CN102174288A - Optical fiber outer paint composite and preparation method thereof - Google Patents

Abstract

The invention provides an optical fiber outer paint composite. The composite comprises the following components in parts by weight: 28-57 parts of first light-cured resin, 36-78 parts of second light-cured resin, 0.8-1.6 parts of antioxidant, 0.1-0.3 part of ultraviolet light absorbent, 1.5-3.2 parts of photoinitiator, 0.6-1.8 parts of water-based wetting agent, 0.3-1.4 parts of water-based leveling agent and 0.2-1.1 parts of water-based defoaming agent, wherein the first light-cured resin has a structure shown in the formula I and the second light-cured resin has a structure shown in the formula II. Active diluent is not added in the optical fiber outer paint composite provided by the invention and water-based light-cured resin is used as a main raw material, thus no pollution on the environment and operating personnel is caused; and the composite has the advantages of good mechanical strength and thermal stability. The invention also provides a preparation method of the optical fiber outer paint composite.

Description

A kind of optical fiber outer layer coating composition and preparation method thereof

technical field

The invention relates to the field of coatings, and more particularly to an optical fiber outer layer coating composition and a preparation method thereof.

Background technique

With the rapid development of optical fiber communication technology, the amount of optical fiber coating composition used as optical fiber protection is increasing, and related technologies and researches are also increasing. Optical fiber coating compositions are generally divided into two types of coatings, one is the inner coating, which provides certain flexibility and low temperature resistance to the optical fiber, and the other is the outer coating, which brings good mechanical properties and resistance to the optical fiber. Hydrolyzable, protect the optical fiber from external environmental damage. The outer coating of optical fiber requires high modulus, high glass transition temperature, good water resistance and heat resistance.

There are three kinds of resins currently used to prepare optical fiber outer layer coatings. The first category is Chinese patent ZL02825387.6, Chinese patent ZL 03130687. U.S. Patent US6668122B2 discloses polyurethane acrylic resin optical fiber outer coating; the second is epoxy acrylate optical fiber outer coating disclosed in US Patent US6362249B2; the third is Chinese Patent 200810082777.1, Chinese Patent ZL00819203.0, and Chinese Patent 90102226.8 , Chinese patent ZL03130687.X, Chinese patent ZL03109931.9, U.S. patent US5837750, U.S. patent US5847021, U.S. patent US6472450B2 disclosed urethane acrylate and epoxy acrylate blend class optical fiber outer layer coating; the water resistance of optical fiber outer layer coating On the issue of improving performance and thermal stability, US Patent US5199098 uses aliphatic isocyanate cyclic trimer, non-polar aliphatic polymer diol and hydroxy acrylate to prepare the outer layer of optical fiber coating, which has good water resistance and thermal stability. Good performance; US Patent US5891930 introduces siloxane structure into epoxy acrylate, which improves the water resistance and good thermal stability of the paint film.

At present, the optical fiber outer coating compositions reported in the prior art are all solvent-based UV-curable coatings. In order to reduce the viscosity of the resin, a reactive diluent is usually added to the coating composition. The reactive diluent is acrylic monolayer body, will harm the body of paint preparation operators and bring huge pollution to the environment, and will also pollute the environment; although the addition of reactive diluents reduces the viscosity of the resin, its cost is relatively high, which increases the cost of the paint; The reactive diluent is a small molecular compound, although it participates in the resin photocuring film formation, but because the molecular weight is too small, it will cause serious shrinkage of the paint film, resulting in increased internal stress. With the requirement of environmental protection, the preparation of water-based optical fiber outer layer coating composition without active diluent monomer is a development trend, however, there are no reports of such coatings in all patents and literatures at present.

Contents of the invention

The technical problem to be solved by the present invention is to provide an optical fiber outer coating composition and a preparation method thereof, which does not contain active diluents, does not cause any pollution to the environment and operators, and has good mechanical strength and thermal stability.

In order to solve the problems referred to above, the invention provides a kind of optical fiber coating composition, by weight parts, comprising:

28 to 57 parts of the first photocurable resin; 36 to 78 parts of the second photocurable resin; 0.8 to 1.6 parts of antioxidant; 0.1 to 0.3 parts of ultraviolet light absorber; 1.5 to 3.2 parts of photoinitiator; ～1.8 parts; 0.3～1.4 parts of water-based leveling agent; 0.2-1.1 parts of water-based defoamer; the first photocurable resin has the structure shown in formula I:

Wherein _R1 is an acrylate group; _R2 is a diisocyanate cyclic trimer group; _R3 is a polymer diol group; n is the degree of polymerization, 1≤n≤50;

The second photocurable resin has a structure shown in formula II:

Among them, R ₁ is an acrylate group; R ₄ is a diisocyanate group with a ring structure; R ₅ is a methyl group, a butyl group; R ₆ is a tertiary amino group; m is the degree of polymerization, 1≤n≤20.

Preferably, the antioxidant is selected from phenolic antioxidants; the ultraviolet absorber is selected from benzophenones and benzotriazole ultraviolet absorbers.

Preferably, the photoinitiator is selected from one or more mixtures of α-hydroxy ketones or acyl phosphorus oxide radical photoinitiators; the water-based wetting agent is polyether modified polydimethylsilane Oxygen type wetting agent.

Preferably, the water-based leveling agent is selected from ionic acrylic copolymers and polyether-modified polydimethylsiloxane-type leveling agents; the water-based defoamer is a silicone-type defoamer.

The present invention also provides a preparation method of an optical fiber outer layer coating composition, comprising:

In parts by weight, 28 to 57 parts of the first photocurable resin; 36 to 78 parts of the second photocurable resin; 0.8 to 1.6 parts of antioxidant; 0.1 to 0.3 parts of ultraviolet light absorber; 1.5 to 3.2 parts of photoinitiator ; 0.6-1.8 parts of water-based wetting agent; 0.3-1.4 parts of water-based leveling agent; 0.2-1.1 parts of water-based defoamer are mixed, and stirred at 1000rpm-1200rpm for 15-20min to obtain an optical fiber outer layer coating composition;

The first photocurable resin is shown in formula I, and the second photocurable resin is shown in formula II; wherein R ₁ is an acrylate group; R ₂ is a diisocyanate cyclic trimer group; R ₃ is a polymer two Alcohol group; n is the degree of polymerization, 1≤n≤50; R ₁ is an acrylate group; R ₄ is a diisocyanate group with a ring structure; R ₅ is a methyl, butyl group; R ₆ is a tertiary amino group ; m is the degree of polymerization, 1≤n≤20.

Preferably, the preparation method of the first photocurable resin includes:

a1) Under the protection of nitrogen, mix polyethylene glycol monomethyl ether and diisocyanate cyclic trimer, heat and stir at 60-65°C for 2-3 hours, and obtain the first intermediate product;

b1) at 70-75°C, mix the first intermediate product, organic solvent, hydroxyacrylate and polymerization inhibitor, and keep warm for 2-3 hours to obtain the second intermediate product;

c1) At 80-85°C, mix the polymer diol with the second intermediate product, react for 2-3 hours, add 78-261mol deionized water, stir for 30min, and remove the organic solvent under reduced pressure to obtain a solid content of 48 - 55% by weight of the first photocurable resin.

Preferably, the diisocyanate cyclic trimer is 2,4-toluene diisocyanate cyclic trimer, 4,4'-diphenylmethane diisocyanate cyclic trimer, 3,3'-diisocyanate Methyl-4,4'-diphenylmethane diisocyanate cyclic trimer, 1,6-methylene diisocyanate cyclic trimer or isophorone diisocyanate cyclic trimer; said polymer The diol is polyether diol, polyester diol, polycarbonate diol or polycaprolactone diol with a number average molecular weight of 1000-8000 Daltons.

Preferably, the preparation method of the second photocurable resin includes:

a2) Under nitrogen protection, at 65-80°C, mix cyclic diisocyanate, dibasic hydroxy acid, and cyclic polymer diol, and keep warm for 3-5 hours to obtain a third intermediate product;

b2) at 75-85°C, adding an organic solvent, hydroxy acrylate and a polymerization inhibitor to the third intermediate product, and keeping the reaction for 2 hours to obtain the fourth intermediate product;

c2) Cool the fourth intermediate product to 45-50°C, add a neutralizing agent therein, stir for 10 minutes, add 73-159 mol of deionized water, stir for 40 minutes, and remove the organic solvent under reduced pressure to obtain a solid content of 43- 54 wt% of the second photocurable resin.

Preferably, the organic solvent is acetone or butanone; the hydroxy acrylate is hydroxyethyl acrylate, pentaerythritol triacrylate or trimethylolpropane diacrylate; the polymerization inhibitor is p-hydroxyanisole or Quinol.

Preferably, the dibasic hydroxy acid is dimethylol propionic acid or dimethylol butyric acid; the cyclic diisocyanate is isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,4-cyclohexyl diisocyanate, 2,4-toluene diisocyanate or 4,4'-diphenylmethane diisocyanate; the neutralizer is triethylamine, N,N-dimethylethanolamine or triethanolamine; The cyclic polymer diol is epoxy resin E54, E41 or E21.

The invention provides an optical fiber outer layer coating composition, comprising: 28-57 parts of the first photocurable resin; 36-78 parts of the second photocurable resin; 0.8-1.6 parts of antioxidant; 0.1-0.3 parts of ultraviolet absorber 1.5-3.2 parts of photoinitiator; 0.6-1.8 parts of water-based wetting agent; 0.3-1.4 parts of water-based leveling agent; 0.2-1.1 parts of water-based defoamer; The cured resin can be dissolved in water-soluble solvents, and does not require reactive diluents to dilute the concentration of the reaction system, which reduces the harm of coatings to the external environment, protects the environment and reduces the physical hazards of reactive diluents to construction workers. Moreover, it is proved by experimental results that the glass transition temperature, elasticity and elastic modulus of the optical fiber outer layer coating composition provided by the invention all meet the use requirements, and the thermal stability and mechanical properties are all improved.

The present invention also provides a preparation method of an optical fiber outer coating composition, comprising 28 to 57 parts of the first photocurable resin; 36 to 78 parts of the second photocurable resin; 0.8 to 1.6 parts of an antioxidant; and an ultraviolet absorber 0.1-0.3 parts; 1.5-3.2 parts of photoinitiator; 0.6-1.8 parts of water-based wetting agent; 0.3-1.4 parts of water-based leveling agent; to obtain the optical fiber outer layer coating composition; the preparation method provided by the invention is simple and easy, does not require special production equipment, reduces costs, and is suitable for large-scale industrial production.

Description of drawings

The first photocurable resin nuclear magnetic resonance collection spectrum prepared by Fig. 1 embodiment 1 of the present invention;

Fig. 2 is the nuclear magnetic resonance spectrum of the second photocurable resin prepared in Example 4 of the present invention.

Detailed ways

In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with the examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention rather than limiting the patent requirements of the present invention.

Aiming at the problems existing in the prior art, the technical scheme provided by the present invention is as follows: a water-based UV-curable coating that can be used as an optical fiber outer coating and a preparation method thereof, and its composition and parts by weight are as follows: 28-57 parts by weight such as The first photocurable resin shown in formula I, 36-78 parts by weight of the second photocurable resin shown in formula II, 0.8-1.6 parts by weight antioxidant, 0.1-0.3 parts by weight UV absorber, 1.5-3.2 parts by weight Parts of photoinitiator, 0.6-1.8 parts by weight of water-based wetting agent, 0.3-1.4 parts by weight of water-based leveling agent, and 0.2-1.1 parts by weight of water-based defoamer.

The first photocurable resin is a nonionic water-based polyurethane acrylate resin, and its structural formula is as follows:

Wherein, R ₁ is an acrylate group;

R ₂ is a diisocyanate cyclic trimer group;

R ₃ is a polymer glycol group;

n is the degree of polymerization, 1≤n≤50.

According to the present invention, the preparation of the first photocurable resin is as follows: a1) Under the protection of nitrogen, mix polyethylene glycol monomethyl ether and diisocyanate cyclic trimer, heat and stir at 60-65°C for 2-3 hour, obtain the first intermediate product;

b1) at 70-75°C, mix the first intermediate product, organic solvent, hydroxyacrylate and polymerization inhibitor, and keep warm for 2-3 hours to obtain the second intermediate product;

c1) At 80-85°C, mix the polymer diol with the second intermediate product, react for 2-3 hours, add 78-261mol deionized water, stir for 30min, and remove the organic solvent under reduced pressure to obtain a solid content of 48 - 55% by weight of the first photocurable resin.

The molar ratio of the polyethylene glycol monomethyl ether to the diisocyanate cyclic trimer is preferably 1 to 2: 4 to 5; the molar ratio of the organic solvent to the hydroxy acrylate is 2: 1; the polymerization inhibitor The additive amount of the agent is 0.0001-0.001 mol, and the molar ratio of the polymer diol to polyethylene glycol monomethyl ether is 1-1.5:0.5-1. The polyethylene glycol monomethyl ether according to the present invention preferably has a molecular weight of 76-2000 Daltons. Among the diisocyanate cyclic trimers are 2,4-toluene diisocyanate cyclic trimer, 4,4'-diphenylmethane diisocyanate cyclic trimer, 3,3'-dimethyl- 4,4'-Diphenylmethane diisocyanate cyclic trimer, 1,6-methylene diisocyanate cyclic trimer, isophorone diisocyanate cyclic trimer. The polymer diols are polyether diols, polyester diols, polycarbonate diols, and polycaprolactone diols with a number average molecular weight of 1000-8000 Daltons. things. Preferred are polypropylene glycol, polyethylene adipate diol, polybutylene succinate diol and polybutylene oxalate diol with a number average molecular weight of 1000-3000 Daltons.

According to the present invention, the organic solvent is preferably butanone and acetone. The hydroxy acrylate is preferably hydroxyethyl acrylate, pentaerythritol triacrylate, trimethylol propane diacrylate. Described polymerization inhibitor is preferably p-hydroxyanisole, hydroquinone.

The second photocurable resin is anionic water-based polyurethane acrylate resin, and its structural formula is as follows:

Wherein, R ₁ is an acrylate group;

R ₄ is a diisocyanate group with a ring structure;

R ₅ is methyl, butyl;

R ₆ is a tertiary amino group;

m is the degree of polymerization, 1≤n≤20.

The second photocurable resin is anionic water-based urethane acrylate, and the preparation of the second photocurable resin is as follows: a2) Under nitrogen protection, at 65-80°C, cyclic diisocyanate, dibasic hydroxy acid, cyclic The polymer diol is mixed, and the heat preservation reaction is carried out for 3-5 hours to obtain the third intermediate product;

b2) at 75-85°C, adding an organic solvent, hydroxy acrylate and a polymerization inhibitor to the third intermediate product, and keeping the reaction for 2 hours to obtain the fourth intermediate product;

c2) Cool the fourth intermediate product to 45-50°C, add a neutralizing agent therein, stir for 10 minutes, add 73-159 mol of deionized water, stir for 40 minutes, and remove the organic solvent under reduced pressure to obtain a solid content of 43- 54 wt% of the second photocurable resin.

According to the present invention, the diisocyanate having a cyclic structure, the dibasic hydroxy acid and the cyclic polymer diol are in a molar ratio of 3-4:1.5-2.5:0.5-1. The molar ratio of the third intermediate product, organic solvent, and hydroxyacrylate is 1:2˜4:1˜2; the molar ratio of the polymerization inhibitor and the third intermediate product is 0.0001˜0.0005:1. The molar ratio of the pH neutralizer to the fourth intermediate product is 1-2:1.

According to the present invention, the dibasic hydroxy acid is preferably dimethylol propionic acid, dimethylol butyric acid. As the diol containing ring structure, it is preferable to use all diol compounds containing ring structure in the molecular chain, preferably to use epoxy resin E54, E41 or E21.

Described cyclic diisocyanate is aliphatic and aromatic diisocyanate containing cyclic structure, there is no limitation to the cyclic structure in molecular chain, preferably isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate ), 1,4-cyclohexyl diisocyanate, 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate. The pH neutralizer is preferably an amine compound, more preferably triethylamine, N,N-dimethylethanolamine, triethanolamine. The organic solvent is preferably butanone or acetone. The hydroxy acrylate is preferably hydroxyethyl acrylate, pentaerythritol triacrylate, trimethylolpropane diacrylate. The polymerization inhibitor is preferably p-hydroxyanisole, hydroquinone.

The invention also discloses a preparation method of an optical fiber outer layer coating composition, comprising:

First prepare the first photocurable resin and the second photocurable resin, and prepare 28 to 57 parts of the first photocurable resin in parts by weight; 36 to 78 parts of the second photocurable resin; 0.8 to 1.6 parts of antioxidant; 0.1-0.3 parts of absorbent; 1.5-3.2 parts of photoinitiator; 0.6-1.8 parts of water-based wetting agent; 0.3-1.4 parts of water-based leveling agent; ～20min, to obtain the optical fiber water-based outer coating;

The antioxidant phenolic antioxidant, the ultraviolet light absorber is benzophenones, benzotriazole ultraviolet light absorbers, and the photoinitiator is α-hydroxy ketones or acyl phosphorus oxidation One or more mixtures of free radical photoinitiators, the water-based wetting agent is a polyether-modified polydimethylsiloxane-type wetting agent, and the water-based defoamer is selected from organosilicon-type defoamers The foaming agent and the water-based leveling agent are selected from ionic acrylic copolymers and polyether modified polydimethylsiloxane type leveling agents.

The scheme of the present invention will be set forth below with specific examples.

Example 1

The light-curable resin was prepared according to the molar ratio of raw materials and deionized water shown in Example 1 in Table 1. Under the protection of nitrogen, add 1.5 mol of polyethylene glycol monomethyl ether to the diisocyanate cyclic trimer with an isocyanate content of 4.2 mol at 65°C, keep stirring and react for 2.5 hours to obtain the first intermediate product; heat up to 70°C , add 2 mol of organic solvent, 1 mol of hydroxy acrylate and 0.0005 mol of polymerization inhibitor to the first intermediate product, keep the reaction for 2 hours to obtain the second intermediate product; raise the temperature to 80°C, add 0.9 mol of polymer binary Alcohol, keep warm for 2.5 hours, add 78mol of deionized water, stir for 30min, remove the organic solvent under reduced pressure, and obtain the photocurable resin represented by formula I with 55% solid content.

The photocurable resin prepared in Example 1 was characterized by nuclear magnetic resonance, and its hydrogen spectrum is as follows: ¹ H NMR: 0.91ppm, 1.10ppm, 1.32ppm, 1.56ppm, 1.73ppm, 2.02ppm, 2.29ppm, 3.09ppm, 3.35ppm, 3.52ppm, 3.62ppm, 3.81ppm, 4.04ppm, 4.28ppm, 4.84ppm, 5.85ppm, 6.16ppm, 6.38ppm, 7.04ppm, 7.24ppm ( _CDCl3 ).

Example 2

The light-curable resin was prepared according to the molar ratio of raw materials and deionized water shown in Example 2 in Table 1. Under the protection of nitrogen, add 1.5 mol of polyethylene glycol monomethyl ether to the diisocyanate cyclic trimer with an isocyanate content of 4.2 mol at 65°C, keep stirring and react for 2.5 hours to obtain the first intermediate product; heat up to 70°C , add 2 mol of organic solvent, 1 mol of hydroxy acrylate and 0.0005 mol of polymerization inhibitor to the first intermediate product, keep the reaction for 2 hours to obtain the second intermediate product; raise the temperature to 80°C, add 0.9 mol of polymer binary Alcohol, keep warm for 2.5 hours, add 261mol of deionized water, stir for 30min, remove the organic solvent under reduced pressure, and obtain the photocurable resin represented by formula I with a solid content of 51wt%.

The photocurable resin prepared in Example 2 was characterized by nuclear magnetic resonance, and its hydrogen spectrum is as follows: ¹ H NMR: 1.11ppm, 1.40ppm, 1.71ppm, 1.93ppm, 2.52ppm, 2.62ppm, 3.20ppm, 3.24ppm, 3.54ppm, 3.65ppm, 4.25ppm, 4.36ppm, 4.43ppm, 5.58ppm, 6.15ppm.

Example 3

The light-curable resin was prepared according to the molar ratio of raw materials and deionized water shown in Example 3 in Table 1. Under the protection of nitrogen, add 1.5 mol of polyethylene glycol monomethyl ether to the diisocyanate cyclic trimer with an isocyanate content of 4.2 mol at 65°C, keep stirring and react for 2.5 hours to obtain the first intermediate product; heat up to 70°C , add 2 mol of organic solvent, 1 mol of hydroxy acrylate and 0.0005 mol of polymerization inhibitor to the first intermediate product, keep the reaction for 2 hours to obtain the second intermediate product; raise the temperature to 80°C, add 0.9 mol of polymer binary Alcohol, keep warm for 2.5 hours, add 177mol of deionized water, stir for 30min, remove the organic solvent under reduced pressure, and obtain the photocurable resin represented by formula I with a solid content of 48wt%.

The photocurable resin prepared in Example 3 was characterized by nuclear magnetic resonance, and its hydrogen spectrum is as follows: ¹ H NMR: 1.56ppm, 2.35ppm, 3.26ppm, 3.65ppm, 3.98ppm, 4.08ppm, 4.16ppm, 4.25ppm, 5.80ppm, 6.07ppm, 6.45ppm, 7.43ppm, 7.47ppm.

Example 4

According to the raw materials shown in Example 4 in Table 1 and the composition ratio of deionized water to prepare a photocurable resin, under the protection of nitrogen, 3.5 mol of diisocyanate with a ring structure was added to 2 mol of hydrophilic diisocyanate at 65 ° C. In the polyalcohol compound and 0.6mol polymer diol containing a ring structure, heat preservation reaction for 3-5 hours to obtain the first intermediate product; keep the temperature at 75°C, and add 3mol organic solvent to the first intermediate product , 2 mol of hydroxyacrylate and 0.0004 mol of polymerization inhibitor, keep warm for 2 hours, cool down to 45°C, add 1.6 mol of pH neutralizer, stir for 10 minutes, add 73 mol of deionized water, stir for 40 minutes, remove the organic solvent under reduced pressure , to obtain a photocurable resin represented by formula II with a solid content of 54 wt%.

The photocurable resin prepared in Example 4 was characterized by nuclear magnetic resonance, and its hydrogen spectrum is as follows: ¹ H NMR: 1.04ppm, 1.23ppm, 1.61ppm, 2.12ppm, 2.45ppm, 2.71ppm, 2.89ppm, 3.31ppm, 3.94ppm, 4.17ppm, 4.40ppm, 5.84ppm, 6.19ppm, 6.41ppm, 6.78ppm, 7.10ppm, 7.25ppm (CDCl3).

Example 5

According to the raw materials shown in Example 5 in Table 1 and the composition ratio of deionized water to prepare a photocurable resin, under the protection of nitrogen, 3.5 mol of diisocyanate with a ring structure was added to 2 mol of hydrophilic diisocyanate at 70 ° C. In the polyalcohol compound and 0.6mol polymer diol containing ring structure, heat preservation reaction for 3-5 hours to obtain the first intermediate product; keep the temperature at 80°C, add 3mol organic solvent to the first intermediate product , 2 mol of hydroxyacrylate and 0.0004 mol of polymerization inhibitor, keep warm for 2 hours, cool down to 50°C, add 1.6 mol of pH neutralizer, stir for 10 minutes, add 131 mol of deionized water, stir for 40 minutes, remove the organic solvent under reduced pressure , to obtain a photocurable resin represented by formula II with a solid content of 48 wt%.

The photocurable resin prepared in Example 5 was characterized by nuclear magnetic resonance, and its hydrogen spectrum is as follows: ¹ H NMR: 1.11ppm, 1.16ppm, 1.69ppm, 2.58ppm, 2.76ppm, 2.80ppm, 3.54ppm, 3.95ppm, 4.07ppm, 4.22ppm, 4.47ppm, 5.82ppm, 6.43ppm, 6.05ppm, 6.69ppm, 7.02ppm.

Example 6

According to the raw materials shown in Example 6 in Table 1 and the composition ratio of deionized water to prepare a photocurable resin, under the protection of nitrogen, 3.5 mol of diisocyanate with a ring structure was added to 2 mol of hydrophilic diisocyanate at 85 ° C. In the polyalcohol compound and 0.6mol polymer diol containing a ring structure, heat preservation reaction for 3-5 hours to obtain the first intermediate product; keep the temperature at 85°C, add 3mol organic solvent to the first intermediate product , 2 mol of hydroxyacrylate and 0.0004 mol of polymerization inhibitor, keep warm for 2 hours, cool down to 55°C, add 1.6 mol of pH neutralizer, stir for 10 minutes, add 159 mol of deionized water, stir for 40 minutes, remove the organic solvent under reduced pressure , to obtain a photocurable resin represented by formula II with a solid content of 43 wt%.

The photocurable resin prepared in Example 6 was characterized by nuclear magnetic resonance, and its hydrogen spectrum is as follows: ¹ H NMR: 1.14ppm, 1.21ppm, 1.67ppm, 2.48ppm, 2.74ppm, 2.85ppm, 3.30ppm, 3.81ppm, 3.96ppm, 4.12ppm, 4.43ppm, 5.81ppm, 6.23ppm, 6.72ppm, 7.06ppm, 7.15ppm.

Example 7

According to the components and proportions thereof shown in Example 7 in Table 2, weigh the photocurable resin shown in Formula I prepared in Example 1, the photocurable resin shown in Formula II in Example 4, antioxidant, ultraviolet The light absorber, photoinitiator, water-based wetting agent, water-based leveling agent and water-based defoamer were added into a high-speed mixer, and stirred at 1000 rpm for 15 minutes to obtain an optical fiber outer layer coating composition.

Detect the optical fiber outer coating composition prepared in Example 7,

Adhesion test: test according to GB/T 9286-1998.

Glass transition temperature Tg test: Take 10 mg of the optical fiber outer layer coating composition obtained after photocuring, and raise the temperature of the sample from room temperature to 200°C at a rate of 10°C/min in a high-purity nitrogen atmosphere.

Elasticity and elastic modulus test: The optical fiber outer layer coating composition sample obtained after photocuring is pressed into a 1mm thick sample on a flat vulcanizer, and a dumbbell-shaped sample is cut into a dumbbell-shaped sample with a parallel part length of 25mm and a width of 4mm. The property tests were then carried out at 20°C with a tensile rate of 50mm/min.

Test results: the coating has good adhesion to the inner layer of the optical fiber, the glass transition temperature Tg is 130°C, the elastic modulus is 3MPa, and the elasticity is 120%; the test method:

Example 8

According to the components and proportions thereof shown in Example 8 in Table 2, weigh the photocurable resin shown in Formula I prepared in Example 2, the photocurable resin shown in Formula II in Example 5, antioxidant, ultraviolet The light absorber, photoinitiator, water-based wetting agent, water-based leveling agent and water-based defoamer were added into a high-speed mixer, and stirred at a speed of 1100 rpm for 20 minutes to obtain an optical fiber outer layer coating composition.

According to the method of Example 7, the optical fiber outer layer coating composition prepared in Example 8 was tested. The coating had good adhesion to the inner layer of the optical fiber, the glass transition temperature Tg was 140° C., the elastic modulus was 3.5 MPa, and the elasticity was 110%.

Example 9

According to the components and proportions thereof shown in Example 9 in Table 2, weigh the photocurable resin shown in Formula I prepared in Example 3, the photocurable resin shown in Formula II in Example 6, antioxidant, ultraviolet The light absorber, photoinitiator, water-based wetting agent, water-based leveling agent and water-based defoamer were added into a high-speed mixer, and stirred at a speed of 1200 rpm for 25 minutes to obtain an optical fiber outer layer coating composition.

According to the method of Example 7, the optical fiber outer layer coating composition prepared in Example 9 was tested. The coating has good adhesion to the inner layer of the optical fiber, the glass transition temperature Tg is 150° C., the elastic modulus is 4.2 MPa, and the elasticity is 130%.

Example 10

According to the components and proportions thereof shown in Example 10 in Table 2, weigh the photocurable resin shown in Formula I prepared in Example 2, the photocurable resin shown in Formula II in Example 6, antioxidant, ultraviolet The light absorber, photoinitiator, water-based wetting agent, water-based leveling agent and water-based defoamer were added into a high-speed mixer, and stirred at a speed of 1200 rpm for 25 minutes to obtain an optical fiber outer layer coating composition.

According to the method of Example 7, the optical fiber outer layer coating composition prepared in Example 10 was tested. The coating had good adhesion to the inner layer of the optical fiber, the glass transition temperature Tg was 145° C., the elastic modulus was 3.8 MPa, and the elasticity was 115%.

Example 11

According to the components shown in Example 11 in Table 2 and their proportioning ratio, weigh the photocurable resin shown in Formula I prepared in Example 1, the photocurable resin shown in Formula II in Example 4, antioxidant, ultraviolet The light absorber, photoinitiator, water-based wetting agent, water-based leveling agent and water-based defoamer were added into a high-speed mixer, and stirred at a speed of 1200 rpm for 25 minutes to obtain an optical fiber outer layer coating composition.

According to the method of Example 7, the optical fiber outer layer coating composition prepared in Example 10 was tested. The coating had good adhesion to the inner layer of the optical fiber, the glass transition temperature Tg was 105° C., the elastic modulus was 2.8 MPa, and the elasticity was 140%.

Table 1 The first photocurable resin prepared in Examples 1-3 and the second photocurable resin components prepared in Examples 4-6

Table 2 The components of the optical fiber outer layer coating composition prepared in Examples 7-11

Through the optical fiber outer layer coating composition prepared in Examples 7-Example 11, and its detection, the optical fiber outer layer coating composition prepared by the present invention, after curing, the elasticity and modulus of elasticity all meet the requirements for use, and the coating composition No active diluent is added to the product, which reduces the image of the construction personnel and the construction environment, and protects the health of the construction personnel.

Above, a kind of optical fiber outer layer coating composition provided by the present invention and its preparation method have been introduced in detail. In this paper, specific examples have been used to illustrate the principle and implementation of the present invention. The description of the above examples is only used to help Understanding the method of the present invention and its core idea, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made to the present invention, and these improvements and modifications also fall into the Into the scope of protection of the claims of the present invention.

Claims (10)

1. a fiber outer layer coating composition is characterized in that, counts by weight, comprising:

28～57 parts of first light-cured resins; 36～78 parts of second light-cured resins; 0.8～1.6 part in oxidation inhibitor; 0.1～0.3 part of ultraviolet absorbers; 1.5～3.2 parts of light triggers; 0.6～1.8 part of aqueous wetting agent; 0.3～1.4 part of water-based flow agent; 0.2～1.1 part of water-based defoamer; Described first light-cured resin has structure shown in the formula I:

R wherein ₁For acrylate-based; R ₂Be vulcabond cyclic trimer base; R ₃Be the polymer diatomic alcohol group; N is the polymerization degree, 1≤n≤50;

Described second light-cured resin has the structure shown in the formula II:

R wherein ₁For acrylate-based; R ₄For having the diisocyanate based of ring texture; R ₅Be methyl, butyl; R ₆Be tertiary amine groups; M is the polymerization degree, 1≤n≤20.

2. coating composition according to claim 1 is characterized in that described oxidation inhibitor is selected from phenolic antioxidant; Described ultraviolet absorbers is selected from benzophenone class, azimidobenzene class ultraviolet absorbers.

3. coating composition according to claim 1 is characterized in that, described light trigger is selected from one or more mixtures in Alpha-hydroxy ketone or the acyl group phosphorous oxides radical photoinitiator; Described water-based wetting agent is polyether-modified polydimethylsiloxane type wetting agent.

4. coating composition according to claim 1 is characterized in that, described water-based flow agent is selected from ionic acrylic interpolymer and polyether-modified polydimethylsiloxane type flow agent; Described water-based defoamer is an organosilicon type defoamer.

5. the preparation method of a fiber outer layer coating composition is characterized in that, comprising:

Count by weight 28～57 parts of first light-cured resins; 36～78 parts of second light-cured resins; 0.8～1.6 part in oxidation inhibitor; 0.1～0.3 part of ultraviolet absorbers; 1.5～3.2 parts of light triggers; 0.6～1.8 part of aqueous wetting agent; 0.3～1.4 part of water-based flow agent; 0.2～1.1 part of mixing of water-based defoamer is stirred 15～20min with the 1000rpm-1200rpm rotating speed, obtains a kind of optical fiber water-based outer layer coating composition;

Described first light-cured resin is suc as formula shown in the I, and second light-cured resin is suc as formula shown in the II; R wherein ₁For acrylate-based; R ₂Be vulcabond cyclic trimer base; R ₃Be the polymer diatomic alcohol group; N is the polymerization degree, 1≤n≤50; R ₁For acrylate-based; R ₄For having the diisocyanate based of ring texture; R ₅Be methyl, butyl; R ₆Be tertiary amine groups; M is the polymerization degree, 1≤n≤20.

6. preparation method according to claim 6 is characterized in that, the preparation method of described first light-cured resin comprises:

A1) under the nitrogen protection, poly glycol monomethyl ether is mixed with the vulcabond cyclic trimer, 60～65 ℃ of insulated and stirred were reacted 2～3 hours, obtained first intermediate product;

B1) under 70～75 ℃, first intermediate product, organic solvent, hydroxy acrylate and stopper to be mixed, insulation reaction 2～3 hours obtains second intermediate product;

C1) under 80～85 ℃, polymer diatomic alcohol is mixed with second intermediate product, reacted 2～3 hours, add the 78-261mol deionized water, stir 30min, organic solvent is removed in decompression, and obtaining solid content is first light-cured resin of 48-55wt%.

7. preparation method according to claim 6, it is characterized in that, be 2 in the described vulcabond cyclic trimer, 4-tolylene diisocyanate cyclic trimer, 4,4 '-'-diphenylmethane diisocyanate cyclic trimer, 3,3 '-dimethyl-4,4 '-'-diphenylmethane diisocyanate cyclic trimer, 1,6-methylene diisocyanate cyclic trimer or isophorone diisocyanate cyclic trimer; Described polymer diatomic alcohol is number-average molecular weight 1000～8000 daltonian polyether Glycols, polyester diol, PCDL or polycaprolactone glycol.

8. preparation method according to claim 6 is characterized in that, the preparation method of described second light-cured resin comprises:

A2) under the nitrogen protection,, ring-type vulcabond, dihydroxylic acid, cyclic polymer dibasic alcohol are mixed, insulation reaction 3-5 hour, obtain the 3rd intermediate product at 65-80 ℃;

B2) under 75-85 ℃, organic solvent, hydroxy acrylate and stopper are added the 3rd intermediate product, insulation reaction 2 hours obtains the 4th intermediate product;

C2) described the 4th intermediate product is cooled to 45-50 ℃, to wherein adding neutralizing agent, stirs 10min, add the deionized water of 73-159mol, stir 40min, organic solvent is removed in decompression, and obtaining solid content is second light-cured resin of 43-54wt%.

9. according to claim 7,8 described preparation methods, it is characterized in that described organic solvent is acetone or butanone; Described hydroxy acrylate is Hydroxyethyl acrylate, pentaerythritol triacrylate or trimethylolpropane diacrylate; Described stopper is MEHQ or Resorcinol.

10. preparation method according to claim 8 is characterized in that, described dihydroxylic acid is dimethylol propionic acid or dimethylolpropionic acid; Described ring-type vulcabond is isophorone diisocyanate, methylene-bis (4-cyclohexyl isocyanate), 1,4-cyclohexyl diisocyanate, 2,4 toluene diisocyanate or 4,4 '-'-diphenylmethane diisocyanate; Described neutralizing agent is triethylamine, N, N-dimethylethanolamine or trolamine; Described cyclic polymer dibasic alcohol is Resins, epoxy E54, E41 or E21.

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