WO2008066112A1 - Composition de résine durcissable sous l'effet d'un rayonnement - Google Patents

Composition de résine durcissable sous l'effet d'un rayonnement Download PDF

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Publication number
WO2008066112A1
WO2008066112A1 PCT/JP2007/073052 JP2007073052W WO2008066112A1 WO 2008066112 A1 WO2008066112 A1 WO 2008066112A1 JP 2007073052 W JP2007073052 W JP 2007073052W WO 2008066112 A1 WO2008066112 A1 WO 2008066112A1
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group
meth
structural unit
curable resin
resin composition
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PCT/JP2007/073052
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English (en)
Japanese (ja)
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Hiroshi Miyazawa
Hiroyuki Ishii
Takahiko Kurosawa
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Jsr Corporation
Dsm Ip Assets B.V.
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Publication of WO2008066112A1 publication Critical patent/WO2008066112A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/12—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to nitrogen-containing macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/045—Light guides
    • G02B1/048—Light guides characterised by the cladding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention relates to a liquid curable resin composition for forming a cladding layer of a polymer-clad optical fiber.
  • optical fiber suitable for high-capacity, high-speed digital signal communication is being widely used instead of a so-called electric wire made of a metal wire that has been conventionally used.
  • Various types of optical fibers are known, depending on their structure and form.
  • the most basic structure of optical fibers is a core layer made of glass, quartz, or transparent resin, and the core layer.
  • the clad layer is provided in contact with the outer side, and the outer side of the clad layer is further provided with a polymer coating layer made of a radiation curable resin or the like.
  • all-silica optical fibers are often used in which both the core layer and the cladding layer are made of quartz.
  • the typical diameter of the optical fiber core wire is about 125 m when combined with the core layer of about 50 m and the cladding layer, and about 250 to 500 m when combined with the resin coating layer.
  • optical modules having various functions such as optical signal transmission 'reception' branching 'switching have been developed for various optical information communication, and the optical axes of these optical modules and optical fibers. It is known that connecting and aligning are important in suppressing attenuation of optical signals.
  • the diameter of the core layer of a conventional optical fiber core is small as described above. Since it is difficult to align the optical axis when connecting to an optical module, an optical fiber core with a core diameter increased to about 200 m is used. ! /
  • an optical fiber core having such a large diameter typically has a cladding layer made of a curable transparent resin, a polymer-clad optical fiber (plastic-clad optical fiber or polymer Also called a clad fiber).
  • a curable transparent resin As the curable transparent resin constituting the clad layer, an example using a fluorine-containing ultraviolet curable composition containing fluorine-containing urethane (meth) acrylate or fluorine-containing (meth) acrylate oligomer is known! /, Ru (patent document;! ⁇ 3).
  • a type having a core layer made of glass or quartz a type having a hard polymer clad optical fiber and a core layer made of transparent resin is called a plastic fiber.
  • a hard plastic clad optical fiber is used for communication over a relatively long distance because of its high optical transmission efficiency, and a plastic fiber is used for communication over a relatively short distance.
  • the curable transparent resin material used for the clad layer of such a polymer-clad optical fiber has a low refractive index and a stable transparency over time; for obtaining good coatability.
  • the resin material used for the clad layer of the conventional polymer clad optical fiber has a low refractive index and transparency, good coatability, adhesion to the core layer, strength 'polymer clad with excellent flexibility
  • a problem that it is difficult to obtain a layer, and in particular, it is difficult to obtain a polymer clad layer having stable transparency even when the polymer clad optical fiber is left in a high temperature environment.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-10340
  • Patent Document 2 Japanese Patent Laid-Open No. 10-160947
  • Patent Document 3 Japanese Patent Laid-Open No. 11-119036
  • the object of the present invention is to provide properties suitable as a clad material for polymer clad optical fibers, in particular, low refractive index and stable transparency, good coatability, adhesion to the core layer, strength 'flexibility' It is in providing the radiation-curable resin composition excellent in the.
  • the present inventor uses a radiation-curable resin composition comprising a specific fluorine-containing polymer, a specific fluorine-containing (meth) atrelate monomer, and a (meth) acrylate monomer having a specific structure not containing fluorine as essential requirements. And found that this purpose can be achieved.
  • the total amount of the composition is 100% by mass, (A) 20 to 65% by mass of an ethylenically unsaturated group-containing fluorine-containing copolymer,
  • the radiation curable resin composition to be contained is provided.
  • the polymer clad layer obtained from the resin composition of the present invention is particularly excellent in a low refractive index and stable transparency, good coatability, adhesion to the core layer, strength and flexibility.
  • the ethylenically unsaturated group-containing fluorine-containing polymer (A) is not particularly limited as long as it is a polymer having an ethylenically unsaturated group and a fluorine atom, but the fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Olefin-based copolymers are preferred.
  • the composition of the present invention exhibits basic performance as a clad forming material for polymer clad optical fibers such as low refractive index, high mechanical strength, and adhesion to a core layer such as glass or quartz.
  • the ethylenically unsaturated group-containing fluoropolymer is obtained by reacting the compound containing an ethylenically unsaturated group and an isocyanate group described below with the hydroxyl group of the hydroxyl group-containing fluoropolymer.
  • a compound containing an ethylenically unsaturated group and an isocyanate group [1] A compound containing an ethylenically unsaturated group and an isocyanate group:
  • the compound containing an ethylenically unsaturated group and an isocyanate group is not particularly limited as long as it is a compound containing at least one ethylenically unsaturated group and at least one isocyanate group in the molecule. It is not something.
  • the compound which has a (meth) atalyloyl group is more preferable.
  • examples of such compounds include (meth) acrylic acid, (meth) atari mouth alkylide, anhydrous (meth) acrylic acid, 2- (meth) ataryl oxychetyl isocyanate, 2- (meth) atariloy A single type of vanate or a combination of two or more types.
  • such a compound can also be cF Fl I synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
  • RCFIIate xylylene diisocyanate, methylenebis (4-cyclohexylenoisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane are preferred.
  • hydroxyl group-containing (meth) acrylate 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferred! /.
  • a hydroxyl group-containing polyfunctional (meth) atalylate for example, Osaka Organic Chemical Co., Ltd., trade name HEA; Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA, PET-30; Product name Alonix M-215, M-233, M-305, M-400, etc.
  • the hydroxyl group-containing fluoropolymer preferably contains the following structural units (a), (b) and ().
  • R 1 represents a fluorine atom, a fluoroalkyl group or a group represented by OR 2 (R 2 represents an alkyl group or a fluoroalkyl group)]
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group
  • — (CH 2 ) —OR 5 or OCOR 5 represents a group HHCII (R 5 represents an alkyl group or a glycidyl group)
  • X is 0 or 1
  • R u represents a hydrogen atom or a methyl group
  • R 12 represents a hydrogen atom or a hydroxyalkyl group
  • V represents a number of 0 or 1
  • the fluoroalkyl group of R 1 and R 2 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorohexyl. And a fluoroalkyl group having 1 to 6 carbon atoms such as a perfluorocyclohexyl group.
  • the alkyl group for R 2 include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group.
  • the structural unit (a) can be introduced by using a fluorine-containing butyl monomer as a polymerization component.
  • a fluorine-containing butyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom.
  • fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; (Metino Levinino Leetenore), Novoleo Mouth (Echnolevininore Ete Nore), Novoleo Mouth (Propino Levinino Leete Nore).
  • fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene
  • alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers (Metino Levinino Leetenore), Novoleo Mouth (Echnolevininore Ete Nore), Novoleo Mouth (Propino Levinino Leete Nore).
  • Perfluoro alkyl butyl ether
  • Perfluoro alkoxyalkyl vinyl ether
  • perfluoro propoxypropyl butyl ether
  • hexafluoropropylene and perfluoro (alkyl butyl ether) or perfluoro (alkoxy alkyl butyl ether) are more preferred and used in combination!
  • the content of the structural unit (a), the total amount of the structural units of the hydroxyl group-containing fluoropolymer in (a) ⁇ (c ') is 100 mol 0/0, 20 and 70 mol 0/0. This is because when the content is less than 20 mol%, it may be difficult to develop a low refractive index, which is an optically fluorine-containing material characteristic of the present invention. If the content exceeds 70 mol%, the solubility, transparency, or adhesion to the substrate of the hydroxyl group-containing fluoropolymer may decrease.
  • examples of the alkyl group of R 4 include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group,
  • examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.
  • the structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component.
  • bur monomers include methyl buule tenole, ethino levinino ree tenole, n-propino levino ree tenole, isopropino levino ree tenole, n-butyl butyl ether, isobutyl butyl ether.
  • Tert-Butyl bininore etherenole n-pentinorevininoreethenore, n-hexinorevininoreethenore, n-octinorevininoreethenore, n-dodecinorevininoreethenore, 2-ethinorehexino Anolequinolevinoleatenore such as revininorenotere, cyclohexenorevininoreteorenore or cycloanol kirbüll ethers; such as ethyl ether, butylaryl ether, etc.
  • carboxylic acid bisesters such as butyl acetate, butyl propionate, butyl butyrate, bivalinate, valproate, versatic butyl and stearate; methyl (meth) acrylate and ethyl (meta ) Atalylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) (Meth) acrylic acid esters such as acrylate, etc .; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids, etc., alone or in combination of two or more .
  • the content of the structural unit (b) is 10 to 70 mol% when the total amount of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer is 100 mol%. It is. The reason for this is that when the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, when the content exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluorine-containing polymer may deteriorate.
  • the content of the structural units (b), with respect to the total weight of the hydroxyl group-containing fluoropolymer preferably from the force S 20 to 60 mole 0/0, 30 to 60 mol force to the 0/0 S more preferred.
  • the hydroxyalkyl group of R 12 includes 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group. Group, 6-hydroxyhexyl group and the like.
  • the structural unit (c ') can be introduced by using a hydroxyl group-containing bull monomer as a polymerization component.
  • hydroxyl-containing bur monomers include 2-hydroxyethylenovininoleetenore, 3-hydroxypropinorevininoleetenore, 2-hydroxypropinorevininoreetenore, 4-hydroxybutinolebi Hydroxyl-containing butyl ethers such as Ninoreethenore, 3-Hydroxybutinorevininore Ethenore, 5-Hydroxypentinorevininoreetenore, 6-Hydroxyhexinorevininore Iter, 2-Hydroxyethylaryl ether, Examples include hydroxyl-containing aryl ethers such as 4-hydroxybutyl aryl ether and glycerol monoallyl ether, and aryl alcohol.
  • 2-hydroxyethyl (metatalylate, force prolatatatone (meth) atalylate, polypropylene glycol (meth) atrelate, etc.) can also be used as the hydroxyl group-containing butyl monomer.
  • the content of the structural unit (c ') is 5 to 70 monolayers when the total amount of the structural units (a) to (c') in the hydroxyl group-containing fluoropolymer is 100 mol%. % S is preferable.
  • the reason for this is that when the content rate is less than 3 ⁇ 4 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be lowered, whereas when the content rate exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxy group-containing fluoropolymer may be deteriorated.
  • the content of the structural units (c '), with respect to the total weight of the hydroxyl group-containing fluoropolymer preferably from the force S 5 to 40 mole 0/0, 5-30 Even more preferably the molar 0/0.
  • the hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).
  • R 9 and R 1Q represent the same or different hydrogen atom, alkyl group, halogenated alkyl group or aryl group
  • the alkyl groups of R 9 and R 1Q include an alkyl group strength S having 1 to 3 carbon atoms such as a methylol group, an ethyl group, a propyl group, and a halogenated alkyl group.
  • an alkyl group strength S having 1 to 3 carbon atoms such as a methylol group, an ethyl group, a propyl group, and a halogenated alkyl group.
  • trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, etc. C1-C4 fluoroalkyl group isotropic S
  • aryl group as phenyl group, benzyl group, Examples thereof include a naphthyl group.
  • the structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (1).
  • An example of such an azo group-containing polysiloxane compound is a compound represented by the following formula (8).
  • R ′′ to R lb represent the same or different hydrogen atom, alkyl group or cyan group, and R 17 to R 2 ° represent the same or different hydrogen atom or alkyl group.
  • P q is the number !! ⁇ 6, r, s is the number 0 ⁇ 6, t is the number !! ⁇ 200, u is the number !! ⁇ 20]
  • the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).
  • the alkyl group represented by R 13 to R 16 is an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, etc.
  • R 17 to R 2 ° alkyl groups include carbon groups such as methyl, ethyl, and propyl groups.
  • the azo group-containing polysiloxane compound represented by the above formula (8) is particularly preferably a compound represented by the following formula (10).
  • the content of the structural unit (d) is the total amount of the structural units of the hydroxyl group-containing fluoropolymer in (a) ⁇ (c ') is 100 mol 0/0, 0 .; ! preferable to be to 10 mol 0/0.
  • the reason for this is that when the content is less than 0.1 mol%, the surface slipperiness of the coating after curing may be reduced, and the scratch resistance of the coating may be reduced. If it exceeds 10 mol%, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling or the like may easily occur during coating.
  • the content of the structural unit (e) should be determined so that the content of the structural unit (d) contained therein falls within the above range.
  • the hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit ⁇ .
  • R Z1 is a group represented by the following formula (12).
  • the structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component.
  • a reactive emulsifier examples include compounds represented by the following formula (13). Yes
  • the content of the structural unit (f) is the total amount of the structural units of the hydroxyl group-containing fluoropolymer in (a) ⁇ (c ') is 100 mol 0/0, 0,; ! preferable to be to 5 mol 0/0.
  • the reason for this is that when the content is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved.
  • the content is within 5 mol%, the curable resin composition is used. This is because the adhesiveness of the film does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.
  • the (A) component ethylenically unsaturated group-containing fluoropolymer has a compound containing a hydroxyl group, an ethylenically unsaturated group, and an isocyanate group contained in the structural unit (c ′) of the hydroxyl group-containing fluoropolymer. It can be obtained by reacting with a reactive group such as an isocyanate group.
  • a reactive group such as an isocyanate group.
  • the molar ratio of the isocyanate group of the compound containing the ethylenically unsaturated group and the isocyanate group to the hydroxyl group of the hydroxyl group-containing fluoropolymer is 1.;! It is preferable to use a ratio.
  • the ethylenically unsaturated group-containing fluorine-containing polymer is a hydroxyl group-containing fluorine-containing polymer in addition to the structural unit (a) and the structural unit (b) derived from the hydroxyl group-containing fluorine-containing polymer.
  • the structural unit (c ′) has the following structural unit (c) produced by reacting with a compound containing an ethylenically unsaturated group and an isocyanate group.
  • the hydroxyl group-containing fluoropolymer has the structural unit (d), structural unit (e), structural unit (f), etc., these structural units are composed of an ethylenically unsaturated group and an isocyanate group.
  • the ethylenically unsaturated group-containing fluoropolymer also has the structural unit (d), the structural unit (e), the structural unit ⁇ and the like.
  • R 6 represents a hydrogen atom or a methyl group
  • R 7 represents a group represented by the following formula (4) or (5)
  • V represents a number of 0 or 1
  • R 8 represents a hydrogen atom or a methyl group
  • the molecular weight of the ethylenically unsaturated group-containing fluorine-containing copolymer should be 5,000-500,000 as the number average molecular weight in terms of polystyrene measured with tetrahydrofuran as a solvent by gel permeation chromatography (GPC). preferable.
  • GPC gel permeation chromatography
  • the ethylenically unsaturated group-containing fluorine-containing copolymer preferably has a polystyrene-equivalent number average molecular weight of 10,000 to 300,000, and is preferably 10,000 to 100,000. More preferably.
  • the ethylenically unsaturated group-containing fluorine-containing copolymer as the component (A) is usually compounded in an amount of 20 to 65% by mass, preferably 20 to 50% by mass, based on the total amount of the composition. Particularly preferably, 30 to 40% by mass is blended. If it is less than 20% by mass, the refractive index of the cured product will increase, and the adhesion to the core layer tends to decrease. If it exceeds 65% by mass, the blending amount of component (B) and component (C) will be reduced. As a result, the solubility of the component (A) may decrease, and it may be difficult to obtain a highly transparent cured product.
  • (B) 2-perfluoroalkylethyl (meth) acrylate having 1 to 18 carbon atoms: Component (B) blended in the composition of the present invention has 11 carbon atoms. It is 2-perfluoro oral alkyl ethyl (meth) acrylate which is ⁇ 18, and is usually represented by the following formula (14).
  • the component (B) is blended together with the component (C) described later in order to reduce the refractive index of the cured product, in addition to the purpose of ensuring the solubility of the component (A).
  • 2-perfluorooctylethyl (meth) acrylate is preferable because it is suitable for dissolving the component (A) and is easily available.
  • the component (B), 2-perfluoroalkylethyl (meth) acrylate, is usually added in an amount of 20 to 60% by mass, preferably 25 to 60% by mass, based on the total amount of the composition. It is particularly preferably 40 to 50% by mass. If it is less than 20% by mass, the solubility of the component (A) may be impaired, and the refractive index of the cured product may be reduced. If it exceeds 70% by mass, the viscosity of the composition will be reduced and the coating property will be reduced. Is damaged.
  • the compatibility between the (A) component ethylenically unsaturated group-containing fluorine-containing copolymer and the (meth) acrylate monomer is often limited.
  • the solubility is improved and a uniform composition can be obtained.
  • the mixing ratio of the component (B) and the component (C) is preferably 2: 3 to 5: 1 as a mass ratio, more preferably 2: 3 to 4: 1.
  • Component (C) blended in the composition of the present invention does not have an aromatic structure and a polar group, and It is a compound having two or more tyrenically unsaturated groups. Since the component (C) does not have a polar group, when used in combination with the component (B), the solubility of the component (A) is increased to give a uniform composition. Further, since the component (C) does not have an aromatic structure, a cured product having a low refractive index is given.
  • the polar group includes dissociable groups such as a carboxyl group and an amino group, and polarizable groups such as a carbonyl group and an alkylene oxide group having 3 or less carbon atoms, but a hydroxyl group is excluded.
  • the component (C) is not particularly limited as long as it has a structure that satisfies the above requirements.
  • component (C) include, for example, neopentyl dalycol di (meth) acrylate, neopentyl glycol hydroxybivalate di (meth) acrylate, trimethylol propane tri (meth) acrylate.
  • the component (C) one type may be used alone, or two or more types may be used in combination.
  • the component (C) is usually blended in an amount of 10 to 35% by mass, preferably 15 to 35% by mass, particularly preferably 15 to 30% by mass, based on the total amount of the composition. If it is less than 10% by mass, the solubility of component (A) may be impaired, and if it exceeds 35% by mass, the blending amount of component (A) and component (B) will be reduced, resulting in refraction of the cured product. The rate increases and the adhesion to the core layer is impaired.
  • composition of the present invention may further contain (D) (meth) acrylic acid or a dimer thereof.
  • (D) acrylic acid or a dimer thereof.
  • the component (D) is usually 0 to 10% by mass, preferably 1 to 7% by mass, based on the total amount of the composition. If it exceeds 10% by mass, the storage stability of the composition may be impaired. [0053] When the composition of the present invention is cured by irradiation with light such as ultraviolet rays, it is desirable to add (E) a photopolymerization initiator.
  • photopolymerization initiator examples include, for example, 1-hydroxycyclohexylphenylenoketone, 2,2-dimethoxy-1-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, Anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-clobenbenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-aminoaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin chinoleatenore , Penzino Resimethino Leketanol, 1- (4-Isopropinorefenenole) -2-Hydoxy-2-methylpropane 1-one, 2-Hydroxy-1-methyl-1-phenyl Pane 1-on, Thioxanthone, Jetylthioxanthone, 2-Is
  • a photosensitizer can also be used in combination.
  • photosensitizers include triethylamine, jetylamine, N-methyljetanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate; 103, 104, 105 (above, manufactured by UCB).
  • the thermal polymerization initiator and the photopolymerization initiator can be used in combination.
  • the polymerization initiator is preferably blended in an amount of 0.;! To 10% by mass, particularly 0.3 to 7% by mass, based on the total amount of the composition.
  • composition of the present invention does not have an aromatic structure and a polar group other than the components (F) (A), (B) and (C) as long as the effects of the invention are not impaired.
  • F ethylenically unsaturated group
  • Individual compounds can be blended.
  • Such a compound having no aromatic structure and polar group and having one ethylenically unsaturated group include a bull group-containing ratatam such as N-bullpyrrolidone and N-bull force prolatatum;
  • Vinylinoatenoles such as hydroxybutinorevininoreethenore, laurinorevininoreethenore, cetinolevininoreethenore, 2-ethenorehexinorevininoreethenore; ru (meth) acrylamide, N, N-dimethyl Acrylamides such as aminopropyl (meth) acrylamide t-octyl (meth) acrylamide;
  • alicyclic structures such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate (Meta) Atarirate;
  • Component (F) is a power that is usually added in an amount of 0 to 30% by mass, preferably 0, based on the total amount of the composition
  • the composition of the present invention includes (G) (A) component, (B) component, as long as the effects of the invention are not impaired. It is possible to add a compound having an ethylenically unsaturated group other than the components (C) and (F).
  • the component (G) include aromatic structure-containing (meth) acrylate, polar group-containing (meth) acrylate, such as a carboxyl group and an alkylene oxide structure, and the like.
  • the component (G) has a tendency to increase the refractive index of the cured product, as in the case of the aromatic structure-containing (meth) acrylate, and the solubility of the component (A) like the polar group-containing (meth) acrylate. Since the total amount of the composition is 100% by mass, the amount of component (G) is preferably 5% by mass or less.
  • G Commercially available products of these components (G) include, for example, Upimer UV, SA1002 (above, manufactured by Mitsubishi Chemical Corporation), Alonix M-215, M-315, M-325 (above, manufactured by Toagosei Co., Ltd.), Sartoma I can mention CN4000 (Cartoma Co., Inc.), Aronix TO-1210 (Toago Gosei Co., Ltd.), etc.
  • composition of the present invention various additives, for example, an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, and a silane coupling agent are added to the composition of the present invention as necessary, as long as the characteristics of the present invention are not impaired.
  • additives for example, an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, and a silane coupling agent are added to the composition of the present invention as necessary, as long as the characteristics of the present invention are not impaired.
  • the viscosity of the composition of the present invention is preferably 0.8 to 5. OPa's at 25 ° C, and particularly preferably 1.5 to 6 Pa's.
  • the liquid curable resin composition of the present invention may be used in combination with heat curing in addition to force radiation curing by radiation.
  • the radiation means infrared rays, visible rays, ultraviolet rays, X-rays, electron rays, ⁇ rays, / 3 rays, ⁇ rays, and the like.
  • the cured product of the liquid curable yarn and composite of the present invention preferably exhibits a yang ratio of 200 MPa to 500 MPa.
  • a cable layer made of a thermoplastic resin can be provided in contact with the outside of the optical fiber upjacket layer.
  • Nonionic reactive emulsifier (NE 30, manufactured by Asahi Denka Kogyo Co., Ltd.) 20 ⁇ Og was charged, cooled to 50 ° C with dry ice methanol, and oxygen in the system was removed again with nitrogen gas.
  • the obtained hydroxyl group-containing fluoropolymer 1 was measured for a polystyrene-reduced number average molecular weight by GPC, which was about 70,000. Further, from the measurement results of fluorine content by the alizarin complexone method, both NMR analysis results of 'H-NMR and 13 c NMR, and elemental analysis results, each monomer constituting the hydroxyl group-containing fluoropolymer 1 was determined. When the ratio of the components was determined, the structural unit derived from hexafluoropropylene (structural unit (a)), the structural unit derived from perfluoro (propyl butyl ether) (structural unit (a)), and derived from ethyl bulle ether.
  • structural unit (b) a structural unit derived from hydroxyethyl butyl ether
  • structural unit (c ′) a structural unit derived from hydroxyethyl butyl ether
  • structural unit (c ′) a structural unit derived from hydroxyethyl butyl ether
  • the total amount of structural units (a) to (c ′) is 100 mol%. They were 25: 25: 25: 25 monole% respectively.
  • ethylenically unsaturated group-containing fluoropolymer 1 The obtained ethylenically unsaturated group-containing fluorine-containing polymer is referred to as “ethylenically unsaturated group-containing fluoropolymer 1”.
  • the dilution solvent used at this time can be used as a component of the ultraviolet curable resin.
  • Each component having the composition shown in Table 1 was charged into a reaction vessel equipped with a stirrer and stirred for 1 hour while controlling the liquid temperature at 50 ° C. to obtain a liquid curable resin composition.
  • liquid curable resin compositions obtained in the examples and comparative examples were cured by the following method to prepare test pieces, and the following evaluations were performed. The results are also shown in Table 1.
  • the resin composition was applied onto a glass plate using an applicator bar so that the film thickness was 200 m. 1. Oj / cm 2 ultraviolet rays were irradiated under nitrogen to prepare a test piece. According to JIS K7105, the refractive index at 25 ° C. was measured using an Abbe refractometer manufactured by Atago Co., Ltd.
  • the total light transmittance of the cured film was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). The measurement was performed on the cured film immediately after production and on the cured film after standing at 120 ° C. for 72 hours.
  • the adhesive strength stability of the cured products was measured.
  • the liquid composition was applied onto a slide glass using an applicator with a thickness of 381 m, and irradiated with 0.1 lj / cm 2 of ultraviolet light in a nitrogen atmosphere to obtain a cured film having a thickness of about 200 m.
  • the cured film on the glass slide was allowed to stand for 24 hours at a temperature of 23 ° C and a humidity of 50%. Thereafter, a strip sample was prepared from the cured film so that the stretched portion had a width of 10 mm.
  • This sample was subjected to an adhesion test using a tensile tester according to JIS Z0237. The adhesion force was determined from the tensile strength at a tensile speed of 50 mm / min.
  • Biscote 17F 2 Perfluorooctyl cetyl (meth) acrylate (manufactured by Osaka Organic Chemical Co., Ltd.).
  • Irgacure 184 1-hydroxycyclohexyl monophenolate ketone (Ciba Specialo Chemicals).
  • Kyner ADS copolymer of VDF / TFE / HFP vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene (manufactured by Arkema).
  • each example shows the composition viscosity, the cured product's Young's modulus' mechanical strength (breaking strength and elongation), refractive index, transparency (haze), and exposure to high temperature conditions. Even after being applied, good transparency is maintained. It also has good adhesion to quartz, which is the core layer material. On the other hand, in Comparative Example 1 in which the amount of the component (C) is excessive, the balance of the amount of the component (B) and the component (C) is lost, so the solubility of the component (A) is reduced. The cured product has poor transparency!
  • Comparative Example 2 using an ethylenically unsaturated group instead of component (A) and a hydroxyl group-containing fluorine-containing polymer, the viscosity of the composition is too low, and the fluorine polymer is contained in the composition. Since it does not dissolve, it has poor transparency. Further, in Comparative Example 3 using V, a fluoropolymer, which does not correspond to the component (A), the fluoropolymer does not dissolve in the composition, and therefore the transparency is poor.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)

Abstract

La présente invention concerne une composition de résine durcissable sous l'effet d'un rayonnement présentant des caractéristiques propres à en faire un matériau de plaquage pour les fibres optiques plaquées de polymère, présentant, en particulier, un faible indice de réfraction, une transparence stable, une bonne aptitude à l'enduction, une bonne adhérence au matériau noyau, ainsi qu'une très grande résistance et une très grande souplesse. Plus précisément, l'invention concerne une composition de résine durcissable sous l'effet d'un rayonnement qui contient, si la quantité totale de composition est considérée comme égale à 100 % en poids, (A) 20 à 65 % en poids d'un copolymère contenant du fluor contenant un groupe éthyléniquement insaturé, (B) 20 à 60 % en poids d'un (méth)acrylate de 2-perfluoroalkyléthyle comportant 11 à 18 atomes de carbone, et (C) 10 à 35 % en poids d'un composé autre que le composant (A) et le composant (B), ne possédant ni structure aromatique ni groupe polaire, mais comportant au moins deux groupes éthyléniquement insaturés.
PCT/JP2007/073052 2006-11-29 2007-11-29 Composition de résine durcissable sous l'effet d'un rayonnement WO2008066112A1 (fr)

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JP5184059B2 (ja) * 2006-11-29 2013-04-17 Ｊｓｒ株式会社 放射線硬化性樹脂組成物
JP2008208226A (ja) * 2007-02-27 2008-09-11 Jsr Corp 放射線硬化性樹脂組成物
JP4982209B2 (ja) * 2007-02-27 2012-07-25 Ｊｓｒ株式会社 放射線硬化性樹脂組成物

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JPS6136374A (ja) * 1984-07-30 1986-02-21 Dainippon Toryo Co Ltd 含フツ素樹脂被覆組成物
JPS6296508A (ja) * 1985-10-23 1987-05-06 Sumitomo Chem Co Ltd 硬化性樹脂組成物
JPS6451418A (en) * 1987-08-21 1989-02-27 Asahi Glass Co Ltd Actinic radiation curable composition
JPH01113416A (ja) * 1987-10-27 1989-05-02 Dainippon Toryo Co Ltd 塗料用樹脂組成物
JPH05279435A (ja) * 1992-04-01 1993-10-26 Asahi Glass Co Ltd 活性エネルギー線硬化性組成物
JP2001131402A (ja) * 1999-10-29 2001-05-15 Asahi Glass Co Ltd 硬化性組成物
JP2002080547A (ja) * 2000-07-04 2002-03-19 Daikin Ind Ltd 活性エネルギー線硬化性水性フッ素樹脂組成物および含フッ素被覆物の形成方法
JP2003183322A (ja) * 2001-12-21 2003-07-03 Jsr Corp エチレン性不飽和基含有含フッ素重合体、並びにそれを用いた硬化性樹脂組成物及び反射防止膜
JP2005089536A (ja) * 2003-09-12 2005-04-07 Jsr Corp 硬化性樹脂組成物及び反射防止膜
JP2005290133A (ja) * 2004-03-31 2005-10-20 Jsr Corp 紫外線硬化型低屈折率材組成物及び反射防止膜
JP2006097003A (ja) * 2004-08-31 2006-04-13 Jsr Corp 樹脂組成物及び反射防止膜

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6136374A (ja) * 1984-07-30 1986-02-21 Dainippon Toryo Co Ltd 含フツ素樹脂被覆組成物
JPS6296508A (ja) * 1985-10-23 1987-05-06 Sumitomo Chem Co Ltd 硬化性樹脂組成物
JPS6451418A (en) * 1987-08-21 1989-02-27 Asahi Glass Co Ltd Actinic radiation curable composition
JPH01113416A (ja) * 1987-10-27 1989-05-02 Dainippon Toryo Co Ltd 塗料用樹脂組成物
JPH05279435A (ja) * 1992-04-01 1993-10-26 Asahi Glass Co Ltd 活性エネルギー線硬化性組成物
JP2001131402A (ja) * 1999-10-29 2001-05-15 Asahi Glass Co Ltd 硬化性組成物
JP2002080547A (ja) * 2000-07-04 2002-03-19 Daikin Ind Ltd 活性エネルギー線硬化性水性フッ素樹脂組成物および含フッ素被覆物の形成方法
JP2003183322A (ja) * 2001-12-21 2003-07-03 Jsr Corp エチレン性不飽和基含有含フッ素重合体、並びにそれを用いた硬化性樹脂組成物及び反射防止膜
JP2005089536A (ja) * 2003-09-12 2005-04-07 Jsr Corp 硬化性樹脂組成物及び反射防止膜
JP2005290133A (ja) * 2004-03-31 2005-10-20 Jsr Corp 紫外線硬化型低屈折率材組成物及び反射防止膜
JP2006097003A (ja) * 2004-08-31 2006-04-13 Jsr Corp 樹脂組成物及び反射防止膜

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