WO2008066112A1 - Radiation curable resin composition - Google Patents
Radiation curable resin composition Download PDFInfo
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- 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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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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Abstract
Disclosed is a radiation curable resin composition having characteristics suitable for a cladding material for polymer-clad optical fibers, particularly having low refractive index, stable transparency, good coatability, adequate adhesion to the core layer, and excellent strength and flexibility. Specifically disclosed is a radiation curable resin composition which contains, when the total amount of the composition is taken as 100% by mass, (A) 20-65% by mass of an ethylenically unsaturated group-containing fluorine-containing copolymer, (B) 20-60% by mass of a 2-perfluoroalkylethyl (meth)acrylate having 11-18 carbon atoms, and (C) 10-35% bymass of a compound other than the component (A) and the component (B), which does not have an aromatic structure nor a polar group but has two or more ethylenically unsaturated groups.
Description
明 細 書 Specification
放射線硬化性樹脂組成物 Radiation curable resin composition
技術分野 Technical field
[0001] 本発明は、ポリマークラッド光ファイバのクラッド層形成用液状硬化性樹脂組成物に 関する。 [0001] The present invention relates to a liquid curable resin composition for forming a cladding layer of a polymer-clad optical fiber.
背景技術 Background art
[0002] 情報通信用ケーブルとしては、従来用いられてきた金属線からなるいわゆる電線に 替わり、高容量、高速度のデジタル信号通信に適した光ファイバが多用されつつある 。光ファイバは、その構造や形態に応じて、さまざまな種類が知られている力 最も基 本となる構造である光ファイバ心線は、ガラス、石英又は透明樹脂からなるコア層と該 コア層の外側に接して設けられたクラッド層を有しており、さらに該クラッド層の外側を 放射線硬化性樹脂等によるポリマー被覆層を設けられた構造を有してレ、る。中でも、 コア層とクラッド層が共に石英からなる全石英光ファイバが多用されている。光フアイ バ心線の典型的な口径は、コア層 50 m程度、クラッド層と合わせた状態で 125 m程度であり、樹脂被覆層をも合わせた状態で 250〜500 m程度である。 [0002] As an information communication cable, an 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. Of these, 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.
[0003] 一方、多様な光情報通信のために、光信号の送信'受信 '分岐'スイッチング等の 各機能を有する光モジュールが開発されており、これらの光モジュールと光ファイバ 心線の光軸を位置合わせして接続することが、光信号の減衰を抑制する上で重要で あることが知られている。従来の光ファイバ心線のコア層の口径は上記の通り小さぐ 光モジュールと接続する際の光軸合わせが困難であるため、コア径を 200 m程度 に大きくした光ファイバ心線が用いられて!/、る。 [0003] On the other hand, 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. ! /
[0004] このような大口径を有する光ファイバ心線は、典型的には、硬化性の透明樹脂から なるクラッド層を有しているため、ポリマークラッド光ファイバ(プラスチッククラッド光フ アイバ又は、ポリマークラッドファイバともいう。)と呼ばれている。クラッド層を構成する 硬化性の透明樹脂としては、フッ素含有ウレタン (メタ)アタリレートやフッ素含有 (メタ )アタリレートオリゴマー等を含有するフッ素含有紫外線硬化性組成物を用いた例が 知られて!/、る(特許文献;!〜 3)。
[0005] さらに、ポリマークラッド光ファイバのうち、ガラス又は石英からなるコア層を有するタ イブが、ハードポリマークラッド光ファイバ、透明樹脂からなるコア層を有するタイプが 、プラスチックファイバと呼ばれている。ハードプラスチッククラッド光ファイバは、光伝 送効率が高いため、比較的長距離の通信用であり、プラスチックファイバは、比較的 短距離の通信用に用いられる。 [0004] Since 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). 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). [0005] Further, among polymer clad optical fibers, 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.
[0006] このようなポリマークラッド光ファイバのクラッド層に用いられる硬化性の透明樹脂材 料には、低い屈折率と経時的に安定した透明性とを有すること;良好な塗布性を得る ための適当な粘度を有していること;コア層との密着性に優れること;ヤング率や破断 強度 ·破断伸び等で表される強度、柔軟性を有することなどの特性が要求されている [0006] 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. Appropriate viscosity; excellent adhesion to the core layer; properties such as Young's modulus, strength at break, strength represented by elongation at break, and flexibility
[0007] しかし、従来のポリマークラッド光ファイバのクラッド層に用いられる樹脂材料では、 低い屈折率と透明性、良好な塗布性、コア層との密着性、強度 '柔軟性に優れたポリ マークラッド層を得ることが困難であり、特に、ポリマークラッド光ファイバを高温環境 下に放置した場合であっても安定した透明性を有するポリマークラッド層を得ることが 困難であるという問題があった。 [0007] However, 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 There is 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.
特許文献 1 :特開平 10— 10340号公報 Patent Document 1: Japanese Patent Laid-Open No. 10-10340
特許文献 2:特開平 10— 160947号公報 Patent Document 2: Japanese Patent Laid-Open No. 10-160947
特許文献 3:特開平 11 - 119036号公報 Patent Document 3: Japanese Patent Laid-Open No. 11-119036
発明の開示 Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
[0008] 本発明の目的は、ポリマークラッド光ファイバのクラッド材として好適な特性を備え、 特に、低い屈折率と安定した透明性、良好な塗布性、コア層との密着性、強度 '柔軟 性に優れた放射線硬化性樹脂組成物を提供することにある。 [0008] 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.
課題を解決するための手段 Means for solving the problem
[0009] そこで本発明者は、特定のフッ素含有ポリマーと特定のフッ素含有 (メタ)アタリレー トモノマー、フッ素を含有しない特定構造の(メタ)アタリレートモノマーを必須要件と する放射線硬化性樹脂組成物により、かかる目的が達成できることを見出した。 [0009] Therefore, 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.
[0010] すなわち、本発明は、組成物全量を 100質量%として、
(A)エチレン性不飽和基含有含フッ素共重合体を 20〜65質量%、That is, in the present invention, 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,
(B)炭素数が 1;!〜 18である 2—パーフルォロアルキルェチル(メタ)アタリレートを 20 〜60質量%、ならびに (B) 20 to 60% by mass of 2-perfluoroalkylethyl (meth) atalylate having 1 to 18 carbon atoms;
(C) (A)成分および (B)成分以外であって、芳香族構造および極性基を有さず、ェ チレン性不飽和基を 2以上有する化合物を 10〜35質量% (C) 10 to 35% by mass of a compound other than the component (A) and the component (B), which does not have an aromatic structure and a polar group and has two or more ethylenically unsaturated groups
含有する放射線硬化性樹脂組成物を提供するものである。 The radiation curable resin composition to be contained is provided.
発明の効果 The invention's effect
[0011] 本発明の樹脂組成物により得られるポリマークラッド層は、特に、低い屈折率と安定 した透明性、良好な塗布性、コア層との密着性、強度 ·柔軟性に優れている。 [0011] 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.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
[0012] (A)エチレン性不飽和基含有含フッ素重合体: [0012] (A) Ethylenically unsaturated group-containing fluoropolymer:
エチレン性不飽和基含有含フッ素重合体 (A)は、エチレン性不飽和基とフッ素原 子を有する重合体であれば、特に限定されないが、側鎖にエチレン性不飽和基を有 する含フッ素ォレフィン系共重合体が好ましい。 (A)成分により本発明の組成物は低 屈折率、高い機械強度、ガラスや石英等のコア層への密着性等のポリマークラッド光 ファイバのクラッド形成用材料としての基本性能を発現する。 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. By the component (A), 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.
[0013] エチレン性不飽和基含有含フッ素重合体は、以下に述べる、エチレン性不飽和基 とイソシァネート基とを含有する化合物と水酸基含有含フッ素重合体の水酸基とを反 応させて得られる。 [0013] 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.
[0014] (1)エチレン性不飽和基とイソシァネート基とを含有する化合物: [1] A compound containing an ethylenically unsaturated group and an isocyanate group:
エチレン性不飽和基とイソシァネート基とを含有する化合物としては、分子内に少 なくとも 1個のエチレン性不飽和基と少なくとも 1個のイソシァネート基とを含有してい る化合物であれば特に制限されるものではない。 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.
また、上記エチレン性不飽和基として、後述する硬化性樹脂組成物をより容易に硬 化させることができることから、(メタ)アタリロイル基を有する化合物がより好ましい。 このような化合物としては、 (メタ)アクリル酸、 (メタ)アタリ口イルク口ライド、無水(メタ )アクリル酸、 2— (メタ)アタリロイルォキシェチルイソシァネート、 2- (メタ)アタリロイ
ァネートの一種単独又は二種以上の組み合わせが挙げられる。 Moreover, since the curable resin composition mentioned later can be hardened | cured more easily as said ethylenically unsaturated group, 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.
尚、イソシァネート基を有する(メタ)アタリレートの市販品としては、例えば昭和電工 社製、商品名 力レンズ MOI、 AOI、 BEI等が挙げられる。 In addition, as a commercial item of (meth) atalylate having an isocyanate group, for example, trade name lenses MOI, AOI, BEI and the like manufactured by Showa Denko KK can be mentioned.
[0015] また、このような化合物は、ジイソシァネート及び水酸基含有 (メタ)アタリレートを反 応させて合成するc F Fl Iこともできる。 [0015] Further, such a compound can also be cF Fl I synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
RCFII ネート、キシリレンジイソシァネート、メチレンビス(4ーシクロへキシノレイソシァネアート )、 1 , 3—ビス(イソシァネートメチル)シクロへキサンが好ましい。 RCFIIate, xylylene diisocyanate, methylenebis (4-cyclohexylenoisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane are preferred.
[0016] 水酸基含有(メタ)アタリレートの例としては、 2 ヒドロキシェチル (メタ)アタリレート 、ペンタエリスリトールトリ(メタ)アタリレートが好まし!/、。 [0016] As examples of the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferred! /.
尚、水酸基含有多官能 (メタ)アタリレートの市販品としては、例えば、大阪有機化 学社製、商品名 HEA;日本化薬社製、商品名 KAYARAD DPHA、 PET— 30 ;東亞合成社製、商品名 ァロニックス M— 215、 M— 233、 M— 305、 M— 400等 として人手すること力 Sでさる。 In addition, as a commercial item of 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.
[0017] (2)水酸基含有含フッ素重合体: (2) Hydroxyl group-containing fluoropolymer:
水酸基含有含フッ素重合体は、好ましくは、下記構造単位 (a)、 (b)及び ( )を含 んでなる。 The hydroxyl group-containing fluoropolymer preferably contains the following structural units (a), (b) and ().
(a)下記式(1)で表される構造単位。 (a) A structural unit represented by the following formula (1).
(b)下記式 (2)で表される構造単位。 (b) A structural unit represented by the following formula (2).
(c' )下記式(7)で表される構造単位。 (c ′) A structural unit represented by the following formula (7).
[化 1コ [Chemical 1
(1) (1)
[式中、 R1はフッ素原子、フルォロアルキル基又は OR2で表される基(R2はアルキ ル基又はフルォロアルキル基を示す)を示す] [Wherein 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)]
[式中、 R3は水素原子又はメチル基を示し、 R4はアルキル基、—(CH2) —OR5若しく は OCOR5で表 HHCIIされる基(R5はアルキル基又はグリシジル基を示し、 Xは 0又は 1の [Wherein 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
ROCCIII ROCCIII
数を示す)、カルボキシル基又はアルコキシカルボ二ル基を示す] A number), a carboxyl group or an alkoxycarbonyl group]
[化 3コ [Chemical 3
11 11
― (7) ― (7)
¾)vOR12 ¾) v OR 12
[式中、 Ruは水素原子又はメチル基を示し、 R12は水素原子又はヒドロキシアルキル 基を示し、 Vは 0又は 1の数を示す] [Wherein R u represents a hydrogen atom or a methyl group, R 12 represents a hydrogen atom or a hydroxyalkyl group, and V represents a number of 0 or 1]
[0018] (i)構造単位 (a) : [0018] (i) Structural unit (a):
上記式(1)において、 R1及び R2のフルォロアルキル基としては、トリフルォロメチル 基、パーフルォロェチル基、パーフルォロプロピル基、パーフルォロブチル基、パー フルォ口へキシル基、パーフルォロシクロへキシル基等の炭素数 1〜6のフルォロア ルキル基が挙げられる。また、 R2のアルキル基としては、メチル基、ェチル基、プロピ ル基、ブチル基、へキシル基、シクロへキシル基等の炭素数 1〜6のアルキル基が挙 げられる。 In the above formula (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. Examples of 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.
[0019] 構造単位(a)は、含フッ素ビュル単量体を重合成分として用いることにより導入する こと力 Sできる。このような含フッ素ビュル単量体としては、少なくとも 1個の重合性不飽 和二重結合と、少なくとも 1個のフッ素原子とを有する化合物であれば特に制限され るものではない。このような例としては、テトラフルォロエチレン、へキサフルォロプロ ピレン、 3, 3, 3—トリフルォロプロピレン等のフルォロレフィン類;アルキルパーフル ォロビニルエーテル又はアルコキシアルキルパーフルォロビニルエーテル類;パーフ ノレォロ(メチノレビニノレエーテノレ)、ノ ーフノレオ口(ェチノレビニノレエーテノレ)、ノ ーフノレオ 口(プロピノレビニノレエーテノレ) . ノ ーフノレオ口(ブチノレビニノレエーテノレ)、ノ ーフノレオ口
(イソブチルビュルエーテル)等のパーフルォロ(アルキルビュルエーテル)類;パー フルォロ(プロポキシプロピルビュルエーテル)等のパーフルォロ(アルコキシアルキ ルビニルエーテル)類の一種単独又は二種以上の組み合わせが挙げられる。 The structural unit (a) can be introduced by using a fluorine-containing butyl monomer as a polymerization component. Such 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. Examples thereof include 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) such as (isobutyl butyl ether); Perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl butyl ether) may be used alone or in combination of two or more.
これらの中でも、へキサフルォロプロピレンとパーフルォロ(アルキルビュルエーテ ル)又はパーフルォロ(アルコキシアルキルビュルエーテル)がより好ましぐこれらを 組み合わせて用いることがさらに好まし!/、。 Of these, hexafluoropropylene and perfluoro (alkyl butyl ether) or perfluoro (alkoxy alkyl butyl ether) are more preferred and used in combination!
[0020] 尚、構造単位 (a)の含有率は、水酸基含有含フッ素重合体中の構造単位 (a)〜(c ' )の合計量を 100モル0 /0としたときに、 20〜70モル0 /0である。この理由は、含有率 が 20モル%未満になると、本発明が意図するところの光学的にフッ素含有材料の特 徴である、低屈折率の発現が困難となる場合があるためであり、一方、含有率が 70 モル%を超えると、水酸基含有含フッ素重合体の有機溶剤への溶解性、透明性、又 は基材への密着性が低下する場合があるためである。 [0020] 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.
また、このような理由により、構造単位(a)の含有率を、水酸基含有含フッ素重合体 の全体量に対して、 25〜65モル0 /0とするのがより好ましぐ 30〜60モル0 /0とするの 力 Sさらに好ましい。 Moreover, such a reason, the content of the structural units (a), with respect to the total weight of the hydroxyl group-containing fluoropolymer, more preferably tool 30-60 mole to a 25 to 65 mole 0/0 force to the 0/0 S more preferred.
[0021] (ii)構造単位 (b) : [0021] (ii) Structural unit (b):
式(2)において、 R4のアルキル基としては、メチル基、ェチル基、プロピル基、へキ シル基、シクロへキシル基、ラウリル基等の炭素数 1〜; 12のアルキル基が挙げられ、 アルコキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基等が 挙げられる。 In the formula (2), 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.
[0022] 構造単位 (b)は、上述の置換基を有するビュル単量体を重合成分として用いること により導入すること力できる。このようなビュル単量体の例としては、メチルビュルエー テノレ、ェチノレビニノレエーテノレ、 n—プロピノレビニノレエーテノレ、イソプロピノレビニノレエ一 テノレ、 n—ブチルビュルエーテル、イソブチルビュルエーテル、 tert—ブチルビ二ノレ エーテノレ、 n—ペンチノレビニノレエーテノレ、 n—へキシノレビニノレエーテノレ、 n—ォクチ ノレビニノレエーテノレ、 n—ドデシノレビニノレエーテノレ、 2—ェチノレへキシノレビニノレエーテ ノレ、シクロへキシノレビニノレエーテノレ等のァノレキノレビニノレエーテノレもしくはシクロアノレ キルビュルエーテル類;ェチルァリルエーテル、ブチルァリルエーテル等のァリルェ
一テル類;酢酸ビュル、プロピオン酸ビュル、酪酸ビュル、ビバリン酸ビュル、力プロ ン酸ビュル、バーサチック酸ビュル、ステアリン酸ビュル等のカルボン酸ビュルエステ ル類;メチル(メタ)アタリレート、ェチル(メタ)アタリレート、 n—ブチル(メタ)アタリレー ト、イソブチル(メタ)アタリレート、 2—メトキシェチル(メタ)アタリレート、 2—エトキシェ チル (メタ)アタリレート、 2 - (n—プロポキシ)ェチル (メタ)アタリレート等の(メタ)ァク リル酸エステル類;(メタ)アクリル酸、クロトン酸、マレイン酸、フマル酸、ィタコン酸等 の不飽和カルボン酸類等の一種単独又は二種以上の組み合わせが挙げられる。 [0022] The structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component. Examples of such 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. Monotells; 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 .
[0023] 尚、構造単位 (b)の含有率は、水酸基含有含フッ素重合体中の構造単位 (a)〜(c ,)の合計量を 100モル%としたときに、 10〜70モル%である。この理由は、含有率 が 10モル%未満になると、水酸基含有含フッ素重合体の有機溶剤への溶解性が低 下する場合があるためであり、一方、含有率が 70モル%を超えると、水酸基含有含フ ッ素重合体の透明性、及び低反射率性等の光学特性が低下する場合があるためで ある。 [0023] 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.
また、このような理由により、構造単位 (b)の含有率を、水酸基含有含フッ素重合体 の全体量に対して、 20〜60モル0 /0とするの力 Sより好ましく、 30〜60モル0 /0とするの 力 Sさらに好ましい。 Moreover, such a reason, 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.
[0024] (iii)構造単位(c ' ): [Iii] (iii) Structural unit (c ′):
式(7)において、 R12のヒドロキシアルキル基としては、 2—ヒドロキシェチル基、 2— ヒドロキシプロピル基、 3—ヒドロキシプロピル基、 4ーヒドロキシブチル基、 3—ヒドロキ シブチル基、 5—ヒドロキシペンチル基、 6—ヒドロキシへキシル基等が挙げられる。 In the formula (7), 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.
[0025] 構造単位 (c ' )は、水酸基含有ビュル単量体を重合成分として用いることにより導入 すること力 Sできる。このような水酸基含有ビュル単量体の例としては、 2—ヒドロキシェ チノレビニノレエーテノレ、 3—ヒドロキシプロピノレビニノレエーテノレ、 2—ヒドロキシプロピノレ ビニノレエーテノレ、 4ーヒドロキシブチノレビニノレエーテノレ、 3—ヒドロキシブチノレビニノレ エーテノレ、 5—ヒドロキシペンチノレビニノレエーテノレ、 6—ヒドロキシへキシノレビニノレエ 一テル等の水酸基含有ビュルエーテル類、 2—ヒドロキシェチルァリルエーテル、 4 ーヒドロキシブチルァリルエーテル、グリセロールモノアリルエーテル等の水酸基含有 ァリルエーテル類、ァリルアルコール等が挙げられる。
また、水酸基含有ビュル単量体としては、上記以外にも、 2—ヒドロキシェチル (メタ タリレート、力プロラタトン(メタ)アタリレート、ポリプロピレングリコール(メタ)アタリレー ト等を用いることができる。 [0025] The structural unit (c ') can be introduced by using a hydroxyl group-containing bull monomer as a polymerization component. Examples of such 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. In addition to the above, 2-hydroxyethyl (metatalylate, force prolatatatone (meth) atalylate, polypropylene glycol (meth) atrelate, etc.) can also be used as the hydroxyl group-containing butyl monomer.
[0026] 尚、構造単位 (c ' )の含有率を、水酸基含有含フッ素重合体中の構造単位 (a)〜(c ' )の合計量を 100モル%としたときに、 5〜70モノレ%とすること力 S好ましい。この理由 は、含有率力 ¾モル%未満になると、水酸基含有含フッ素重合体の有機溶剤への溶 解性が低下する場合があるためであり、一方、含有率が 70モル%を超えると、水酸 基含有含フッ素重合体の透明性、及び低反射率性等の光学特性が低下する場合が あるためである。 [0026] 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 ¾ 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.
また、このような理由により、構造単位 (c ' )の含有率を、水酸基含有含フッ素重合 体の全体量に対して、 5〜40モル0 /0とするの力 Sより好ましく、 5〜30モル0 /0とするのが さらに好ましい。 Moreover, such a reason, 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.
[0027] (iv)構造単位 (d)及び構造単位 (e): [0027] (iv) Structural unit (d) and structural unit (e):
水酸基含有含フッ素重合体は、さらに下記構造単位 (d)を含んで構成することも好 ましい。 The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).
[0028] (d)下記式(6)で表される構造単位。 [0028] (d) A structural unit represented by the following formula (6).
[式中、 R9及び R1Qは、同一でも異なっていてもよぐ水素原子、アルキル基、ハロゲン 化アルキル基又はァリール基を示す] [Wherein R 9 and R 1Q represent the same or different hydrogen atom, alkyl group, halogenated alkyl group or aryl group]
[0029] 式(6)にお!/、て、 R9及び R1Qのアルキル基としては、メチノレ基、ェチル基、プロピル 基等の炭素数 1〜3のアルキル基力 S、ハロゲン化アルキル基としてはトリフルォロメチ ノレ基、パーフルォロェチル基、パーフルォロプロピル基、パーフルォロブチル基等の 炭素数 1〜4のフルォロアルキル基等力 S、ァリール基としてはフエニル基、ベンジル基 、ナフチル基等がそれぞれ挙げられる。
[0030] 構造単位(d)は、前記式 ½)で表されるポリシロキサンセグメントを有するァゾ基含 有ポリシロキサン化合物を用いることにより導入することができる。このようなァゾ基含 有ポリシロキサン化合物の例としては、下記式(8)で表される化合物が挙げられる。 [0029] In the formula (6), 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. As trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, etc., C1-C4 fluoroalkyl group isotropic S, and 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).
[式中、 R"〜Rlbは、同一でも異なっていてもよぐ水素原子、アルキル基又はシァノ 基を示し、 R17〜R2°は、同一でも異なっていてもよぐ水素原子又はアルキル基を示し 、 p、 qは;!〜 6の数、 r、 sは 0〜6の数、 tは;!〜 200の数、 uは;!〜 20の数を示す][Wherein 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]
[0031] 式(8)で表される化合物を用いた場合には、構造単位(d)は、構造単位(e)の一部 として水酸基含有含フッ素重合体に含まれる。 [0031] When the compound represented by the formula (8) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).
[0032] (e)下記式 (9)で表される構造単位。 [0032] (e) A structural unit represented by the following formula (9).
[化 6] [Chemical 6]
R14 Rl 7 R18 R13 R 14 Rl 7 R 18 R 13
I I I I I I I I
-C— (CH2)qCONH(CH2)— Si— (OSi) t(CH2) s HOC(CH2)^-C— -C— (CH 2 ) q CONH (CH 2 ) — Si— (OSi) t (CH 2 ) s HOC (CH 2 ) ^-C—
(9) (9)
R16 R19 i2。 R15 R 16 R 19 i 2 . R 15
[式中、 R"〜Rlb、 R"〜R U、 p、 q、 r、 s及び tは、上記式(8)と同じである] [Wherein R ″ to R lb , R ″ to R U , p, q, r, s, and t are the same as the above formula (8)]
[0033] 式(8)および(9)において、 R13〜R16のアルキル基としては、メチル基、ェチル基、 プロピル基、へキシル基、シクロへキシル基等の炭素数 1〜 12のアルキル基が挙げ られ、 R17〜R2°のアルキル基としては、メチル基、ェチル基、プロピル基等の炭素数 1[0033] In the formulas (8) and (9), 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.
〜3のアルキル基が挙げられる。 ˜3 alkyl groups.
[0034] 本発明において、上記式(8)で表されるァゾ基含有ポリシロキサン化合物としては、 下記式(10)で表される化合物が特に好ましい。 In the present invention, the azo group-containing polysiloxane compound represented by the above formula (8) is particularly preferably a compound represented by the following formula (10).
[化 7] [Chemical 7]
HO—- OC(CH2)2— ( J Q)HO—- OC (CH 2 ) 2 — (JQ)
[0035] 尚、構造単位 (d)の含有率は、水酸基含有含フッ素重合体中の構造単位 (a)〜(c ' )の合計量を 100モル0 /0としたときに、 0.;!〜 10モル0 /0とすることが好ましい。この 理由は、含有率が 0. 1モル%未満になると、硬化後の塗膜の表面滑り性が低下し、 塗膜の耐擦傷性が低下する場合があるためであり、一方、含有率が 10モル%を超え ると、水酸基含有含フッ素重合体の透明性に劣り、コート材として使用する際に、塗 布時にハジキ等が発生し易くなる場合があるためである。 [0035] 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.
また、このような理由により、構造単位(d)の含有率を、水酸基含有含フッ素重合体 の全体量に対して、 0.;!〜 5モル0 /0とするのがより好ましぐ 0.;!〜 3モル0 /0とするの 力 Sさらに好ましい。同じ理由により、構造単位(e)の含有率は、その中に含まれる構 造単位(d)の含有率を上記範囲にするよう決定することが望ましレ、。 Moreover, such a reason, the content of the structural units (d), with respect to the total weight of the hydroxyl group-containing fluoropolymer, 0;.! ~ 5 mol 0/0 and more preferred to implement 0 .;! the force S further preferred and to 3 mol 0/0. For the same reason, it is desirable that 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.
[0036] (V)構造単位 (f) : [0036] (V) Structural unit (f):
水酸基含有含フッ素重合体は、さらに下記構造単位 ωを含んで構成することも好 ましい。 The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit ω.
[0037] (f)下記式(11)で表される構造単位。 [0037] (f) A structural unit represented by the following formula (11).
[式中、 RZ1は、下記式(12)で表される基である。 [Wherein, R Z1 is a group represented by the following formula (12).
[化 9コ [Chemical 9
η ~ OCH2CH(OCH2CH2) OH (12) η ~ OCH 2 CH (OCH 2 CH 2 ) OH (12)
[式中、 nは;!〜 20の数、 mは 0〜4の数、 kは 3〜50の数を示す」 [Where n is a number from! To 20; m is a number from 0 to 4; k is a number from 3 to 50]
構造単位 (f)は、反応性乳化剤を重合成分として用いることにより導入することがで きる。このような反応性乳化剤としては、下記式(13)で表される化合物が挙げられる
〇 The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formula (13). Yes
[式中、 n、 m及び kは、上記式(12)と同じである] [Wherein n, m and k are the same as in the above formula (12)]
[0039] 尚、構造単位 (f)の含有率は、水酸基含有含フッ素重合体中の構造単位 (a)〜(c ' )の合計量を 100モル0 /0としたときに、 0· ;!〜 5モル0 /0とすることが好ましい。この理由 は、含有率が 0. 1モル%以上になると、水酸基含有含フッ素重合体の溶剤への溶解 性が向上し、一方、含有率が 5モル%以内であれば、硬化性樹脂組成物の粘着性が 過度に増加せず、取り扱いが容易になり、コート材等に用いても耐湿性が低下しない ためである。 [0039] 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. On the other hand, when 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.
また、このような理由により、構造単位 (f)の含有率を、水酸基含有含フッ素重合体 の全体量に対して、 0. ;!〜 3モル0 /0とするのがより好ましぐ 0. 2〜3モル0 /0とするの 力 Sさらに好ましい。 Moreover, such a reason, the content of the structural unit (f), with respect to the total weight of the hydroxyl group-containing fluoropolymer, 0.1;! ~ 3 mole 0/0 and more preferred to implement 0 . force for the 2-3 mole 0/0 S more preferred.
[0040] (3)エチレン性不飽和基含有含フッ素重合体: [0040] (3) Ethylenically unsaturated group-containing fluoropolymer:
(A)成分であるエチレン性不飽和基含有含フッ素重合体は、水酸基含有含フッ素 重合体の構造単位 (c ' )が有する水酸基とエチレン性不飽和基とイソシァネート基と を含有する化合物が有するイソシァネート基等の反応性基とが反応することにより得 られる。なお、この場合の、エチレン性不飽和基とイソシァネート基とを含有する化合 物が有するイソシァネート基と、水酸基含有含フッ素重合体が有する水酸基とのモル 比を、 1. ;!〜 1. 9の割合とすることが好ましい。 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. In this case, 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.
[0041] したがって、(A)エチレン性不飽和基含有含フッ素重合体は、水酸基含有含フッ素 重合体由来の構造単位 (a)および構造単位 (b)に加えて、水酸基含有含フッ素重合 体の構造単位 (c ' )がエチレン性不飽和基とイソシァネート基とを含有する化合物と 反応して生成する下記構造単位 (c)を有する。また、水酸基含有含フッ素重合体が 前述の構造単位 (d)、構造単位 (e)、構造単位 (f)等を有する場合には、これらの構 造単位はエチレン性不飽和基とイソシァネート基とを含有する化合物と反応しないた
め、(A)エチレン性不飽和基含有含フッ素重合体も同様に構造単位 (d)、構造単位 (e)、構造単位 ω等を有する。 [0041] Therefore, (A) 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. When 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. Do not react with compounds containing Therefore, (A) the ethylenically unsaturated group-containing fluoropolymer also has the structural unit (d), the structural unit (e), the structural unit ω and the like.
構造単位 (c) ; Structural unit (c);
[化 11] [Chemical 11]
HHCII HHCII
RCOCIII 6 RCOCIII 6
(3) (3)
H2)vOR7 H 2 ) v OR 7
[式中、 R6は水素原子又はメチル基を示し、 R7は下記式 (4)又は(5)で表わされる基 を示し、 Vは 0又は 1の数を示す [Wherein R 6 represents a hydrogen atom or a methyl group, R 7 represents a group represented by the following formula (4) or (5), and V represents a number of 0 or 1
[化 12] [Chemical 12]
R8 R 8
— C-N— (CH2)2 0-C-C=CH2 (4) — CN— (CH 2 ) 2 0-CC = CH 2 (4 )
o o o o
(式 (4)及び(5)中、 R8は水素原子又はメチル基を示す) ] (In the formulas (4) and (5), R 8 represents a hydrogen atom or a methyl group)]
エチレン性不飽和基含有含フッ素共重合体の分子量は、ゲルパーミエーシヨンクロ マトグラフィー(GPC)で、テトラヒドロフランを溶剤として測定したポリスチレン換算数 平均分子量として 5, 000-500, 000であることが好ましい。この理由は、数平均分 子量が 5, 000未満になると、硬化物の機械的強度が低下する場合があるためであり 、一方、数平均分子量が 500, 000を超えると、組成物の粘度が高くなり、コーティン グが困難となる場合があるためである。 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. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the cured product may be lowered. On the other hand, when the number average molecular weight exceeds 500,000, the viscosity of the composition is decreased. This is because there is a case where coating becomes difficult and the coating becomes difficult.
また、このような理由により、エチレン性不飽和基含有含フッ素共重合体のポリスチ レン換算数平均分子量を 10, 000—300, 000とするの力より好ましく、 10, 000〜1 00, 000とするのがさらに好ましい。
[0043] これら (A)成分であるエチレン性不飽和基含有含フッ素共重合体は、組成物全量 に対して、通常 20〜65質量%配合される力 好ましくは 20〜50質量%配合され、 特に好ましくは 30〜40質量%配合される。 20質量%未満では硬化物の屈折率が上 昇するほか、コア層との密着性が低下する傾向があり、 65質量%を超えると(B)成分 および (C)成分の配合量が圧迫される結果、(A)成分の溶解性が低下し、透明性の 高い硬化物が得られにくくなる場合がある。 For these reasons, 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. [0043] 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.
[0044] (B)炭素数が 1;!〜 18である 2—パーフルォロアルキルェチル(メタ)アタリレート: 本発明の組成物に配合される(B)成分は、炭素数が 11〜 18である 2—パーフルォ 口アルキルェチル (メタ)アタリレートであり、通常、下記式(14)で表される。 (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).
CH =CHCOOCH CH (CF ) F (14) CH = CHCOOCH CH (CF) F (14)
[式中、 nは 6〜; 12の数を示す] [Wherein n represents 6 to; 12 represents a number]
(B)成分は、後述する(C)成分と共に、 (A)成分の溶解性を確保する目的の他、硬 化物の屈折率を低減するために配合される。中でも、 2—パーフルォロォクチルェチ ル (メタ)アタリレートが、(A)成分を溶解するために好適であり、また入手も容易であ る点、で好ましい。 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). Among these, 2-perfluorooctylethyl (meth) acrylate is preferable because it is suitable for dissolving the component (A) and is easily available.
[0045] (B)成分である 2—パーフルォロアルキルェチル(メタ)アタリレートは、組成物全量 に対して、通常 20〜60質量%配合される力 好ましくは 25〜60質量%であり、特に 好ましくは 40〜50質量%である。 20質量%未満であると (A)成分の溶解性が損な われる他、硬化物の屈折率が低下する可能性があり、 70質量%を越えると組成物の 粘度が低下して、塗布性が損なわれる。 [0045] 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.
[0046] (A)成分であるエチレン性不飽和基含有含フッ素共重合体と(メタ)アタリレートモノ マーとの相溶性は、多くの場合限定的である力 (B)成分及び後述の(C)成分の組 み合わせと混合することにより、溶解性が改善されて、均一な組成物を得ることができ る。特に、(B)成分と(C)成分の配合比が、質量比として 2 : 3〜5 : 1であることが好ま しぐ 2 : 3〜4 : 1がさらに好ましい。 [0046] The compatibility between the (A) component ethylenically unsaturated group-containing fluorine-containing copolymer and the (meth) acrylate monomer is often limited. By mixing with the combination of components C), the solubility is improved and a uniform composition can be obtained. In particular, 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.
[0047] (C)芳香族構造および極性基を有さず、エチレン性不飽和基を 2以上有する化合 物: [0047] (C) Compound having no aromatic structure and no polar group and having two or more ethylenically unsaturated groups:
本発明の組成物に配合される(C)成分は、芳香族構造および極性基を有さず、ェ
チレン性不飽和基を 2以上有する化合物である。 (C)成分は、極性基を有しないため 、(B)成分と併用することにより、(A)成分の溶解性を高めて均一な組成物を与える。 また、(C)成分が芳香族構造を有さないことにより、低い屈折率を有する硬化物を与 X·る。 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.
ここで、極性基とは、カルボキシル基ゃァミノ基等の解離性基のほか、カルボニル 基や炭素数 3以下のアルキレンォキシド基等の分極性基が含まれるが、水酸基は除 かれる。 (C)成分は、前記要件を満たす構造であれば特に限定されない。 Here, 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.
[0048] また(C)成分の具体例としては、例えば、ネオペンチルダリコールジ (メタ)アタリレ ート、ネオペンチルグリコールヒドロキシビバリン酸エステルジ(メタ)アタリレート、トリメ チロールプロパントリ(メタ)アタリレート、トリメチロールプロパントリオキシェチル(メタ) アタリレート、ペンタエリスリトールトリ(メタ)アタリレート、ペンタエリスリトールテトラ(メタ )アタリレート、ポリエステルジ (メタ)アタリレート、 1 , 4—ブタンジオールジ (メタ)アタリ レート、 1 , 6—へキサンジオールジ (メタ)アタリレート等の脂肪族構造含有 (メタ)ァク リレート等が挙げられる。 [0048] Specific examples of the component (C) include, for example, neopentyl dalycol di (meth) acrylate, neopentyl glycol hydroxybivalate di (meth) acrylate, trimethylol propane tri (meth) acrylate. , Trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, 1, 4-butanediol di (meta) ) Aliphatic structure-containing (meth) acrylates such as acrylate and 1,6-hexanediol di (meth) acrylate.
[0049] 以上に挙げた (C)成分の中では、単官能又は多官能の脂肪族構造含有 (メタ)ァク リレートが好ましぐネオペンチルグリコールジ(メタ)アタリレート又はネオペンチルダ リコールヒドロキシビバリン酸エステルジ (メタ)アタリレートが特に好ましい。 (C)成分 は、 1種類単独で用いてもよぐまた、 2種類以上を併用してもよい。 [0049] Among the above-mentioned components (C), neopentyl glycol di (meth) acrylate or neopentyl glycol recall hydroxybivaline in which monofunctional or polyfunctional aliphatic structure-containing (meth) acrylate is preferred Acid ester di (meth) acrylate is particularly preferred. As the component (C), one type may be used alone, or two or more types may be used in combination.
[0050] (C)成分は、組成物全量に対して、通常 10〜35質量%配合されるが、好ましくは 1 5〜35質量%であり、特に好ましくは 15〜30質量%である。 10質量%未満であると (A)成分の溶解性が損なわれる可能性があり、 35質量%を越えると (A)成分及び( B)成分の配合量が圧迫される結果、硬化物の屈折率が増大し、コア層への密着性 が損なわれる。 [0050] 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.
[0051] 本発明の組成物には、更に、 (D) (メタ)アクリル酸又はその 2量体を配合することが できる。 (D)成分を配合することにより、コア層、特にガラス又は石英からなるコア層と クラッド層との密着性を改善することができる。 [0051] The composition of the present invention may further contain (D) (meth) acrylic acid or a dimer thereof. By blending component (D), the adhesion between the core layer, particularly the core layer made of glass or quartz, and the clad layer can be improved.
[0052] (D)成分は、組成物全量に対して、通常 0〜; 10質量%配合される力 好ましくは 1 〜7質量%である。 10質量%を越えると組成物の保存安定性を損なう場合がある。
[0053] 本発明の組成物を、紫外線等の光の照射により硬化する場合には、(E)光重合開 始剤を配合することが望ましレ、。 [0052] 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.
[0054] (E)光重合開始剤の具体例としては、例えば、 1ーヒドロキシシクロへキシルフェニ ノレケトン、 2, 2—ジメトキシ一 2—フエニルァセトフエノン、キサントン、フルォレノン、ベ ンズアルデヒド、フルオレン、アントラキノン、トリフエニルァミン、カルバゾール、 3—メ チルァセトフエノン、 4—クロ口べンゾフエノン、 4, 4'—ジメトキシベンゾフエノン、 4, 4' ージァミノべンゾフエノン、ミヒラーケトン、ベンゾインプロピルエーテル、ベンゾインェ チノレエーテノレ、ペンジノレジメチノレケターノレ、 1一(4一イソプロピノレフェニノレ)ー2—ヒド 口キシ一 2—メチルプロパン一 1—オン、 2—ヒドロキシ一 2—メチルー 1—フエニルプ 口パン 1 オン、チォキサントン、ジェチルチオキサントン、 2—イソプロピルチォキ サントン、 2 クロ口チォキサントン、 2 メチルー 1 〔4 (メチルチオ)フエニル〕ー2 モルホリノ一プロパン 1 オン、 2, 4, 6 トリメチルベンゾィルジフエニルフォス フィンオキサイド、ビス一(2, 6 ジメトキシベンゾィル) 2, 4, 4 トリメチルペンチ ノレフオフフィンォキシド; IRGACURE184、 369、 651、 500、 907、 CGI1700, CG 11750、 CGI1850, CG24 - 61; Darocure 1116, 1173 (以上、チノ 'スぺシャノレ ティー.ケミカルズ社製); LucirinTPO (BASF社製);ュベタリル P36 (UCB社製)等 が挙げられる。 [0054] (E) Specific examples of the photopolymerization initiator 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-Isopropylthioxanth 2 Chloroxanthone, 2 Methyl-1 [4 (Methylthio) phenyl] -2 Morpholinopropane 1 ON, 2, 4, 6 Trimethylbenzoyldiphenylphosphine oxide, Bis (2, 6 dimethoxybenzoyl) 2, 4, 4 Trimethylpentyl Nolfoffinoxide; IRGACURE184, 369, 651, 500, 907, CGI1700, CG 11750, CGI1850, CG24-61; Darocure 1116, 1173 LucirinTPO (manufactured by BASF); ubeitalyl P36 (manufactured by UCB) and the like.
[0055] (E)光重合開始剤を用いる場合には、さらに光増感剤を併用することもできる。光 増感剤としては、例えば、トリェチルァミン、ジェチルァミン、 N メチルジェタノ一ノレ ァミン、エタノールァミン、 4ージメチルァミノ安息香酸、 4ージメチルァミノ安息香酸メ チル、 4ージメチルァミノ安息香酸ェチル、 4ージメチルァミノ安息香酸イソァミル;ュ ベタリル P102、 103、 104、 105 (以上、 UCB社製)等が挙げられる。また、本発明の 液状硬化性樹脂組成物を熱および紫外線を併用して硬化させる場合には、前記熱 重合開始剤と光重合開始剤を併用することもできる。 [0055] (E) When a photopolymerization initiator is used, a photosensitizer can also be used in combination. Examples of 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). In addition, when the liquid curable resin composition of the present invention is cured by using heat and ultraviolet rays in combination, the thermal polymerization initiator and the photopolymerization initiator can be used in combination.
[0056] (E)重合開始剤は、組成物全量に対して、 0. ;!〜 10質量%、特に 0. 3〜7質量% 配合するのが好ましい。 [0056] (E) 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.
[0057] 本発明の組成物には、発明の効果を損なわない限度で、(F) (A)成分、(B)成分 および (C)成分以外の、芳香族構造及び極性基を有さず、エチレン性不飽和基を 1
個有する化合物を配合することができる。 [0057] The 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. 1 ethylenically unsaturated group Individual compounds can be blended.
このような、芳香族構造及び極性基を有さず、エチレン性不飽和基を 1個有する化 合物の具体例としては、 N—ビュルピロリドン、 N—ビュル力プロラタタム等のビュル 基含有ラタタム; Specific examples of 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;
ヒドロキシブチノレビニノレエーテノレ、ラウリノレビニノレエーテノレ、セチノレビニノレエーテノレ、 2—ェチノレへキシノレビニノレエーテノレ等のビニノレエーテノレ類; ル (メタ)アクリルアミド、 N, N—ジメチルァミノプロピル (メタ)アクリルアミド tーォクチ ル (メタ)アクリルアミド等のアクリルアミド類; Vinylinoatenoles such as hydroxybutinorevininoreethenore, laurinorevininoreethenore, cetinolevininoreethenore, 2-ethenorehexinorevininoreethenore; ru (meth) acrylamide, N, N-dimethyl Acrylamides such as aminopropyl (meth) acrylamide t-octyl (meth) acrylamide;
イソボルニル(メタ)アタリレート、ボルニル(メタ)アタリレート、トリシクロデカニル(メタ) アタリレート、ジシクロペンタニル(メタ)アタリレート、 4ーブチルシクロへキシル(メタ) アタリレート等の脂環式構造含有 (メタ)アタリレート; Contains alicyclic structures such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate (Meta) Atarirate;
2—ヒドロキシェチル(メタ)アタリレート、 2—ヒドロキシプロピル(メタ)アタリレート、 2— ヒドロキシブチル (メタ)アタリレート、メチル (メタ)アタリレート、ェチル (メタ)アタリレー ト、プロピル(メタ)アタリレート、イソプロピル(メタ)アタリレート、ブチル(メタ)アタリレー ト、ァミル (メタ)アタリレート、イソブチル (メタ)アタリレート、 t—ブチル (メタ)アタリレー ト、ペンチル (メタ)アタリレート、イソアミル (メタ)アタリレート、へキシル (メタ)アタリレー レート、 2—ェチルへキシル(メタ)アタリレート、ノニル(メタ)アタリレート、デシル(メタ) タ)アタリレート、ラウリノレ (メタ)アタリレート、ステアリノレ (メタ)アタリレート、イソステアリ ノレ (メタ)アタリレート、テトラヒドロフルフリノレ (メタ)アタリレート、ブトキシェチル (メタ)ァ タリレート、エトキシジエチレングリコール (メタ)アタリレート等の脂肪族構造含有 (メタ 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) Atalylate, hexyl (meth) attarelate, 2-ethyl hexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, laurinore (meth) atelate, stearino ret (meta) ateari Rate, isosteari nore (meth) atarylate, tetra Contains aliphatic structures such as hydrofurfurinole (meth) acrylate, butoxychetyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate (meta
)アタリレートなどが挙げられる。 ) Atarirate.
[0058] (F)成分は、組成物全量に対して、通常 0〜30質量%配合される力 好ましくは 0[0058] 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
〜25質量%であり、特に好ましくは 0〜20質量%である。 30質量%を越えると組成 物及びその硬化物の透明性を損なう場合がある。 -25% by mass, particularly preferably 0-20% by mass. If it exceeds 30% by mass, the transparency of the composition and its cured product may be impaired.
[0059] 本発明の組成物には、発明の効果を損なわない限度で、(G) (A)成分、(B)成分、
(C)成分および (F)成分以外の、エチレン性不飽和基を有する化合物を配合するこ と力できる。 (G)成分としては、芳香族構造含有 (メタ)アタリレート、カルボキシル基 やアルキレンォキシド構造等の極性基含有 (メタ)アタリレート等が挙げられる。 (G)成 分は、芳香族構造含有 (メタ)アタリレートのように硬化物の屈折率を増大させる傾向 がある他、極性基含有 (メタ)アタリレートのように (A)成分の溶解性を減少させる傾向 があるため、(G)成分の配合量は、組成物全量を 100質量%として、 5質量%以下と することが好ましい。 [0059] 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). Examples of 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.
[0060] これら(G)成分の市販品として、例えば、ュピマー UV、 SA1002 (以上、三菱化学 社製)、ァロニックス M— 215、 M— 315、 M— 325 (以上、東亞合成社製)、サートマ 一 CN4000 (サートマ一 ·カンパニー ·インク製)、アローニックス TO— 1210 (東亞合 成社製)等を挙げること力 Sできる。 [0060] 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.
[0061] 本発明の組成物には、必要に応じて、本発明の特性を損なわない範囲で各種添加 剤、例えば、酸化防止剤、着色剤、紫外線吸収剤、光安定剤、シランカップリング剤 、熱重合禁止剤、レべリング剤、界面活性剤、保存安定剤、可塑剤、滑剤、溶媒、フ イラ一、老化防止剤、濡れ性改良剤、塗面改良剤等を配合することができる。 [0061] In the 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. , Thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, fillers, anti-aging agents, wettability improvers, coating surface improvers, etc. .
[0062] 本発明の組成物の粘度は、 25°Cにおいて、 0. 8〜5. OPa ' sであることが好ましぐ 1. 5〜6Pa' sであることが特に好ましい。 [0062] 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.
[0063] なお、本発明の液状硬化性樹脂組成物は、放射線によって硬化される力 放射線 硬化に加えて熱硬化を併用することもできる。ここで放射線とは、赤外線、可視光線、 紫外線、 X線、電子線、 α線、 /3線、 γ線等をいう。 [0063] It should be noted that 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. Here, the radiation means infrared rays, visible rays, ultraviolet rays, X-rays, electron rays, α rays, / 3 rays, γ rays, and the like.
[0064] 本発明の液状硬化性糸且成物の硬化物は、好ましくは 200MPa〜500MPaのヤン グ率を示すのが好ましい。また、アップジャケット層を形成するには、膜厚 100〜350 〃mに被覆するのが好ましい。さらに、光ファイバアップジャケット層の外側に接して 熱可塑性樹脂からなるケーブル層を設けることもできる。 [0064] 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. In order to form an upjacket layer, it is preferable to coat the film to a thickness of 100 to 350 μm. Furthermore, a cable layer made of a thermoplastic resin can be provided in contact with the outside of the optical fiber upjacket layer.
実施例 Example
[0065] 次に実施例を挙げて本発明を詳細に説明するが、本発明は何らこれら実施例に限 定されるものではない。 Next, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples.
[0066] 製造例 1 (水酸基含有含フッ素共重合体の合成)
内容積 2. 0Lの電磁攪拌機付きステンレス製オートクレープを窒素ガスで十分置換 した後、酢酸ェチノレ 400g、パーフルォロ(プロピルビュルエーテル)(FPVE) 53. 2g 、ェチルビュルエーテル(EVE) 36· lg、ヒドロキシェチルビュルエーテル(HEVE) 44. Og、過酸化ラウロイル 1 · 00g、上記式(10)で表されるァゾ基含有ポリジメチル シロキサン (VPS 1001、和光純薬工業社製) 6. Og及びノニオン性反応性乳化剤(N E 30、旭電化工業社製) 20· Ogを仕込み、ドライアイス メタノールで 50°Cまで 冷却した後、再度窒素ガスで系内の酸素を除去した。 Production Example 1 (Synthesis of hydroxyl-containing fluorine-containing copolymer) After fully replacing the stainless steel autoclave with an electromagnetic stirrer with an internal volume of 2.0 L with nitrogen gas, 400 g of ethynole acetate, 53. Hydroxyethyl butyl ether (HEVE) 44. Og, lauroyl peroxide 100 g, azo group-containing polydimethylsiloxane represented by the above formula (10) (VPS 1001, manufactured by Wako Pure Chemical Industries, Ltd.) 6. Og and 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.
次いで、へキサフルォロプロピレン (HFP) 120. 0gを仕込み、昇温を開始した。ォ 一トクレーブ内の温度が 60°Cに達した時点での圧力は 5. 3 X 105Paを示した。その 後、 70°Cで 20時間攪拌下に反応を継続し、圧力が 1. 7 X 105Paに低下した時点で オートクレープを水冷し、反応を停止させた。室温に達した後、未反応モノマーを放 出してオートクレープを開放し、固形分濃度 26. 4%のポリマー溶液を得た。得られ たポリマー溶液をメタノールに投入しポリマーを析出させた後、メタノールにて洗浄し 、 50°Cにて真空乾燥を行い 220gの水酸基含有含フッ素重合体を得た。これを「水 酸基含有含フッ素重合体 1」とする。 Next, 120.0 g of hexafluoropropylene (HFP) was charged, and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C was 5.3 X 10 5 Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours, and when the pressure dropped to 1.7 × 10 5 Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was discharged and the autoclave was opened to obtain a polymer solution having a solid content concentration of 26.4%. The obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer. This is designated as “hydroxy group-containing fluoropolymer 1”.
得られた水酸基含有含フッ素重合体 1について、 GPCによるポリスチレン換算数平 均分子量を測定したところ、約 70000であった。また、ァリザリンコンプレクソン法によ るフッ素含量の測定結果、 'H-NMR, 13c NMRの両 NMR分析結果および元素 分析結果から、水酸基含有含フッ素重合体 1を構成する各単量体成分の割合を決 定したところ、へキサフルォロプロピレン由来の構造単位(構造単位(a) )、パーフル ォロ(プロピルビュルエーテル)由来の構造単位(構造単位(a) )、ェチルビュルエー テル由来の構造単位(構造単位(b) )、ヒドロキシェチルビュルエーテル由来の構造 単位 (構造単位 (c ' ) )が、構造単位(a)〜(c ' )の合計量を 100モル%として、それぞ れ、 25 : 25 : 25 : 25モノレ%であった。 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. The structural unit (structural unit (b)), a structural unit derived from hydroxyethyl butyl ether (structural unit (c ′)), the total amount of structural units (a) to (c ′) is 100 mol%. They were 25: 25: 25: 25 monole% respectively.
製造例 2 ( (A)エチレン性不飽和基含有含フッ素共重合体の合成) Production Example 2 ((A) Synthesis of fluorine-containing copolymer containing ethylenically unsaturated groups)
電磁攪拌機、ガラス製冷却管及び温度計を備えた容量 1リットルのセパラブルフラ スコに、製造例 1で得られた水酸基含有含フッ素重合体 1を 41. 0g、重合禁止剤とし て 2, 6 ジー t ブチルメチルフエノール 0. 01g、希釈溶剤として 2 パーフルォロ
ォクチルェチル(メタ)アタリレート 41 · Og、及びネオペンチルグリコールジ(メタ)アタリ レート 17. Ogを仕込み、 50°Cで水酸基含有含フッ素重合体 1が溶解して、溶液が透 明、均一になるまで攪拌を行った。 In a 1 liter separable flask equipped with a magnetic stirrer, glass cooling tube and thermometer, 41.0 g of the hydroxyl group-containing fluoropolymer 1 obtained in Production Example 1 was used as a polymerization inhibitor, 2, 6 G Butylmethylphenol 0.01 g, 2 perfluoro as diluent Octylethyl (meth) atarylate 41 · Og and neopentylglycol di (meth) atalylate 17. Og is charged, and the hydroxyl-containing fluoropolymer 1 dissolves at 50 ° C, making the solution transparent and uniform. Stir until.
次いで、この系に、 2—メタクリロイルォキシェチルイソシァネート 0· 90gを添カロし、 溶液が均一になるまで攪拌した後、ジブチルチンジラウレート 0. 015gを添加して反 応を開始し、系の温度を 55〜65°Cに保持し 5時間攪拌を継続することにより、ェチレ ン性不飽和基含有含フッ素重合体を得た。得られたエチレン性不飽和基含有含フッ 素重合体を「エチレン性不飽和基含有含フッ素重合体 1」とする。このとき用いた希釈 溶剤は、紫外線硬化樹脂の成分として用いることができる。 Next, 0-90 g of 2-methacryloyloxychetyl isocyanate was added to this system and stirred until the solution was uniform, then 0.015 g of dibutyltin dilaurate was added to start the reaction, By maintaining the temperature of the system at 55 to 65 ° C and continuing stirring for 5 hours, an ethylenically unsaturated group-containing fluoropolymer was obtained. 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.
[0068] 実施例;!〜 3、比較例;!〜 5 [0068] Examples;! To 3, comparative examples;! To 5
表 1に示す組成の各成分を、攪拌機を備えた反応容器に仕込み、液温度を 50°C に制御しながら 1時間攪拌し、液状硬化性樹脂組成物を得た。 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.
[0069] 試験例 1 [0069] Test Example 1
前記実施例及び比較例で得た液状硬化性樹脂組成物を、以下のような方法で硬 化させて試験片を作製し、下記の各評価を行った。結果を表 1に併せて示す。 The 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.
[0070] 1.粘度: [0070] 1. Viscosity:
実施例および比較例で得られた組成物の 25°Cにおける粘度を B型粘度計を用い て測定した。 The viscosity at 25 ° C. of the compositions obtained in Examples and Comparative Examples was measured using a B-type viscometer.
[0071] 2.ヤング率: [0071] 2. Young's modulus:
250 m厚のアプリケーターバーを用いてガラス板上に液状硬化性樹脂組成物を 塗布し、これを窒素下で lj/cm2のエネルギーの紫外線で照射して硬化させ、ヤン グ率測定用フィルムを得た。このフィルムから、延伸部が幅 6mm、長さ 25mmとなる よう短冊状サンプルを作成し、温度 23°C、湿度 50%で引っ張り試験を行った。引つ 張り速度は lmm/minで 2. 5%歪みでの抗張力力、らヤング率を求めた。 Apply a liquid curable resin composition on a glass plate using a 250 m thick applicator bar, and cure it by irradiating it with ultraviolet rays of lj / cm 2 energy under nitrogen to form a film for measuring the yang ratio. Obtained. A strip-shaped sample was prepared from this film so that the stretched part had a width of 6 mm and a length of 25 mm, and a tensile test was performed at a temperature of 23 ° C. and a humidity of 50%. The tensile rate was lmm / min, and the tensile strength at 2.5% strain and Young's modulus were obtained.
[0072] 3.破断強度および破断伸び: [0072] 3. Breaking strength and breaking elongation:
引張試験器(島津製作所社製、 AGS— 50G)を用い、試験片の破断強度および破 断伸びを下記測定条件にて測定した。 Using a tensile tester (manufactured by Shimadzu Corporation, AGS-50G), the breaking strength and breaking elongation of the test piece were measured under the following measurement conditions.
引張速度 :50mm/分
標線間距離 (測定距離): 25mm Tensile speed: 50mm / min Distance between marked lines (measurement distance): 25mm
測定温度 :23°C Measurement temperature: 23 ° C
相対湿度 :50%RH Relative humidity: 50% RH
[0073] 4.屈折率: [0073] 4. Refractive index:
ガラス板上に膜厚が 200 mとなるようにアプリケーターバーを用いて樹脂組成物 を塗布し、 1. Oj/cm2の紫外線を窒素下で照射し、試験片を作製した。 JIS K710 5に従い、ァタゴ社製アッベ屈折計を用いて、 25°Cにおける屈折率を測定した。 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.
[0074] 5.透明性(ヘイズ): [0074] 5. Transparency (Haze):
硬化膜の全光線透過率を、カラーヘイズメーター(スガ試験機社製)を用い、 JIS K7105に準拠して測定した。測定は、製造直後の硬化膜および 120°C72時間放置 後の硬化膜について、それぞれ行った。 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.
[0075] 6·密着力: [0075] 6. Adhesion strength:
実施例および比較例で得られた組成物に関し、その硬化物の密着力安定性を測 定した。液状組成物を 381 m厚のアプリケーターを用いてスライドガラス上に塗布 し、窒素雰囲気下で 0. lj/cm2の紫外線を照射し、厚さ約 200 mの硬化フィルム を得た。このスライドガラス上の硬化フィルムを、温度 23°C、湿度 50%下に 24時間静 置した。その後、この硬化フィルムから延伸部が幅 10mmとなるように短冊状サンプ ルを作成した。このサンプルを引っ張り試験器を用いて JIS Z0237に準拠して密着 力試験を行った。引張速度は 50mm/minでの抗張力から密着力を求めた。 With respect to the compositions obtained in Examples and Comparative Examples, 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.
[0076] 7.硬化速度: [0076] 7. Curing rate:
200 m厚のアプリケーターを用いて石英ガラス板上に組成物を塗布し、それに 3 . 5KWメタルハライドランプ(オーク社製、 SMX— 3500/F— OS)を用い、空気雰 囲気下にお!/、て紫外線照射量 20mj/cm2と 1. Oj/cm2の 2条件で紫外線を照射し 、硬化フィルムを得た。次いで、 23°C、相対湿度 50%で 24時間放置した後、このフィ ルムから、延伸部が幅 6mm、長さ 25mmとなるよう短冊状サンプルを作成して試験 片とした。次に、引っ張り試験機にて試験片のヤング率 (MPa)を測定した。紫外線 照射量 20mj/cm2におけるヤング率を lj/cm2におけるヤング率で除して得られる 値を硬化
速度とした。 Apply the composition onto a quartz glass plate using an applicator with a thickness of 200 m, and then use a 3.5 KW metal halide lamp (OMX, SMX-3500 / F—OS) in an air atmosphere! /, The cured film was obtained by irradiating ultraviolet rays under two conditions of 20 mj / cm 2 and 1. Oj / cm 2 . Next, after standing for 24 hours at 23 ° C and 50% relative humidity, a strip-shaped sample was prepared from this film so that the stretched part had a width of 6 mm and a length of 25 mm, and was used as a test piece. Next, the Young's modulus (MPa) of the test piece was measured with a tensile tester. Curing the value obtained by dividing the Young's modulus at 20 mj / cm 2 with the ultraviolet ray by the Young's modulus at lj / cm 2 It was speed.
[表 1]
[table 1]
ビスコート 17F; 2 パーフルォロォクチルェチル(メタ)アタリレート(大阪有機化学ェ 業社製)。 Biscote 17F; 2 Perfluorooctyl cetyl (meth) acrylate (manufactured by Osaka Organic Chemical Co., Ltd.).
Irgacure 184; 1—ヒドロキシ シクロへキシル一フエ二ノレ一ケトン(チバ ·スぺシャノレ ティ'ケミカルズ社製)。 Irgacure 184; 1-hydroxycyclohexyl monophenolate ketone (Ciba Specialo Chemicals).
Lucirin ; 2, 4, 6 トリメチルベンゾィルジフエニルフォスフィンオキサイド(BASFジ ャパン社製)。 Lucirin; 2, 4, 6 Trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan).
カイナー ADS; VDF/TFE/HFPフッ化ビニリデン、テトラフルォロエチレンおよび へキサフルォロプロピレンの共重合体 (アルケマ社製)。 Kyner ADS; copolymer of VDF / TFE / HFP vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene (manufactured by Arkema).
表 1から明らかなように、各実施例は、組成物の粘度、硬化物のヤング率'機械強 度 (破断強度および破断伸び) ·屈折率 ·透明性 (ヘイズ)に優れ、高温条件に暴露さ れた後でも良好な透明性を維持している。また、コア層の材質である石英との密着力 も良好である。これに対して、(C)成分量が過多である比較例 1では、(B)成分と(C) 成分の配合量バランスが崩れているため、(A)成分の溶解性が低下した結果、硬化 物の透明性が劣って!/、る。 (A)成分に替えてエチレン性不飽和基を有しな!/、水酸基 含有含フッ素重合体を用いた比較例 2では、組成物の粘度が過小であり、フッ素重 合体が組成物中に溶解しないため透明性も劣っている。また、(A)成分に該当しな V、フッ素重合体を用いた比較例 3では、フッ素重合体が組成物中に溶解しな!/、ため 、透明性が劣っている。
As is clear from Table 1, 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! In 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.
Claims
[化 1] [Chemical 1]
[式中、 Rはフッ素原子、フルォロアルキル基又は ORで表される基(Rはアルキ ル基又はフルォロアルキル基を示す)を示す] [Wherein R represents a fluorine atom, a fluoroalkyl group or a group represented by OR (R represents an alkyl group or a fluoroalkyl group)]
構造単位 (b) : Structural unit (b):
[化 2] [Chemical 2]
[式中、 R3は水素原子又はメチル基を示し、 R4はアルキル基、一(CH ) — OR5若しく は OCOR5で表される基(R5はアルキル基又はグリシジル基を示し、 Xは 0又は 1の 数を示す)、カルボキシル基又はアルコキシカルボ二ル基を示す]
又は(5)で表わされる基 [Wherein, R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkyl group, a group represented by one (CH 3) — OR 5 or OCOR 5 (R 5 represents an alkyl group or a glycidyl group, X represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group] Or a group represented by (5)
[式中、 R及び R は、同一でも異なっていてもよぐ水素原子、アルキル基、ハロゲン 化アルキル基又はァリール基を示す] [Wherein R and R are the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]
[3] 更に、(D) (メタ)アクリル酸又はその 2量体を含有する請求項 1又は 2記載の放射 線硬化性樹脂組成物。 [3] The radiation curable resin composition according to claim 1 or 2, further comprising (D) (meth) acrylic acid or a dimer thereof.
[4] 更に、(E)光重合開始剤を含有する請求項 1〜3のいずれ力、 1項記載の放射線硬 化性樹脂組成物。
[4] The radiation-curable resin composition according to any one of claims 1 to 3, further comprising (E) a photopolymerization initiator.
[5] 光ファイバクラッド層形成用である請求項 1〜4のいずれ力、 1項記載の放射線硬化 性樹脂組成物。 [5] The radiation-curable resin composition according to any one of claims 1 to 4, which is used for forming an optical fiber clad layer.
[6] 請求項;!〜 5の!/、ずれか 1項記載の放射線硬化性樹脂組成物の硬化物からなる硬 化膜。 [6] A cured film comprising a cured product of the radiation curable resin composition according to claim 1;
[7] ガラス、石英又は透明樹脂からなるコア層と、該コア層の外側に接して請求項 6記 載の硬化膜からなるクラッド層とを有するポリマークラッド光ファイバ。
[7] A polymer-clad optical fiber having a core layer made of glass, quartz, or a transparent resin, and a clad layer made of a cured film according to claim 6, in contact with the outside of the core layer.
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JP5184059B2 (en) * | 2006-11-29 | 2013-04-17 | Jsr株式会社 | Radiation curable resin composition |
JP4982209B2 (en) * | 2007-02-27 | 2012-07-25 | Jsr株式会社 | Radiation curable resin composition |
JP2008208226A (en) * | 2007-02-27 | 2008-09-11 | Jsr Corp | Radiation-curable resin composition |
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JPH05279435A (en) * | 1992-04-01 | 1993-10-26 | Asahi Glass Co Ltd | Active energy ray-curable composition |
JP2001131402A (en) * | 1999-10-29 | 2001-05-15 | Asahi Glass Co Ltd | Curable composition |
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JP2005089536A (en) * | 2003-09-12 | 2005-04-07 | Jsr Corp | Curable resin composition and antireflection coating |
JP2005290133A (en) * | 2004-03-31 | 2005-10-20 | Jsr Corp | Ultraviolet-curable low-refractive index material composition and antireflection film |
JP2006097003A (en) * | 2004-08-31 | 2006-04-13 | Jsr Corp | Resin composition and antireflection coating |
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- 2007-11-20 JP JP2007300351A patent/JP2008195920A/en not_active Withdrawn
- 2007-11-29 WO PCT/JP2007/073052 patent/WO2008066112A1/en active Application Filing
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JPS6136374A (en) * | 1984-07-30 | 1986-02-21 | Dainippon Toryo Co Ltd | Fluorine-containing resin coating composition |
JPS6296508A (en) * | 1985-10-23 | 1987-05-06 | Sumitomo Chem Co Ltd | Curable resin composition |
JPS6451418A (en) * | 1987-08-21 | 1989-02-27 | Asahi Glass Co Ltd | Actinic radiation curable composition |
JPH01113416A (en) * | 1987-10-27 | 1989-05-02 | Dainippon Toryo Co Ltd | Coating resin composition |
JPH05279435A (en) * | 1992-04-01 | 1993-10-26 | Asahi Glass Co Ltd | Active energy ray-curable composition |
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JP2002080547A (en) * | 2000-07-04 | 2002-03-19 | Daikin Ind Ltd | Active energy ray-curable aqueous fluororesin composition and method for forming material coated with fluorine-containing coat |
JP2003183322A (en) * | 2001-12-21 | 2003-07-03 | Jsr Corp | Ethylenically unsaturated group-containing fluoropolymer and curable resin composition and anti- reflective film using the same |
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JP2005290133A (en) * | 2004-03-31 | 2005-10-20 | Jsr Corp | Ultraviolet-curable low-refractive index material composition and antireflection film |
JP2006097003A (en) * | 2004-08-31 | 2006-04-13 | Jsr Corp | Resin composition and antireflection coating |
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