JP3383361B2 - 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 relates to a liquid curable resin composition, and more specifically, it forms a cured film having good adhesion to a substrate and excellent long-term durability, and liquid storage stability. It relates to a liquid curable resin composition which is good and is particularly suitable for coating an optical fiber.

[0002]

2. Description of the Related Art Since glass fibers used for optical fibers are brittle and easily damaged, they are coated with an ultraviolet (UV) curing resin for protection and reinforcement.

From the viewpoint of long-term reliability of the optical fiber, the UV curable resin used here is required to have a small change in mechanical properties such as Young's modulus over time. For this reason,
It is required to lower the content of the uncured material in the UV curable resin film after UV irradiation.

However, in order to improve the productivity of the optical fiber, it is necessary to increase the drawing speed from the molten glass fiber preform, and accordingly, the UV irradiation amount decreases in the coating process with the UV curable resin.
There is a problem that the content of the uncured material in the V-cured resin becomes high.

Therefore, at the same time as the development of resins satisfying the required physical properties for each application, developments for increasing the curing speed and the curing degree are being actively studied. Furthermore, in terms of long-term reliability, a resin design with physical properties, heat resistance and weather resistance in terms of appearance,
Also, studies on additives and the like have been conducted, but none of them has been found to be completely satisfactory.

Among the resins for coating the optical fiber, the UV-curing resin used as the primary coating material has further improved interfacial adhesion with the glass fiber so that structural irregularities and microbending do not occur at the interface between the glass fiber and the coating material. Required. As a countermeasure against this, there has been an attempt to add a silane coupling agent such as alkoxysilane having one amino group or mercapto group in the molecule. However, the adhesion to these glasses is not sufficient, and
If you store this for a long time under moist heat or heat,
There is a problem that the adhesion of the cured product to glass is reduced. Further, the conventional resin composition has a problem in storage stability such as a decrease in adhesion to glass when stored in a liquid composition as it is for a long period of time.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a liquid curable resin composition which is excellent in long-term adhesion to glass as well as having heat resistance and weather resistance.

[0008]

In view of such circumstances, the inventors of the present invention have conducted intensive studies and as a result, (a) a urethane (meth) acrylate oligomer having a specific alkoxysilane, and (b) a (meth) acrylate. We have found that a liquid curable resin composition containing a system-based and / or vinyl-based compound and (c) a polymerization initiator can remarkably improve the above-mentioned problems such as adhesion to glass, and completed the present invention.

That is, in the present invention, 1 to 50% of the following (a), (b) and (c) (a) molecular end groups have the following general formula (1) --NHCO--X-(CH ₂ ) _n -Si (OR ¹ ) ₃ (1) [In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X represents a sulfur atom or -N (R ² )-(R ² represents a hydrogen atom, 15 to 70% by weight of a urethane (meth) acrylate-based oligomer, which is an end group represented by (C1 to C10 alkyl group or phenyl group), and n represents a number of 1 to 10 (b ) 5 to 60% by weight of (meth) acrylate compound
And / or 2 to 20% by weight of a vinyl compound, and (c) an optical fiber containing 0.1 to 10% by weight of a polymerization initiator.
A liquid curable resin composition for iber coating is provided.

The component (a) used in the present invention is, for example, a diol having a polyoxyalkylene structure having 2 to 10 carbon atoms having at least one kind of oxyalkylene group in the molecule as a basic skeleton, a polyisocyanate, and the following general formula: (2)

Embedded image The above-mentioned terminal group (1) represented by HX- (CH ₂ ) _n —Si (OR ¹ ) ₃ (2) (wherein R ¹ , X and n are the same as described above) is formed. And a hydroxyl group-containing (meth) acrylate compound.

Examples of the diol having an oxyalkylene group used in this reaction include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, or two or more kinds of ions. Examples thereof include polyether diols obtained by ring-opening copolymerization of a polymerizable cyclic compound.
As the ion-polymerizable cyclic compound used here, ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, Examples thereof include cyclic ethers such as glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and benzoic acid glycidyl ester.
Further, a polyether obtained by ring-opening copolymerization of the above ion-polymerizable cyclic compound and cyclic imine such as ethyleneimine, β-propiolactone, cyclic lactone such as glycolic acid lactide, or dimethylcyclopolysiloxane. It is also possible to use diols. Specific combinations of two or more types of ion-polymerizable cyclic compounds shown above include, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene. Examples thereof include oxide and ethylene oxide. The ring-opening copolymer of these ion-polymerizable cyclic compounds may be bonded randomly.

Among the above polyether diols, commercially available products include, for example, PTMG1000 and PTMG2000.
(Above, manufactured by Mitsubishi Kasei Co., Ltd.), PPG1000, E
XCENOL2020, 1020 (above Asahi Ohrin Co., Ltd.), PEG1000, Unisafe DC110
0, DC1800 (above, NOF Corporation), PPT
G2000, PPTG1000, PTG400, PTG
L2000 (above, Hodogaya Chemical Co., Ltd.), Z-30
01-4, Z-3001-5, PBG2000A, PB
G2000B (above, Daiichi Kogyo Seiyaku Co., Ltd. product) etc. are mentioned.

Further, as the diol having an oxyalkylene group, polyester diol, polycarbonate diol, polycaprolactone diol and the like can be mentioned in addition to the above polyether diol.

As the polyester diol, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,
6-hexanediol, neopentyl glycol, 1,
4-cyclohexanedimethanol, 3-methyl-1,5
-Pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and other polyhydric alcohols and phthalic acid, isophthalic acid, terephthalic acid, maleic acid,
Examples thereof include polyester polyols obtained by reacting with a polybasic acid such as fumaric acid, adipic acid and sebacic acid. As a commercial item, Clapor P-2010,
PMIPA, PKA-A, PKA-A2, PNA-20
00 (above, manufactured by Kuraray Co., Ltd.) and the like are available.

As the polycarbonate diol,
For example, 1,6-hexane polycarbonate and the like are listed, and commercially available products are DN-980, 981, 982, 9
83 (above, Nippon Polyurethane Co., Ltd. product), PC-80
00 (manufactured by US PPG Co., Ltd.) and the like are available. Further, as polycaprolactone diol, ε-caprolactone and, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-
Hexanediol, neopentyl glycol, 1,4-
Examples thereof include polycaprolactone diol obtained by reacting with cyclohexanedimethanol and a divalent diol such as 1,4-butanediol. These diols are Praxel 205, 205AL, 212, 212A
L, 220, 220AL (all manufactured by Daicel Corporation) and the like can be obtained as commercial products.

Many diols not included in the above can also be used. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1 , 4-cyclohexanedimethanol, bisphenol A ethylene oxide addition diol, bisphenol A butylene oxide addition diol, bisphenol F ethylene oxide addition diol, bisphenol F butylene oxide addition diol, hydrogenated bisphenol A ethylene oxide addition diol,
Butylene oxide addition diol of hydrogenated bisphenol A, ethylene oxide addition diol of hydrogenated bisphenol F, butylene oxide addition diol of hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecane dimethanol, β-methyl-δ-
Examples thereof include valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, polydimethylsiloxane terminal diol compound, and polydimethylsiloxane carbitol-modified polyol.

These polyester diols, polycarbonate diols and polycaprolactone diols can be used in combination with polyether diols. The mode of polymerization of these constituent units is not particularly limited, and may be random polymerization, block polymerization, or graft polymerization.

Further, a diamine may be used in combination with the above diol for the reaction. Examples of the diamine used here include ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,4′-diaminodiphenylmethane, and other diamines, diamines containing a hetero atom, and polyetherdiamine. The preferable molecular weight of the above diol is usually 5 in terms of number average molecular weight.
It is more preferably 0 to 15000, and particularly 100 to 8000.

On the other hand, the hydroxyl group-containing (meth) acrylate compound which is another raw material of the component (a) is, for example, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate , 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6
-Hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate or the following general formula (3)

[0020]

[Chemical 4]

(Wherein R ² represents a hydrogen atom or a methyl group, and m represents a number of 1 to 15, preferably 1 to 4), a (meth) acrylate, an alkyl glycidyl ether, an allyl glycidyl ether, Examples thereof include compounds obtained by an addition reaction of a glycidyl group-containing compound such as glycidyl (meth) acrylate and (meth) acrylic acid. Among them, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like are preferable.

Examples of the polyisocyanate as the raw material of the component (a) 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, 1,4-hexamethylene diisocyanate, bis (2-isocyanate ethyl) fumarate, 6-isopropyl -1,3-phenyl diisocyanate, 4-diphenyl propane diisocyanate, lysine diisocyanate, etc. are mentioned. These polyisocyanates may be used alone or in combination of two or more.

In the present invention, the use of the acrylate-based oligomer having the above-mentioned terminal group (1) makes it possible to dramatically improve the adhesion to glass. Therefore, the compound (2) which introduces the group (1) is an important compound in order to effectively bring out the effect of the present invention. Examples of this compound (2) include, in the formula (2), n = 3 N-β- (aminoethyl) γ-aminopropyl having β- (aminoethyl) -amino group in HX and methyl group in R ^1. Trimethoxysilane, n having an amino group on HX and an ethyl group on R ¹
= 3 γ-aminopropyltriethoxysilane, N-phenylamino group on HX, N = 3 N-phenyl-γ-aminopropyltrimethoxysilane having a methyl group on R ¹ , X is a mercapto group, and R ¹ is on R ¹ . N = 3 with an alkyl group
.Gamma.-mercaptopropyltrialkoxysilane and the like. Of these compounds, those having a mercapto group in X are preferable, and particularly n = 3 having a methyl group in R ^1.
.Gamma.-mercaptopropyltrimethoxysilane is preferred. As commercial products, KBM573, 803, KBE9
03 (above, manufactured by Shin-Etsu Silicone Co., Ltd.), A-189,
1100, 1120 (all manufactured by Nippon Unicar Co., Ltd.),
SH6020, 6062, SZ6083 (above, Toray
Dow Corning Silicone Co., Ltd. and the like can be mentioned. By the addition of this compound, in addition to the urethane (meth) acrylate-based oligomer having a (meth) acryloyl group derived from the hydroxyl group-containing (meth) acrylate compound at both ends, the above-mentioned end group (1) is added to the molecular end instead of the acryloyl group. The urethane (meth) acrylate-based oligomer that it has can also be prepared together.

The conventional synthesis of urethane (meth) acrylate oligomer can be achieved by reacting the above-mentioned diol, polyisocyanate, and hydroxyl group-containing (meth) acrylate compound. Specifically, the isocyanate group of diisocyanate is It is carried out by reacting the hydroxyl group of the diol and the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound. However, in the present invention, instead of the hydroxyl group-containing (meth) acrylate compound, a part thereof is replaced with the compound (2), and the urethane (meth) having the terminal group (1) as the object of the present invention is obtained.
Synthesize an acrylate oligomer. This is due to the addition of the above compound (2) to the reactive group (XH) in the compound (2).
However, it is intended to carry out the same reaction as the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound. This reaction is performed, for example, by the following method.

A. A method in which a diol, polyisocyanate, and the compound (2) are charged at once and reacted, and then a hydroxyl group-containing (meth) acrylate compound is reacted. B. Reacting diol and polyisocyanate,
Then, the compound (2) is reacted, and finally a hydroxyl group-containing (meth) acrylate compound is reacted. C. A method in which a polyisocyanate and the above compound (2) are first reacted, then a hydroxyl group-containing (meth) acrylate compound is reacted, and finally a diol is reacted. D. Method in which the addition order of the compound (2) and the hydroxyl group-containing (meth) acrylate compound is changed by the above methods a to c and the reaction is carried out. Incidentally, the diol, polyisocyanate, hydroxyl group-containing (meth) acrylate compound, and the compound (2) The use ratio of each is 1 to 3 equivalents of the isocyanate group contained in the polyisocyanate to 1 equivalent of the hydroxyl group contained in the diol, the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound and the reactive group of the compound (2). It is preferable that the sum of and is 0.1 to 1.5 equivalents. Further, the ratio of the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound to the reactive group of the compound (2) used is 1 equivalent of the reactive group of the compound (2) to 1 equivalent of the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound. It is preferably the equivalent or less, and particularly preferably 0.01 equivalent or more and 0.5 equivalent or less. If the amount of the compound (2) exceeds 1 equivalent, the amount of acryloyl groups in the urethane (meth) acrylate-based oligomer decreases, and a cured product having satisfactory performance cannot be obtained.
On the contrary, if it is less than 0.01 equivalent, the effect of improving the adhesiveness cannot be obtained. For the same reason, it is preferable to adjust the raw material ratio so that 1 to 50% of the terminal groups of the urethane (meth) acrylate-based oligomer become the terminal groups represented by the formula (1).

In the above reaction, usually, a total amount of the reaction product is a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, and triethylenediamine-2-methyltriethylenediamine. 0.01 to 1 with respect to 100 parts by weight
Use parts by weight. The reaction temperature is usually 10 to 90.
It is preferably carried out at a temperature of 30 ° C., especially 30 to 80 ° C.

The preferred number average molecular weight of the urethane (meth) acrylate oligomer used in the present invention is 100 to 2
It is preferably 0000, and particularly preferably 120 to 15000. When the number average molecular weight of the urethane (meth) acrylate-based oligomer is less than 100, the elongation at break of the resulting cured product is reduced and the toughness is apt to be lowered, and when used as a coating material for an optical fiber, the transmission of the optical fiber is reduced. If the number average molecular weight exceeds 20,000, the viscosity of the composition becomes high and it becomes difficult to handle.

Urethane (meta) thus obtained
The blending ratio of the acrylate-based oligomer in the composition of the present invention is usually preferably 15 to 70% by weight, but the coatability when coating the optical fiber, the flexibility of the coating material after curing, and the long-term reliability are maintained. Therefore, it is particularly preferable to set the content to 20 to 60% by weight. Mixing ratio of component (a) is 1
If it is less than 5% by weight, the elongation at break of the cured product of the resulting composition decreases, while if it exceeds 70% by weight, the viscosity of the composition increases and the handleability deteriorates.

The liquid curable resin composition of the present invention contains, in addition to the urethane (meth) acrylate oligomer, a polymerizable diluent which is the component (b) described below, and (c).
A polymerization initiator as a component may be added, and other additives may be added as required.

Component (b), which acts as a polymerizable diluent, is a compound that is liquid or solid at room temperature and has at least one ethylenically unsaturated group in its molecule. ) A (meth) acrylate compound having an acryloyl group or a compound having a vinyl group is preferably used. The (meth) acrylate compound is classified into a monofunctional compound and a polyfunctional compound, but any compound can be used. When a cured product having a relatively low elastic modulus is desired, a monofunctional compound is mainly used, but the elastic modulus of the cured product can be adjusted by using a polyfunctional compound in an appropriate ratio.

Examples of the monofunctional compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, and the like.
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, ethoxyethyl (meth) acrylate, methoxypolyethylene Glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, disi Lopentadienyl (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, and the following formulas (4) to (6)

[0032]

[Chemical 5]

Examples include compounds represented by:

Commercially available monofunctional compounds include Aronix M111, M113, M114 and M117 (all manufactured by Toa Gosei Chemical Industry Co., Ltd.) and KAYARAD T.
C110S, R629, R644 (Nippon Kayaku Co., Ltd.), Viscoat 3700 (Osaka Organic Chemical Co., Ltd.)
Manufactured) and the like.

Examples of polyfunctional compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris ( 2-hydroxyethyl) isocyanurate tri (meth) acrylate,
Examples include tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, and epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A. . Commercially available products include UPIMER UV, SA1002, SA2007 (all manufactured by Mitsubishi Petrochemical Co., Ltd.), Viscoat 700 (manufactured by Osaka Organic Chemical Co., Ltd.), KAYARAD R-604, DPC.
A-20, 30, 60, 120, HX-620, D-3
10, 330 (above, manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, 215, 315, 325 (above, manufactured by Toa Gosei Chemical Industry Co., Ltd.) and the like. The molecular weight of these (meth) acrylate compounds is usually 200-
The range is about 3000. Of the above, particularly preferable examples of the (meth) acrylate compound include commercially available products Aronix M111, M113, M114, and M.
117 (above, manufactured by Toagosei Chemical Industry Co., Ltd.), KAYA
RAD TC110S, R629, R644 (above, Nippon Kayaku Co., Ltd. make) are mentioned. By using these (meth) acrylate compounds, the flexibility of the cured product is improved and the flexibility at low temperature is also improved. In addition, by using two or more of these (meth) acrylate compounds in combination, the curing rate of the resulting composition can be improved.

The content of these (meth) acrylate compounds in the composition of the present invention is preferably 5 to 60% by weight, more preferably 10 to 40% by weight. If the blending ratio is less than 5% by weight, the Young's modulus of the resulting composition at a low temperature after curing tends to increase, and the transmission loss tends to increase when coated on an optical fiber. If it exceeds 60% by weight, the composition is cured. Sex tends to decrease.

The vinyl-based polymerizable diluent, which is one of the component (b) used in the present invention, improves the adhesion to glass and the curability. Specific examples thereof include N-vinylpyrrolidone, N-vinylcaprolactam, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether and the like. The vinyl-based polymerizable diluent is 2 to 2 in the composition of the present invention.
It is preferable to add 0% by weight, particularly 3 to 15% by weight. When the content is more than 20% by weight, the water absorption of the obtained composition after curing becomes high, the water resistance and alkali resistance are lowered, and the flexibility at low temperature tends to be deteriorated.

The composition of the present invention is cured by heat and / or radiation. The radiation here means infrared rays, visible rays, ultraviolet rays and X-rays, electron beams, α rays, β
Rays, ionizing radiation such as gamma rays. When the composition of the present invention is heat-cured, a radical polymerization initiator is usually used as the polymerization initiator as the component (c), and examples of the radical polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-oxybenzoate, and azobisisobutyronitrile.

Further, the composition of the present invention can be treated with visible light, and / or
Alternatively, in the case of ultraviolet curing, a photopolymerization initiator and optionally a photosensitizer are used as the polymerization initiator as the component (c). Examples of such a photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone,
2,2-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 and the like can be mentioned. Also, as a commercial product, IR
UGACURE 184, 651, 500, 907, CG
I369, CG24-61 (above, Ciba Geigy Co., Ltd.
Manufactured by Lucirine LR8728 (BASF Corporation)
), Darocure 1116, 1173 (above, manufactured by Merck Ltd.), Yubecryl P36 (manufactured by UCB Ltd.)
Etc. can be mentioned.

As the photosensitizer, triethylamine, diethylamine, N-methyldiethanolamine,
Ethanolamine, 4-dimethylaminobenzoic acid, 4-
There are methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate and the like, and commercially available products include Yubecryl P102 and 10.
3, 104, 105 (above, UCB Co., Ltd. make) etc. are mentioned. These polymerization initiators can be added to the composition of the present invention in an amount of 0.
It is preferable to add 1 to 10% by weight. If the blending ratio is too small, sufficient curing cannot be achieved. On the contrary, if the blending ratio is too large, further improvement in the curing rate cannot be expected, and it is preferable to be within the above range for practical use.

If desired, additives other than the above-mentioned essential components may be added to the composition of the present invention. As such additives, for example, antioxidants, colorants, ultraviolet absorbers,
Light stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, softeners, lubricants, solvents, fillers, antiaging agents, leak improvers, coating improvers, etc. is there. Commercially available antioxidants include Irgano
x1010, 1035, 1076, 1222 (above, manufactured by Ciba-Geigy Co., Ltd.) and the like. Examples of the ultraviolet absorber include Tinuvin P, 234, 320, 326,
327, 328, 213 (above, Ciba Geigy Co., Ltd.)
Made), Sumisorb 110, 130, 140, 22
0, 250, 300, 320, 340, 350, 400
(Above, manufactured by Sumitomo Chemical Co., Ltd.) and the like. Examples of commercially available light stabilizers include Tinvuin 292, 144,
622LD (above, manufactured by Ciba Geigy Co., Ltd.), SANOL LS-770, 765, 292, 2626, 1114,
744 (above, Sankyo Chemical Industry Co., Ltd.) and the like,
As the silane coupling agent, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and as commercially available products, SH6062, SZ6030
(The above is Toray Dow Corning Silicone Co., Ltd.
Manufactured by Shin-Etsu Silicone Co., Ltd., and commercially available anti-aging agents include Antigene W, S, P, 3C, 6C, and R.
DG, FR, AW (above, Sumitomo Chemical Co., Ltd. product) etc. are mentioned.

In the composition of the present invention, other additives such as epoxy resin, polyamide, polyamideimide,
Polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene / styrene block copolymer, styrene /
Ethylene / butene / styrene Bronck copolymer, styrene / isoprene / styrene block copolymer, petroleum resin, xylene resin, ketone resin, fluorine-based oligomer,
Polymers such as silicone-based oligomers and polysulfide-based oligomers, or oligomers can also be blended.

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 prepared is usually 100 to 20000 cps / 25 ° C, preferably 2000 to 15000 cps / 25 ° C.

[0044]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" means "parts by weight".

Urethane Acrylate Synthesis Example 1 In a reaction vessel equipped with a stirrer, 5.5 parts of tolylene diisocyanate and a ring-opening copolymer of tetrahydrofuran and 3-methyltetrahydrofuran having a number average molecular weight of 2,000 42.
0 part and 0.01 part of 2,6-di-t-butyl-p-cresol, which is a polymerization inhibitor, were charged as an additive.
Then, these were stirred and ice-cooled until the liquid temperature became 10 ° C. or lower. When the liquid temperature becomes 10 ° C or lower, 0.04 part of dibutyltin dilaurate is added to adjust the liquid temperature to 20 to 3
The mixture was stirred for 2 hours while controlling at 0 ° C. And there γ-
0.5 part of mercaptopropyltrimethoxysilane was added, and the mixture was stirred at 30 to 40 ° C. for 1 hour. After stirring for 1 hour,
Hydroxyethyl acrylate (2.2 parts) was added, and stirring was continued at a liquid temperature of 50 to 60 ° C. for 4 hours, and the reaction was terminated when the residual isocyanate was 0.1% by weight or less. The urethane acrylate resin liquid obtained by this method is referred to as UA-1.

Urethane Acrylate Synthesis Example 2 In a reaction vessel equipped with a stirrer, 3.0 parts of tolylene diisocyanate, 50.5 parts of ethylene oxide / butene oxide ring-opening copolymer having a number average molecular weight of 4000, and polymerization inhibition as an additive Agent 2,6-di-t-butyl-p
-0.01 parts of cresol were charged. Then, these were stirred and ice-cooled until the liquid temperature became 10 ° C. or lower. When the liquid temperature became 10 ° C or lower, 0.04 part of dibutyltin dilaurate was added, and the mixture was stirred for 2 hours while controlling the liquid temperature at 20 to 30 ° C. Then, 0.3 part of γ-mercaptopropyltrimethoxysilane was added thereto, and the temperature was 30 to 40 ° C.
It was stirred for 1 hour. After stirring for 1 hour, 1.2 parts of hydroxyethyl acrylate was added, and stirring was continued at a liquid temperature of 50 to 60 ° C. for 4 hours, and the reaction was terminated when the residual isocyanate was 0.1% by weight or less. The urethane acrylate resin liquid obtained by this method is referred to as UA-2.

Comparative Synthetic Example 1 Urethane Acrylate 1 In a reaction vessel equipped with a stirrer, 5.5 parts of tolylene diisocyanate and a ring-opening copolymer of tetrahydrofuran and 3-methyltetrahydrofuran having a number average molecular weight of 2,000 42.
0 part and 0.01 part of 2,6-di-t-butyl-p-cresol, which is a polymerization inhibitor, were charged as an additive.
Then, these were stirred and ice-cooled until the liquid temperature became 10 ° C. or lower. When the liquid temperature becomes 10 ° C or lower, 0.04 part of dibutyltin dilaurate is added to adjust the liquid temperature to 20 to 3
The mixture was stirred for 2 hours while controlling at 0 ° C. After that, 2.5 parts of hydroxyethyl acrylate was added, and the liquid temperature was 5
Stirring was continued at 0 to 60 ° C. for 4 hours, and the reaction was terminated when the residual isocyanate content was 0.1% by weight or less.
The urethane acrylate resin liquid obtained by this method is referred to as UA-3.

Comparative Synthetic Example 2 Urethane Acrylate 2 In a reaction vessel equipped with a stirrer, 5.5 parts of tolylene diisocyanate and a ring-opening copolymer of tetrahydrofuran and 3-methyltetrahydrofuran having a number average molecular weight of 2,000 42.
0 part and 0.01 part of 2,6-di-t-butyl-p-cresol, which is a polymerization inhibitor, were charged as an additive.
Then, these were stirred and ice-cooled until the liquid temperature became 10 ° C. or lower. When the liquid temperature becomes 10 ° C or lower, 0.04 part of dibutyltin dilaurate is added to adjust the liquid temperature to 20 to 3
The mixture was stirred for 2 hours while controlling at 0 ° C. And 0.08 part of methanol was added there and it stirred at 30-40 degreeC for 1 hour. After stirring for 1 hour, 2.2 parts of hydroxyethyl acrylate was added, and stirring was continued at a liquid temperature of 50 to 60 ° C. for 4 hours, and the reaction was terminated when the residual isocyanate content was 0.1% by weight or less. The resin solution of urethane methacrylate obtained by this method is referred to as UA-4.

Examples 1 to 4 and Comparative Examples 1 and 2 Each component having the composition shown in Table 1 was charged into a reaction vessel equipped with a stirrer, and stirred and homogenized for 3 hours while controlling the liquid temperature at 50 to 60 ° C., A liquid curable resin composition was obtained.

[0050]

[Table 1]

Test Example A test piece was prepared by the following method using the liquid compositions 1 to 6 obtained in the above Examples and Comparative Examples, and the adhesion to glass was measured as described below. Preparation of test piece: A liquid material is applied on a quartz plate using an applicator bar having a thickness of 150 μm, and ultraviolet rays of 100 mJ / cm ² are irradiated in a nitrogen atmosphere to form a cured film having a thickness of 200 μm. This was cut into 1 cm widths and measured using this.

Measurement of adhesion force with glass: The cured film on the quartz plate was peeled off at a speed of 50 mm / min from the direction right above the quartz plate, and the adhesion force (g / cm) per 1 cm width of the cured film was measured. did.

Test Example 1 Measurement of Adhesion with Glass after Storage under Wet and Heat: The above test piece was stored at a temperature of 60 ° C. and humidity of 95%, and the adhesion with glass after a certain period of time was measured. The results are shown in Table 2 as a rate of change over time.

[0054]

[Table 2]

Test Example 2 Measurement of Adhesion with Glass after Storage as Liquid Composition: The liquid compositions obtained in the above examples were stored at a temperature of 25 ° C. and a humidity of 60%, and after a certain period of time, A test piece was prepared by the above method, and the adhesion with glass was measured. The results are shown in Table 3 as a rate of change over time.

[0056]

[Table 3]

[0057]

EFFECTS OF THE INVENTION The liquid curable resin composition of the present invention has a high adhesiveness with glass, and has an extremely small change over time in the adhesive strength under moist heat or heat storage as compared with the conventional ones. have. Furthermore, even when stored in a liquid state for a long period of time, the adhesive strength of the cured product does not significantly change, and the liquid storage stability is excellent. Therefore, it is a particularly excellent material as a coating material that requires adhesion to glass such as optical fiber coating.

─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Norihiko Saito 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Mitsufumi Suwa 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) Reference JP-A-59-232110 (JP, A) JP-A-60 -18538 (JP, A) JP-A-60-26022 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G02B 6/44 C08F 290/00 -290/14 C08F 299/00 -299/08 C08G 18/67

Claims (2)

(57) [Claims] 1. The following (a), (b) and (c) (a) 1 to 50% of the molecular end groups are represented by the following general formula (1) --NHCO--X-(CH ₂ ) _n --Si. (OR ¹ ) ₃ (1) [In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X represents a sulfur atom or -N (R ² )-(R ² represents a hydrogen atom, a carbon number. 1 to 10 alkyl group or phenyl group), and n represents a number of 1 to 10], 15 to 70% by weight of a urethane (meth) acrylate-based oligomer which is a terminal group represented by (b) ( 5 to 60% by weight of (meth) acrylate compound
And / or 2 to 20% by weight of a vinyl compound, and (c) an optical fiber containing 0.1 to 10% by weight of a polymerization initiator.
Liquid curable resin composition for iber coating . 2. The optical fiber according to claim 1, wherein the urethane (meth) acrylate-based oligomer as the component (a) has a structure of one kind or two or more kinds selected from polyether, polycarbonate and polyester.
Liquid curable resin composition for bar coating .