in Example 1 except that 55 parts of urethane acrylate [B-2] was used instead of urethane acrylate [A-2]. Obtained.

Test Example 1 Film Test Using the liquid composition obtained above, test specimens were prepared as described below and evaluated. Table 1 shows the results. 1. Preparation of test piece A liquid material was applied on a glass plate using a 150 micron thick applicator, and then applied to the glass plate at 25 mJ / cm ² or 500 mJ.
/ Cm ² was applied to obtain a cured film. Then
The cured film was peeled off from the glass plate, and the condition was adjusted at 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test piece. 2. Measurement of Young's modulus (based on JIS K7127) The Young's modulus of the test piece at 23 ° C. was measured with a tensile tester under the conditions of a tensile speed of 1 mm / min and a distance between marked lines of 25 mm. 3. After weighing initial weight of the gel fraction cured film (an initial weight W _0), methyl ethyl ketone in a Soxhlet extractor and extracted for 12 hours using a solvent. Thereafter, the film was dried in a vacuum dryer at 50 ° C. for 12 hours, left at room temperature for 1 hour, and weighed (hereinafter referred to as dry weight W ₁ ). The gel fraction was calculated from the following equation.

[0062]

(Equation 1)

4. After weighing the initial weight of the cured film with an ultraviolet ray having a weight change of 500 mJ / cm ^2, the film was subjected to a heat and light resistance test (assuming the initial weight is W ₀ ), left at room temperature for 1 hour, and weighed ( a dry weight W _1). The weight change was calculated from the following equation.

[0064]

(Equation 2)

5. Heat resistance test Cured film by UV light of 500mJ / cm ² at 120 ℃
Was placed in a thermostat for 15 days, and after taking out, the external appearance of the film was observed, followed by measurement of Young's modulus and gel fraction. Table 1 shows the results. 6. The cured film by UV light resistance test 500 mJ / cm ² UVB-
The film was exposed for 200 hours using a Q-PANEL QUV-accelerated light resistance tester using a 313 lamp, and after taking out the film, the appearance of the film was observed, and then the gel fraction and weight change were measured.
Table 1 shows the results.

[0066]

[Table 1]

2. Drawing Test Two layers of the composition obtained above were applied to an optical fiber using a combination of Table 2 using an optical fiber drawing device, and the coated optical fiber was obtained by further irradiating ultraviolet rays. The average optical fiber diameter of the core material of the coated optical fiber is 12
5 μm, and the diameter of the coated optical fiber is 200 μm after the first coating layer is applied and cured, and 250 μm after the second coating layer is applied and cured.
m. Drawing speed 180, 360, 720 m / min
Regarding the three levels, coated optical fibers were collected and subjected to the following evaluation. Table 2 shows the results. (1) Gel Fraction The coated optical fiber was cut into a length of 4 cm, weighed (the initial weight was W ₀ ), and extracted with a Soxhlet extractor using methyl ethyl ketone as a solvent for 12 hours. Then, the coated optical fiber was dried in a vacuum drier for 50 minutes.
After drying at 12 ° C. for 12 hours, the mixture was allowed to stand at room temperature for 1 hour, and then weighed (the dry weight was W ₁ ). The coated optical fiber was weighed only recovered weight fired optical fibers and removing the coating layer in an electric furnace at 700 ° C. 30 minutes further (optical fiber weight and W _F). The gel fraction of the coating layer of the coated optical fiber was calculated from the following equation.

[0068]

(Equation 3)

2. Environmental test (1) Light resistance A coated optical fiber drawn at 360 (m / min) was left under a fluorescent lamp (illuminance: 2000 lux) for 30 days.
The appearance change, weight change, and amount of generated hydrogen gas were evaluated. (Evaluation method) a) Change in appearance The interface between the coating layer and the fiber and the coating layer was observed with a microscope, and the presence or absence of voids, peeling, droplets, and foreign matter was examined. b) Weight change The weight change before and after standing under a fluorescent lamp was determined by the following method. Standing before the weight = W _b after leaving the coated fiber weight = W _a left after the coated fiber of the coated fiber was baked for 30 minutes in an electric furnace at 700 ° C. removing the coating layer, the weight was determined to recover the optical fiber only = W _f

[0070]

(Equation 4)

C) Amount of hydrogen gas generated A hydrogen gas was measured before and after the light resistance test. The measuring method was as follows. The coated optical fiber was precisely weighed, placed in a vial of known capacity, and heated at 100 ° C. for 4 hours. Next, gas was sampled from the headspace portion of the vial using a gas tight syringe, and introduced into gas chromatography to quantify the amount of hydrogen gas generated. The quantification was performed by the absolute calibration curve method. Table 2 shows the results.

[0072]

[Table 2]

[0073]

The liquid curable resin composition of the present invention has a high curing rate, a combination of a low Young's modulus and a high gel fraction of the cured product, and has excellent heat resistance, light resistance, light yellowing resistance and heat yellowing resistance. It is an excellent material with a small amount of hydrogen gas generation and particularly excellent as an optical fiber coating material. In addition, since the composition of the present invention is excellent in heat resistance, curability, and adhesion, it can be used for various substrates such as metals, plastics, wood, ceramics, glass coating materials, light molding materials, three-dimensional three-dimensional molding materials, and printing plates. It is also useful as a material.

Continued on the front page (72) Inventor: Satoshi Otaka 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor: Takeshi Watanabe 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Inside (72) Inventor Shinichiro Iwanaga 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Katsutoshi 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor John T. Vandeberg United States 60010 West Oak Drive, Burlington, Illinois 415 (56) References JP-A-4-154828 (JP, A) JP-A-4-222883 (JP, A) JP-A-53-82506 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 C08F 299/06 C03C 25/26-25/36 G02B 6/44

Claims (2)

(57) [Claims] (I) A polyether polyol compound containing, as a structural unit, a group represented by the following formulas (A), (B) and (C) (A): (1), (2) and (3) Embedded image (B) Polyisocyanate compound (C) Urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate compound
(II) Reactive diluent consisting of monofunctional compound 5-6%
0%; (III) 0.1 to 10% of a polymerization initiator; and (IV) a remaining curable resin composition for coating an optical fiber. 2. The resin composition according to claim 1, wherein the reactive diluent contains no polyfunctional compound and is used for the primary coating layer.