JPS63297369A - Urethane (meth)acrylate mixture, polymer composition and coating agent - Google Patents

Abstract

NEW MATERIAL:A urethane (meth)acrylate mixture which is a reaction product of a compound of formula (R is 1-4C alkyl) with a hydroxy(meth)acrylate compound. USE:A coating agent for optical glass fiber and an ultraviolet-curable top-coating agent. PREPARATION:The titled substance can be produced by reacting a compound of formula with a hydroxy(meth)acrylate compound in the presence of a catalyst (e.g. tert-amine or dibutyltin laurate) and a polymerization inhibitor in a reactive diluent (e.g. acryloxylmorpholine) at 60-90 deg.C.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel urethane (meth)acrylate mixture, a resin composition containing the same, and a coating agent for optical glass fibers, and particularly for protecting the glass surface of optical fibers. It is useful as a UV curable top coating to protect applied brimery or buffer coatings.

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

The original fiber is generally made of glass since it is used in the telecommunications field. However, glass fibers are inherently fragile and are easily destroyed and difficult to handle because they are chemically agitated by water vapor.

Therefore, optical glass fibers have conventionally been coated with a resin on one surface. Conventionally, epoxy resin, urethane resin, etc. have been used as such resin coating materials.
It takes a long time to harden, resulting in poor productivity, and it also lacks flexibility, which has the disadvantage of impairing transmission characteristics due to lateral pressure. Recently, ultraviolet curable compositions containing urethane acrylate have been extensively studied in order to improve the above-mentioned drawbacks, and a method for forming an ultraviolet curable composition for optical glass fibers and such a coating has been published.
and JP-A-59-170154.

They have selected very low modulus primary coatings as a means of solving the above problems, with some success.

However, to provide a low modulus, the hardness and toughness desired in the coating in contact with the glass is sacrificed and it is desirable to apply a top coating over the primary coaching.

UV-curable compositions related to this have been studied. For example, an ultraviolet curable top coating composition is proposed in JP-A-59-170155.

(Problems to be Solved by the Invention) Many of the UV-curable top coating compositions currently in use contain N-vinylpyrrolidone, which has a fast curing speed and reduces the decline in Young's modulus at high temperatures. It is used because it has the following advantages. However, the cured film of the ultraviolet curable top coating composition containing N-vinylpyrrolidone has a large water absorption property, which poses a problem in that the glass fiber is easily damaged by water.

(Means for Solving the Problems) In order to solve the above problems, the inventors of the present invention have conducted intensive research and have synthesized a new urethane (meth)acrylate mixture, which has a high curing speed and a high curing rate. The present invention has been completed by successfully providing a resin composition which is particularly suitable for dog coats of optical glass fibers for optical transmission, as the resulting resin coating exhibits less decline in Young's modulus at high temperatures and has a lower water absorption rate. did.

That is, the present invention is based on the formula (1) (1) (wherein R is a carbon number 1 such as a methyl group or an ethyl group, respectively).
~4 alkyl group is shown. ) A urethane (meth)acrylate mixture (C) which is a reaction product of a compound (a) having the following formula and a hydroxy (meth)acrylate compound (b).

(2) Urethane (meth)acrylate mixture (C)
A resin composition comprising:

(3) Urethane (meth)acrylate mixture (C)
The present invention relates to a coating agent for optical glass fiber characterized by containing the following.

Compound (a) having formula (1) used in the present invention can be easily obtained from the market. For example, Hüls (
Co., Ltd., PD Knee T1890 (all R's are methyl groups in formula (1)), and the like.

The urethane (meth)acrylate mixture (c) of the present invention comprises a compound (a) having the formula (1) and hydroxy (meth)acrylate
It can be obtained by reacting an acrylate compound (b). Examples of hydroxy(meth)acrylate compounds include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, e-caprolactone-β-hydroxyethyl (
meth)acrylate adducts (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-1, Plaxel PIM-1, Plaxel PA-2, etc.), and the like. A compound having the formula (1) (
In the reaction between a) and the hydroxy(meth)acrylate compound (b), the amount of the hydroxy(meth)acrylate compound (b) is preferably 0.9 to 1 per chemical equivalent of the incyanate group of the compound (a). .5 chemical weight, particularly preferably 1. a to 1.1 chemical equivalents can be used. This reaction can be carried out in the presence of a known catalyst such as a tertiary amine, dibutyltin silacrate, dioctyltin dilatate, etc., in order to promote the reaction between incyanate groups and hydroxyl groups. In addition, in order to prevent gelation due to radical polymerization during one reaction, 50 to 200
It is preferable to add 0 ppm of a polymerization inhibitor such as hydroquinone, methoquinone, methylhydroquinone, p-benzoquinone, or phenothiazine.

The reaction temperature is preferably 60 to 90'C. It is also preferred to carry out the reaction in a reactive diluent which is inert under the reaction conditions and which also acts as a viscosity reducing agent. Examples of such reactive diluents include acryloylmorpholine, hydrogenated dicyclopentadiene acrylate (
For example, 1 Hitachi Chemical Co., Ltd., FA-513A), inbornyl acrylate, dicyclopentadieneoxyethyl acrylate (1 Hitachi Chemical Co., Ltd., F'A-
512A), hydrogenated β-naphthol acrylate, phenyloxyethyl acrylate, adamancune acrylate, phenyloxyethyl acrylate, dioxane glycol diacrylate (for example, 1, manufactured by Nippon Kayaku Co., Ltd., KAYARAD R-604).

Examples thereof include ethylenically unsaturated monomers such as triacrylate of tris(2-hydroxyethyl)in cyanuric acid and diacrylate of tricyclodecane dimethylol. In the resin composition and coating agent (hereinafter both referred to as composition) of the present invention.

The urethane (meth)acrylate mixture is 5 to 5 in one composition.
It is preferably used in a range of 60% by weight.

- It is particularly preferable to use it in a range of 10 to 40% by weight.

In the compositions of the present invention, polyurethane acrylate mixtures are preferred over polyurethane methacrylate mixtures.

In the composition of the present invention, various known ethylenically unsaturated compounds can be used as components other than the polyurethane (meth)acrylate mixture. Specific examples of ethylenically unsaturated compounds include the reactive diluents mentioned above, and polyurethane (meth)acrylates, such as polyurethane (meth)acrylates of polyether polyols having busy ether groups in the molecule, and carbonate groups. Polyurethane (meth)acrylate of carbonate polyol,
Epoxy (meth)acrylates such as polyurethane (meth)acrylates of polyester polyols having ester groups or polyurethane (meth)acrylates having both ether groups and ester groups in the molecule, e.g. (meth)acrylates of bisphenol A epoxy resins. , (meth)acrylate of bisphenol F epoxy resin.

Polyester (meth)acrylates, such as (meth)acrylates of urethane-modified epoxy resins of bisphenol A, e.g. diol compounds.

Ethylene glycol, fluoropylene glycol, diethylene glycol, cyclopyrene glycol.

1,5-bentalediol, 1,6-hexanediol, etc.) and dibasic acids (e.g., succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, etc.). (Meth) of lactone-modified polyester diol consisting of (meth)acrylate, diol compound, dibasic acid and ε-caprolactone
acrylate etc.

Polycarbonate (meth)acrylate, e.g.

Examples include (meth)acrylate of polycarbonate diol containing 1,6-hexanediol as a diol component. The preferred ethylenically unsaturated compound is 1
For example, acryloylmorpholine, hydrogenated dicyclopentadiene acrylate, inbornyl acrylate, triacrylate of tris(2-hydroxyethyl)in cyanuric acid.

Examples include polycarbonate acrylate, polyurethane acrylate, and epoxy acrylate. The above-mentioned ethylenically unsaturated compounds may be used alone or in combination of two or more compounds in any proportion, if necessary.

The ethylenically unsaturated compound is 40 to 90% by weight in one composition.
It is preferable to use it in the range of 60 to 8 in the composition.
It is preferably used in a range of 5% by weight. These ethylenically unsaturated compounds can be synthesized by known methods and are easily available on the market. The compositions of the present invention can also 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 isopropyl ether, 2,2-jethoxyacetophenone, 4'-phenococo-2,2-dichloroacetophenone, etc. of the acetophenone series, 2-hydroxy-2-methylpropiophenone, 4'-impropyl-2- and dooxy-2-methylpropiophenone.

Propiophenones such as 4'-dodecyl 2-hydroxy-2-methylpropiophenone, benzyl dimethyl ketal, 1-hydroxycyclosillphenyl ketone and 2-dithylanthraquinone.

Examples include anthraquinone-based photopolymerization initiators such as 2-chloroanthraquinone, and thioxanthone-based photopolymerization initiators. Particularly preferred examples include benzyl dimethyl ketal and 1-hydroxycyclohexylphenyl ketone. These photopolymerization initiators may be used alone or in a mixture of two or more in any proportion. Its usage is 1 normal.

0.1-10% by weight of the composition, preferably 1-5%
Weight%.

Modifying resins and various additives may be added to the coating agent of the present invention, if desired. Modifying resins include epoxy resins, polyurethane, polybutadiene, polyethers, polyamideimide silicone resins, phenol resins, etc. Can be done. The amount of the modifying resin used is preferably in the range of 0 to 10% by weight in the composition, and
Preferably, 5% by weight is used. Also, as the above additives.

pyrutrimethoxysilane, vinyltriacetoxysilane, etc.), surfactants (e.g. BH- manufactured by Toshi Silicon C Co., Ltd.)
3749, etc.) 1 polymerization inhibitors (for example, methoquinone, methylhydroquinone, etc.). The organosilicon compound is used in the range of 0 to 3% by weight in the coating agent, the surfactant is used in the range of 0 to 5% by weight in the coating agent, and the polymerization inhibitor is used in the range of 0 to 1% by weight in the composition. is preferable.

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 with the coating agent for optical glass fiber of the present invention, the optical glass base material is drawn at a speed of 1 to 7 seconds, for example, and then coated with the primary coating agent, and then irradiated with ultraviolet rays. Once cured, the coating agent of the present invention is then applied as a top coating agent over the primary coat, preferably at 20%
Coat with a thickness of ~300μ.

The coating agent of the present invention is easily cured by ultraviolet irradiation. The coating agent of the present invention can be cured by ultraviolet irradiation using a conventional method.

For example, ultraviolet rays may be irradiated using a low-pressure or high-pressure mercury lamp or a xenon lamp.

(Example) The present invention will be specifically explained below using examples.

Note that each part in the examples is 1 part by weight.

[Example of synthesis of ethylenically unsaturated compounds]

Synthesis Example 1 [Epoxy acrylate] Bisphenol A-based epoxy resin with an epoxy equivalent of 187 (manufactured by Shell Chemical Co., Ltd., Epicoat 828) 9 was used in a reactor equipped with a stirrer, a temperature controller, a thermometer, and a condenser.
59 parts, 362 parts of acrylic acid.

Add 4.7 parts of dimethylbenzylamine and 0.7 parts of methoquinone and react at 95°C for 15 hours to obtain an acid value of 1.519 KO.
Obtain H/f epoxy acrylate.

Viscosity (50°C) 255F Synthesis Example 2 [Polyurethane acrylate] In the same reactor as Synthesis Example 1, polytetramethylene diisocyanate)
! 555.6 parts of 2-hydroxyethyl acrylate, 0.5 parts of methoquinone,
0.2 part of di-n-butyltin dilaurate was charged, and after raising the temperature, the reaction was carried out at 75 to 80°C. The reaction was continued until completion as indicated by approximately 0.1% or less free incyanate groups. The product has the following properties.

Viscosity (60℃) 960P Synthesis Example 3 [Polyester acrylate] After stirring, polyester polyol, which is a reaction product of neopentyl glycol, adipic acid, and e-caprolactone, was placed in a reactor equipped with a temperature controller, a thermometer, and a condenser. (Manufactured by Daicel Chemical Industries, Ltd., Plaxel L-220AL, molecular weight approximately 20
00°011 value 57.5) 720 parts, acrylic acid 78 parts.

0.0 parts, 3201 m of benzene, and 80 parts of cyclohexane were charged, heated, and reacted until the amount of water produced was 12.9 parts, and then cooled. The reaction temperature was 82-86°C.

The reaction mixture was mixed with 1280 parts of benzene and 3 parts of cyclohexane.
After dissolving in 20 parts and neutralizing with 20% caustic soda aqueous solution, the mixture was washed three times with 500 parts of 20% saline. The solvent was distilled off under reduced pressure to obtain 610 parts of a pale yellow liquid.

This material has the following properties.

Viscosity (25℃) 40 p acid
Value (ηKOH/7) 0.0 1111i
Synthesis Example 4 [Polycarbonate acrylate] In the same reactor as in Synthesis Example 1, a compound of the following structural formula (manufactured by Nippon Polyurethane Co., Ltd., DI-981, OH value 112.
2~KOH/f, average molecular weight 100G), 700 parts of acrylic acid, 121 parts of p-toluenesulfonic acid, 1.0 part of hydrocarbon, 560 parts of benzene, and 140 parts of cyclohexane.

By heating, the produced water is distilled and condensed together with the solvent, and only the water is removed from the system in a separator, and the solvent is returned to the reactor.

It was cooled when 25.2 parts of water had been produced. The reaction temperature is 8
The temperature was 0-86°C. The reaction mixture was dissolved in 960 parts of benzene and 240 parts of cyclohexane, neutralized with 20% caustic Nogoo aqueous solution, and washed three times with 500 parts of 20% brine. The solvent was distilled off under reduced pressure to obtain 667 parts of a pale yellow solid. This thing.

It has the following properties.

Melting point 43℃ Acid value 0.0 21qKOH/f urethane (
Examples of meth)acrylate mixtures Example 1 Compound (a) (manufactured by Hüls Co., Ltd., Engineering PD Knee T1890) + 14, which was prepared by the following structural formula into a 2-ton reactor.
7.5 parts, 500 parts of acryloylmorpholine.

Prepared and heated and melted at 90-95℃, Metokino 70.9
55% of hydroxyethyl acrylate)
2.5 parts were added dropwise while maintaining the reaction temperature at 75-80 DEG C. and the reaction was continued until completion as indicated by about 0.1 or less free incyanate groups. A urethane acrylate mixture containing 15 units of acryloylmorpholine was obtained. It was a pale yellow transparent solid at room temperature.

Example 2 Reactor VC1 1104 parts of the compound (a) used in Example 1 (manufactured by Hüls Co., Ltd., Engineering PD Knee T1890),
300 parts of hydrogenated dicyclopentadiene acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513A) was charged at 90 to 95°C.
1.0 parts of methoquinone was added to 1 and 2-
595.4 parts of hydroxypropyl acrylate was added dropwise while maintaining the reaction temperature at 75 to 80°C, and the reaction was continued in the same manner as in Example 1. A urethane acrylate mixture containing 15% of hydrogenated dicyclopentadiene acrylate was obtained. It was a pale yellow transparent solid at room temperature.

Example 3 In Example 1, 2-hydroxyethyl acrylate) 5
52.5 parts of 2-hydroxyethyl methacrylate) 59
The reaction was carried out in the same manner as in Example 1 except that the amount was changed to 5.4 parts.

A urethane methacrylate mixture containing 7% of acryloylmorpholine 1a was obtained. It was a pale yellow transparent solid at room temperature.

Example 4 In Example 1, 2- and droxyethyl acrylate) 55
The same procedure was carried out except that 2.5 parts of e-caprolactone-β-hydroxyethyl acrylate adduct (manufactured by Daicel Chemical Industries, Ltd., Plaxel FA-2) was changed to 410 parts and 289.2 parts of 2-hydroxyethyl acrylate. The reaction was carried out in the same manner as in Example 1.

A urethane acrylate mixture containing 14 units of acryloylmorpholine was obtained. It was a pale yellow transparent solid at room temperature.

[Example of coating agent]

Example 5 30 parts of the urethane acrylate mixture obtained in Example 1 1 Polycarbonate cyacrylate obtained in Example 4 L/-) 4
Part a, triacrylate of tris(2-hydroxyethyl)isocyanuric acid (manufactured by Hitachi Chemical Co., Ltd., FA-73
1A) 15 parts, 10 parts of acryloylmorpholine and 1-
Hydroxycyclohexylphenylketone (Ciba Geigy C), Irgacure 184. photopolymerization initiator)
Coating agent A was prepared by mixing 3 parts of methyl hydroquinone and 0.01 part of methyl hydroquinone. Table 1 shows the properties of the cured product.

Example 6 20 parts of the urethane acrylate mixture obtained in Example 2 (1) 5 parts of the polyurethane acrylate obtained in Example 2, hydrogenated dicyclopentadiene acrylate (Hitachi Chemical Co., Ltd.)
Co., Ltd., FA-513A) 25 parts.

Coating agent B was prepared by mixing 20 parts of inbornyl acrylate, 5 parts of 1-hydroxycyclohexylphenyl ketone, and 0.01 part of methyl hydroquinone. Table 1 shows the properties of the cured product.

Example 7 5 parts of the urethane methacrylate mixture obtained in Example 3, 10 parts of the urethane acrylate mixture obtained in Example 1, 4 s m of the epoxy acrylate obtained in Synthesis Example 1, water 'fA
25 parts of dicyclopentadiene acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513A), 1 part of acryloylmorpholine
Coating agent C was prepared by mixing 5 parts of benzyl dimethyl ketal (Irgacure-651, photopolymerization initiator, manufactured by Chipaken Geigy Co., Ltd.), and 0.01 part of methyl hydroquinone. Table 1 shows the properties of the cured product.

Example 8 50 parts of the urethane acrylate mixture obtained in Example 4 1 30 parts of the polyester acrylate obtained in Synthesis Example 3, 20 parts of acryloylmorpholine and 3 parts of 1-hydroxycyclohexylphenyl ketone.

A coating agent was prepared by mixing 0.01 part of methyl hydroquinone. Table 1 shows the properties of the cured product.

Comparative Example 1 Coating agent E was prepared in the same manner as in Example 5, except that the urethane acrylate mixture obtained in Example 1 was changed to all N-vinylpyrrolidone. Table 1 shows the properties of the cured product.

Table 1 In Table 1 above.

[Breaking strength: Kg/rum2. Elongation at break: %, Young's modulus +? /Dragon 2] measurement + A, B, C, D
The compositions of and E were prepared using a high pressure mercury lamp (lamp output 2
KW) was irradiated at a position 8 cIn below the light source arranged in parallel (conveyor speed 20 m/min) to produce a sort with a thickness of 250 μm, and this was used for measurement.

Measurement of [Water Absorption]: A test piece was prepared under the same conditions as those used for measuring the breaking strength, etc. described above.

Using this, the sample was immersed in pure water at 20° C. for 24 hours, and its weight and amount were measured before and after the test, and the increase in weight due to water absorption was expressed as .

Example 9 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/sec. In the next successive step, the primary is coated with a coating agent (a mixture of 50% polyurethane acrylate, 45% monoacrylate of 1 mole adduct of tetrahydrofurfuryl alcohol OE - caprolactone, and 5% photopolymerization initiator) by die coating method. It was then cured by irradiating it with ultraviolet light. Next, the resulting primary-coated optical glass fibers were top-coated with the resin compositions A and D of Examples 5 to 8, respectively, and then cured by irradiation with ultraviolet rays from a high-pressure mercury lamp. In the obtained coated optical glass fiber, no change in transmission loss was observed up to %-60°C even when top coated with any of the resin compositions A to D.

(Effects of the Invention) The coating agent of the present invention has a fast curing speed (the resulting cured film has a small decrease in Young's modulus at high temperatures, a small water absorption rate, and good alkali resistance).

The hardness of the cured film is high, and 4? is used as the top coating for optical glass fibers for light transmission. suitable for

Claims (3)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, each R represents an alkyl group having 1 to 4 carbon atoms.) Compound (a) and hydroxy (meth)acrylate compound (b) A urethane (meth)acrylate mixture that is a reaction product. (2) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, each R represents an alkyl group having 1 to 4 carbon atoms.) Compound (a) and hydroxy (meth)acrylate compound (b) A resin composition comprising a urethane (meth)acrylate mixture as a reaction product. (3) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, each R represents an alkyl group having 1 to 4 carbon atoms.) Compound (a) and hydroxy (meth)acrylate compound (b) A coating agent for optical glass fiber characterized by containing a urethane (meth)acrylate mixture as a reaction product.