CN1934200A - Curable liquid resin composition - Google Patents
Curable liquid resin composition Download PDFInfo
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- CN1934200A CN1934200A CNA2005800085600A CN200580008560A CN1934200A CN 1934200 A CN1934200 A CN 1934200A CN A2005800085600 A CNA2005800085600 A CN A2005800085600A CN 200580008560 A CN200580008560 A CN 200580008560A CN 1934200 A CN1934200 A CN 1934200A
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- methyl
- acrylate
- polyvalent alcohol
- branch point
- curable liquid
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
Abstract
The invention relates to a curable liquid resin composition comprising the following components (A), (B), and (C): 0.5-50 wt% of a urethane (meth)acrylate oligomer obtained from a polyol (a) having a branched structure comprising at least one branch point and at least three molecular chains extending from that branch point, said molecular chains having a molecular weight of 200 g/mol or more, including a hydroxyl group at the terminal of at least two molecular chains extending from the branch point, a polyisocyanate (b), and a hydroxyl group-containing (meth)acrylate (c); (B) 5-90 wt% of a polymerizable organic compound; and (C) 0.1-10 wt% of a polymerization initiator, wherein the cured product has a Young's modulus of 350 MPa or more at 23 DEG C.
Description
The present invention relates to a kind of curable liquid resin composition.More specifically, the present invention relates to a kind of curable liquid resin composition that is suitable for as fibre coating material (for example secondary materials or carrying substrates material), be particularly suitable for as secondary materials.
In optical fiber was made, after the spinning of fused glass fibre, the coated with resins coating was used for protection and strengthens immediately.As resin coating, known a kind of structure wherein provides a kind of flexible primary coating and a kind of hard secondary coating is provided in the outside of primary coating at fiberglass surfacing.To be provided resin-coated optical fiber and use before the practical application, will be for example four or eight optical fiber be arranged side by side in the plane, and be fixed, thereby form band structure with rectangular cross section with binding material.The resin combination that is used to form the first layer coating is called as primary material, and the resin combination that is used to form second layer coating is called as secondary materials, and the material that is used to bundle several optical fiber is also referred to as the carrying substrates material.
One of effect of secondary materials and carrying substrates material is as strong protective membrane, and this film can not affact on the primary material in the lower level and on the quartz glass fibre external loads to be applied.Therefore, this material is designed to have second-order transition temperature and the high rigidity modulus that is higher than room temperature.Yet, when at production technique curing during secondary materials or carrying substrates material, owing to reason unrelieved stresss such as cooling, contraction may reside in the cured film, and external loads can affact on the lower level and not be absorbed, thereby load affacts on the primary material in the lower level.What caused by this load is to form empty in this primary material and this primary material and silica glass are peeled off to one of phenomenon of primary material infringement, and this is considered to one of reason that causes transmission loss.
As reducing the technology that coat-thickness keeps optical transmission property simultaneously, known usually have the coated optical fiber (Japanese Patent Application Laid-open No.8-5877) of specific stress-time of relaxation and have the optical fiber (by excellent stress-relaxation property is provided for the optical fiber primary coating) (Japanese patent application Laid-open No.2001-31731) that improves weather resistance.Yet, because these methods might not provide the stress-time of relaxation of shortening, so above-mentioned technical problem to be solved still exists.
Japanese patent application Laid-open No.2000-351818 discloses a kind of radiation-curable liquid resin composition that comprises urethane (methyl) origoester acrylate, this urethane (methyl) origoester acrylate per molecule has a branch point, two places in three molecular end of being extended by this branch point have (methyl) acrylic, and do not have (methyl) acrylic in remaining end.Because the Young's modulus of the cured product that is obtained by this composition is 1MPa or lower at 25 ℃, therefore, this composition can not be used as secondary materials.
Therefore; the object of the present invention is to provide a kind of curable liquid resin composition; said composition can be used as protective membrane after curing, can be used as secondary materials especially, and said composition can be formed in the cured layer that wherein only produces small unrelieved stress and be easy to absorb external loads.
Can realize the invention described above purpose by comprising following component (A), (B) and curable liquid resin composition (C):
(A) urethane of 0.5-50wt% (methyl) origoester acrylate, (this polyvalent alcohol has the branched structures of the molecular chain that comprises that at least one branch point and at least three are extended by this branch point to this oligopolymer by polyvalent alcohol (a), described molecular chain has 200g/mol or higher molecular weight, comprises hydroxyl in the ends of at least two molecular chains that extended by branch point), (methyl) acrylate (c) of polyisocyanates (b) and hydroxyl;
(B) polymerizable organic compounds of 5-90wt%; With
(C) polymerization starter of 0.1-10wt%, wherein, cured product has 350MPa or higher Young's modulus at 23 ℃.
Because the cured product that is obtained by curable liquid resin composition of the present invention has the short stress-time of relaxation less than 4 minutes, so this cured product can not make heavy load be applied on the primary material.In addition, cured product has high Young's modulus.Therefore, curable liquid resin composition of the present invention can be used as the secondary materials and the carrying substrates material of optical fiber, can be used as secondary materials especially.
In an embodiment of the invention, urethane (methyl) origoester acrylate (A) obtains by the following method: will have (a) polyvalent alcohol (branching polyvalent alcohol), (b) polyisocyanates of described branched structure and (c) (methyl) acrylate reactions of hydroxyl, and make the hydroxyl that is derived from polyvalent alcohol (a) can be retained in the gained oligopolymer by the mol ratio of regulating raw material.Preferably, nearly allly react to all hydroxyls that are derived from polyvalent alcohol (a).
As the method that these compounds are reacted, can provide following method: the method that (methyl) acrylate one of (a) branching polyvalent alcohol, (b) polyisocyanates and hydroxyl is reacted; With (a) branching polyvalent alcohol and (b) polyisocyanates reaction, and with the product that obtains and (c) method of (methyl) acrylate reactions of hydroxyl; With (b) polyisocyanates and (c) (methyl) acrylate reactions of hydroxyl, and with the product that obtains and (a) method of branching polyol reaction; And with (b) polyisocyanates and (c) (methyl) acrylate reactions of hydroxyl, and with the product that obtains and (a) branching polyol reaction, with the product that obtains further with the method for (methyl) acrylate reactions of (c) hydroxyl etc.
In the reaction of these compounds, preferably use for example copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane or 2,6,7-trimethylammonium-1, the urethane catalyzer of 4-diazabicyclo [2.2.2] octane, this catalyst consumption are 100 weight part total reactant 0.01-1 weight parts.This is reflected at preferably 10-90 ℃, particularly preferably is under 30-80 ℃ the temperature to implement.
In an embodiment of the invention, branching polyvalent alcohol (a) obtains by wherein one of at least the ring-opening polymerization of glycerol or sorbyl alcohol and oxyethane, propylene oxide or butylene oxide ring.
In another embodiment of the present invention, branching polyvalent alcohol (a) is by (this polyvalent alcohol comprises at least three hydroxyls with polyvalent alcohol (a '), and for example preferably have low-molecular-weight relatively triol or tetrol, as the triol of Polyol TP30LW (ethoxylated trimethylolpropane) or as the tetrol of PolyolPP50 (ethoxylation tetramethylolmethane), the two derives from Neste Oxo) react in-situ preparing with (methyl) acrylate (c) of polyisocyanates (b), at least a other polyvalent alcohol (a ") (preferred diol) and hydroxyl.In this embodiment, branching polyvalent alcohol (a) is by polyvalent alcohol (a ') and polyisocyanates reaction, then form with at least a other polyvalent alcohol (a ") (preferred diol) reaction, this at least a other polyvalent alcohol (a ") forms the molecular chain that is extended by branch point.Herein, at least a other polyvalent alcohol (a ") can for example be selected from the group of following polyvalent alcohol " (a2) " (polyvalent alcohol except that (a) or polyol blends).Then, the branching polyvalent alcohol (a) that forms thus and (b) polyisocyanates and (c) (methyl) acrylate reactions formation urethane (methyl) origoester acrylate (A) of hydroxyl.Therefore, there is branch point (nuclear) (being formed by polyvalent alcohol (a ')) in branching polyvalent alcohol (a) in this embodiment, the molecular chain that extends by branch point (by at least a other polyvalent alcohol (a "), preferred diol forms) and from the reactive terminal group of hydroxyl (methyl) acrylate.Polyisocyanates connects branch point (nuclear), by molecular chain and (methyl) acrylate reactions group of branch point extension.
According to the ratio of (methyl) acrylate (c) of polyvalent alcohol (a '), at least a other polyvalent alcohol (a ") (preferred diol), polyisocyanates (b) and hydroxyl, can form the mixture of difunctionality and multifunctional (methyl) acrylate.Therefore, form branching polyvalent alcohol (a) (this polyvalent alcohol (a) with (methyl) acrylate reactions of hydroxyl after form (A)) after, reaction mixture can also comprise free diol (a "), and this glycol can form Difunctional oligomers with (methyl) acrylate reactions of hydroxyl.
As with in the above-described embodiment polyvalent alcohol (a '), can use low molecular weight polyols, this polyvalent alcohol at room temperature is generally liquid, therefore is easy to handle between synthesis phase.Usually can implement down solvent-free with the reaction of described polyvalent alcohol.And, can use relatively inexpensive described polyvalent alcohol and the polyvalent alcohol that is easy to obtain.Type by changing polyvalent alcohol (a ') (for example, hydroxyl value, molecular weight), at least a other polyvalent alcohol (a ") type (for example, molecular weight) of (preferred diol) and the ratio between the reactant can prepare various branched oligomers or branched oligomers and linear oligomer in a still mixture.Therefore, according to needed oligopolymer, prepare various system.
The molecular weight of at least three molecular chains that extended by the branch point of branching polyvalent alcohol (a) is 500g/mol or higher, more preferably 700g/mol or higher preferably.In an embodiment of the invention, the molecular weight of at least three molecular chains that extend by the branch point of branching polyvalent alcohol (a) 1000g/mol or higher preferably.The molecular weight of at least three molecular chains that extended by the branch point of branching polyvalent alcohol (a) is 10000g/mol or lower, more preferably 5000g/mol or lower, most preferably 3000g/mol or lower preferably.In an embodiment of the invention, the molecular weight of at least three molecular chains that extend by the branch point of branching polyvalent alcohol (a) 2000g/mol or lower preferably.
Although not concrete the qualification, the number-average molecular weight of polyvalent alcohol (a) is preferably 1500-20000g/mol, and more preferably 1500-12000g/mol most preferably is 2000-10000, is preferably 2500-8000g/mol especially.
The number-average molecular weight of each side chain of polyvalent alcohol (a) is preferably 500-2000g/mol, more preferably 1000-1500g/mol.
Preferably, branching polyvalent alcohol (a) has 3-6 molecular chain that is extended by branch point, more preferably has 3 or 4 molecular chains that extended by branch point.At least two, preferably at least 3, more preferably all comprise terminal hydroxyl by the molecular chain that branch point extends.
The branching polyvalent alcohol that can get as commerce (can with (methyl) acrylate reactions of polyisocyanates (b) and hydroxyl) can provide the Co. by Daiichi Kogyo Seiyaku, the product that Ltd. produces, for example G3000; By Asahi Glass Urethane Co., Ltd. or Sanyo ChemicalIndustries, Ltd. the product of Sheng Chaning, for example, Sannix GL-3000, Sannix GP-3000, Sannix GP-3700M, Sannix GP-4000, Sannix GEP-2800, Sannix GP-600, Sannix GP-1000, Newpol TL-4500N etc.Of the present invention wherein except polyvalent alcohol (a ') at least a other polyvalent alcohol (a ") (preferred diol) be used to form in another embodiment of branching polyvalent alcohol (a); for example the polyvalent alcohol of the low relatively branching of Polyol TP30LW (ethoxylated trimethylolpropane) or as the tetrol (the two derives from Neste Oxo) of Polyol PP50 (ethoxylation tetramethylolmethane), Sannix TP-400, Sannix GP-250, Sannix GP-400 can be used as and have low-molecular-weight relatively polyvalent alcohol (a ').
The polyvalent alcohol except (a) or the mixture of polyvalent alcohol can be added in (a).The mixture of these other polyvalent alcohols or polyvalent alcohol is defined as (a2).(a2) example comprises aliphatic series or cyclic polyether glycol, polyester glycol, polycarbonate diol and polycaprolactone glycol.Do not limit the polymerization methods of the structural unit of these polyvalent alcohols is concrete.These polyvalent alcohols can be any one of unregulated polymer, block polymer or graftomer.As the example of aliphatic polyether diol, but can provide polyether glycol that polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, poly-heptamethylene glycol, poly-decamethylene glycol, the ring opening copolymer by two or more ionic polymerization ring compounds obtain etc.But example as the ionic polymerization ring compound, can provide for example oxyethane, propylene oxide, 1, the 2-butylene oxide ring, the oxidation 1-butylene, the oxidation iso-butylene, 3,3-dichloromethyl trimethylene oxide, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, the 3-methyltetrahydrofuran, dioxane, trioxane, four oxocane, cyclohexene oxide, Styrene oxide 98min., epoxy chloropropane, glycidyl methacrylate, allyl glycidyl ether, carbonic acid allyl glycidyl ester, butadiene monoxide, one oxidation isoprene, the vinyl trimethylene oxide, the vinyl tetrahydrofuran (THF), the oxyethylene group tetrahydrobenzene, phenylglycidyl ether, the cyclic ethers of butyl glycidyl base ether and phenylformic acid glycidyl ester.And, but can use by the ring compound of above ionic polymerization and the polyether glycol that for example obtains such as the cyclic imide of aziridine, such as the monomer ring opening copolymer of the annular lactone acid of beta-propiolactone or glycollide and dimethyl cyclopolysiloxane.But example as the particular combinations of two or more ionic polymerization ring compounds, can provide following combination: tetrahydrofuran (THF) and propylene oxide, tetrahydrofuran (THF) and 2-methyltetrahydrofuran, tetrahydrofuran (THF) and 3-methyltetrahydrofuran, tetrahydrofuran (THF) and oxyethane, propylene oxide and oxyethane, oxidation 1-butylene and oxyethane, the terpolymer of tetrahydrofuran (THF), oxidation 1-butylene and oxyethane etc.But the ring opening copolymer thing of these ionic polymerization ring compounds can be random copolymers or segmented copolymer.
These polyether glycol commerce can be PTMG650, PTMG1000, PTMG2000 (producing) by Mitsubishi Chemical Corp., PEG1000, Unisafe DC1100, DC1800 is (by Nippon Oil and Fats Co., Ltd. produce), PPTG2000, PPTG1000, PTG400, PTGL2000 is (by Hodogaya Chemical Co., Ltd. produce), Z-3001-4, Z-3001-5, PBG2000A, PBG2000B is (by Daiichi Kogyo Seiyaku Co., Ltd. produce), the Acclaim polypropylene glycol, for example, Acclaim 4200 and Acclaim 200, Desmophen 2061 BD (all are produced by Bayer) etc.
As the cyclic polyether examples of polyhydric alcohols, can provide the glycol of the alkylene oxide adduct of dihydroxyphenyl propane, the glycol of the alkylene oxide adduct of Bisphenol F, Hydrogenated Bisphenol A, A Hydrogenated Bisphenol A F, the glycol of the alkylene oxide adduct of Hydrogenated Bisphenol A, the glycol of the alkylene oxide adduct of A Hydrogenated Bisphenol A F, the glycol of the alkylene oxide adduct of quinhydrones, the glycol of the alkylene oxide adduct of naphthalene quinhydrones, the glycol of the alkylene oxide adduct of anthrahydroquinone, 1, the glycol of the adducts of 4-cyclohexanediol and epoxy alkane thereof, three ring decanediols, the tristane dimethanol, five rings 15 carbon glycol, pentacyclopentadecandimethanol dimethanol etc.In these, the preferably glycol of the alkylene oxide adduct of the glycol of the alkylene oxide adduct of dihydroxyphenyl propane, Hydrogenated Bisphenol A, tristane dimethanol etc.These polyvalent alcohol commerce can for UniolDA400, DA700, DA1000, DB400 (by Nippon Oil and Fats Co., Ltd production), N1162 (by Daiichi Kogyo Seiyaku Co., Ltd. produces), tristane dimethanol (producing) etc. by Mitsubishi Chemical Corp..
As the example of polyester polyol, can provide by polyvalent alcohol and diprotic acid are reacted the polyester polyol that obtains.Above-mentioned examples of polyhydric alcohols comprises ethylene glycol, polyoxyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexylene glycol, neopentyl glycol, 1,4 cyclohexane dimethanol, 3-methyl isophthalic acid, 5-pentanediol, 1,9-nonanediol and 2-methyl isophthalic acid, the 8-ethohexadiol.As the example of diprotic acid, can provide phthalic acid, m-phthalic acid, terephthalic acid, toxilic acid, fumaric acid, hexanodioic acid and sebacic acid.These polyester glycol commerce can be Kurapol P-2010, PMIPA, PKA-A, PKA-A2, PNA-2000 (by Kuraray Co., Ltd produces) etc.
As the example of polycarbonate polyol, can provide the polycarbonate, 1 of polytetrahydrofuran, the polycarbonate of 6-hexylene glycol etc.Commerce as polycarbonate diol can get product, can provide DN-980,981,982,983 (by Nippon Polyurethane Industry Co., Ltd produces), PC-8000 (being produced by PPG), PC-THF-CD (being produced by BASF) etc.
Example as polycaprolactone glycol, can provide by (for example 6-caprolactone and glycol, ethylene glycol, polyoxyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polytetramethylene glycol, 1,6-hexylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butyleneglycol) polycaprolactone glycol that obtains of reaction.This glycol commercial can be PLACCEL 205,205AL, 212,212AL, 220,220AL (by Daicel Chemical Industries, Ltd produces) etc.
Except above-mentioned polyvalent alcohol, can use big weight polyalcohol (a2).As this other examples of polyhydric alcohols, can provide ethylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1, the dihydroxymethyl compound of 6-hexylene glycol, neopentyl glycol, 1,4 cyclohexane dimethanol, Dicyclopentadiene (DCPD), tristane dimethanol, Beta-methyl-δ-Wu Neizhi, hydroxyl terminated poly-butadiene, hydroxy-end capped hydrogenated butadiene polymer, castor oil modified polyvalent alcohol, the glycol end-caps of polydimethylsiloxane, the glycol of polydimethylsiloxane Trivalin SF modification etc.
Except being used in combination polyvalent alcohol, diamines can be used in combination with polyvalent alcohol.As the example of diamines, can provide quadrol, tetramethylene-diamine, hexamethylene-diamine, right-phenylenediamine, 4,4 '-diaminodiphenyl-methane, contain heteroatomic diamines, polyether diamine etc.
In the above-mentioned polyvalent alcohol (a2), the glycol of the alkylene oxide adduct of two pure and mild Hydrogenated Bisphenol As of the alkylene oxide adduct of polyether glycol, dihydroxyphenyl propane preferably.These glycol commercial can for PTMG 650, PTMG 1000, PTMG 2000 (producing), Uniol DA400, DA700, DA1000, DB400 by Mitsubishi Chemical Corp. (by Nippon Oil and FatsCo., Ltd. produce) and N1162 (by Daiichi Kogyo Seiyaku Co., Ltd. produces) etc.
The number-average molecular weight of other polyol component (a2) is 300-5000, preferably 300-2000, more preferably 300-1000.
As the polyisocyanates of component (b), preferably vulcabond.As the vulcabond example, can provide 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, 1, the 3-Xylene Diisocyanate, 1, the 4-Xylene Diisocyanate, 1, the 5-naphthalene diisocyanate, the metaphenylene vulcabond, to phenylene vulcabond, 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, 4,4 '-diphenylmethanediisocyanate, 3,3 '-dimethyl phenylene vulcabond, 4,4 '-xenyl vulcabond, 1, the 6-hexane diisocyanate, isophorone diisocyanate, methylene bis(4-, 2,2, the 4-trimethyl hexamethylene diisocyanate, fumaric acid two (2-isocyanic ester ethyl) ester, 6-sec.-propyl-1, the 3-phenyl diisocyanate, 4-diphenyl propane vulcabond, lysinediisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, the inferior Xylene Diisocyanate of tetramethyl-, 2,5 (or 6)-two (isocyanic ester methyl)-two ring [2.2.1] heptane etc.In these, preferred especially 2,4 toluene diisocyanate, isophorone diisocyanate, Xylene Diisocyanate and methylene bis(4-.
These polyisocyanates (b) can use separately or two or more are used in combination.
Example as hydroxyl (methyl) acrylate (c), can provide (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, 1,4-butyleneglycol list (methyl) acrylate, 2-hydroxyalkyl (methyl) acryloyl phosphoric acid ester, (methyl) vinylformic acid 4-hydroxyl cyclohexyl, 1,6-hexylene glycol list (methyl) acrylate, neopentyl glycol single (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, (methyl) acrylate shown in Dipentaerythritol five (methyl) acrylate and following formula (1) and (2).
R wherein
1Expression hydrogen atom or methyl, n is 1 to 15 integer.
Also can be by the compound that (methyl) vinylformic acid and the addition reaction that contains the compound (for example, alkyl glycidyl base ether, allyl glycidyl ether or (methyl) glycidyl acrylate) of glycidyl obtain as (methyl) acrylate of hydroxyl.In (methyl) acrylate of these hydroxyls, particularly preferably be (methyl) vinylformic acid 2-hydroxy methacrylate and (methyl) vinylformic acid 2-hydroxy propyl ester.
(methyl) acrylate (c) of these hydroxyls can use separately or two or more are used in combination.
In an embodiment of the invention, during preparation urethane (methyl) origoester acrylate (A), the mol ratio of regulating raw material makes that nearly all (preferably owning) is derived from the hydroxyl of polyvalent alcohol (a) and (methyl) acrylate (c) of vulcabond (b) and hydroxyl reacts.In described embodiment, can only keep small amount of hydroxyl groups.
In another embodiment of the present invention, the mol ratio of preferably regulating raw material makes a part of hydroxyl that is derived from polyvalent alcohol (a) can not react with vulcabond (b) and hydroxyl (methyl) acrylate (c), still is present in oligopolymer (A) as hydroxyl.
The amount that urethane (methyl) acrylate component (A) is added in the curable liquid resin composition of the present invention is 0.5-50wt%, is preferably 3-45wt%, more preferably 5-40wt%.If content less than 0.5wt%, then can damage coating character.If content surpasses 50wt%, then the Young's modulus of elasticity of cured product reduces.In an embodiment of the invention, add the main ingredient of urethane (methyl) acrylate (A) as whole urethane (methyl) origoester acrylates in the curable liquid resin composition.
In another embodiment of the present invention, add the properties-correcting agent (for example, rheology modifier) of urethane (methyl) origoester acrylate (A) as the main ingredient of urethane (methyl) origoester acrylate.The purpose of this embodiment is to provide a kind of curable liquid resin composition that improves processing characteristics that has, and concrete is that a kind of secondary resin combination is provided.At present, the preparation method of coated optical fiber comprises: fiber is passed a coating mould that is installed on the equipment that is called as the tower that reels off raw silk from cocoons (draw tower), then the resin combination that applies is solidified.In the wet coating of wet pressing (wet-on-wet application), secondary resin combination and primary resin composition are coated on the optical glass fibre simultaneously, after this, two kinds of resin combinations are solidified simultaneously.Usually, the rheological property of primary resin composition and secondary resin combination is different, that is, described composition has limited rheology consistency.This may cause some problem.Causing high shear rate by move down the drag flow that kinetodesma causes in high pulling speed, is 10 in the exit near the coating cup usually
5s
-1With 10
6s
-1Between.When shearing rate increased, the optical fiber resin composition showed complicated non-newtonian behaviour usually.For this reason, during fiber production, the processing characteristics instability usually takes place, particularly in the wet coating of wet pressing, wherein, primary resin composition and secondary resin combination with various flows change nature are coated.Another important problem relates to the uniformity coefficient of solidifying the back coating.More particularly, in the fiber of high quality through applying, the thickness of coating has high evenness along the length of fiber.Yet, under the speed usually above 25m/sec, relatively little gap between the outside surface of high fiber speed, fiber and the mould, die length, the common influence to the character of its applied pressure and uncured coating composition when composition infeeds in the mould can cause the even level on the solidified coating low as can't to accept.When hope two optical fiber are received a time-out, having the low optical fiber that applies even level may have problems.After being mounted to data network, heterogeneity may be transformed into data transmission problems, for example signal attenuation.Solving the instable mode of processing is to control the rheological property of curable liquid resin composition in some way.
(for example wherein add urethane (methyl) origoester acrylate (A) above-mentioned as properties-correcting agent, rheology modifier) in the embodiment, the main ingredient of urethane (methyl) origoester acrylate is preferably based on urethane (methyl) origoester acrylate of glycol, urethane (methyl) acrylate (A) is for example to be that the consumption of 0.5-10wt% adds to wherein, to obtain more favourable rheological property (if liquid resinous words).Wherein add in the embodiment of urethane (methyl) origoester acrylate (A) as rheology modifier the elastic steady state compliance J of tolerance resin of the present invention
ePreferred 2MPa
-1Or bigger, or bigger 3MPa more preferably
-1Or bigger, most preferably be 4MPa
-1Or bigger, be preferably 5MPa especially
-1Or it is bigger.
Urethane (methyl) acrylate that obtains by hydroxyl (methyl) acrylate reactions with the vulcabond (b) of 1mol and 2mol can add in the curable liquid resin composition of the present invention.Example as this urethane (methyl) acrylate, what provide is (methyl) Hydroxyethyl Acrylate and 2, the reaction product of 4-tolylene diisocyanate, (methyl) Hydroxyethyl Acrylate and 2, the reaction product of reaction product, (methyl) vinylformic acid hydroxy propyl ester and the 2,4 toluene diisocyanate of reaction product, (methyl) Hydroxyethyl Acrylate and the isophorone diisocyanate of 5 (or 6)-two (isocyanic ester methyl)-two ring [2.2.1] heptane and the reaction product of (methyl) vinylformic acid hydroxy propyl ester and isophorone diisocyanate.
Polymerizable monofunctional group's compound can be sneaked in the liquid curable resin composition of the present invention as component (B).Example as the simple function group compound, can provide the N-vinyl pyrrolidone, for example the N-caprolactam contains vinyl lactam, (methyl) isobornyl acrylate for example, (methyl) vinylformic acid norbornene ester, (methyl) acrylate that contains alicyclic structure of (methyl) vinylformic acid three ring esters in the last of the ten Heavenly stems and (methyl) vinylformic acid two ring pentyl esters, (methyl) vinylformic acid benzene methyl, (methyl) vinylformic acid 4-butyl cyclohexyl, acryloyl morpholine, vinyl imidazole, vinyl pyridine, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecane ester, (methyl) vinylformic acid dodecane ester, (methyl) lauryl acrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid isooctadecane base ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) vinylformic acid butoxy ethyl ester, (methyl) vinylformic acid oxyethyl group binaryglycol ester, (methyl) vinylformic acid benzene methyl, (methyl) vinylformic acid phenoxy ethyl, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) vinylformic acid methoxyl group glycol ester, (methyl) vinylformic acid ethoxy ethyl ester, (methyl) vinylformic acid methoxy poly (ethylene glycol) ester, (methyl) vinylformic acid methoxyl group polypropylene glycol ester, diacetone (methyl) acrylamide, isobutoxy methyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, uncle's octyl group (methyl) acrylamide, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) vinylformic acid 7-amino-3,7-dimethyl monooctyl ester, N, N-diethyl (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, hydroxy butyl vinyl ether, the lauryl vinyl ether, cetyl vinylether, 2-ethylhexyl vinyl ether and following formula (3) arrive the compound shown in (6):
Wherein, R
2Expression hydrogen atom or methyl, R
3Expression has a 2-6 carbon atom, the alkylene of 2-4 carbon atom preferably, R
4Expression hydrogen atom or have 1-12 carbon atom, the alkyl of 1-9 carbon atom preferably, m is 0 to 12, preferably 1 to 8 integer;
Wherein, R
5Expression hydrogen atom or methyl, R
6Expression has a 2-8 carbon atom, the alkylene of 2-5 carbon atom preferably, R
7Expression hydrogen atom or methyl, p is preferably 1 to 4 integer;
Wherein, R
8, R
9, R
10And R
11Represent hydrogen atom or methyl respectively, q is 1 to 5 integer.
In these simple function group compounds (B), the compound of the lactan that contains vinyl of N-vinyl pyrrolidone, for example N-caprolactam, (methyl) isobornyl acrylate, lauryl acrylate and following formula (6) preferably.
These simple function group compound (B) commerce can for IBXA (by Osaka OrganicChemical Industry Co., Ltd. production), Aronix M-111, M-113, M-114, M-117, TO-1210, Aronix M-110 (by Toagosei Co., Ltd. produces) etc.
Consider the reduction stress relaxation time, the amount of the polymerizable monofunctional group's compound (B) in curable liquid resin composition of the present invention is preferably 5-90wt%, more preferably 10-80wt%.
Curable liquid resin composition of the present invention comprises that polymerization starter is as component (C).As polymerization starter, can use thermal polymerization or light trigger.
When with thermofixation curable liquid resin composition of the present invention, use thermal polymerization, for example superoxide or azo-compound.As the specific examples of thermal polymerization, can provide benzoyl peroxide, peroxidized t-butyl perbenzoate, Diisopropyl azodicarboxylate etc.
When with photocuring curable liquid resin composition of the present invention, use light trigger.Preferably add photosensitizers when needing in addition.Example as light trigger, can provide 1-hydroxy-cyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, xanthone, Fluorenone, phenyl aldehyde, fluorenes, anthraquinone, triphenylamine, carbazole, the 3-methyl acetophenone, the 4-chlorobenzophenone, 4,4 '-dimethoxy-benzophenone, 4,4 '-diaminobenzophenone, Michler's keton, the bitter almond oil camphor propyl ether, ethoxybenzoin, the benzyl dimethyl ketal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, thioxanthone, diethyl thioxanthone, the 2-isopropyl thioxanthone, the 2-clopenthixal ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino third-1-ketone, 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide, two-(2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide; Irgacure 184,369,651,500,907, CGI 1700, CGI 1750, CGI 1850, CG 24-61 (by Ciba Specialty Chemicals Co., Ltd. produces), Lucirin LR8728 (producing), Darocur 1116,1173 (producing), Ubecryl P36 (producing) etc. by UCB by Merck by BASF.As the example of photosensitizers, can provide triethylamine, diethylamine, N methyldiethanol amine, thanomin, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl esters, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester; Ubecryl P102,103,104,105 (producing) etc. by UCB.
If with heat and UV-light the two solidify curable liquid resin composition of the present invention, can be used in combination thermal polymerization and light trigger so.The amount that is used in the polymerization starter (C) in the curable liquid resin composition of the present invention is 0.1-10wt%, particularly preferably is 0.5-7wt%.
The polymerizable polyfunctional compound also can add in the curable liquid resin composition of the present invention as component (D).Example as polyfunctional compound (D), can provide trimethylolpropane tris (methyl) acrylate, (methyl) vinylformic acid trimethylolpropane tris 2-ethoxyethyl acetate, tetramethylolmethane three (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol diacrylate, TEG two (methyl) acrylate, three ring basic dimethanol two (methyl) acrylate in the last of the ten Heavenly stems two, polyoxyethylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, the both-end of bisphenol A diglycidyl ether (methyl) vinylformic acid addition compound, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, polyester two (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, two (methyl) acrylate of the oxyethane of dihydroxyphenyl propane or the glycol of propylene oxide adduct, two (methyl) acrylate of the oxyethane of Hydrogenated Bisphenol A or the glycol of propylene oxide adduct, epoxy (methyl) acrylate that (methyl) acrylate is added and prepare to the diglycidylether of dihydroxyphenyl propane, triethylene glycol divinyl ether etc.
In these polymerizable polyfunctional compounds (D), two (methyl) acrylate and three (2-hydroxyethyl) isocyanuric acid esters three (methyl) acrylate of the glycol of the ethylene oxide adduct of three the ring last of the ten Heavenly stems two basic dimethanol two (methyl) acrylate, dihydroxyphenyl propanes preferably.
Commerce as these polymerizable polyfunctional compounds (D) can get product, can provide Yupimer UV SA1002 (producing), Aronix M-215, M-315, M-325, TO-1210 (by Toagosei Co. by Mitsubishi Chemical Corp., Ltd. produce), GX-8345 (by Daiichi Kogyo Seiyaku Co., Ltd produces) etc.
These polymerizables polyfunctional compound's (D) add-on 5-90wt% preferably particularly preferably is 10-80wt% in the curable liquid resin composition of the present invention.If add-on is less than 5wt% or surpass 90wt%,, thereby cause coating inhomogeneous so owing to the coating alteration of form.
The characteristic that needs only composition does not have negative impact, just the various additives of for example antioxidant, tinting material, UV absorption agent, photostabilizer, silane coupling agent, thermal polymerization, levelling agent, tensio-active agent, sanitas, softening agent, lubricant, solvent, filler, protective agent, wettability improving agent and coatingsurface improving agent can be chosen wantonly to be added in the radiation-curable liquid resin composition of the present invention.
With heat or radiation curing curable liquid resin composition of the present invention.The radiation of Shi Yonging herein refers to infrared rays, visible light, ultraviolet ray, X-ray, electron beam, α-ray, beta-rays, gamma-radiation etc.
Cured product according to the curable liquid resin composition of method for preparing had less than 4 minutes, and preferred 3 minutes or shorter, more preferably 2 minutes or shorter stress relaxation time.If stress relaxation time is 4 minutes or longer, then, can keep coating stress during the producd fibers or during handling, it is for example to form the problem that cavity and primary layer are peeled off from silica glass in primary layer that this stress causes concrete.
Cured product has 350MPa or higher at 23 ℃, preferred 400MPa or higher, more preferably 500MPa or higher Young's modulus of elasticity.
Embodiment
The present invention is described by the following examples in more detail.Yet, the invention is not restricted to these embodiment.Among the embodiment, " umber " refers to " parts by weight ".
Synthetic (A-1)
In being housed, the reactor of agitator adds 6.651g isophorone diisocyanate, 0.024g2,6-ditertbutylparacresol, 0.080g dibutyl tin laurate and 0.008g thiodiphenylamine.With ice this mixture is cooled to 10 ℃ or lower stirring simultaneously.Be added dropwise to the 6.651g Hydroxyethyl Acrylate, simultaneously temperature is controlled at 20 ℃ or lower after, mixture reaction 1 hour is stirred simultaneously.After to add the 89.763g number-average molecular weight be 6000 polyglycerol (G3000 is by Daiichi KogyoSeiyaku Co., and Ltd produces), mixture was stirred 3 hours down at 70-75 ℃.When remaining isocyanate content is 0.1wt% or more hour, termination reaction.This liquid resin is called as " oligopolymer (A-1) ".
Synthetic (A-2)
In being housed, the reactor of agitator adds 16.489g isophorone diisocyanate, 0.024g2,6-ditertbutylparacresol, 0.080g dibutyl tin laurate and 0.008g thiodiphenylamine.With ice this mixture is cooled to 10 ℃ or lower stirring simultaneously.Be added dropwise to the 8.666g Hydroxyethyl Acrylate, simultaneously temperature is controlled at 20 ℃ or lower after, mixture reaction 1 hour is stirred simultaneously.After adding the open loop glycol (by DaiichiKogyo Seiyaku Co., Ltd produces) that the 74.633g number-average molecular weight is 2000 tetrahydrofuran (THF), mixture was stirred 3 hours down at 70-75 ℃.When remaining isocyanate content is 0.1wt% or more hour, termination reaction.This liquid resin is called as " oligopolymer (A-2) ".
Synthetic (U-1)
In being housed, the reactor of agitator adds 44.726g isophorone diisocyanate, 0.024g2,6-ditertbutylparacresol, 0.080g dibutyl tin laurate and 0.008g thiodiphenylamine.With ice this mixture is cooled to 10 ℃ or lower stirring simultaneously.Be added dropwise to the 35.063g Hydroxyethyl Acrylate, simultaneously temperature is controlled at 20 ℃ or lower after, mixture reaction 1 hour is stirred simultaneously.After adding the glycol (producing) of ethylene oxide adduct that the 20.099g number-average molecular weight is 400 dihydroxyphenyl propane, mixture was stirred 3 hours down at 70-75 ℃ by NOF Corporation.When remaining isocyanate content is 0.1wt% or more hour, termination reaction.This liquid resin is called as " oligopolymer (U-1) ".
Synthetic (B-1)
In being housed, the reactor of agitator adds 5.287g 2,4 toluene diisocyanate, 0.024g2,6-ditertbutylparacresol, 0.080g dibutyl tin laurate and 0.008g thiodiphenylamine.With ice this mixture is cooled to 10 ℃ or lower stirring simultaneously.Be added dropwise to the 3.525g Hydroxyethyl Acrylate, simultaneously temperature is controlled at 20 ℃ or lower after, mixture reaction 1 hour is stirred simultaneously.After to add the 91.076g number-average molecular weight be 6000 polyglycerol (G3000 is by Daiichi KogyoSeiyaku Co., and Ltd produces), mixture was stirred 3 hours down at 70-75 ℃.When remaining isocyanate concentration is 0.1wt% or more hour, termination reaction.This liquid resin is called as " oligopolymer (B-1) ".
Synthetic (B-2)
In being housed, the reactor of agitator adds 13.480g 2,4 toluene diisocyanate, 0.024g2,6-ditertbutylparacresol, 0.080g dibutyl tin laurate and 0.008g thiodiphenylamine.With ice this mixture is cooled to 10 ℃ or lower stirring simultaneously.Be added dropwise to the 8.990g Hydroxyethyl Acrylate, simultaneously temperature is controlled at 20 ℃ or lower after, mixture reaction 1 hour is stirred simultaneously.After to add the 77.420g number-average molecular weight be 2000 tetrahydrofuran ring opening polymerization thing (by DaiichiKogyo Seiyaku Co., Ltd produces), mixture was stirred 3 hours down at 70-75 ℃.When remaining isocyanate concentration is 0.1wt% or more hour, termination reaction.This liquid resin is called as " oligopolymer (B-2) ".
Synthetic (U-2)
In being housed, the reactor of agitator adds 42.806g 2,4 toluene diisocyanate, 0.024g2,6-ditertbutylparacresol, 0.080g dibutyl tin laurate and 0.008g thiodiphenylamine.With ice this mixture is cooled to 10 ℃ or lower stirring simultaneously.Be added dropwise to the 57.082g Hydroxyethyl Acrylate, simultaneously temperature is controlled at 20 ℃ or lower after, mixture was stirred 3 hours down at 70-75 ℃.When remaining isocyanate content is 0.1wt% or more hour, termination reaction.Thus obtained liquid resin is called as " urethane acrylate (U-2) ".
Synthetic (U-3)
In being housed, the reactor of agitator adds 42.15g 2,4 toluene diisocyanate, 0.024g2,6-ditertbutylparacresol, 0.080g dibutyl tin laurate and 0.008g thiodiphenylamine.With ice this mixture is cooled to 10 ℃ or lower stirring simultaneously.Be added dropwise to 43.48g Hydroxyethyl Acrylate and 14.26g vinylformic acid hydroxyethyl propyl ester, simultaneously temperature is controlled at 20 ℃ or lower after, mixture was stirred 3 hours down at 70-75 ℃.When remaining isocyanate content is 0.1wt% or more hour, termination reaction.Thus obtained liquid resin is called as " urethane acrylate (U-3) ".
Test case
The preparation test membrane: adopt the gluing rod that the curable liquid composition is coated on the sheet glass, thickness is 250 μ m.By dosage is 1J/cm
2Ultraviolet ray radiation curing curable liquid resin composition in air, obtain test membrane.
1. tolerance Young's modulus of elasticity: the band shape sample that test membrane is cut into the long 25mm of wide 6mm.Under the humidity of 23 ℃ temperature and 50%, sample is carried out Elongation test.By the tensile strength calculation Young's modulus under the strain of the rate of extension of 1mm/min and 2.5%.
2. tolerance stress relaxation time: the band shape sample that above-mentioned test membrane is cut into the long 25mm of wide 6mm.Under the humidity of 23 ℃ temperature and 50%, sample is applied 5% strain with the speed of 1000mm/min.The variation of pinblock (Autograph AGS-50 is produced by the Shimazu Corp.) monitor stress by the stretching testing machine that suspends.Time period of 37% that stress is reduced to initial stress is measured as stress relaxation time.
3. the cavity in the observation primary material occurs.
3-1 prepares primary material
In being housed, the reactor of agitator adds 6.6 part 2,4-tolylene diisocyanate, 0.015 part 2,6-ditertbutylparacresol, 0.48 part of dibutyl tin laurate, 0.005 part of thiodiphenylamine and 16.2 parts of IBXA (by Osaka Organic Chemical Industry, Ltd. produces).With ice this mixture is cooled to 10 ℃ or lower stirring simultaneously.Be added dropwise to 2.9 parts of Hydroxyethyl Acrylate, simultaneously temperature is controlled at 20 ℃ or lower after, mixture reaction 1 hour is stirred simultaneously.After to add 50.0 umber average molecular weights be 2000 polytetramethylene glycol (being produced by Mitsubishi Chemical Corp.), mixture was stirred 4 hours down at 50-60 ℃.When remaining isocyanate content is 0.1wt% or more hour, termination reaction.After adding 10.8 parts of isobornyl acrylate (producing), 4.8 parts of caprolactams, 5.6 parts of lauryl acrylates and 0.2 part of Irganox 1035 (producing), mixture was stirred 30 minutes down at 40-50 ℃ by Ciba-Geigy Ltd. by Rohm andHaas Japan K.K..Adding 0.1 part of diethylamine, simultaneously temperature is controlled at after 30-40 ℃, mixture was stirred 30 minutes.Then, add a two-(2, the 6-anisoyl)-2,4,4-tri-methyl-amyl phosphine oxide and a Dacocure 1173 (being produced by Merck) are controlled at temperature 50-60 ℃ simultaneously, and stir this mixture up to the liquid that obtains homogeneous phase transparent.Obtain primary material thus.
The 3-2 tensile fiber
Utilize fiber draw unit (by Yoshida Kogyo Co., Ltd. produces), be coated on the glass fibre primary material and curing.The composition of embodiment and Comparative Examples is coated on the solidified primary material.
The stretching condition of optical fiber is as follows.The diameter of glass fibre is 125 μ m.Be coated on the metal wire primary material and curing, make that the diameter of the optical fiber after solidifying is 200 μ m.The composition of embodiment and Comparative Examples is coated on the primary material that forms thus, makes that the diameter after solidifying is 250 μ m.As the UV radiation devices, the UV lamp " SMX 3.5kw " that uses ORC Corp. to produce.Optical fiber rate of extension assessment coating character with 1000m/min.
3-3 observes empty occurrence rate
In above-mentioned fiber being immersed 60 ℃ hot water after 72 hours, utilize empty occurrence rate and naked looking in the microscopic examination primary material to observe primary material peeling off from the silica glass.
Judge
Have 350MPa or higher Young's modulus of elasticity, less than 4 minutes stress relaxation rates, the sample in cavity is not judged as acceptable product.
Table 1
| Embodiment | Comparative Examples | |||||||
| 1 | 2 | 3 | 1 | 2 | 3 | 4 | 5 | |
| Oligopolymer/urethane acrylate | ||||||||
| A-1 | 32.00 | 37.50 | 74.00 | |||||
| A-2 | 32.00 | |||||||
| U-1 | 42.00 | 42.00 | ||||||
| B-1 | 48.40 | 62.90 | ||||||
| B-2 | 50.40 | 37.50 | ||||||
| U-2 | 14.50 | 12.50 | ||||||
| U-3 | 34.70 | 34.70 | ||||||
| Monomer | ||||||||
| Isobornyl acrylate | 9.45 | 17.42 | 26.92 | 9.45 | 9.45 | 17.42 | 17.42 | 26.92 |
| The N-caprolactam | 8.71 | 8.71 | 8.71 | |||||
| SA1002 *1 | 1.93 | 7.74 | 1.93 | 1.93 | 7.74 | 7.74 | ||
| Viscoat#700 *2 | 19.30 | 19.30 | 19.30 | |||||
| Irgacure 184 *3 | 2.99 | 2.91 | 2.99 | 2.99 | 2.99 | 2.91 | 2.91 | 2.99 |
| Sumilizer GA- 80 *4 | 0.29 | 0.30 | 0.29 | 0.29 | 0.29 | 0.30 | 0.30 | 0.29 |
*1Mitsubishi Chemical Co.，Ltd.
*2Osaka Organic Chemical Industry Ltd.
*3Ciba Specialty Chemicals Co.，Ltd.
*4Sumitomo Chemical Co.，Ltd.
Table 2
| Embodiment | Comparative Examples | |||||||
| 1 | 2 | 3 | 1 | 2 | 3 | 4 | 5 | |
| Young's modulus of elasticity (MPa) | 510 | 570 | 600 | 300 | 700 | 330 | 700 | 850 |
| Stress relaxation rate (min) | 1.8 | 1.4 | 1.8 | 1.1 | 4.2 | 0.8 | 4.5 | 5.3 |
| Fibrotic cavitys | Do not have | Do not have | Do not have | Do not have | Have | Do not have | Have | Have |
| Judge | Qualified | Qualified | Qualified | Defective | Defective | Defective | Defective | Defective |
Can clearly be seen that by table 1 and 2, the resin combination of embodiment demonstrates heavily stressed relaxation rate and gratifying Young's modulus of elasticity as secondary materials, and expresses said composition for example do not have to form the defective that cavity and primary material are peeled off from silica glass in primary material.
Mixture by three pure and mild glycol or tetrol and glycol synthetic two, three or four-functional group urethane acrylate oligomer
(DBTDL 0.05wt%) adds in the reactor that has dry air stream, stirs and be cooled to 10 ℃ with Irganox 1035 (0.09wt%), isophorone diisocyanate (IPDI) and dibutyl tin laurate.Then add triol Polyol TP30LW (ethoxylated trimethylolpropane with 629 OH values, from Neste Oxo) or tetrol Polyol PP50 (the ethoxylation tetramethylolmethane with 638 OH values, from Neste Oxo), and reactor stirred 1 hour down at 10 ℃.Then, add vinylformic acid 2-hydroxy methacrylate (HEA) at 10 ℃ by dropping funnel.Reaching mid point after about 1 hour, reactor is heated to 20 ℃.(have Mw=2000g/mol, the polypropylene glycol of OH value 56.6 Bayer), after this, is heated to 80 ℃ with reaction mixture then to add glycol Desmophen 2061BD.Proceed reaction and be lower than 0.05% up to NCO content.Add polyvalent alcohol and glycol, IPDI and HEA with stoichiometric number.
In the table 3, listed the oligopolymer that uses method for preparing.In the table 4, the molecular weight of oligopolymer and the steady state compliance J of coating composition have been provided
e, this coating composition comprises synthetic oligomer mixture in the 48.5wt% table 3,48.5wt% ethoxylation vinylformic acid nonyl benzene phenolic ester (ENPA) and 3wt%Irgacure 184.Below provided mensuration J
eMethod.
Determine steady state compliance (J
e)
Instrument and tolerance
Determine steady state compliance (J by dynamic mechanical tolerance
e).Carry out these dynamic mechanical experiments with the Rheometric Scientific that round trip 200-2000g * cm power reequilibrate torque transducer, 25mm Invar parallel plate, nitrogen furnace and cooled with liquid nitrogen device are housed (existing TA instrument) ARES-LS rheometer.During the experiment beginning, at room temperature, resin sample is contained between the parallel plate of rheometer.With the distance setting of parallel plate at 1.6mm.Close after the gas stove, this sample was cleaned about 5 minutes with nitrogen.
With 100 and 0.1rad/s between radian frequency (3 frequencies of every decade, with descending order tolerance), temperature is 5 ℃ and carries out the isothermal frequency sweeping and move this experiment at interval, by 20 ℃ of beginnings and with step-length is 5 ℃ of reduction temperature, up to the hardening of instrument tolerance sample (for the sample of being quoted, the limit is usually between-20 ℃ of peace treaties-30 approximately ℃).Must be noted that the strain that is applied is just in time in the linear-viscoelastic scope.Usually the numerical value of strain amplitude is about 20-40% under the room temperature, and under the minimum temperature, this numerical value drops to 0.01-0.02%.Function as radian frequency is collected dynamic modulus (G
*=(G
' 2+ G
" 2)
0.5) and phasing degree (δ).Phasing degree tangent value (tan δ) is that the data point of negative value (because noise) is removed from set.
By time-temperature stack makes up master curve
By time-temperature stack, adopt work (J.D.Ferry, " ViscoelasticProperties of Polymer " (1980), the John Wiley ﹠amp of Ferry; Sons Inc.) the frequency sweeping result that will collect under differing temps T is (as the dynamic modulus G of the function of angular frequency
*With phasing degree δ) be attached in the so-called master curve.Select 20 ℃ of conducts with reference to temperature (T
Ref).For this purpose, the commercial stream parameter that uses exploitation such as Winter software package IRIS according to one's analysis
TM
To move to upper frequency to be connected at metric dynamic property under the lesser temps (T) at reference temperature (T
Ref) under the data collected.By being moved along logarithm radian frequency axle, phasing degree and dynamic modulus curve determine to move horizontally factor a
T, adopt equation 1 and 2:
δ(ω，T)＝δ(a
Tω，T
ref)(1)
G
*(ω，T)＝G
*(a
Tω，T
ref)(2)
Note, obtain phasing degree (δ) and dynamic modulus (G simultaneously
*) good superimposed curves.Usually, for material according to the invention, this is possible.In this work, commonly used but optional vertical shifting factor b along the viscosity axle
TBe unallowed.
Extract steady state compliance
In order to extract steady state compliance, dynamic master curve is mapped again with different forms.With storage compliance J ' (=G '/G
* 2) and loss compliance J " (=G "/G
* 2) be depicted as the function of radian frequency.Can use rheological data analysis package IRIS
TM(be purchased Development from IRIS, 14 Elm Street, Amherst, MA 01002-2007 is USA) with Rheometric Scientific rheometer control software Orchestrator
TMBe used for this data conversion.Can be by Ferry (J.D.Ferry, " Viscoelastic Properties of Polymer " (1980), John Wiley ﹠amp; Sons Inc.) obtains the mathematical computations details.
Usually, the storage compliance curve has platform at low radian frequency, but is easy to be subjected to noise jamming.Therefore, must be noted that the data under crossing low frequency are not included in the analysis.Because rheometer can not be measured the accurate numerical value of storage compliance, loss compliance is 20 times of storage compliance or higher, so will remove from master curve in the data point as lower frequency, this frequency surpasses 100 frequency less than phasing degree tangent value (tan δ).Usually, be the plateau value that the 500-2000rad/s place finds storage compliance J ' at radian frequency.
In order to remove noise from data, we are by extracting the numerical value of steady state compliance with following process.Use software package IRIS
TMVersion 7 calculates relax time spectrum by master curve, the minimum number pattern of the thrifty model of this version utilization employing Winter etc., this thrifty model has been carried out (Winter H.H. in IRIS software, Baumg rtel M., Soskey is ' A Parsimonious Model forViscoelastic Liquids and Solids ', A.A.Collyer Ed. ' Techniques in RheologicalMeasurement ' Chapman ﹠amp P.1993; Hall, London).For the embodiment among the application, usually in the decade of each frequency of master curve, use time of relaxation less than one.As spectrum calculation result, obtain zero-shear viscosity and steady state compliance value.According to the precision of the determined steady state compliance of this method normally ± 10%.
Table 3
| Mol ratio difunctionality: trifunctional or difunctionality: four functional oligomers | IPDI (g) | TP30LW (g) | PP50 (g) | HEA (g) | Acclaim 4200(g) (Mw4000) | Desmophen 2061BD (g) (Mw2000) |
| 100∶0 | 83.48 | 43.6 | 372.22 | |||
| 85∶15 | 83.78 | 5.82 | 36.18 | 373.52 | ||
| 50∶50 | 84.12 | 12.65 | 27.45 | 375.07 | ||
| 85∶15 | 83.85 | 6.87 | 34.73 | 373.85 | ||
| 50∶50 | 84.20 | 13.32 | 26.38 | 375.40 |
Table 4
| Mol ratio difunctionality: trifunctional or difunctionality: four functional oligomers | Molecular weight as calculated (g/mol) | Je (the MPa of composition -1) 48.5: 48.5: 3wt% oligopolymer: ENPA: Irgacure 184 |
| 100: 0 pure difunctionalitys | 2660 | 4.0 |
| 85: 15 difunctionality/trifunctionals | 3445 | 7.2 |
| 50: 50 difunctionality/trifunctionals | 5278 | 22 |
| 85: 15 difunctionality/four senses | 3839 | 10 |
| 50: 50 difunctionality/four senses | 6592 | ＞100 |
The data of table 4 show that the Mw of oligopolymer (or oligomer mixture) depends on number and the difunctionality/trifunctional or the functional ratio of difunctionality/four of the molecular chain that is extended by branch point in the polyvalent alcohol.
The result of table 4 shows, the elastic steady state compliance J of tolerance liquid resin composition
eAmount (J along with three/four functional oligomers in the composition
eAlong 100: 0 to 85: 15 to 50: 50 difunctionalitys: three/four senses and increase) and the number of the molecular chain that extends by branch point (for mixture with four functional oligomers, J
eHigher) increase and increase.Elasticity is important parameters, particularly improves for the higher wet processing characteristics of wet pressing that causes usually of secondary resin combination: Je.
Claims (22)
1. curable liquid resin composition, described composition comprise following component (A), (B) and (C):
(A) urethane of 0.5-50wt% (methyl) origoester acrylate, described oligopolymer is by polyvalent alcohol (a), (methyl) acrylate (c) of polyisocyanates (b) and hydroxyl obtains, described polyvalent alcohol (a) has the branched structures of the molecular chain that comprises that at least one branch point and at least three are extended by described branch point, described molecular chain has 200g/mol or higher molecular weight, comprise hydroxyl at least two ends by the molecular chain of described branch point extension;
(B) polymerizable organic compounds of 5-90wt%; With
(C) polymerization starter of 0.1-10wt%,
Wherein, described cured product has 350MPa or higher Young's modulus at 23 ℃.
2. curable liquid resin composition as claimed in claim 1, wherein, each comprises hydroxyl by the molecular chain that the described branch point of (a) extends.
3. curable liquid resin composition as claimed in claim 1, wherein, described molecular chain has 500g/mol or higher molecular weight.
4. curable liquid resin composition, described composition comprise following component (A), (B) and (C):
(A) urethane of 5-45wt% (methyl) origoester acrylate, described oligopolymer is by polyvalent alcohol, (methyl) acrylate of polyisocyanates and hydroxyl obtains, wherein said polyvalent alcohol has branched structure, comprise hydroxyl and have the side chain number-average molecular weight of 500-2000 that described oligopolymer comprises and is derived from described hydroxyl groups in each branching molecule chain (after this being called as side chain) end;
(B) polynierizable monofunctional compounds of 5-90wt%; With
(C) polymerization starter of 0.1-10wt%.
5. as any described curable liquid resin composition among the claim 1-4, wherein, described cured product has 500MPa or higher Young's modulus at 23 ℃.
6. as any described curable liquid resin composition among the claim 1-5, wherein, the stress relaxation time of described cured product was less than 4 minutes.
7. as any described curable liquid resin composition among the claim 1-6, wherein, steady state compliance J
eBe 2MPa
-1Or it is higher.
8. as any described curable liquid resin composition among the claim 1-7, wherein, the described polyvalent alcohol (a) of described component (A) has 3-6 molecular chain that is extended by described branch point, and at least two described molecular chains that extended by described branch point comprise hydroxyl.
9. as any described curable liquid resin composition among the claim 1-8, described composition comprises other urethane (methyl) acrylate of at least a being different from (A).
10. curable liquid resin composition as claimed in claim 9, wherein, described at least a other urethane (methyl) acrylate is based on urethane (methyl) origoester acrylate of glycol.
11. as any described curable liquid resin composition among the claim 1-10, wherein, described curable liquid resin composition is the secondary coating composition of curable liquid, curable liquid ink composite or curable liquid substrate material.
12. be used for the purposes of coated optics glass fibre as secondary coating composition, ink composite or substrate material as any described curable liquid resin composition among the claim 1-11.
13. cured product, any described curable liquid resin composition obtains among the claim 1-11 by solidifying.
14. the optical fiber through applying, it comprises the glass optical fiber with primary coating; A kind of optical fiber through applying, it comprises the glass optical fiber with primary coating and secondary coating; A kind of optical fiber through applying, it comprise have primary coating, the glass optical fiber of secondary coating and hard-pressed bale coating; A kind of optical fiber through applying, it comprises glass optical fiber and single-layer coating; A kind of optical fiber through applying, it comprises glass optical fiber, single-layer coating and hard-pressed bale coating, and every kind of fiber through applying is chosen wantonly has the ink composite that is coated on it, a kind of comprise at least two described through applying and the fibre ribbons of optional optical fiber through being coated with China ink, wherein, at least a in described coating or the composition derives from any described radiation-hardenable composition among the claim 1-9.
15. method that is used to prepare the branching polyvalent alcohol, described branching polyvalent alcohol comprises at least one branch point and at least three molecular chains that extended by described branch point, comprise hydroxyl at least two ends by the molecular chain of described branch point extension, described method comprises the reaction of the polyvalent alcohol that will comprise at least three hydroxyls (a ') and polyisocyanates (b) and at least a other polyvalent alcohol (a "); wherein; described polyvalent alcohol (a ') forms the branch point of described branching polyvalent alcohol; and described at least a other polyvalent alcohol (a ") forms the described molecular chain by described branch point extension, and wherein, the described polyisocyanates described molecular chain that connects described branch point and extend by described branch point.
16. method as claimed in claim 15, wherein, the molecular weight of at least three molecular chains that extended by described branch point is 200g/mol or higher.
17. as claim 15 or the described method of claim 16, wherein, described other polyvalent alcohol is a glycol.
18. as any described method among the claim 15-17, wherein, described branching polyvalent alcohol comprises 3 or 4 molecular chains that extended by described branch point.
19. the branching polyvalent alcohol obtains by any described method among the claim 15-18.
20. be used to prepare the method for urethane (methyl) acrylate, wherein, (methyl) acrylate (c) with the described branching polyvalent alcohol of claim 19 and polyisocyanates (b) and hydroxyl further reacts to form urethane (methyl) origoester acrylate.
21. urethane (methyl) origoester acrylate obtains by the described method of claim 20.
22. urethane (methyl) origoester acrylate is as the purposes of rheology modifier, described oligopolymer is by polyvalent alcohol (a), (methyl) acrylate (c) of polyisocyanates (b) and hydroxyl obtains, described polyvalent alcohol (a) has the branched structures of the molecular chain that comprises that at least one branch point and at least three are extended by described branch point, described molecular chain has 200g/mol or higher molecular weight, comprises hydroxyl at least two ends by the molecular chain of described branch point extension.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP084054/2004 | 2004-03-23 | ||
| JP2004084054A JP2005272498A (en) | 2004-03-23 | 2004-03-23 | Liquid curable resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1934200A true CN1934200A (en) | 2007-03-21 |
Family
ID=34962293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800085600A Pending CN1934200A (en) | 2004-03-23 | 2005-03-23 | Curable liquid resin composition |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1727867A1 (en) |
| JP (1) | JP2005272498A (en) |
| CN (1) | CN1934200A (en) |
| WO (1) | WO2005090488A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102439057A (en) * | 2009-05-19 | 2012-05-02 | 氰特表面技术有限公司 | Radiation curable compositions |
| CN105372752A (en) * | 2014-08-13 | 2016-03-02 | 住友电气工业株式会社 | Optical fiber and process for producing the same |
| CN107603525A (en) * | 2017-09-25 | 2018-01-19 | 广西众昌树脂有限公司 | The method for improving liquid resin adhesive strength |
| CN108061933A (en) * | 2016-11-07 | 2018-05-22 | 住友电气工业株式会社 | Optical fibre core |
| CN111580230A (en) * | 2020-03-02 | 2020-08-25 | 华中科技大学 | Flexible optical fiber, preparation method and drivable laser scalpel based on optical fiber |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5098722B2 (en) * | 2008-03-17 | 2012-12-12 | Ｊｓｒ株式会社 | Curable resin composition, film laminate for sticking, and laminate for impact absorption |
| JP5113782B2 (en) * | 2009-02-18 | 2013-01-09 | 大日精化工業株式会社 | Synthetic artificial leather, method for producing the same, prepolymer and adhesive composition |
| KR101869579B1 (en) * | 2011-03-08 | 2018-06-20 | 닛폰고세이가가쿠고교 가부시키가이샤 | Active-energy-curable resin compositon and coating agent |
| US20130011108A1 (en) * | 2011-07-06 | 2013-01-10 | Ofs Fitel, Llc | UV Curable Acrylate Buffer Coating for Optical Fiber |
| US9488774B2 (en) | 2014-04-01 | 2016-11-08 | Corning Incorporated | Primary optical fiber coating composition containing non-radiation curable component |
| US9891379B2 (en) | 2014-11-14 | 2018-02-13 | Corning Incorporated | Optical fiber coating compositions with acrylic polymers |
| US10370557B2 (en) | 2014-11-19 | 2019-08-06 | Dsm Ip Assets B.V. | D1563 radiation curable secondary coating for optical fibers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994019185A1 (en) * | 1991-12-16 | 1994-09-01 | Dsm N.V. | Liquid curable resin composition |
| JP3988267B2 (en) * | 1998-08-20 | 2007-10-10 | Ｊｓｒ株式会社 | Adhesive for optical disc |
| JP3383227B2 (en) * | 1998-11-06 | 2003-03-04 | リンテック株式会社 | Semiconductor wafer backside grinding method |
-
2004
- 2004-03-23 JP JP2004084054A patent/JP2005272498A/en active Pending
-
2005
- 2005-03-23 WO PCT/NL2005/000220 patent/WO2005090488A1/en not_active Application Discontinuation
- 2005-03-23 CN CNA2005800085600A patent/CN1934200A/en active Pending
- 2005-03-23 EP EP05722073A patent/EP1727867A1/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102439057A (en) * | 2009-05-19 | 2012-05-02 | 氰特表面技术有限公司 | Radiation curable compositions |
| CN105372752A (en) * | 2014-08-13 | 2016-03-02 | 住友电气工业株式会社 | Optical fiber and process for producing the same |
| CN108061933A (en) * | 2016-11-07 | 2018-05-22 | 住友电气工业株式会社 | Optical fibre core |
| CN108061933B (en) * | 2016-11-07 | 2020-06-26 | 住友电气工业株式会社 | Optical fiber core wire |
| CN107603525A (en) * | 2017-09-25 | 2018-01-19 | 广西众昌树脂有限公司 | The method for improving liquid resin adhesive strength |
| CN111580230A (en) * | 2020-03-02 | 2020-08-25 | 华中科技大学 | Flexible optical fiber, preparation method and drivable laser scalpel based on optical fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005090488A1 (en) | 2005-09-29 |
| EP1727867A1 (en) | 2006-12-06 |
| JP2005272498A (en) | 2005-10-06 |
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