JPH0556299B2 - - Google Patents

Description

[Detailed Description of the Invention] Background and Problems of the Invention Resins that are cured by irradiation with active energy rays can be cured in seconds because they use electrical energy and there is almost no evaporation of the solvent. Reduces pollution, does not require high temperatures for curing, so there is no thermal deformation of the coated object, the curing equipment can be made smaller and save space, and the wavelength of energy rays is short, so image reproducibility is good, etc. For example, it has a wide range of uses in the fields of paint, printing industry, electronic industry, etc. as ultraviolet ray curing paint, electron beam curing paint, photoresist, electron beam resist, X-ray resist, plate-making material, etc. Active energy ray-curable resin compositions are attracting attention as optical fiber coating compositions. That is, for protection, the optical fiber is coated with a protective layer immediately after being drawn. This protective film not only prevents scratches on the glass in subsequent processes, but also prevents fiber deterioration and microbending that causes signal attenuation even after the product is manufactured. is also necessary. As the drawing speed of optical fiber increases, there is a need to shorten the curing time of coating compositions, and active energy ray-curable resin compositions that cure in seconds, such as ultraviolet rays and electron beams, are used for optical fibers. It is attracting attention as a coating composition. Optical fiber coating compositions, particularly primary coating compositions, are required to have a low modulus within the service temperature range (-40°C to 80°C) and a high elongation at break. It is also required to have water resistance such as low water absorption and little change in the physical properties of the coating after a hot water immersion test. In addition, in order to efficiently coat the optical fiber with a uniform film thickness, it is necessary to maintain a suitable viscosity (approximately 3,000 centipoise to approximately 7,000 centipoise).
centipoise). Initially, silicone-based coatings were used, but
Because it is thermosetting, it is difficult to keep up with the increasing speed of wire drawing, and today, UV-curable urethane acrylate-based coatings have been developed.
(JP-A-58-223638, JP-A-60-181170) However, urethane acrylate resins generally have a high viscosity, and it is often difficult to coat them as they are. JP-A-58-223638 describes the use of monoethylenically unsaturated monomers that can form strong hydrogen bonds, but since these monomers are water-soluble or have strong hydrophilic properties, water resistance is a concern. Ru. Furthermore, JP-A-60-181170 states that phosphoric acid esters and fatty acid esters can be used as viscosity reducing agents, but since these do not have photopolymerizability, depending on the amount used, the cured coating may There are problems such as adhesiveness. Due to its low modulus performance, silicone rubber has traditionally been used as an insulation material for electrical equipment, as a vibration and shock absorbing material, and as a sealing material, packing material, etc.
Widely used as coating material and lining material. Silicone rubber has excellent electrical properties, heat resistance, cold resistance, and weather resistance, but has drawbacks such as being expensive, requiring a long time or high temperature for curing, and being a two-component type. An object of the present invention is to provide a composition having an appropriate viscosity, good coating film properties (low modulus, high elongation at break), and good water resistance as a composition for primary coating of optical fiber. Solution The present invention provides: (a) 30 to 90% by weight of a reaction product obtained by reacting a polyol with a polyisocyanate and a lactone-(meth)acrylate adduct; (b) a mono(meth)acrylate represented by the following formula;
70-10% by weight (In the formula, X is an alkyl group, a phenyl group, or an alkyl-substituted phenyl group, R is a hydrogen atom or a methyl group, and n is an integer of 2 to 6.) Provided is an active energy ray-curable coating composition for optical fiber, which comprises dispersed fine resin particles. By using urethane acrylate made by reacting polyol with polyisocyanate and lactone/(meth)acrylate adduct as the resin component, compared to conventional urethane acrylate,
Excellent physical properties of the coating film (low initial Young's modulus, high elongation at break) were obtained. In order to coat optical fiber industrially, the coating composition must have an appropriate viscosity (approximately 3,000 to 10,000 cps). Since urethane acrylate resin is either a viscous liquid or a solid, a low viscosity monomer that can be copolymerized with urethane acrylate resin is used to obtain the appropriate viscosity. Young's modulus increases, elongation at break decreases, and water absorption increases, reducing the excellent coating performance of urethane acrylate resins. The monomer having the structure at point A is the above reaction product (a)
Maintains good coating film performance even when combined with The active energy ray-curable optical fiber coating composition of the present invention significantly improves the physical properties of a cured coating film compared to a composition that does not contain minute resin particles.
That is, a pseudo-network structure is formed between the polymer chains of the matrix resin and the fine resin particles, improving low modulus performance and elongation. In particular, the interaction between the matrix resin and minute resin particles due to this pseudo-network formation works effectively even when the matrix resin is in a rubber state, giving a high elongation rate. The decrease is small. Furthermore, addition of fine resin particles increases hardness and elongation, and selection of fine resin particles also improves wear resistance, fatigue resistance, and refractive index. Furthermore, the composition, which is liquid before curing, has a yield value by adding fine resin particles, and although it does not flow in a static state, it easily becomes fluidized by applying shear stress, so it can be used as a coating composition. When coating an object, the sagging limit is high, so a thick coating layer can be formed with one coating. The active energy ray-curable coating composition for optical fibers of the present invention is particularly useful as a primary coating agent for optical fibers, but it is also useful as other paints, coatings, molded bodies, adhesives, and as a substitute for silicone rubber. Useful. Detailed Discussion Polyols/Polyisocyanates/Lactones
Polyol, a reaction product of (meth)acrylate adduct The polyol herein means a synthetic organic polymer compound having two hydroxyl groups in the molecule. Examples include polyether polyols,
Includes polyester polyols, polyurethane polyols, polybutadiene polyols, silicone polyols, and the like. An example is shown below. ) Polyether polyol compounds such as polyalkylene glycols (e.g. polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol) or alkylene oxides (e.g. ethylene oxide, propylene oxide, tetrahydrofuran) are combined with polyhydric alcohols (e.g. ethylene glycol, Diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, 1,3-butanediol, 1,4-butanediol, 1,5-
polyester polyol compounds, such as polybasic acids (e.g. phthalic acid, isophthalic acid, terephthalic acid); Acid, tetrahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, hexahydrophthalic acid, hemicic acid, hexic acid, succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, dodecenylsuccinic acid, trimethic acid, pyromellitate acids) or their anhydrides and polyhydric alcohols (e.g. ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol) , neopentyl glycol, 1,2,6-hexanetriol, pentaerythritol, sorbitol, bisphenol A), polyester polyols obtained by condensation reactions with the above polyhydric alcohols and epoxy compounds (e.g. Casiura E, n-butyl glycidyl ether). , allyl glycidyl ether)
polyester polyol obtained by the reaction of the above epoxy compound and the above polybasic acid, higher fatty acids (such as soybean oil, linseed oil,
Safflower oil, coconut oil, dehydrated castor oil, tung oil,
ε
- Polymerized polyester polyols obtained by ring-opening polymerization of caprolactone and the above polyhydric alcohol; ) Polyurethane polyol compounds, such as polyisocyanate compounds (e.g. ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1-methyl -2,4-diisocyanate cyclohexane, 1-methyl-2,6-
Diisocyanate cyclohexane, ω, ω′-diisocyanate diethylbenzene, ω, ω′-diisocyanate dimethylaminotoluene, ω,
ω′-Diisocyanate dimethylxylene, ω,
ω'-diisocyanate diethylxylene, lysine diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 4,4'-methylenebis(cyclohexylisocyanate), ω,
ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, isophorone diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-methylenebis(phenyl isocyanate), triphenylmethane triisocyanate) or polymers thereof Excess amount of polyhydric alcohol (e.g. ethylene glycol, propylene glycol, 1,3-butyl glycol, neopentyl glycol, 2,2,
4-trimethyl-1,3-pentadiol, hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin, sorbitol, sorbitan,
Among polyurethane polyols obtained by addition reaction with sucrose, pentaerythritol, etc.), polyether polyols, polyester polyols, and polymerized polyester polyols, polyol compounds with a relatively low molecular weight and polyols as described above are used. polyurethane polyols obtained by addition reaction with isocyanate compounds; ) polybutadiene compounds, such as hydrogenated or unadded 1,4-polybutadiene diol; ) silicone compounds, such as dimethyl(poly)siloxane, methylphenyl(poly) A block copolymer or graft copolymer of siloxane, methylvinyl(poly)siloxane, cyanoalkylmethyl(poly)siloxane, fluorinated alkylmethyl(poly)siloxane, or any combination thereof, which has two or more hydroxyl groups. is at the end of the molecule or within the molecule; Polyisocyanates The polyisocyanate compounds mentioned above can be used as starting materials for the polyurethane polyol compounds. Lactone-(meth)acrylate adduct The lactone-(meth)acrylate adduct used in the present invention is produced by reacting a lactone with a hydroxy(meth)alkyl acrylate. Here, the lactone has the general formula, (In the formula, R ₁ and R ₂ represent hydrogen and hydrocarbon residues, respectively.
n is an integer from 4 to 7). A preferred lactone for use in the present invention is ε-caprolactone. Examples of the hydroxyalkyl (meth)acrylate used to produce the lactone-(meth)acrylate adduct include 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and
-Hydroxypropyl (meth)acrylate, 4
-hydroxybutyl acrylate, 2-hydroxy-3-chloro-propyl (meth)acrylate, etc. can be used. Reaction product of polyol, polyisocyanate and lactone-(meth)acrylate adduct The reaction product of polyol, polyisocyanate and lactone-(meth)acrylate adduct of the present invention can be produced by any of the methods described below. 1) Polyol, polyisocyanate, and lactone-(meth)acrylate adduct are charged all at once and reacted. 2) Polyisocyanate and lactone (meth)
The acrylate adduct is first reacted and then reacted with the polyol. 3) React the polyol with the polyisocyanate and then react with the lactone-(meth)acrylate adduct. For example, when using a difunctional polyol, a difunctional isocyanate, or a monofunctional lactone-(meth)acrylate adduct, it is preferable to adopt method 3) in order to obtain a reaction product with a desired molecular weight. . In addition, when using a trifunctional or higher functional polyol and/or a trifunctional or higher functional isocyanate,
In order to prevent gelation during the reaction, the polyisocyanate is reacted with a monofunctional lactone-(meth)acrylate adduct to reduce the NCO group of the polyisocyanate (preferably react to have one NCO group in the molecule). ) and then reacting the polyol, that is, it is preferable to adopt method 2). The molar ratio of polyol to polyisocyanate and lactone-(meth)acrylate used is 1.2 to 1.2 to 1 equivalent of polyol.
5 mol, lactone-(meth)acrylate adduct
0.3 to 5 moles, and the ratio of the total number of OH groups in the polyol and lactone-(meth)acrylate adduct to the number of NCO groups in the polyisocyanate.
The OH/NCO ratio should be greater than 1 so that no free isocyanate groups remain in the reaction product. In the synthesis of the above reaction products, common polymerization inhibitors (e.g. hydroquinone,
hydroquinone monomethyl ether, etc.) from 100 to 5,000 ppm, preferably from 500 to 2,000 ppm of the total weight,
and a urethanization catalyst (e.g. triethylamine, stannous octoate, dibutyltin dilaurate, etc.) of 100 to 5000 ppm, preferably 500 to 2000 ppm of the total weight, preferably at 30 to 150°C.
The reaction is carried out at a temperature of 30-100 °C. The NCO group can be detected, for example, by a conventional amine back titration method or by checking for absorption near 2200 cm ^-1 in an infrared absorption spectrum. The reaction can be carried out in the presence of a solvent. Examples of solvents include ethyl acetate, butyl acetate, benzene, toluene, xylene, methyl ethyl ketone,
Organic solvents commonly used in urethanization reactions can be used, such as methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, and ethoxyethyl acetate. These organic solvents may be used alone or in combination. After the reaction is completed, the monomer of formula (A) is added, and the organic solvent is removed by heating if necessary under reduced pressure. Mono(meth)acrylate (A) The mono(meth)acrylate used in the present invention has the formula (wherein, (Meth)acrylate, a (meth)acrylate of phenol and propylene oxide adducts of alkylphenols. The average number of moles of propylene oxide added is preferably 2 to 6 based on the viscosity. Specific examples of aliphatic alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-propyl alcohol.
-butyl alcohol, isobutyl alcohol,
Examples of alkyl-substituted phenols include sec-butyl alcohol and tert-butyl alcohol, and include cresol, nonylphenol, p-cumylphenol, benzylphenol, and the like. In the present invention, mono(meth)acrylates may be used alone or in combination of two or more. Micro resin particles Various methods have been proposed to produce micro resin particles, one of which involves suspension polymerization or suspension polymerization of an ethylenically unsaturated monomer with a crosslinkable comonomer in an aqueous medium. This method uses emulsion polymerization to create a dispersion of fine resin particles, and then removes water by solvent replacement, azeotropy, centrifugation, drying, etc. to obtain fine resin particles. Ethylenically unsaturated monomers and crosslinkable copolymers are co-coated in organic solvents or non-aqueous organic solvents that dissolve moles but do not dissolve polymers, such as high SP organic solvents such as esters, ketones, and alcohols. This is a method called the NAD method or precipitation method, in which the resulting fine resin particle copolymer is dispersed through polymerization. The fine resin particles of the present invention may be produced by any of the above methods. JP-A No. 58-129066 by the present inventors
The method for producing fine resin particles using a water-soluble resin having an amphoteric group described in the above publication may also be used. The particle size needs to be 0.01 to 2μ from the viewpoint of miscibility, reactivity, and storage stability. The smaller the particle size, the easier it is to form a pseudo network with the matrix resin. Examples of ethylenically unsaturated monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Alkyl esters of acrylic acid or methacrylic acid and other monomers having ethylenically unsaturated bonds that can be copolymerized with them, such as styrene,
Examples include α-methylstyrene, vinyltoluene, t-butylstyrene, ethylene, propylene, vinyl acetate, vinyl propionate, acrylonitrile, methacrylonitrile, dimethylaminoethyl (meth)acrylate, and the like. Two or more types of these monomers may be used. The crosslinkable copolymerizable monomer is a monomer having two or more radically polymerizable ethylenically unsaturated bonds in the molecule and/or two types of ethylenically unsaturated monomers each carrying mutually compatible groups. Contains group-containing monomers. Examples of monomers having two or more radically polymerizable ethylenically unsaturated groups in the molecule include polymerizable unsaturated monocarboxylic acid esters of polyhydric alcohols;
Examples include polymerizable unsaturated alcohol esters of polybasic acids and aromatic compounds substituted with two or more vinyl groups, examples of which include the following compounds. Ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanedioldia Acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate , glycerol diacrylate, glycerol allyloxy dimethacrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,
1,1-trishydroxymethylethane triacrylate, 1,1,1-trishydroxymethylethane dimethacrylate, 1,1,1-trishydroxymethylethane trimethacrylate, 1,
1,1-trishydroxymethylpropane diacrylate, 1,1,1-trishydroxymethylpropane triacrylate, 1,1,1-trishydroxymethylpropane dimethacrylate,
1,1,1-trishydroxymethylpropane trimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate and divinylpenzene. In addition, two groups each carrying a group that can react with each other
Examples of monomers having ethylenically unsaturated groups include epoxy group-containing ethylenically unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate, and carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, and crotonic acid. Monomers are the most representative, but mutually reactive groups are not limited to these.
For example, various compounds have been proposed, such as amine and carbonyl, epoxide and carboxylic acid anhydride, amine and carboxylic acid chloride, alkyleneimine and carbonyl, organoalkoxysilane and carboxyl, hydroxyl and isocyanate, etc., and the present invention broadly encompasses these. It is something to do. Fine resin particles produced in an aqueous medium or a non-aqueous organic medium can be isolated by a method such as filtration, spray drying, or freeze drying, and then they can be reduced to an appropriate particle size using a mill or the like. It can be used after being pulverized, or a synthesized dispersion can be used by replacing the medium with the solvent. Generally, it is desirable to control the particle size of the particles obtained by the polymerization method. 0.01
For particles of ~0.6 μ, emulsion polymerization method and NAD method are
The precipitation method is most suitable for particles of 0.2 to 2μ, and the suspension polymerization method is most suitable for particles of 1μ or more. In addition, rheology control is possible by adjusting the particle size distribution by the polymerization process or by mixing the particles after polymerization, if necessary. The glass transition point, solubility parameter, and refractive index of the fine resin particles can be controlled by the constituent components of the particles themselves in relation to the matrix resin. In addition, in the structure, by arranging functional groups or unsaturated groups that can react with each other or with the matrix resin on the surface of the resin particles, the interaction between the resin particles and between the resin particles and the matrix resin can be further enhanced. Furthermore, on the surface or inside of the resin particles, a sensitizer that is effective during curing with active energy rays, a promoter substance that promotes the reaction, and a functional substance that allows the composition to exhibit high functionality after curing are included. Of course, it is also possible to do so. Active energy ray-curable coating composition for optical fiber Active energy rays include ultraviolet rays, electron beams, X-rays, and radiation. In the active energy ray-curable coating composition for optical fiber of the present invention, active energy rays include ultraviolet rays, electron beams, X-rays, and radiation. (a) polyol/polyisocyanate/lactone-(meth)acrylate oligomer, and (b) mono(meth)acrylate of formula A and fine resin particles as essential components, and as optional components (1) sensitizer (ultraviolet light). (Required for curing) (2) Polymerizable monomer (3) Can contain other additives. Sensitizers for (1) include benzophenone, Michler's ketone, xanthone, thioxanthone, 2-chlorothioxanthone, benzyl, 2-ethyl anthraquinone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4' -isopropyl-2-methyl-propiophenone, methylbenzoylformate, benzoin methyl ether,
Benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, trichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2
- Phenyl acetophenone etc. can be used. As the polymerizable monomer in (2), polymerizable monomers that are commonly used for the purpose of viscosity dilution may be used, but the various performances required for optical fiber coating materials (low initial Young's modulus, high rupture Its use should be limited to a range that does not impair its properties (elongation, water resistance, etc.). These polymerizable monomers include methyl (meth)acrylate and ethyl (meth)acrylate.
Acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
lauryl (meth)acrylate, nonyl (meth)
Alkyl (meth)acrylates such as acrylate 2-hydroxyethyl (meth)acrylate,
Hydroxyalkyl (meth)acrylates such as 2-hydroxypropyl (meth)acrylate 2-ethoxyethyl (meth)acrylate, 4
-Alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate 2-phenoxyethyl (meth)acrylate,
Aryloxyalkyl acrylates such as 2-nonylphenoxyethyl (meth)acrylate Cycloalkyl acrylates such as cyclohexyl acrylate, cyclopentyl acrylate, isobornyl acrylate Cycloalkenyl (meth)acrylate such as dicyclopentenyloxyethyl (meth)acrylate ) Acrylates Aminoalkyl acrylates such as diethylaminoethyl (meth)acrylate Styrene, vinyltoluene, vinyl acetate, N-
Examples include polymerizable monomers such as vinyl compounds such as vinylpyrrolidone. Other additives in (3) include fillers (for example, inorganic fine powder such as colloidal silica and extender pigments),
These include coloring agents, surface conditioners such as silicone and fluorine compounds, and lightening agents. (a) The blending ratio of the reaction product obtained by reacting a polyol with a polyisocyanate and a lactone-(meth)acrylate adduct and (b) the mono(meth)acrylate represented by formula (A) is (i) ) Reaction product: 30 to 90% by weight (b) Mono(meth)acrylate: 70 to 10% by weight. If the reaction product (a) exceeds this ratio, the viscosity will be high and it will be difficult to coat the optical fiber. If the mono(meth)acrylate (b) exceeds this ratio, curing properties will decrease. If the amount of fine resin particles added is too small, the desired effect will not be achieved, and if it is too large, the workability of the composition will deteriorate, or the performance of the resulting coating layer will be deteriorated. 0.1 to 40% by weight, preferably 1 to 30% by weight of the total nonvolatile content
should account for When the composition of the present invention is used as a coating agent for optical fiber, for example, die ironing, spraying,
It can be applied to the surface of an optical fiber by a known technique such as fluidized dipping and cured by irradiation with active energy rays. The present invention will be explained in detail below using Reference Examples, Examples, and Comparative Examples. In these, "parts" and "%" are based on weight. Reference Example 1 Production of an emulsifier having an amphoteric group In a reaction vessel equipped with a stirrer, a nitrogen inlet tube, a temperature controller, a condenser, and a decanter, 134 parts of bishydroxyethyl taurine, 130 parts of neopentyl glycol, and azelaic acid were added. 236 parts of phthalic anhydride, 186 parts of phthalic anhydride, and 27 parts of xylene were charged, and the temperature was raised. Water produced by the reaction is azeotroped with xylene and removed. The temperature was raised to 190°C over about 2 hours from the start of reflux, stirring and dehydration were continued until the acid value equivalent to carboxylic acid reached 145, and then the mixture was cooled to 140°C. Next, while maintaining the temperature at 140° C., 314 parts of “Cardilla E10” (Versatellite glycidyl ester manufactured by Shell) was added dropwise over 30 minutes, and stirring was continued for 2 hours to complete the reaction. The obtained polyester resin had an acid value of 59, a hydroxyl value of 90, and an Mn of 1054. Reference Example 2 Production of fine resin particles In a reaction vessel equipped with a stirrer, a cooler, and a temperature control device, 380 parts of deionized water, 50 parts of the emulsifier having a zwitterionic group obtained in Reference Example 1, and 7 parts of dimethylethanolamine were added. and stirred at 80℃.
Dissolve the azobiscyanovaleric acid in this while
2.5 parts dissolved in 50 parts deionized water and 1.6 parts dimethylethanolamine, and 75 parts ethylene glycol dimethacrylate, 50 parts styrene, 50 parts methyl methacrylate, n-butyl acrylate.
A mixed solution of 75 parts was added dropwise over a period of 90 minutes, and stirring was continued for an additional 90 minutes to obtain an aqueous dispersion of fine resin particles with a nonvolatile content of 43% and an average particle diameter of 45 mμ. By azeotropically replacing the aqueous dispersion with xylol, the nonvolatile content was reduced to 40%.
% micro resin dispersion (A). Reference Example 3 Production of fine resin particles Deionized water was prepared using the same equipment as Reference Example 2.
580 parts, 15 parts of the emulsifier having a zwitterionic group obtained in Reference Example 1 and 2.2 parts of dimethylethanolamine were charged, and dissolved while stirring at a temperature of 80°C.
Add 2.5 parts of azobiscyanovaleric acid to this in deionized water.
50 parts and 1.6 parts of dimethylethanolamine, and 25 parts of ethylene glycol dimethacrylate, 60 parts of styrene, and 60 parts of methyl methacrylate.
A mixture of 100 parts of n-butyl acrylate and 5 parts of NK Ester M230G (manufactured by Shin-Nakamura Chemical Co., Ltd., acrylate having 23 ethylene oxide chains) was added dropwise over 90 minutes, and then an additional 90 parts of n-butyl acrylate was added dropwise over 90 minutes. After continuous stirring for minutes, the average particle size was 180 mμ with a non-volatile content of 29%.
An aqueous dispersion of minute resin particles was obtained. This aqueous dispersion was subjected to solvent replacement by azeotropy using butanol to obtain a fine resin dispersion (B) containing 20% non-volatile components. Reference example 4 1 equipped with a stirrer, cooler and temperature control device
400 parts of butyl acetate and the average molecular weight
2047 polyoxytetramethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., trade name PTMG 2000, OH value
54.8) 316.5 parts and xylylene diisocyanate
After charging 43.6 parts and stirring thoroughly, 0.40 part of diptyltin dilaurate was added, and the temperature was raised to 80°C and maintained for 1 hour. Next, 2-hydroxyethyl acrylate modified with one ε-caprolactone (manufactured by Daicel Chemical Industries, trade name Plaxel FA-1) 39.1
1 part and 0.40 part of hydroquinone were added, and stirring was continued at 80°C for 20 hours. It was confirmed by infrared absorption spectrum that the absorption of NCO groups had disappeared, and a polyether urethane acrylate resin solution (resin solid content 50%) was obtained. Reference example 5 1 equipped with a stirrer, cooler and temperature control device
400 parts of ethyl acetate and the average molecular weight
1996 tetrahydrofuran-propylene oxide copolymer resin (manufactured by Hodogaya Chemical Co., Ltd., trade name
Add 314.8 parts of PPTG2000, OH value 56.2) and 44.5 parts of xylylene diisocyanate, stir thoroughly, then add 0.40 parts of diptyltin dilaurate and heat at 80°C.
The temperature was raised to 1 and kept for 1 hour. Next, 2-hydroxyethyl acrylate modified with one ε-caprolactone (manufactured by Daicel Chemical Industries, Ltd., trade name Plaxel FA-1)
Add 39.9 parts and 0.40 parts of hydroquinone, and heat at 80℃ for 2 hours.
Continuing to stir for hours, confirm that the absorption of NCO groups has disappeared using an infrared absorption spectrum, and confirm that the polyether urethane acrylate resin solution (resin solid content 50%)
I got it. Reference example 6 1 equipped with a stirrer, cooler and temperature control device
400 parts of ethyl acetate, average molecular weight
1,4-polybutadiene having hydroxyl groups at both ends of 2564 (manufactured by Idemitsu Petrochemical Co., Ltd., trade name POLY BD)
After charging 317.4 parts of R-45HT, OH value 43.76) and 34.9 parts of xylylene diisocyanate and stirring thoroughly, 0.40 part of diptyltin dilaurate was added and heated at 80°C.
The temperature was raised to 1 and kept for 1 hour. Next, 2-hydroxyethyl acrylate modified with two ε-caprolactones (manufactured by Daicel Chemical Industries, Ltd., trade name Plaxel FA-1)
Add 46.8 parts and 0.40 parts of hydroquinone and heat at 80℃ for 2 hours.
Continuing to stir for hours, confirm that the absorption of NCO groups has disappeared using an infrared absorption spectrum, and confirm that the polybutadiene urethane acrylate resin solution (resin solid content
%) was obtained. Reference example 7 1 equipped with a stirrer, cooler and temperature control device
400 parts of ethyl acetate, average molecular weight
1650 dimethylpolysiloxane polyol (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-60A, OH value 68) 301.5
After adding 51.5 parts of xylylene diisocyanate and stirring thoroughly, dibutyltin dilaurate was added.
0.40 part was added and the temperature was raised to 80°C and maintained for 1 hour. Next, 2-hydroxyethyl acrylate modified with one ε-caprolactone (manufactured by Daicel Chemical Industries, Ltd., trade name Plaxel FA-1)
Add 46.2 parts and 0.40 parts of hydroquinone, and heat at 80℃ for 2 hours.
Continuing to stir for hours, confirm that the absorption of NCO groups has disappeared using an infrared absorption spectrum, and confirm that the polysilicone urethane acrylate resin solution (resin solid content 50
%) was obtained. Example 1 120 parts of the polyether urethane acrylate resin solution obtained in Reference Example 4 A monomer having the following structure (Kyoeisha Yushi Chemical Industry Co., Ltd.)
Co., Ltd., product name RNK-0148) After blending 60 parts with 7.5 parts of the fine resin dispersion obtained in Reference Example 2 and 2 parts of benzyl methyl ketal, ethyl acetate and xylol were distilled off under reduced pressure to obtain a coating composition. Physical Property Test The composition was coated on a glass plate to a thickness of 100 μm, and a cured film was obtained by irradiating with ultraviolet rays under the conditions shown below. Next, the cured film was peeled off from the glass plate and used as a tensile test sample, and a tensile test using Tensilon was conducted. It has good elongation at break and initial Young's modulus. The results are shown in Table 1. Ultraviolet irradiation conditions Nippon Battery high pressure mercury lamp HI-40N (80w/cm type,
Place the length of the lamp (using a condensing device) perpendicular to the conveyor traveling direction, and set the conveyor speed to 3 m/min at a height of 80 mm from the conveyor surface. Tensile test conditions using Tensilon Tensilon tensile testing machine (manufactured by Toyo Baldwin Co., Ltd., Model HI-100) was used to test the film with a length of 50 mm and a width
-40℃, 20℃ and 80℃ per 10mm sample
When measuring the elongation at break, the tensile speed was 50 mm/min.
The initial Young's modulus measurement was carried out at a tensile speed of 1 mm/min. The initial Young's modulus was measured by measuring the modulus at 2.5% elongation. Viscosity measurement Table 1 shows the results of measuring the viscosity at 25°C using an EM viscometer (Tokyo Keiki Co., Ltd.). Hot water immersion test A film prepared for a physical property test was immersed for one month in a constant temperature water bath adjusted to 80°C. Thereafter, the film was taken out, placed indoors for two days, and after drying, a physical property test was conducted. The results are shown in Table 1. Absorption rate measurement Absorption rate was measured by JIS K 7209B method. Example 2 80 parts of the polyether urethane acrylate resin solution of Reference Example 4 Monomer having the following structure (Toagosei Chemical Industry Co., Ltd.)
manufactured by TO-674) After blending 60 parts with 7.5 parts of the fine resin particle dispersion of Reference Example 2 and 2 parts with benzyl methyl ketal, ethyl acetate and xylol were distilled off under reduced pressure to obtain a coating composition. Various tests were conducted in exactly the same manner as in Example 1 using this composition.
The results are shown in Table 1. Example 3 80 parts of the polyether urethane acrylate resin solution of Reference Example 4 A monomer having the following structure (manufactured by Sanyo Chemical Industries, Ltd.,
Product name Neomar PHA-405) After blending 60 parts with 7.5 parts of the fine resin dispersion of Reference Example 2 and 2 parts with benzyl dimethyl ketal, ethyl acetate and xylol were distilled off under reduced pressure to obtain a coating composition. Various tests were conducted in exactly the same manner as in Example 1 using this composition.
The results are shown in Table 1. Example 4 120 parts of the polyether urethane acrylate resin solution of Reference Example 5 40 parts of the monomer used in Example 1 7.5 parts of the fine resin particle dispersion of Reference Example 2 After blending 2 parts of benzyl dimethyl ketal, ethyl acetate under reduced pressure, Xylol was distilled off to obtain a coating composition. Various tests were conducted in exactly the same manner as in Example 1 using this composition.
The results are shown in Table 1. Example 5 100 parts of the polyether urethane acrylate resin solution of Reference Example 6 50 parts of the monomer used in Example 1 15 parts of the fine resin dispersion of Reference Example 3 After blending 2 parts of benzyl methyl ketal, ethyl acetate and xylol were added under reduced pressure. was distilled off to obtain a coating composition. Various tests were conducted in exactly the same manner as in Example 1 using this composition.
The results are shown in Table 1. Example 6 140 parts of the polysilicon urethane acrylate resin solution of Reference Example 7 30 parts of the monomer used in Example 1 15 parts of the fine resin particle dispersion of Reference Example 3 After blending 2 parts of benzyl methyl ketal, ethyl acetate under reduced pressure, Butanol was distilled off to obtain a coating composition. Various tests were conducted in exactly the same manner as in Example 1 using this composition.
The results are shown in Table 1. Comparative Example 1 N instead of the monomer used in Example 1
-An ultraviolet curable composition was obtained in exactly the same manner except that 40 parts of vinylpyrrolidone was used. Various tests were conducted on this composition in exactly the same manner as in Example 1. The results are shown in Table 1. Comparative Example 2 An ultraviolet curable composition was obtained in exactly the same manner as in Example 1, except that the fine resin particle dispersion obtained in Reference Example 2 was not used. Various tests were conducted on this composition in exactly the same manner as in Example 1. The results are shown in Table 1. Example 7 Silica glass fibers were spun to have a diameter of 125μ, and immediately after spinning, the compositions of Examples 1 to 4 were coated to a film thickness of 100μ, and irradiated with ultraviolet rays to obtain a primary coated glass fiber. I was able to do that. The primary coated glass fiber had sufficient flexibility even when bent without cracking or peeling. In addition, each primary coated glass fiber was heated at −60°C.
No increase in transmission loss was observed up to this point. 【table】

Claims (1)

[Scope of Claims] 1(a) 30 to 90% by weight of a reaction product obtained by reacting a polyol with a polyisocyanate and a lactone-(meth)acrylate adduct (b) A mono(meth) represented by the following formula: acrylate
70-10% by weight (In the formula, X is an alkyl group, phenyl group, alkyl-substituted phenyl group, R is a hydrogen atom or a methyl group, n
represents an integer from 2 to 6. 1.) A coating composition for active energy ray-curable optical fibers, comprising a composition comprising: 2. The coating composition for optical fiber according to item 1, wherein the polyol is selected from polyether polyols, polyester polyols, polyurethane polyols, polybutadiene polyols, and silicone polyols. 3. A group in which the polyether polyol is polyethylene glycol, polypropylene glycol, ethylene oxide/propylene oxide copolymer, polytetramethylene glycol, tetramethylene oxide/ethylene oxide copolymer, tetramethylene oxide/propylene oxide copolymer, or a mixture thereof. 2. The coating composition for optical fiber according to item 2. 4. The optical fiber coating composition according to any one of items 1 to 3, wherein the fine resin particles are a polymer or copolymer of monomers having internally crosslinked polymerizable unsaturated groups.