JPH02138190A - Urethane(meth) acrylate, resin composition and coating agent - Google Patents

Abstract

NEW MATERIAL:Urethane (meth)acrylate. USE:A coating agent for light-transmitting optical glass fiber. PREPARATION:Triisocyanate expressed by the formula is reacted with a hydroxy(meth)acrylate compound, preferably using at a ratio of chemical equivalent of hydroxyl group of the latter of 1.0-1.1 to chemical equivalent of the former isocyanate of 1.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel urethane (meth)acrylate, a resin composition containing the same, and a coating agent for optical glass fibers for light transmission.

(Prior Art) Since optical fibers have excellent information transmission performance and are relatively immune to external interference, their use has increased significantly in recent years, especially in the communications field.

Optical fibers are generally glass-broken because they are used in the telecommunications field. However, glass fibers are inherently brittle and are easily broken due to chemical agitation by water vapor, making them difficult to handle. Therefore, conventionally, optical glass fibers are
The surface is coated with resin. Conventionally, epoxy resins, urethane resins, etc. have been used as such resin coating materials, but they require a long time to harden, resulting in poor productivity.They also lack flexibility, which has the disadvantage of impairing transmission characteristics due to lateral pressure. There is. Recently, ultraviolet curable compositions containing urethane acrylate have been actively studied in order to improve the above-mentioned drawbacks, and ultraviolet curable compositions for optical glass fibers and methods for forming such coatings have been published, for example in Japanese Patent Laid-Open No. 58-2
No. 23638 and Japanese Patent Application Laid-open No. 59-170154.

These have selected very low modulus primary coatings as a means of solving the above problems with some success. However, in order to provide a low modulus, the hardness and toughness desired in a coating that contacts the glass are sacrificed, and it is desirable to apply a top coating over the primary coating, and the associated UV curable properties Compositions are being considered. For example, an ultraviolet curable top coating composition is proposed in JP-A-59-170155.

(Problems to be Solved by the Invention) Many UV-curable top coating compositions currently in use contain N-vinylpyrrolidone, which provides fast curing speed and less reduction in Young's modulus at high temperatures. It is used because it has the following advantages. However, there are problems such as the storage stability of the ultraviolet curable top coach containing N-vinylpyrrolidone and the liquid ink composition, and the high water absorption of the cured film. In addition, the causes of loss of transmission characteristics include the above-mentioned lateral pressure and hydrogen gas, but lateral pressure can be suppressed by coating with a material having a low elastic modulus. The hydrogen problem has not been fully resolved. Even with conventional UV-curable coating materials, large amounts of UV rays are generated in a short period of time when exposed to high temperatures, and large amounts of UV rays are also generated when left under borrowed light for long periods of time and then placed at relatively low temperatures. This causes transmission loss.

(Means for Solving the Problems) In order to solve the above problems, the present inventors conducted intensive research and developed a new urethane (meth)acrylate, which was cured by using it in a top coating composition. The speed is fast, the storage stability of the liquid is good, and the Young's modulus of the resin coating obtained by curing is small at high temperatures, and by using it in a coating composition, the cured coating can be stored under borrowed light for a long period of time. The present invention has been completed by successfully providing a resin composition that generates a small amount of hydrogen even when left to stand at high temperatures and is particularly suitable as a coating agent for optical glass fibers for light transmission.

That is, the present invention provides: 1) a triisocyanate prisoner having the following structural formula (1) and a hydroxy (meth)acrylate compound (urethane (meth)acrylate which is a reaction product); 2) the structure described in item 1); A triisocyanate prisoner and a hydroxy (meth)acrylate compound [F
]) A resin composition characterized by containing urethane (meth)acrylate which is a reaction product of The present invention relates to a coach ink agent for optical glass fibers, which is characterized by containing urethane (meth)acrylate, which is a reaction product of a meth)acrylate compound (B).

The urethane (meth)acrylate of the present invention has the structural formula (1
) with triisocyanate and hydroxy(meth)
It can be produced by reacting an acrylate compound (B). The triisocyanate having the structural formula (1), which is a raw material for the urethane (meth)acrylate of the present invention, can be easily obtained manually from the market. For example, Desmodur RF (manufactured by Bayer), etc.

Specific examples of the hydroxy(meth)acrylate compound (B) include hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono( meth)acrylate, ε-caprolactone-β
-Hydroxyethyl (meth)acrylate adduct (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-1, FM-1, F
A-2, etc.), pentaerythritol tri(meth)acrylate, etc.

For 1 chemical equivalent of the incyanate group of structural formula (11), the hydroxy(meth)acrylate compound has 0.9 to 2.0 of the hydroxyl group of the hydroxy(meth)acrylate compound.
Preference is given to using 0 chemical equivalents, particularly preferably 1.0 to 1.1 chemical equivalents. This reaction can be carried out in the presence of a known catalyst such as a tertiary amine, dibutyltin dilaurate, dioctyltin dilaurate, etc., in order to promote the reaction between the incyanate group and the hydroxyl group. In addition, in order to prevent gelation due to radical polymerization during the reaction, 50 to 2000 ppm of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, p-benzoquinone, or phenotiazine is added before the reaction. It is preferable. The reaction temperature is preferably 6.0 to 90°C. Additionally, a solvent or monomer can be used as a diluent when stirring or the like is difficult during the reaction. Specific examples of the solvent include methyl ethyl ketone, toluene, ethyl acetate, and ethyl cellosolve acetate. Specific examples of monomers include hydrogenated dicyclopentadiene acrylate (e.g., FA-513A, manufactured by Hitachi Chemical), dicyclopentadieneoxyethyl acrylate (e.g., FA-512A, manufactured by Hitachi Chemical). , inbornyl acrylate, phenyloxyethyl acrylate, tetrahydrofurfuryl acrylate, tricyclodecane dimethylol diazimontalate, tris(2-hydroxyethyl)
Isocyanurate triacrylate (manufactured by Hitachi Chemical, F
A-731A), phenyloxypolyethoxyacrylate, phenyloxypolypropoxyacrylate, acrylate of ε-caprolactone adduct of tetrahydrofurfuryl alcohol (manufactured by Nippon Kayaku ■, KAYARAD
TC-11O8), diethylene glycol di(meth)
Acrylate (for example, KAYARAD manufactured by Nippon Kayaku)
R-604), acrylates of ε-caprolactone adducts of polyethoxy or polypropoxy compounds of phenol derivatives, and acryloylmorpholine.

In the resin composition and coating agent (hereinafter referred to as composition) of the present invention, urethane (meth)acrylate is preferably used in an amount of 0.1 to 60% by weight, particularly 0.5 to 60% by weight. It is preferable to use it in a range of 40% by weight. In the composition, various known ethylenically unsaturated compounds can be used as components other than the urethane (meth)acrylate of the present invention. Specific examples of ethylenically unsaturated compounds include the monomers mentioned above, polyurethane (meth)acrylate of polyether polyol having an ether group in the molecule, polyurethane (meth)acrylate of carbonate polyol having a carbonate group, and ester group. Polyurethane (meth)acrylate of polyester polyol with
Epoxy (meth)acrylate such as meth)acrylate, (meth)acrylate of bisphenol A epoxy resin, (meth)acrylate of bisphenol F epoxy resin, (meth)acrylate of bisphenol A urethane-modified epoxy resin, polyester ( meth)acrylates, e.g. diol compounds (e.g.
ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, l,5-bentanediol, 1,6-hexanediol, etc.) and dibasic acids (e.g., succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, etc.) phthalic acid, etc.); (meth)acrylates of lactone-modified polyester diols consisting of diol compounds, dibasic acids, and ε-caprolactone; polycarbonate (meth)acrylates, such as 1.
Examples include (meth)acrylate of polycarbonate diol containing 6-hexanediol as a diol component. Particularly preferred ethylenically unsaturated compounds include, for example, hydrogenated dicyclopentadiene acrylate (FA-513A, manufactured by Hitachi Chemical Co., Ltd.), acrylate of ε-caprolactone adduct of tetrahydrofurfuryl alcohol (manufactured by Nippon Kaya Co., Ltd., KAYARAD TC-11O3), tris(2-hydroxyethyl)isocyanurate triacrylate, polyurethane acrylate, acryloylmorpholine, and the like.

The above ethylenically unsaturated compound may be added in an amount of 1ff if necessary.
i or two or more kinds of compounds can be used as a mixture in any ratio. The amount of the ethylenically unsaturated compound to be used in the composition is preferably 40 to 99.9% by weight, particularly preferably 60 to 97.5% by weight.

The composition of the present invention can be cured by known methods. For example, it can be cured by ultraviolet light. In the case of curing with ultraviolet light, it is necessary to use a photoinitiator. As the photopolymerization initiator, any known photopolymerization initiator may be used, but it is required to have good storage stability after blending. Examples of such photopolymerization initiators include benzoin alkyl ethers such as benzoin ethyl ether, benzoin isobutyl ether, and benzoin inopropyl ether, 2,2-jethoxyacetophenone, 4-phenoxy-2,2-dichloroacetophenone, and the like. acetophenone series, 2-hydroxy-2-methylpropiophenone, 4-improvil-2-hydroxy-
Propiophenones such as 2-methylpropiophenone and 4-dotecyl-2-hydroxy-2-methylpropiophenone, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone and 2-ethylanthraquinone, 2-chloroanthraquinone Examples include anthraquinone-based photopolymerization initiators such as thioxanthone-based photopolymerization initiators. Particularly preferred are benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, and the like. These photopolymerization initiators may be
Two or more types may be mixed and used in any ratio.

The amount used is usually 1 to 10% by weight of the composition,
Preferably it is 2 to 5% by weight.

Modifying resins and various additives may be added to the composition of the present invention, if desired. Examples of modifying resins include epoxy resins, polyurethane, polybutadiene, polyethers, polyamideimide, silicone resins, and phenolic resins. be able to. The amount of the modifying resin used is preferably in the range of 0 to 10% by weight in the coating agent, particularly in the range of 0 to 10% by weight.
Preferably, 5% by weight is used. In addition, the above-mentioned additives include organosilicon compounds such as γ-methacryloxyglobiltrimethoxysilane, vinyltriacetoxysilane, etc.)
, surfactant (for example, Toshi Silicon ■, 5H-374)
9), polymerization inhibitors (for example, methoquinone, methylhydroquinone, etc.), and the like. The organic silicon compound is in the range of 0 to 3% by weight in the coating agent, the surfactant is in the range of 0 to 3% by weight in the coating agent, and the polymerization inhibitor is in the range of 0 to 1% by weight in the composition. It is preferable to use

When coating an optical glass fiber with the coating agent for optical glass fiber of the present invention, a die coating method is suitable as a coating method.

When coating an optical glass fiber using the coating agent for optical glass fibers of the present invention, a line is drawn on the optical glass base material at a speed of, for example, 1 to 5 m/sec, the primary coating agent is coated on this, and the line is irradiated with ultraviolet rays. The top coating is then applied over the primary coat. The composition of the present invention is easily cured by ultraviolet irradiation. Curing of the composition of the present invention by irradiation with ultraviolet rays can be carried out by a conventional method. For example, ultraviolet rays may be irradiated using a low-pressure or high-pressure mercury lamp or a xenon lamp.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. In addition,
Parts in the examples are parts by weight.

[Example of synthesis of ethylenically unsaturated compounds]

Synthesis example 1. (Polyurethane acrylate) Polytetramethylene glycol (molecular weight 2040, OH value 55.0)
408 parts of ethylene glycol, 37.2 parts of ethylene glycol, and 355.6 parts of inphorone diisocyanate were charged, and the temperature was raised to 80°C.
The reaction mixture was cooled to 60°C for 2 hours.
-191.3 parts of hydroxyethyl acrylate, 0.5 parts of methoquinone, and 02 parts of di-n-butyltin placrylate were charged, and after raising the temperature, the reaction was carried out at 75 to 80°C. Approximately 01
The reaction was continued until completion as indicated by less than % free isocyanate groups.

Synthesis example 2. (Polyurethane acrylate) Polypropylene glycol (molecular weight approximately 2000) iooo part and polyester diol (manufactured by Daicel Chemical Industries, Ltd., Plaxel L)
-220AL, 1000 parts of molecular-ft approximately 2000) and 333.4 parts of inphorone diisocyanate),
The reaction was carried out at 80°C for 10 hours, and then 378.4 parts of ε-caprolactone-β hydroxyethyl acrylate adduct (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-2) was added, and after raising the temperature, the temperature was 75-80°C. The reaction was carried out at °C. Approximately 0.
The reaction was continued until completion as indicated by less than 1% free incyanate groups.

Synthesis example 3. (Polycarbonate acrylate) Compound H (-0+CHz-)60- C-3-7HO-1 with the following structural formula:
70H 700 parts, acrylic acid 121 parts, p-)
14 parts of luenesulfonic acid, hydroquinone t, om, 560 parts of benzene, and 140 parts of cyclohexane are charged and heated. The produced water is distilled and condensed together with the solvent, and only the water is removed from the system in a separator. The solvent is returned to the reactor. . Water is 25.
Once two parts were formed, it was cooled. The reaction temperature is 80-86
It was ℃.

The reaction mixture was mixed with 960 parts of benzene and 24 parts of cyclohexane.
After neutralizing with a 20% aqueous solution of caustic soda, the solution was washed three times with 500 parts of a 20% saline solution. The solvent was distilled off under reduced pressure to obtain a pale yellow solid.

[Examples of urethane (meth)acrylate] Example 1 Triisocyanate 465 represented by the following structural formula
(Bayer fM, f Smodor RF), 359 parts of 2-hydroxyethyl acrylate, 0.1 part of methoquinone
and 275 parts of hydrogenated dicyclopentadiene acrylate (Hitachi Chemical N, FA-513A) as a diluent, and after raising the temperature, the reaction was carried out at 80°C. The reaction was continued until completion. The product has a clear, highly viscous character at 25°C.

The physical properties of this product are a viscosity (60°C) of 175p and a refractive index (23°C) of 1.5521.

Example 8 Example 2゜Triisocyanate represented by the following structural formula 465
(manufactured by Bayer AG, Desmodur RF), 1063 parts of ε-caprolactone-β-hydroxyethyl acrylate adduct (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-2), and 170 parts of acryloylmorpholine as a diluent. The reaction was carried out in the same manner as in 1, and a transparent product with high viscosity was obtained at 25°C. The physical properties of this product are viscosity (60°C) 350p, refractive index (23°C) 1.54
It is 81.

Example 3 465 parts of Desmodur RF, 402 parts of 2-hydroxyethyl methacrylate, 01 part of methoquinone, and 289 parts of isobornyl acrylate as a diluent were prepared. Example 1
The reaction was carried out in the same manner as above to obtain a highly viscous and transparent product at 25°C. The physical properties of this product are as follows: viscosity (60°C) 18
9p and a refractive index (23°C) of 1.5530.

Example 4 Desmodur RF465m, 402 parts of 2-hydroxypropyl acrylate, 01 part of methoquinone, acrylate of ε-caprolactone adduct of tetrahydrofurfuryl alcohol as a diluent (manufactured by Nippon Kayaku, KAYAR)
AD TC-11O8) 289 parts were charged, Example 1
The reaction was carried out in the same manner as above to obtain a highly viscous and transparent product at 25°C. The physical properties of this product are viscosity (60'C)
250p, and the refractive index (23°C) is 1.5453.

[Example of resin composition]

Example 5゜20 parts of polyurethane acrylate obtained in Synthesis Example 1, 30 parts of urethane acrylate obtained in Example 1, hydrogenated dicyclopentadiene acrylate (Hitachi Kasei, FA-51)
3A) 30 parts, 10 parts of polycarbonate acrylate obtained in Synthesis Example 3, and l-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigy ■, Irgacure 18)
4 and 0.05 parts of methoquinone were mixed to prepare resin composition A for optical glass fiber top coating.

Example 6゜30 parts of polyurethane acrylate obtained in Synthesis Example 1, 25 parts of urethane acrylate obtained in Example 2, hydrogenated dicyclopentadiene acrylate (manufactured by Hitachi Chemical, FA-51)
3A) 45 parts, tri(hydroxyethyl)incyanurate triacrylate (manufactured by Hitachi Chemical, FA-731
Resin composition B for optical glass fiber top coating was prepared by mixing 10 parts of A), 3 parts of Irgakiair-184, and 0.05 part of methoquinone.

Example 7゜25 parts of polyurethane acrylate obtained in Synthesis Example 1, 5 parts of urethane methacrylate obtained in Example 3, 35 parts of urethane acrylate obtained in Example 4, hydrogenated dicyclopentadiene acrylate (manufactured by Hitachi Chemical Co., Ltd.) FA-513A)3
5 parts, 3 parts of Irgacure 184, 0.0 methoquinone
5 parts were mixed to prepare a resin composition C for optical glass fiber top coating.

Example 8 50 parts of polyurethane acrylate obtained in Synthesis Example 2, acrylate of ε-caprolactone adduct of tetrahydrofurfuryl alcohol (manufactured by Nippon Kayaku, KAYARAD)
A resin composition for optical glass fiber primary coating was prepared by mixing 45 parts of TC-11O8), 2 parts of the urethane acrylate obtained in Example 1, 3 parts of Irugaki Air-184, and 0.05 part of methoquinone.

Acrylate of ε-caprolactone adduct of tetrahydrofurfuryl alcohol (manufactured by Nippon Kayaku, KAYARA
DTC-11O8) 41.4 parts, 06 parts of the urethane acrylate obtained in Example 2, a.

A resin composition E for optical glass fiber primary coating was prepared by mixing 3 parts of Gacure 184 and 0.05 part of methoquinone.

Comparative Example 1゜In Example 5, the urethane acrylate obtained in Example 1 was
- Resin composition F for optical glass fiber top coating was prepared in the same manner as in Example 5 except that vinyl pyrrolidone was used.

Comparative Example 2 Optical glass fiber primary coachib resin composition G was prepared in the same manner as in Example 8, except that the urethane acrylate obtained in Example 1 was omitted.

Table 1 shows the properties of the prepared resin compositions A-G and their cured products.

In Table 1 above, [Stability of liquid composition] Two sets of acids A to G were left at 60° C. for one month, and the state thereafter was observed.

○・・・No abnormality at all X...Gelation occurs at °C.

Measurement of [Young's modulus, kg/mm2]: Compositions A, B,
C and FK were irradiated with a metal halide lamp (lamp output 2 kW) at a position 3 cm below the light source (conveyor speed 20/rmn), and a 250 μm thick sheet was exploded, and measurements were made using this.

[Measurement of hydrogen generation amount cc/g): Compositions A-G were irradiated at a position 8 cm below the light source with metal halide lamps (lamp output 2 KW) arranged in parallel at 10,500 m, J/'
cm2 and exploded a sheet with a thickness of 250 μm.The sheet was left under a 30W fluorescent lamp at a position of 3Qcm under the light source for 10 days.Then, the sheet was placed in a headspace bottle and heated at 150℃. After standing for 24 hours, the amount of hydrogen generated was measured by gas chromatography.

Example 10 A base material for optical glass fiber was heated to about 2000°C, and
It was spun into an optical glass fiber with an outer diameter of 125 microns at a speed of m/s. In the next successive step, primary coating resin compositions R and F were respectively coated by die coating method and cured by irradiation with ultraviolet rays. Next, the primary-coated optical glass fiber was top-coated with top-coating resin composition A, B, or C, and then cured by irradiating ultraviolet rays with a metal-ride lamp. In all of the obtained coated optical glass fibers, no change in transmission loss was observed up to -40°C.

(Effects of the Invention) The resin composition and coating agent using the novel urethane (meth)acrylate of the present invention have a fast curing speed, and the obtained cured film has a small decrease in Young's modulus at high temperatures.
In addition, it generates a small amount of hydrogen and is suitable for coating optical glass fibers for optical transmission.

Claims (1)

[Claims] 1. Triisocyanate (A) having the following structural formula▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ Urethane (meth)acrylate is a reaction product of hydroxy (meth)acrylate compound (B). 2. Triisocyanate having the structural formula described in item 1 (
A resin composition characterized by containing urethane (meth)acrylate which is a reaction product of A) and a hydroxy (meth)acrylate compound (B). 3. Triisocyanate having the structural formula described in item 1 (
A coating agent for optical glass fiber characterized by containing urethane (meth)acrylate which is a reaction product of A) and a hydroxy (meth)acrylate compound (B).