JPH055775B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a coating material for optical communication fiber and an optical communication fiber coated with a cured product of the coating material. There is little change in adhesion or peeling force over time, and specifically, even when placed in water, an increase in peelability from glass is prevented as much as possible, and even when placed in the air at high temperatures, A coating agent for optical communication fibers that provides a coating having stable adhesion to a glass surface, which does not excessively increase the adhesion to glass and make processing steps after coating difficult, and the coating agent. The present invention relates to an optical communication fiber coated with a cured material. PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION A variety of optical communication fibers have been known, such as quartz glass, multi-component glass, and plastic fibers, but in reality, their light weight and low Silica glass-based materials have been put into practical use due to their loss properties, non-inductive properties, heat resistance, weather resistance, and transmission capacity. However, since this silica glass fiber is extremely thin and easily deteriorates over time, the surface of the silica glass fiber is coated with an appropriate material. Silicone resin is used as a coating material because it has low temperature dependence, can be used over a wide temperature range, is effective in maintaining strength and relieving stress, and is less likely to cause transmission loss due to microbends and less likely to generate noise due to scattering. is considered preferable. However, although this silicone resin has good compatibility with glass due to its chemical structure, the strength of the cured film is weak, so it has the disadvantage that the film can be torn or peeled off from the glass surface during the coating process or post-coating process. There is. On the other hand, polyether or polyester acrylates have also been put into practical use as coating materials for optical communication fibers, but these organic resins have strong cured coatings, so the coating may be damaged during the coating process or post-coating treatment process. Although it has the advantage of not breaking, and is attracting attention in this respect, it is not compatible with glass, and in particular, the adhesion or peeling force of the coating to optical communication fibers changes significantly over time.
If left in water, it will gradually peel off from the glass surface, which will increase the transmission loss of the optical communication fiber. Furthermore, if the coating is left under high-temperature conditions even in air, the adhesion to the glass surface will increase more than necessary, which will make the post-coating process difficult. The present invention was developed in view of the above circumstances, and has good adhesion to a glass surface even when left underwater, and does not increase adhesion excessively even under high temperature conditions. A coating agent for optical communication fibers that provides a coating (cured product) with little change in adhesive force or peeling force over time, maintains appropriate adhesion, and facilitates post-coating treatment steps, and a cured product of the coating agent. The purpose of the present invention is to provide an optical communication fiber coated with Means and Effects for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies and found that polymerizable carbon and carbon dioxide are present in the molecules of polyether compounds or acrylates of polyester compounds. Aminoalkylsilanes such as γ-aminopropyltrialkoxysilane and the following general formula are used as photopolymerizable compounds having one or more double bonds. (However, in the formula, m and n represent 0 or a positive number,
0≦m+n≦10) or an acetylene alcohol in which some or all of the hydrogen atoms bonded to the carbon atoms in the formula are replaced with halogen atoms, the resulting coating material can be dissolved in water. The inventors have discovered that it is possible to minimize the decrease in adhesion to the glass surface even under high temperature conditions, and to provide a cured product with minimal increase in adhesion even under high-temperature conditions. This is what we have come to complete. Therefore, the present invention provides (A) a photopolymerizable compound having one or more polymerizable carbon-carbon double bonds in the molecule, (B) an aminoalkylsilane, (C) the following general formula (1) (However, in the formula, m and n represent 0 or a positive number,
0≦m+n≦10) or an acetylene alcohol represented by the above formula (1) in which some or all of the hydrogen atoms bonded to the carbon atoms are replaced with halogen atoms, and (D) a photopolymerization initiator. The present invention provides a coating agent for optical communication fiber characterized by containing the present invention, and an optical communication fiber characterized by being coated with a cured product of the coating agent. The present invention will be explained in more detail below. The photopolymerizable compound having one or more polymerizable carbon/carbon double bonds in the molecule of component (A) constituting the coating material of the present invention includes, as its functional group, an acrylic group, a methacrylic group, and groups thereof. Examples include those having a group selected from groups in which part or all of the hydrogen atoms bonded to the carbon atoms of There is no problem even if those having one carbon-carbon double bond and those having two or more carbon-carbon double bonds coexist. The skeleton of this photopolymerizable compound is not particularly limited, and various skeletons may be employed. Specifically, polyether compounds such as polytetramethylene glycol, polypropylene glycol, and random copolymers of tetrahydrofuran and propylene oxide,
Examples include polyester compounds such as poly-ε-caprolactone, and as the component (A) of the present invention, compounds obtained by modifying the molecular chain terminals of these compounds with acrylic or methacryl are used. Next, the aminoalkylsilane of component (B) is not particularly limited, and various kinds can be used. Specifically, the aminoalkyl group includes primary amino groups such as γ-aminopropyl group, δ-aminobutyl group, and ε-aminopentyl group; secondary amino groups such as N-phenyl-γ-aminopropyl group; , tertiary amino group such as N'-dimethyl-γ-aminopropyl group, N-
Groups with multiple amino groups such as β(aminoethyl)-γ-aminopropyl groups, or groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are replaced with halogen atoms, etc. Mention may be made of silane compounds. In addition, the aminoalkylsilane of component (B) may contain an alkoxy group, a hydroxyl group, an alkyl group, an alkenyl group, an aryloxy group, or an aryl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Aryloxy groups include phenoxy groups, alkenyl groups include vinyl groups, allyl groups, etc., aryl groups include phenyl groups, tolyl groups, etc. Examples of the group include a methyl group, an ethyl group, a propyl group, a butyl group, and a group in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are replaced with halogen atoms. Note that among these aminoalkylsilanes, γ-aminopropyltrialkoxylacine is particularly preferred. In addition, the acetylene alcohol of component (C) is expressed by the following general formula (1). (However, in the formula, m and n represent 0 or a positive number,
0≦m+n≦10). Specifically, a commercially available product is Surf Inol 104 (m+n=0, Nissin Chemical Industry Co., Ltd.).
Surf Inol 440 (m + n = 3.5, product name manufactured by Nissin Chemical Industry Co., Ltd.), Surf Inol 465 (m
+n=10, trade name manufactured by Nissin Chemical Industry Co., Ltd.). In addition, as component (C), the above formula
Those in which part or all of the hydrogen atoms bonded to the carbon atoms in (1) are replaced with halogen atoms are also preferably used. Here, m and n in the above formula (1) are 0 or positive numbers satisfying 0≦m+n≦10, as described above,
When m+n exceeds 10, the peelability of the resulting coating material in water after being hardened onto a glass plate increases, making it impossible to achieve the object of the present invention. A polymerization initiator is further added as component (D) to the coating material of the present invention, and examples of such polymerization initiators include IRGAKYUR 184 (trade name manufactured by Ciba Geigy Co., Ltd.) and DAROCKYUR 1173 (trade name manufactured by Merck Co., Ltd.). ) product name) etc.
-Hydroxyacetophenone photoinitiator, benzophenone, benzophenone photoinitiator such as 3,3-dimethyl-4-methoxybenzophenone, thioxanthone such as 2,4-diethylthioxanthone, 2-chlorothioisanthone, etc. Examples include photopolymerization initiators. The coating material for optical communication fiber of the present invention includes the above (A)
It contains a mixture of a photopolymerizable compound (component), an aminoalkylsilane (component (B)), acetylene alcohol (component (C)), and a polymerization initiator (component (D)). It can be determined depending on the properties required for the coating material for optical communication fiber, but in particular, for 100 parts by weight of component (A),
Component (B) is preferably 0.1 part by weight or more,
More preferably, it is 0.5 to 2 parts by weight. (A) Ingredient 100
When component (B) is less than 0.1 parts by weight based on parts by weight,
The object of the present invention may not be achieved due to increased peelability in water after the coating is cured on the glass plate. In addition, the amount of (C) component is (A) component
The amount of component (C) is preferably 0.1 parts by weight or more, more preferably 0.5 to 2 parts by weight, per 100 parts by weight. If the amount of component (C) is less than 0.1 part by weight relative to 100 parts by weight of component (A), the adhesion to the glass under high temperature conditions after curing the coating material on the glass plate will be extremely increased. In some cases, the object of the present invention may not be achieved. Furthermore, the blending amount of component (D) is the same as that of component (A).
The amount is preferably 1 to 5 parts by weight per 100 parts by weight. In addition, antioxidants, light stabilizers, etc. may be added to this optical communication fiber coating material as necessary, and metal oxides such as finely powdered silica such as fumed silica, titanium oxide, aluminum oxide, etc. , fillers such as carbon black, and other additives may be added. When coating an optical communication fiber with the coating material of the present invention, a method is preferably employed in which the coating material of the present invention is applied to the surface of the optical communication fiber and cured by irradiation with ultraviolet rays. The coating material for optical communication fibers of the present invention is suitably used as a coating material for quartz-based optical communication fibers, but it can also be used as a coating material for multi-component glass-based or plastic-based optical communication fibers. It can also be suitably used as an adhesive for other glasses and as a coating agent for printed circuit boards. Effects of the Invention As explained above, the coating material for optical communication fiber of the present invention exhibits stable adhesion to quartz-based optical communication fiber and has good adhesion to glass surfaces even in water. In addition, the coating material for optical communication fiber of the present invention provides a cured product that does not easily peel off from the glass surface, thereby providing an optical communication fiber with low transmission loss. Since the coating does not cause an excessive increase in adhesion to glass under high temperature conditions in air, processing steps after coating can be carried out easily. Therefore, the optical communication fiber coated with the cured product of the coating material of the present invention has excellent transmission properties and can be easily subjected to processing steps such as when connecting optical communication fibers to each other. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below. Example 1 50 g of a random copolymer of tetrahydrofuran and propylene oxide with an average molecular weight of 4000 and acrylic modified polymer at the molecular chain end, oligoester acrylate (structural formula: p≒2.5 Manufactured by Toagosei Chemical Industry Co., Ltd. Product name: Aronix M
-117) 50 g, 0.5 g of γ-aminopropyltrimethoxysilane as an adhesion aid, tetramethyldecynediol (structural formula: Manufactured by Nissin Chemical Industry Co., Ltd. Product name: Surf Inol 104)
0.5g, 2-hydroxy-2- as polymerization initiator
3 g of methylpropiophenone (trade name: Darokyure 1173, manufactured by Merck & Co., Ltd.) was mixed to obtain a coating material for optical communication fibers having a viscosity of 6300 cp at 25°C. This coating was applied to a glass fiber with a diameter of 125 μm at room temperature to a thickness of 100 μm at a speed of 30 m/min. When the film was cured, an optical communication fiber uniformly coated with the cured product of this coating material was obtained. On the other hand, the coating material for optical communication fiber obtained above was coated on a glass plate in a width of 25 mm and a thickness of 0.6 mm, and the coating was cured by irradiating ultraviolet rays under the same conditions as above at 80°C. and those heated in a dryer.
For each sample immersed in 25°C water, the 90° tensile peeling force (pulling speed 30 mm/min) was measured using Autograph AGS-500B (trade name, manufactured by Shimadzu Corporation). The results are shown in Table 1. Comparative Example 1 A coating material having a viscosity of 6750 cp at 25° C. was prepared in the same manner as in Example 1 except that γ-aminopropyltrimethoxysilane and tetramethyldecynediol (trade name: Surfynol 104) were not added. When this coating material was applied to a glass fiber in the same manner as in Example 1 and the coating film was cured by ultraviolet irradiation, an optical communication fiber uniformly coated with the cured product of this coating material was obtained. . On the other hand, the tensile peeling force of the cured film of this coating material was measured in the same manner as in Example 1. Results first
Shown in the table. Comparative Example 2 A coating material having a viscosity of 6410 cp at 25° C. was prepared in the same manner as in Example 1 except that tetramethyldecynediol (trade name: Surfynol 104) was not added. When this coating material was applied to a glass fiber in the same manner as in Example 1 and the coating film was cured by ultraviolet irradiation, an optical communication fiber uniformly coated with the cured product of this coating material was obtained. . On the other hand, the tensile peeling force of the cured film of this coating material was measured in the same manner as in Example 1. Results first
Shown in the table. Comparative Example 3 A coating having a viscosity of 6650 cp at 25° C. was prepared in the same manner as in Example 1 except that γ-aminopropyltrimethoxysilane was not added. This coating material was applied to a glass fiber in the same manner as in Example 1,
When this coating film was cured by irradiation with ultraviolet rays, an optical communication fiber uniformly coated with the cured product of this coating material was obtained. On the other hand, the tensile peeling force of the cured film of this coating material was measured in the same manner as in Example 1. Results first
Shown in the table. Comparative example 4 Instead of tetramethyldecynediol (product name: Surfynol 104) (Product name: Surf Inol manufactured by Nissin Chemical Industry Co., Ltd.)
A coating material having a viscosity of 6260 cp at 25° C. was prepared in the same manner as in Example 1 except that 0.5 g of 485) was added. When this coating material was applied to a glass fiber in the same manner as in Example 1 and the coating film was cured by ultraviolet irradiation, an optical communication fiber uniformly coated with the cured product of this coating material was obtained. . Next, the tensile peeling force of the cured film of this coating material was measured in the same manner as in Example 1. The results are shown in Table 1. Example 2 Polymer 70 in which the molecular chain end of polytetramethylene glycol with an average molecular weight of 3000 was modified with acrylic
g, as a reactive diluent q≒4 (trade name: Aronix M-113 manufactured by Toagosei Chemical Industry Co., Ltd.) 30g, γ-aminopropyltriethoxysilane 2.0g as an adhesion aid, (Product name: Surf Inol manufactured by Nissin Chemical Industry Co., Ltd.)
465) and 3 g of 2-hydroxy-2-methylpropiophenone (product name: Darokyuur 1173, manufactured by Merck & Co., Ltd.) as a polymerization initiator were mixed to obtain a coating material having a viscosity of 4550 cp at 25°C. When this coating material was applied to a glass fiber in the same manner as in Example 1 and the coating film was cured by ultraviolet irradiation, an optical communication fiber uniformly coated with the cured product of this coating material was obtained. . On the other hand, the tensile peeling force of the cured film of this coating material was measured in the same manner as in Example 1. The results are shown in Table 1. Example 3 60 g of polyε-caprolactone with an average molecular weight of 3000, acrylic-modified polymer at the molecular chain end, as a reactive diluent (Product name: R-629 manufactured by Nippon Kayaku Co., Ltd.) 40g, γ-aminopropyltrimethoxysilane 1.0g as an adhesion aid, polyoxyethylenetetramethyldecynediol diether (structural formula: Manufactured by Nissin Chemical Industry Co., Ltd. Product name: Surf Inol 440)
2.0g, 2-hydroxy-2- as polymerization initiator
3 g of methylpropiophenone (trade name: Darokyure 1173, manufactured by Merck & Co., Ltd.) was mixed to obtain a coating material having a viscosity of 7320 cp at 25°C. When this coating material was applied to a glass fiber in the same manner as in Example 1 and the coating film was cured by irradiation with ultraviolet rays, an optical communication fiber uniformly coated with the cured product of this coating material was obtained. . On the other hand, the tensile peeling force of the cured film of this coating material was measured in the same manner as in Example 1. The results are shown in Table 1.

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Claims (1)

[Claims] 1 (A) One polymerizable carbon-carbon double bond in the molecule
(B) aminoalkylsilane, (C) the following general formula (1) (However, in the formula, m and n represent 0 or a positive number, and 0≦m+n≦10) or the above formula (1)
1. A coating material for optical communication fibers, comprising: (D) a photopolymerization initiator in which some or all of the hydrogen atoms bonded to carbon atoms in the fiber are replaced with halogen atoms; and (D) a photopolymerization initiator. 2. An optical communication fiber coated with a cured product of the coating material according to claim 1.