CN101268157A - Curable liquid resin optical fiber upjacket composition - Google Patents

Abstract

The present invention provides a curable liquid resin composition which exhibits excellent removability from an adjacent coating layer after curing and is less deteriorated when exposed to high temperature and high humidity conditions, thereby being suitable for an optical fiber upjacket material. The curable liquid resin optical fiber upjacket composition comprises a urethane (meth) acrylate or (meth) acrylate oligomer, a reactive diluent, a polymerization initiator, and a polysiloxane compound having a molecular weight of 1250 to 35000.

Description

Curable Liquid Resin Optical Fiber Tight Packing Composition

technical field

The present invention relates to a curable liquid resin optical fiber packing composition coated and cured on the surface of a resin-coated optical fiber.

Background technique

In optical fiber manufacturing, glass fibers are produced by spinning molten glass and then provided with a resin coating on the glass fibers for containment and reinforcement. This step is called "fiber stretching". As the resin coating, there is known a structure in which a flexible primary coating is formed on the surface of an optical fiber, and then a rigid secondary coating is coated on the primary coating. There is also known a structure in which resin-coated optical fibers are arranged side by side on a plane and bound with a binding material to form a ribbon-shaped coating. A resin composition used to form a primary coating is called a primary material, a resin composition used to form a secondary coating is called a secondary material, and a resin composition used to form a strip-shaped coating is called a strip. matrix material.

The outer diameter of the resin-coated optical fiber is usually about 250 μm. To improve hand handling, an additional layer of resin is coated on the resin-coated optical fiber to increase the outer diameter to about 500-900 μm. Such resin coatings are often referred to as "tight cladding". Since no optical properties are required for the tight cladding, it is not necessary for the tight cladding to have transparency. Tight cladding may be colored for visual identification. Importantly, the tight cladding can be easily removed from the resin-coated fiber without causing damage to the underlying primary or secondary coating when the resin-coated fiber is spliced.

Curable resins used as optical fiber coating materials (including materials for tight cladding) need to have outstanding coatability to withstand high-speed fiber drawing, sufficient strength and flexibility, excellent heat resistance, excellent Excellent weather resistance, outstanding resistance to acids, alkalis, etc., excellent oil resistance, low water absorption and hygroscopicity, low hydrogen generation, excellent storage stability, etc.

However, because prior art tight wrapping materials are firmly adhered to either the overlying matrix material layer or the underlying primary or secondary coating, the tight wrapping may become vulnerable when the matrix material layer is removed to expose the resin-coated coating. or the primary or secondary coating may be damaged when the tight cladding is removed from the resin-coated optical fiber. This hampers the usability of fiber optic connections.

As a curable liquid resin optical fiber tight composition having improved removability, a composition containing three types of polysiloxane compounds (Patent Document 1) and a composition containing organic or inorganic material particles (Patent Document 1) have been disclosed. Literature 2 and 3).

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-287717

[Patent Document 2] Japanese Patent Application Laid-Open No. 9-324136

[Patent Document 3] Japanese Patent Application Laid-Open No. 2000-273127

However, the removability of the tight envelope formed using the above composition is insufficient. Or it can be said that even if the tight cladding has excellent immediate removability after the tight cladding optical fiber is manufactured, the removability of the tight cladding will deteriorate with time.

Contents of the invention

The object of the present invention is to provide a curable liquid resin optical fiber compact composition, which can be used as a good optical fiber coating material and has excellent properties of being removable from adjacent coatings after curing. At the same time, the coating has sufficient strength and weather resistance.

In the present invention, various urethane (meth)acrylate-containing curable liquid resin compositions were prepared, and the performance and removability of the obtained cured products as optical fiber tight claddings were examined. As a result, it was found that the object of the present invention can be achieved by adding a polysiloxane compound having a specific molecular weight.

The invention provides a curable liquid resin optical fiber tight package composition, comprising:

(A) 30-90wt% polyurethane (meth)acrylate,

(B) 1-70wt% reactive diluent,

(C) 0.1-10 wt% of a polymerization initiator, and

(D) 1-50 wt% of a polysiloxane compound having an average molecular weight of 1500-35000, wherein the total amount of components (A), (B) and (C) is 100 wt%.

The present invention also provides a curable liquid resin optical fiber tight package composition, comprising:

(A) 30-90wt% (meth)acrylate oligomer,

(B) 1-70wt% reactive diluent,

(C) 0.1-10 wt% of a polymerization initiator, and

(D) 1-50 wt% of a polysiloxane compound having an average molecular weight of 1500-35000, wherein the total amount of components (A), (B) and (C) is 100 wt%.

The present invention also provides an optical fiber tight cladding comprising the cured product of the curable liquid resin optical fiber tight cladding composition of the present invention.

The present invention further provides a tightly clad optical fiber comprising a tight cladding of the optical fiber.

The present invention also relates to a method of manufacturing an optical fiber tight cladding, said method comprising the step of curing the liquid resin optical fiber tight cladding composition.

The invention further relates to the use of an optical fiber tight cladding as a coating with good removability and weatherability.

The optical fiber tight cladding obtained by using the resin composition of the present invention has sufficient strength and weather resistance, exhibits excellent removability, and exhibits only less deterioration when exposed to high temperature and high humidity conditions . Therefore, usability of optical fiber connection can be improved.

Detailed ways

For example, the urethane (meth)acrylate (A) of the present invention is produced by reacting a polyol, a diisocyanate, and a hydroxyl group-containing (meth)acrylate. Specifically, urethane (meth)acrylate (A) is prepared by reacting isocyanate groups of diisocyanate with hydroxyl groups of polyol and hydroxyl group-containing (meth)acrylate. Urethane (meth)acrylate obtained by reacting 1 mol of diisocyanate with 2 mol of hydroxyl-containing (meth)acrylate may be added to the curable liquid resin composition of the present invention. Examples of such urethane (meth)acrylates include the reaction product of hydroxyethyl (meth)acrylate and 2,4-toluene diisocyanate, hydroxyethyl (meth)acrylate and 2,5(2,6)- The reaction product of bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, the reaction product of hydroxyethyl (meth)acrylate with isophorone diisocyanate, the reaction product of hydroxypropyl (meth)acrylate with The reaction product of 2,4-toluene diisocyanate and the reaction product of hydroxypropyl (meth)acrylate with isophorone diisocyanate.

The above reaction can be carried out by the following methods: for example, reacting polyols, diisocyanates and hydroxyl-containing (meth)acrylates; reacting polyols with diisocyanates, and then reacting the resulting product with hydroxyl-containing (meth)acrylates Reaction; reacting a diisocyanate with a hydroxyl-containing (meth)acrylate and then reacting the resulting product with a polyol; or reacting a diisocyanate with a hydroxyl-containing (meth)acrylate and then reacting the resulting product with a polyol , and then further react the resulting product with a hydroxyl-containing (meth)acrylate.

As examples of polyols preferably used in this reaction, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols and the like can be given. There is no specific limitation on the polymerization method of the structural units of these polyols, which may be any one of random copolymerization, block copolymerization or graft copolymerization. As examples of polyether polyols, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyhepamethylene glycol, and polydecamethylene glycol, Aliphatic polyether polyols obtained by ring-opening copolymerization of two or more ionically polymerizable cyclic compounds, and the like. As examples of ionically polymerizable cyclic compounds, for example, ethylene oxide, propylene oxide, 1-butylene oxide, isobutylene oxide, 3,3-dichloromethyloxetane, Tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, methane Glycidyl Acrylate, Allyl Glycidyl Ether, Allyl Glycidyl Carbonate, Butadiene Monoxide, Isoprene Monoxide, Vinyl Oxetane, Vinyl Tetrahydrofuran, Vinyl Cyclic ethers such as cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate. In addition, it is possible to use the above ion-polymerizable cyclic compound by combining the above-mentioned ionomerizable cyclic compound with a cyclic imine (such as aziridine), a cyclic lactone acid (such as β-propiolactone or glycolide), or dimethylcyclopolysilane Polyether polyol obtained by ring-opening copolymerization of oxane. As examples of specific combinations of two or more ionomerizable cyclic compounds, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide can be given , Propylene oxide and ethylene oxide, 1-butylene oxide and ethylene oxide, tetrahydrofuran, terpolymer of 1-butylene oxide and ethylene oxide, etc. The ring-opening copolymers of these ionically polymerizable cyclic compounds may be random copolymers or block copolymers.

These aliphatic polyether polyols are commercially available as: PTMG650, PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corp.), PPG400, PPG1000, PPG2000, PPG3000, Excenol 720, 1020, 2020 (manufactured by AsahiGlass Urethane Co., Ltd. .), PEG1000, Unisafe DC1100, DC1800 (manufactured by Nippon Oil and Fats Co., Ltd.), PPTG2000, PPTG1000, PTG400, PTGL2000 (manufactured by Hodogaya Chemical Co., Ltd.), Z-3001-4, Z -3001-5, PBG2000A, PBG2000B (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the like.

Examples of polyether polyols also include cyclic polyether polyols such as alkylene oxide addition polyols of bisphenol A, alkylene oxide addition polyols of bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, Alkylene oxide addition polyol of hydrogenated bisphenol A, alkylene oxide addition polyol of hydrogenated bisphenol F, alkylene oxide addition polyol of hydroquinone, alkylene oxide addition polyol of naphthalene hydroquinone, anthracene Alkylene oxide adduct polyol of hydroquinone, 1,4-cyclohexane polyol and its alkylene oxide adduct polyol, tricyclodecane polyol, tricyclodecane dimethanol, pentacyclopentadecane Polyols and Pentacyclopentadecanedimethanol. Among them, alkylene oxide adduct polyols of bisphenol A and tricyclodecane dimethanol are preferable. These polyols are commercially available as Uniol DA400, DA700, DA1000, DB400 (manufactured by Nippon Oil and Fats Co., Ltd.); Tricyclodecanedimethanol (manufactured by Mitsubishi Chemical Corp.) and the like. Examples of other cyclic polyether polyols include alkylene oxide addition polyols of bisphenol A, alkylene oxide addition polyols of bisphenol F, and alkylene oxide addition polyols of 1,4-cyclohexane polyol .

As an example of the polyester polyol, a polyester polyol obtained by reacting a diol with a dibasic acid can be given. As examples of diols, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexane polyol, neopentyl glycol, Diol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentane polyol, 1,9-nonane polyol, 2-methyl-1,8-octane polyol, etc. . As examples of the dibasic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like can be given. These polyester polyols are commercially available as Kurapol P-2010, PMIPA, PKA-A, PKA-A2, PNA-2000 (manufactured by Kuraray Co., Ltd.) and the like.

As examples of the polycarbonate polyol, polycarbonate of polytetrahydrofuran, polycarbonate of 1,6-hexane polyol, and the like can be given. These polycarbonate polyols are commercially available as the following: DN-980, 981, 982, 983 (produced by Nippon Polyurethane Industry Co., Ltd), PC-8000 (produced by PPG), PC-THF-CD (produced by BASF production) and so on.

As examples of polycaprolactone polyols, polycaprolactone polyols obtained by reacting ε-caprolactone with diols such as ethylene glycol, polyethylene glycol, Propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol Methanol or 1,4-butane polyol, etc. These polyols are commercially available as Placcel 205, 205AL, 212, 212AL, 220, 220AL (manufactured by Daicel Chemical Industries, Ltd) and the like.

In addition to the polyols mentioned above, other polyols can also be used. As examples of such polyols, ethylene glycol, propylene glycol, 1,4-butane polyol, 1,5-pentane polyol, 1,6-hexane polyol, neopentyl glycol, 1, 4-cyclohexanedimethanol, dimethylol compounds of dicyclopentadiene, tricyclodecane dimethanol, beta-methyl-delta-valerolactone, hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenation Polybutadiene, castor oil-modified polyols, polyol-terminated compounds of polydimethylsiloxane, polydimethylsiloxane carbitol-modified polyols, and the like.

Diamines may be used in combination with polyols. As examples of diamines, ethylenediamine, tetramethylenediamine, hexamethylenediamine, p-phenylenediamine and 4,4'-diaminodiphenylmethane, heteroatom-containing Diamine, polyether diamine, etc.

Among these polyols, polyether polyols, especially aliphatic polyether polyols are preferred. In particular, polypropylene glycol and copolymers of 1-butylene oxide and ethylene oxide are preferred. Polyether polyols are commercially available as PPG 400, PPG 1000, PPG 2000, PPG 3000, Excenol 720, 1020, 2020 (manufactured by Asahi Glass Urethane Co., Ltd.) and the like. Copolymers of 1-butylene oxide and ethylene oxide are commercially available as: EO/BO500, EO/BO1000, EO/BO2000, EO/BO3000, EO/BO4000 (manufactured by Daiichi KogyoSeiyaku Co., Ltd. )wait.

As examples of diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene 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'-diphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate ), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenyl propane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, tetramethyl xylene diisocyanate, 2,5(2,6)-bis(isocyanatomethyl )-bicyclo[2.2.1]heptane, etc. Among them, 2,4-toluene diisocyanate, isophorone diisocyanate, xylene diisocyanate, methylene bis(4-cyclohexyl diisocyanate) and the like are particularly preferable.

These diisocyanates may be used alone or in combination of two or more.

As examples of hydroxyl-containing (meth)acrylates, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 2-Hydroxy-3-phenoxypropyl methacrylate, 1,4-butane polyol mono(meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, (meth) 4-hydroxycyclohexyl acrylate, 1,6-hexane polyol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane di(meth)acrylate, Methylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and (meth)acrylate represented by the following formula (1) or (2) Acrylate.

CH ₂ =C(R ¹ )-COOCH ₂ CH ₂ -(OCOCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) _n -OH (1)

Wherein, R ¹ represents a hydrogen atom or a methyl group, and n represents an integer of 1-15.

Compounds obtained by addition reaction of a glycidyl group-containing compound (for example, alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate) with (meth)acrylic acid can also be used. Of these hydroxyl group-containing (meth)acrylates, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are preferable.

These hydroxyl group-containing (meth)acrylate compounds may be used alone or in combination of two or more.

Preferably, a polyol, a diisocyanate, and a hydroxyl-containing (meth)acrylate are used so that, for 1 equivalent of hydroxyl groups in the polyol, isocyanate groups in the diisocyanate and hydroxyl-containing (meth)acrylate The hydroxyl groups are 1.1-3 equivalents and 0.2-1.5 equivalents, respectively.

In the reaction of these compounds, it is preferable to use, for example, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo[2.2.2]octane Or 2,6,7-trimethyl-1,4-diazabicyclo[2.2.2]octane urethanization catalyst, the consumption of this catalyst is 0.01-1 weight of 100 parts by weight of total reactants share. The reaction temperature is usually 10-90°C, preferably 30-80°C.

A compound having a functional group that can add to an isocyanate group can be used instead of part of the hydroxyl group-containing (meth)acrylate. As examples of such compounds, γ-mercaptotrimethoxysilane, γ-aminotrimethoxysilane and the like can be given. Use of these compounds improves adhesion to substrates such as glass.

The amount of polyurethane (meth)acrylate (A) added in the composition of the present invention is 30-90wt%, preferably 55-87wt%, of the total amount of 100wt% of components (A), (B) and (C), More preferably 65-85 wt%. If the amount is less than 30% by weight, the elastic modulus of the composition changes significantly depending on temperature. If the amount exceeds 90% by weight, the viscosity of the curable liquid resin composition will be too high.

Component (A) may also be a (meth)acrylate oligomer, for example a non-urethane (meth)acrylate oligomer such as bisphenol A epoxy acrylate CN120Z available from Sartomer, available from Cognis Photomer 3016 available from UCB, Ebccryl 3700 available from UCB, epoxy phenolic acrylated CN 112 available from Sartomer, etc. The amount of (meth)acrylate oligomer (A) added in the composition of the present invention is 30-90wt%, preferably 55-87wt% of the total amount of 100wt% of components (A), (B) and (C) %, more preferably 65-85wt%.

As the reactive diluent (B), polymerizable monofunctional compounds and polymerizable polyfunctional compounds can be used. Examples of monofunctional compounds include vinyl lactams such as N-vinylpyrrolidone and N-vinylcaprolactam; (meth)acrylates containing alicyclic structures such as isobornyl (meth)acrylate, (meth) ) bornyl acrylate, tricyclodecanyl (meth)acrylate, dicyclopentyl (meth)acrylate; benzyl (meth)acrylate; 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, Vinylimidazole, vinylpyridine, etc. Other examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate ester, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, isobutyl (meth)acrylate, tert-(meth)acrylate Butyl, Amyl (meth)acrylate, Isoamyl (meth)acrylate, Hexyl (meth)acrylate, Heptyl (meth)acrylate, Octyl (meth)acrylate, Iso(meth)acrylate Octyl ester, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, Lauryl (meth)acrylate, Lauryl (meth)acrylate, Octadecyl (meth)acrylate, Isostearyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate , Butoxyethyl (meth)acrylate, Ethoxydiethylene glycol (meth)acrylate, Benzyl (meth)acrylate, Phenoxyethyl (meth)acrylate, Polyethylene glycol Mono(meth)acrylate, Polypropylene glycol mono(meth)acrylate, Methoxyethylene glycol (meth)acrylate, Ethoxyethyl (meth)acrylate, Methoxy (meth)acrylate Polyethylene glycol ester, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylate, N,N-dimethyl(methyl) Acrylamide, tert-octyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyl (meth)acrylate Octyl octyl ester, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, hexadecane Vinyl ether and 2-ethylhexyl vinyl ether, and compounds represented by the following formulas (3)-(6).

Wherein, R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group with 2-6 carbon atoms, preferably 2-4 carbon atoms, R ⁴ represents a hydrogen atom or has 1-12 carbon atoms, preferably 1 - an alkyl group of 9 carbon atoms, r represents an integer of 0-12, preferably 1-8.

Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alkylene group with 2-8 carbon atoms, preferably 2-5 carbon atoms, R ⁷ represents a hydrogen atom or a methyl group, and p represents an integer of 1-4 .

Wherein, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ respectively represent a hydrogen atom or a methyl group, and q represents an integer of 1-5.

Among these polymerizable monofunctional compounds, preferred are vinyl lactams (such as N-vinylpyrrolidone and N-vinylcaprolactam), isobornyl (meth)acrylate, and lauryl (meth)acrylate.

These polymerizable monofunctional compounds are commercially available as IBXA (produced by Osaka Organic Chemical Industry Ltd.), Aronix M-111, M-113, M-114, M-117 and TO-1210 (produced by Toagosei Co. , Ltd. production) etc.

Examples of polymerizable polyfunctional compounds include trimethylolpropane tri(meth)acrylate, trimethylolpropane trioxyethyl(meth)acrylate, pentaerythritol tri(meth)acrylate, triethylene glycol Diacrylate, tetraethylene glycol di(meth)acrylate, tricyclodecane dimethylol diacrylate, 1,4-butane polyol di(meth)acrylate, 1,6-hexane Polyol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Tripropylene glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Bisphenol A diglycidyl Ether two-terminal (meth)acrylic acid adduct, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, tris(2-hydroxyethyl)iso Cyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tricyclodecane dimethylol diacrylate, ethylene oxide or Di(meth)acrylates of propylene oxide adducted bisphenol A, di(meth)acrylates of ethylene oxide or propylene oxide adducted hydrogenated bisphenol A, by adducting (meth)acrylates Epoxy (meth)acrylate prepared from diglycidyl ether of bisphenol A, triethylene glycol divinyl ether, a compound represented by the following formula (7), and the like.

CH ₂ =C(R ¹² )-COO-(CH ₂ -CH(R ¹³ )-O) _o -CO-C(R ¹² )=CH ₂ (7)

Wherein, R ¹² and R ¹³ respectively represent a hydrogen atom or a methyl group, and n represents an integer of 1-100.

Among these polymerizable polyfunctional compounds, preferred are compounds represented by the above formula (7), such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tricyclodecane Dimethylol diacrylate, di(meth)acrylate of ethylene oxide adducted bisphenol A and tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate.

These polymerizable polyfunctional compounds are commercially available as Yupimcr UV, SA1002 (manufactured by Mitsubishi Chemical Corp.), Aronix M-215, M-315, M-325 (manufactured by Toagosei Co., Ltd.) and the like. In addition, Aronix TO-1210 (manufactured by Toagosei Co., Ltd.) can also be used.

The amount of reactive diluent (B) in the composition of the present invention is generally 1-70wt% of the total amount of 100wt% of components (A), (B) and (C), preferably 5-50wt%, particularly preferably 10wt%. -40wt%. If the amount is less than 1 wt%, curability is affected. If the amount exceeds 70 wt%, the coated composition may flow due to low viscosity.

The curable liquid resin composition of the present invention further contains a polymerization initiator as component (C). As the polymerization initiator, a thermal polymerization initiator or a photoinitiator can be used.

If the curable liquid resin composition of the present invention is thermally curable, a thermal polymerization initiator such as a peroxide or an azo compound is generally used. As specific examples of the thermal polymerization initiator, benzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, and the like can be given.

If the curable liquid resin composition of the present invention is photocurable, a photoinitiator is used. Preferably, a photosensitizer can also be added as needed. As examples of photoinitiators, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthracene quinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, -benzoin ethyl ether, benzyl methyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2 -Hydroxy-2-methyl-1-phenyl-1-propanone, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1 -[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxy benzoyl)-2,4,4-trimethylpentylphosphine oxide; Irgacure 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur 1116, 1173 (by Ciba Specialty Chemicals Co., Ltd.); Lucirin TPO (produced by BASF); and Ubecryl P36 (produced by UCB) and the like. As examples of photosensitizers, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate, Ethylaminobenzoate, isoamyl 4-dimethylaminobenzoate; Ubecryl P102, 103, 104, 105 (produced by UCB); Chivacure TPO, etc.

If both heat and ultraviolet rays are used to cure the curable liquid resin composition of the present invention, a thermal polymerization initiator and a photoinitiator may be used in combination. The amount of the polymerization initiator (C) used is preferably 0.1-10 wt%, particularly preferably 0.3-7 wt%, based on the total amount of 100 wt% of components (A), (B) and (C).

The curable liquid resin composition of the present invention further comprises a polysiloxane compound having an average molecular weight of 1500-35000 as component (D). Component (D) is important for improving the removability of the optical fiber tight cladding formed from the resin composition of the present invention from adjacent layers. If the average molecular weight of component (D) is less than 1500, removability may be insufficient. If the average molecular weight exceeds 35000, the removability is not sufficiently improved so that the removability is insufficient. The average molecular weight of component (D) is preferably 1500-35000, more preferably 1500-20000, particularly preferably 3000-15000.

As examples of polysiloxane compounds, polyether-modified polysiloxane, alkyl-modified polysiloxane, urethane acrylate-modified polysiloxane, urethane-modified polysiloxane, polysiloxane modified by methyl styrene group, polysiloxane modified by epoxy polyether, polysiloxane modified by alkyl aralkyl polyether, etc. As the polyether-modified polysiloxane, preferred are polydimethylsiloxane compounds in which a group represented by R ¹⁴ -(R ¹⁵ O) _s -R ¹⁶ - is bonded to at least one silicon Atomic (where R ¹⁴ represents a hydroxyl group or an alkoxy group with 1-10 carbon atoms, R ¹⁵ represents an alkylene group with 2-4 carbon atoms (R ¹⁵ may contain two or more types of alkylene group), R represents an ^alkylene group having 2-12 carbon atoms, and s represents an integer of 1-20). As the alkylene group represented by R ¹⁵ , an ethylene group or a propylene group is preferable, and an ethylene group is particularly preferable. The silicone compound is commercially available as the following: SH28PA: Dimethicone-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Co. Ltd.); Pantad 19, 54: Dimethicone Alkane-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Co. Ltd.); FM0411: Dimethicone-polyoxyalkylene copolymer (manufactured by Chiso Corp.); Dimethicone- Polyoxyalkylene copolymer (containing side chain OH) (manufactured by Dow Corning Toray Co. Ltd.); Bykuv 3510: dimethyl polysiloxane-polyoxyalkylene copolymer (manufactured by BYK-Chemie Japan); DC57: di Methicone-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Co. Ltd.); DC190: dimethylpolysiloxane-PEG/PPG copolymer from Dow Corning, and the like.

The added amount of component (D) is preferably 0.1-50wt% of the total amount of 100wt% of components (A), (B) and (C), preferably 1-50wt%, more preferably 0.5-40wt%, especially preferably 1- 20 wt%, thus ensuring the removability, strength and weatherability of the resulting tight cladding.

The curable liquid resin composition of the present invention further contains a polyol compound having a molecular weight of 1500 or more as component (E). Addition of component (E) can improve the removability of the optical fiber tight cladding formed from the resin composition of the present invention from adjacent layers. If the molecular weight of component (E) is less than 1500, durability is lowered due to problems involving transfer to the ink layer. The molecular weight of the polyol compound is preferably 1500-10000, more preferably 2000-8000.

As examples of the polyol compound used in component (E), polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol and the like can be given. There is no specific limitation on the polymerization method of these polyol structural units, and it may be any one of random polymerization, block polymerization or graft polymerization.

Among these polyol compounds, polyether polyols having a molecular weight of 1500 or more are preferred. As examples of polyether polyols, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyhepamethylene glycol, polydecamethylene glycol , aliphatic polyether polyols obtained by ring-opening copolymerization of two or more ionomerizable cyclic compounds, and the like. As examples of ionically polymerizable cyclic compounds, for example, ethylene oxide, propylene oxide, 1-butylene oxide, isobutylene oxide, 3,3-dichloromethyloxetane, Tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, methane Glycidyl Acrylate, Allyl Glycidyl Ether, Allyl Glycidyl Carbonate, Butadiene Monoxide, Isoprene Monoxide, Vinyl Oxetane, Vinyl Tetrahydrofuran, Vinyl Cyclic ethers such as cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate. In addition, it is possible to use the above ion-polymerizable cyclic compound by combining the above-mentioned ionomerizable cyclic compound with a cyclic imine (such as aziridine), a cyclic lactone acid (such as β-propiolactone or glycolide), or dimethylcyclopolysilane Polyether polyol obtained by ring-opening copolymerization of oxane. As examples of specific combinations of two or more ionomerizable cyclic compounds, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide can be given , Propylene oxide and ethylene oxide, 1-butylene oxide and ethylene oxide, tetrahydrofuran, terpolymer of 1-butylene oxide and ethylene oxide, etc. The ring-opening copolymers of these ionically polymerizable cyclic compounds may be random copolymers or block copolymers.

These aliphatic polyether polyols are commercially available as: PTMG2000 (produced by Mitsubishi Chemical Corp.), PPG2000, PPG3000, Exccnol 2020 (produced by Asahi Glass Urethane Co., Ltd.), DC1800 (produced by Nippon Oil and Fats Co., Ltd.), PPTG2000, PTGL2000 (produced by Hodogaya Chemical Co., Ltd.), PBG2000A, PBG2000B (produced by Daiichi Kogyo Seiyaku Co., Ltd.), Acclaim 4200 (produced by Bayer Polymer LLC.), Pluracol 2010 (BASF Corp.) et al.

Examples of polyether polyols also include cyclic polyether polyols such as alkylene oxide addition polyols of bisphenol A, alkylene oxide addition polyols of bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, Alkylene oxide addition polyol of hydrogenated bisphenol A, alkylene oxide addition polyol of hydrogenated bisphenol F, alkylene oxide addition polyol of hydroquinone, alkylene oxide addition polyol of naphthalene hydroquinone, anthracene Alkylene oxide adduct polyol of hydroquinone, 1,4-cyclohexane polyol and its alkylene oxide adduct polyol, tricyclodecane polyol, tricyclodecane dimethanol, pentacyclopentadecane Polyols and pentacyclopentadecane dimethanol, etc. Examples of other cyclic polyether polyols include alkylene oxide addition polyols of bisphenol A, alkylene oxide addition polyols of bisphenol F, and alkylene oxide addition polyols of 1,4-cyclohexane polyol . Polyols may contain only linear molecules, or may have a branched structure. Polyols can be linear molecules, or can have a branched structure

The curable liquid resin composition of the present invention preferably includes a polyol having a branched structure (hereinafter also referred to as "polyol having a branched structure") containing an alkyl group such as a methyl group or an ethyl group, wherein One hydroxyl group is bonded to each branch end, and the value obtained by dividing the molecular weight of the polyol by the number of hydroxyl groups at the branch end is 500-2000.

As a specific example of a polyhydric alcohol containing a branched structure, it is preferably obtained by ring-opening polymerization of glycerin or pitol and at least one compound selected from ethylene oxide, propylene oxide, and butylene oxide. Polyols, particularly preferred are polypropylene glycol and copolymers of 1-butylene oxide and ethylene oxide.

The value obtained by dividing the molecular weight of the polyol by the number of hydroxyl groups at the end of the branch is preferably 500-2000, more preferably 1000-1500. The number average molecular weight of the polyol is preferably 1500-12000, more preferably 2000-10000, particularly preferably 2500-8000, the polystyrene-equivalent molecular weight being measured by gel permeation chromatography.

The branched structure-containing polyol preferably contains 3 to 6 hydroxyl groups at branch terminals in one molecule.

The polyols are commercially available as PPG2000, PPG3000, Exccnol2020 (manufactured by Asahi Glass Urethane Co., Ltd.) and the like. Copolymers of 1-butylene oxide and ethylene oxide are commercially available as EO/BO2000, EO/BO3000, EO/BO4000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

Polyols containing branched structures are commercially available as: Sannix TP-400, SannixGL-3000, Sannix GP-250, Sannix GP-400, Sannix GP-600, Sannix GP-1000, Sannix GP-3000, Sannix GP -3700M, Sannix GP-4000, Sannix GEP-2800, Newpol TL4500N (manufactured by Sanyo Chemical Industries, Ltd), etc.

The addition amount of component (E) is preferably 0.1-50wt% of the total amount of 100wt% of components (A), (B) and (C), still more preferably 1-30wt%, particularly preferably 1-20wt%, thus Ensures removability, strength and weatherability of the resulting tight cladding.

A flame retardant (F) may also be added to the curable liquid resin composition of the present invention. There are no specific limitations on the flame retardant (F). Examples of the flame retardant (F) include halogen-based (bromo- or chlorine-based) flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, and silicon-based flame retardants.

Examples of brominated flame retardants include tetrabromobisphenol A (TBBPA), decabromodiphenyl oxide, hexabromocyclododecane, tribromophenol, ethylenebistetrabromophthalimide, TBBPA polycarbonate oligomer, brominated polystyrene, TBBPA epoxy oligomer, TBBPA dibromopropyl ether, ethylene bispentabromobiphenol, pentabromobenzyl acrylate, hexabromobenzene, brominated Aromatic triazines, etc.

As examples of phosphorus-based flame retardants, phosphates, halogen-containing phosphates, ammonium polyphosphate, red phosphorus compounds, phosphaphenanthrene, and the like can be given. As specific examples of phosphoric acid esters, triisopropylphenyl phosphate, tris(2-chloroisopropyl)phosphate, cresyl diphenyl phosphate, tricresyl phosphate and the like can be given.

As examples of the chlorine-based flame retardant, chlorinated paraffin, perchloropentadecane, chlorendic acid, and the like can be given.

The amount of the flame retardant (F) in the composition is preferably 1.0-50 wt%, particularly preferably 5-20 wt%, based on the total amount of 100 wt% of components (A), (B) and (C). If the amount is less than 1.0 wt%, the flame retardant effect is insufficient. If the amount exceeds 50% by weight, the flame retardant may bleed out from the resulting cured product, or have a negative effect on the elastic properties of the resulting tight wrap.

As long as the properties of the composition are not adversely affected, for example, antioxidants, colorants, UV absorbers, light stabilizers, silane coupling agents, thermal polymerization initiators, leveling agents, surfactants, preservatives, Various additives of plasticizers, lubricants, solvents, fillers, antiaging agents, wettability improvers and coating surface improvers are optionally added to the curable liquid resin composition of the present invention.

The compositions of the present invention are cured with heat and/or radiation. Radiation as used herein refers to infrared rays, visible light, ultraviolet rays, X-rays, electron beams, α-rays, β-rays, γ-rays, and the like.

The cured product of the curable liquid resin composition of the present invention has a Young's modulus of about 100 MPa to about 600 MPa, preferably about 200 to about 580 MPa. When forming a tight cladding, the composition is preferably coated on the fibers to a thickness of 100-350 μm.

Example

The present invention is described in detail below by way of examples. However, the present invention is not limited to these Examples.

A. Preparation Example: Preparation of Curable Resin Composition (Table 1)

Add 15.381g of tetraethylene nonylphenyl ether acrylate, 0.015g of 2,6-di-tert-butyl p-cresol, 7.80g of toluene diisocyanate and 0.023g of dilauric acid diisocyanate into a reactor equipped with a stirrer Butyl tin. The mixture was cooled with ice to 15-20°C with stirring. After adding 6.00 g of hydroxyethyl acrylate, the mixture was reacted with stirring for 2 hours while controlling the solution temperature at 35° C. or lower. After adding 28.341 g of polytetramethylene glycol with a number average molecular weight of 2000, 1.790 g of polyethylene bisphenol A ether with a number average molecular weight of 400, and 0.022 g of dibutyltin dilaurate, the mixture was stirred at room temperature for 1 hour . The mixture was then stirred for 2 hours at 65°C in an oil bath. The reaction was terminated when the residual isocyanate content was 0.1 wt% or less. The obtained product was a mixed solution of three types of urethane (meth)acrylate oligomers shown in Table 1.

The mixed solution was cooled to room temperature. Add 2.90g Irgacure 184 (produced by Ciba Specialty Chemicals Co., Ltd.), 0.30g Irganox 1035 (produced by Ciba Specialty Chemicals Co., Ltd.), 5.770g N-vinyl-2-pyrrolidone, 15.4 g of polyoxyethylene nonylphenyl ether acrylate (M113: produced by Toagosei Co., Ltd.), 2.275 g of tricyclodecane dimethylol diacrylate (SA 1002: produced by Mitsubishi Chemical Corp.), and After 28.90 g of trimethylolpropane ethoxytriacrylate (Photomer 4149: produced by Osaka Organic Chemical Industry, Ltd.), the mixture was stirred at 50° C. for 1 hour to obtain a curable resin composition of interest.

Embodiment 1-5 and comparative example 1-3

Each component of the composition shown in Table 1 was charged in a reactor equipped with a stirrer. The mixture was stirred at a solution temperature of 50° C. for 1 hour to obtain a curable liquid resin composition.

Test Methods

The curable liquid resin compositions obtained in the above Examples and Comparative Examples were cured according to the following methods to prepare test samples. The following evaluations were performed on the test samples.

1. Young's modulus

The curable liquid resin composition was coated on a glass plate with a coating bar with a gap size of 250 μm, and cured in air with a dose of 1 J/cm ² of ultraviolet rays to obtain a Young’s modulus measurement film. The film was cut into strip-shaped samples so that the portion to be stretched was 6 mm wide and 25 mm long. Tensile measurements were performed on the samples at a temperature of 23°C and a humidity of 50%. Young's modulus was calculated from the tensile strength at a stretch rate of 1 mm/min and a strain of 2.5%.

2. Removability

The primary material (R1164: produced by JSR Corporation), the secondary material (R3180: produced by JSR Corporation) and the ink material (FS Blue Ink: T&KTOKA) were coated on the glass fibers, and were coated with a rewinder (produced by Yoshida Kogyo Co. , Ltd.) was cured by applying ultraviolet rays to obtain a resin-coated optical fiber having an outer diameter of 250 μm. The curable composition shown in Table 1 was coated on the resin-coated optical fiber as a tight-packing material, and cured by applying ultraviolet light with the above-mentioned rewinder to obtain a tight-packed optical fiber with an outer diameter of 500 μm. The resulting tight-packed optical fiber was used as a measurement sample.

As shown in Fig. 1, the tightly wrapped optical fiber was clamped at a position of 3 cm from the end thereof with a thermal stripper (manufactured by Furukawa Electric Co., Ltd.). Then, the tight-clad optical fiber was stretched at a tensile rate of 50 m/min using a tensile tester (produced by Shimadzu Corp.) to measure the coating removal stress when the tight cladding was removed (the maximum stress is shown in Fig. 2). The measurements were performed immediately after fabrication of the tight-packed fiber (hereinafter referred to as "coating removal stress immediately after fabrication"). The measurement can also be performed after placing the tight-packed optical fiber at a temperature of 23°C and a relative humidity of 50% for 7 days (hereinafter referred to as "coating removal stress after high temperature and high humidity test").

This test method for measuring removability is hereinafter referred to as the "50m/min test method"

Compositions of the present invention, when cured, have a coating removal stress immediately after fabrication of not more than 5.5 N when measured using the 50 m/min test method.

The compositions of the present invention, when cured, have a coating removal stress after high temperature and high humidity testing of no more than 5.5 N when measured with the 50 m/min test method.

The results are shown in Table 1.

B. Preparation Examples 6-7 (Table 2)

The tight coating compositions of Examples 6 and 7 were prepared by mixing and heating the ingredients listed in Examples 6 and 7.

Test Methods

1. Young's modulus: see part A of the examples

2. Removability

The primary material (Desolite 3471-1-129A: produced by DSM Desotech, Inc.), the secondary material (3471-2-136: produced by DSM Desotech, Inc.) and the ink material (Cabelite751-017: produced by Desotech, Inc. .production) was coated on the glass fiber, and cured by applying ultraviolet light with a rewinder OFC 52 (produced by Nextrom Technologies, Inc.) to obtain a resin-coated optical fiber with an outer diameter of 250 μm. The curable composition shown in Table 2 was coated on the resin-coated optical fiber as a tight-packing material, and cured by applying ultraviolet light with the above-mentioned rewinder to obtain a tight-packed optical fiber with an outer diameter of 500 μm. The resulting tight-packed optical fiber was used as a measurement sample.

The removability of the cured tight coating was determined by measuring the maximum pressure required to remove the cured tight coating from the optical fiber using a stripping device (Micro-Strip Precision Stripper, available from Micro Electronics Inc.). force. The test method is performed on an Instron Tensile Testing Machine 4201 or equivalent. This method allows for quantitative and reproducible measurements, allowing for system-to-system variation in coating systems. After inserting the fiber into the stripper and clamping the bottom of the device with a small clamp, the stripping device was installed in the bottom grip of the Instron tensile tester. A constant amount of fiber (1 inch) was stripped by the blade, and the length was measured as a sample placed into the stripping apparatus. The fiber tip is held in Instron's pneumatic tip holder. The initial distance between the two grippers is 1 inch. Use an appropriate load cell to determine the maximum force required to remove the tight buffer coating. The crosshead speed of the Instron was set at a constant draw rate of 20 inches/min.

The measurements were performed immediately after fabrication of the tight-packed fiber (hereinafter referred to as "coating removal stress immediately after fabrication"). The measurement can also be performed after placing the tight-packed fiber at a temperature of 85°C and a relative humidity of 85% for 7 days (hereinafter referred to as "coating removal stress after high temperature and high humidity test"). This test method for measuring removability is hereinafter referred to as the "20 in/min test".

The composition of the present invention cured has a coating removal stress immediately after fabrication of less than 1800 g when measured using the 20 in/min test method.

The composition of the present invention cured has a coating removal stress after the high temperature and high humidity test of less than 1800 g when measured using the 20 in/min test method.

The results are shown in Table 2.

The components shown in Table 1 are as follows:

SH28PA: Dimethicone-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Co., Ltd.)

FM0411: Dimethicone-polyoxyalkylene copolymer (manufactured by Chisso Corp.)

SF8428: Dimethicone-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Co., Ltd.)

SH190: Dimethicone-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Co., Ltd.)

Pentad 19: Dimethicone-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Co., Ltd.)

Pentad 54: Dimethicone-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Co., Ltd.)

It can be clearly seen from Table 1 that the cured product of the resin composition of the present invention comprising a polysiloxane compound having an average molecular weight of 1000-35000 has excellent performance as an optical fiber coating material and exhibits excellent removability , so the composition can be used as a tight pack composition.

Table 2

Description of drawings

Fig. 1 is the schematic diagram of tensile testing machine;

Figure 2 is a schematic diagram of coating removal stress when removing the tight cladding.

Claims (16)

1. A curable liquid resin optical fiber tight package composition, said composition comprising: (A) 30-90wt% polyurethane (meth)acrylate, (B) 1-70wt% reactive diluent, (C) 0.1-10 wt% of a polymerization initiator, and (D) 1-50 wt% of a polysiloxane compound having an average molecular weight of 1500-35000, wherein the total amount of components (A), (B) and (C) is 100 wt%. 2. A curable liquid resin optical fiber tight package composition, said composition comprising: (A) 30-90wt% (meth)acrylate oligomer, (B) 1-70wt% reactive diluent, (C) 0.1-10 wt% of a polymerization initiator, and (D) 1-50 wt% of a polysiloxane compound having an average molecular weight of 1500-35000, wherein the total amount of components (A), (B) and (C) is 100 wt%. 3. The composition of claim 1 or 2, further comprising: The polyol compound (E) having a molecular weight of 1500 or more is used in an amount of 0.1 to 50% by weight of the total of 100% by weight of components (A), (B) and (C). 4. The composition according to any one of claims 1-3, wherein said component (D) is polyether polyol. 5. The composition according to any one of claims 1-4, wherein the polysiloxane compound (D) is a polyether-modified polysiloxane. 6. The composition according to any one of claims 1-5, wherein the amount of the polysiloxane compound is 1-20wt% of the 100wt% total amount of components (A), (B) and (C). 7. The composition of any one of claims 1-6, further comprising a flame retardant. 8. The composition of any one of claims 1-7, wherein said composition has a Young's modulus of from about 100 MPa to about 600 MPa after curing. 9. The composition of any one of claims 1-8, wherein the composition, after curing, has a coating removal stress immediately after manufacture of not more than 3.5 N when measured with the 50 m/min test method . 10. The composition of claim 9, wherein said composition after curing has a coating removal stress after high temperature and high humidity testing of not more than 3.5 N when measured with the 50 m/min test method. 11. The composition of any one of claims 1-8, wherein the composition after curing has a post-fabrication coating removal stress of less than 1800 g when measured with the 20 in/min test method. 12. The composition of claim 9 having an Immediate Coating Removal Stress after High Temperature and High Humidity Test of less than 1800 g after curing when measured with the 20 in/min test method. 13. An optical fiber tight cladding comprising a cured product of the composition according to any one of claims 1-7. 14. A kind of tight cladding optical fiber, described tight cladding optical fiber comprises the optical fiber tight cladding as claimed in claim 13. 15. A method for preparing an optical fiber tight cladding, said method comprising the step of curing the composition of any one of claims 1-7. 16. Use of the optical fiber tight cladding according to claim 13 as a tight coating having good removability and less degradation when exposed to high temperature and high humidity.

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