CN1852955A - Radiation-curable liquid resin composition - Google Patents
Radiation-curable liquid resin composition Download PDFInfo
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- CN1852955A CN1852955A CN 200480023614 CN200480023614A CN1852955A CN 1852955 A CN1852955 A CN 1852955A CN 200480023614 CN200480023614 CN 200480023614 CN 200480023614 A CN200480023614 A CN 200480023614A CN 1852955 A CN1852955 A CN 1852955A
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Abstract
The invention relates to a radiation -curable liquid resin composition comprising: (A) 20-90 wt% of a urethane (meth)acrylate oligomer, and (B) 1-35 wt% of - a monomer shown by the following formula (1), wherein R<1> represents a hydrogen atom or a methyl group, R<2> and R<3> individually represent a hydrogen atom or an alkyl group having 1-4 carbon atoms, R<4> represents a hydrogen atom or a methyl group, and n represents an integer of 1-6, or - a monomer including a hydroxyl group.
Description
Technical field
The present invention relates to a kind of radiation-curable liquid resin composition.The invention still further relates to the purposes of described radiation-curable liquid resin composition, optical fiber and fibre ribbon through applying.
Background technology
Radiation-curable liquid resin composition extensively is used in the optical fiber industry, in order to preparation optical fiber, fibre ribbon and optical cable.Usually, coat one deck (being two-layer under many situations) radiation-hardenable membrane prepare fiber cores (after this can be called " core ") at least after for example optical glass fibre is pulled out immediately from matrix, the characteristic that keeps glass fibre itself to be had.After coating each layer, at once usually by uv-radiation fast setting coating.In this technical field, it is desirable to can faster cured coating composition to increase the production rate of optical fiber.When preparing fibre ribbon, optical fiber cable and dependency structure object by the binding core, the fiber cores that radiation-hardenable matrix and binding material can support and protect each to be coated.And by each core is sticked colour band, radiation curable ink can be used for differentiating each core of optical fiber.All these fibre coating materials are radiation-hardenable preferably.Directly first coating that contacts with glass fibre is called as primary coating, and this layer is that flexible coating is in case the glass fibre microbend.Contact with primary coating second coating be called as secondary coating.This layer is a hard coat, and this layer provides more durable extramural cladding for glass fibre.
For example United States Patent (USP) 5,336, described the technology of this fibre coating in 563,5,595,820,5,199,098,4,923,915,4,720,529 and 4,474,830.United States Patent (USP) 5,336,563 and 4,992,524 (primary material), Japanese Unexamined Patent Publication No 10-81705 (secondary coated material), reported typical coated material in Japanese Unexamined Patent Publication No 11-49534 and the US patent 5,146,531 (other coated material).
The influence of mainly benefiting from the monomer type in composition as the solidification rate of the radiation-curable liquid resin composition of fibre coating material.Usually (methyl) acrylate monomer that is used in combination a few types is with the solidification rate of balance coatingsurface and the solidification rate of coated membrane inside.Except various (methyl) acrylate monomer, the N-vinyl monomer that uses for example N-caprolactam and N-ethenyl pyrrolidone usually is to increase the solidification rate of coating.
Yet,, be ideal so can satisfy the composition of high solidification rate and low yellowing simultaneously because the N-vinyl monomer can make the fiber coat yellowing.As secondary coated material, matrix and binding material, it is desirable to the low coated material of viscosity especially, this kind material is easy to handle and can prepare the cured product that Young's modulus is about 50-1200MPa.
The object of the present invention is to provide a kind of liquid resin composition of radiation-hardenable, said composition has low viscosity, although it can prepare Young's modulus and be about the cured product of 50-1200MPa but be easy to processing, have high solidification rate, show good dilutable, can prepare and only have slight look and become the cured product of (yellowing) and excellent surface property and can be used as the primary material in the optical fiber, secondary coated material, substrate material, binding material, printing ink etc.
Summary of the invention
Make us now finding uncannily, be added to by the monomer that will have the monomer of ethylenic unsaturated link(age) and vinyl ether group or at least a hydroxyl at least a molecule in the radiation-curable liquid resin composition of urethane (methyl) acrylate that comprises specified quantitative and can realize above purpose.Can finish the present invention based on this discovery.
Embodiment
Concrete is, the invention provides a kind of radiation-curable liquid resin composition, and said composition comprises:
(A) 20-90wt% urethane (methyl) origoester acrylate and
(B) 1-35wt%
Monomer shown in the-following formula (1)
R wherein
1Expression hydrogen atom or methyl, R
2And R
3Represent hydrogen atom respectively or have the alkyl of 1-4 carbon atom, R
4Expression hydrogen atom or methyl, and n represents the integer of 1-6, or
The monomer of-hydroxyl.
Radiation-curable liquid resin composition of the present invention has low viscosity, although it can prepare Young's modulus and be about the cured product of 50-1200MPa but still be easy to and handle, have high solidification rate, can fully be diluted and can prepare and have the cured product that only slight look becomes (yellowing) and excellent surface property.Therefore, said composition can be used as primary material, secondary coated material, substrate material, binding material, printing ink etc. in optical fiber, especially can be used as secondary coated material, substrate material and binding material.
The present invention is not particularly limited urethane (methyl) acrylate of component (A).For example, urethane (methyl) acrylate (A) can be by obtaining polyol compound (a), polyisocyanate compound (b) and hydroxy functional group ethylenically unsaturated monomers (c) reaction, obtain the end capped compound of a kind of employing reactive compounds, this reactive compounds obtains with for example polyisocyanates (b) and hydroxy functional group ethylenically unsaturated monomers (c) reaction by at least one end with polyol compound (a)." end-capped " refers to functional group and the terminal addition reaction of polyol compound (a) herein.This end-capped structure is bonded on the polyol compound (a) by amino-formate bond.In the presence of catalyzer, implement this urethane reaction.As urethane reaction example, can provide dibutyl tin laurate and diazabicyclo octane crystal.Also may be by only polyisocyanate compound (b) and hydroxy functional group ethylenically unsaturated monomers (c) reaction being obtained urethane (methyl) acrylate (A).
Urethane (methyl) acrylate (A) can be the mixture of a kind of urethane (methyl) acrylate or two or more urethane (methyl) acrylate.Urethane (methyl) acrylate (A) preferably has at least two ethylenic unsaturated groups with the main chain bonding of this oligopolymer.For example, this ethylenic unsaturated group can be positioned at each end of oligopolymer main chain as reactive terminal group.The oligopolymer main chain can have the multipolymer of polyethers, polyolefine, polyester, polycarbonate, hydrocarbon or these compounds as skeleton.The oligopolymer main chain is polyol prepolymer preferably, for example the mixture of polyether glycol, polyolefin polyhydric alcohol, polycarbonate polyol or these prepolymers.The molecular weight of polyol prepolymer is 600-11000 preferably, 700-10000 more preferably, and 900-5100 more preferably also, 900-3100 most preferably, that concrete is 1000-3000g/mol.
The main chain of urethane (methyl) acrylate (A) oligopolymer can be one or more oligopolymer blocks, and this block is by the mutual bonding of amino-formate bond.For example, the polyol prepolymer of one or more types can pass through the methods known in the art bonding.If polyol prepolymer is a polyether glycol, can obtain having the coating of lower glass transition temperatures and superior mechanical properties so.If the oligopolymer main chain is a polyolefin polyhydric alcohol, can obtain the coating that water-repellancy is significantly improved so.Polycarbonate oligomer can pass through for example polycarbonate polyol (a), polyisocyanates (b) and hydroxy functional group ethylenically unsaturated monomers (c) prepared in reaction.
As the particular instance of the method for preparing urethane (methyl) acrylate (A), can provide the method that polyvalent alcohol (a), polyisocyanate compound (b) and hydroxy functional group ethylenically unsaturated monomers (c) are reacted; With the reaction of polyvalent alcohol (a) and polyisocyanate compound (b), the method that the product that obtains and hydroxy functional group ethylenically unsaturated monomers (c) are reacted then; With the reaction of polyisocyanate compound (b) and hydroxy functional group ethylenically unsaturated monomers (c), the method that the product that obtains and polyvalent alcohol (a) are reacted then; With the reaction of polyisocyanate compound (b) and hydroxy functional group ethylenically unsaturated monomers (c), then with the product and polyvalent alcohol (a) reaction that obtain, the method that the product that obtains and hydroxy functional group ethylenically unsaturated monomers (c) are reacted etc. again.
In the reaction of the isocyanate group of the hydroxyl of polyvalent alcohol (a) and polyisocyanate compound (b), preferably keep the stoichiometric balance between hydroxy functional group and the isocyanate functional group, temperature of reaction is controlled at 25 ℃ or higher simultaneously.Should the consume sufficient hydroxy functional group.The mol ratio of isocyanic ester and hydroxy functional group ethylenically unsaturated monomers is 3: 1 to 1.2: 1, preferably 2: 1 to 1.5: 1.The hydroxy functional group ethylenically unsaturated monomers is by amino-formate bond and isocyanate compound bonding.As monomer example, can provide for example hydroxy functional group acrylate of vinylformic acid 2-hydroxy methacrylate and vinylformic acid 2-hydroxy propyl ester with (methyl) acrylate-functional groups.Monomer example as having vinyl ether functional group can provide 4-hydroxy butyl vinyl ether and triethylene glycol mono vinyl ether.As monomer example, can provide toxilic acid and hydroxy functional group maleic acid ester with maleic acid ester functional group.
As the polyvalent alcohol that is used for synthesis of polyurethane (methyl) origoester acrylate (A), can use polyether glycol, polyalkylene polyvalent alcohol, polyester polyol, polycarbonate polyol, polycaprolactone polyol etc.As polyvalent alcohol, can use glycol, triol, tetrol, pentol, six alcohol etc.In these, two pure and mild triols preferably.Glycol more preferably also.In these, particularly preferably be polyether glycol.Polyether glycol can use with other diol combination.But the ring-opening polymerization by the ionic polymerization ring compound prepares polyether glycol usually.But polyether glycol can be the homopolymer of one type ionic polymerization ring compound, but or the multipolymer of two or more types of ionic polymerization ring compounds.The copolymerization mode is not particularly limited, can be in random copolymerization, block copolymerization or the graft copolymerization any one.
But example as the ionic polymerization ring compound that is used to prepare polyether Glycols, can provide for example oxyethane, propylene oxide, the 1-butylene oxide ring, the epoxy Trimethylmethane, trimethylene oxide, 3,3-dimethyl trimethylene oxide, 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 vinyl cyclohexene oxide, phenylglycidyl ether, the cyclic ethers of butyl glycidyl base ether and phenylformic acid glycidyl ester.The polyether glycol as but the ring-opening polymerization of the ionic polymerization ring compound by a type obtains can provide for example polyethers aklylene glycol of polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol, polyhexamethylene glycol, poly-heptamethylene two pure and mild poly-decamethylene glycol.The polyether glycol as but the ring-opening copolymerization of the ionic polymerization ring compound by two or more types obtains can provide poly-(propylidene-ethylidene) glycol, poly-(tetramethylene-ethylidene) glycol, poly-(tetramethylene-propylidene) glycol, poly-(tetramethylene-methyl tetramethylene) glycol, poly-(butylidene-ethylidene) glycol, poly-(butylidene-propylidene) glycol etc.
But can use annular lactone acid, or the polyether glycol that obtains of the ring opening copolymer of dimethyl cyclopolysiloxane by cyclic imide, for example γ-propiolactone or the glycollide of the ring compound of these ionic polymerizations and for example ethylene imine.But particular instance as two or more ionic polymerization ring compounds of combination, can provide tetrahydrofuran (THF) and propylene oxide, tetrahydrofuran (THF) and 2-methyltetrahydrofuran, tetrahydrofuran (THF) and 3-methyltetrahydrofuran, tetrahydrofuran (THF) and oxyethane, propylene oxide and oxyethane, 1-butylene oxide ring and oxyethane, the terpolymer of tetrahydrofuran (THF), 1-butylene oxide ring and oxyethane etc.But the ring opening copolymer thing of these ionic polymerization ring compounds can be random copolymers or segmented copolymer.
From the viewpoint of freeze proof colloidality and water-repellancy is provided for cured product of the present invention, in these polyether glycols, preferably polypropylene glycol, polytetramethylene glycol, poly-(butylidene-propylidene) glycol particularly preferably are polypropylene glycol.The number-average molecular weight of measuring by gel permeation chromatography (GPC) method through the polyether glycol of polystyrene conversion particularly preferably is 900 to 3100, more preferably 1000-3000g/mol.
When using polyethers alkene glycol, polyethers alkene preferably has the linear hydrocarbons or the branched hydrocarbon of two or more terminal hydroxy groups.This hydrocarbon is non-aromatic compound preferably, and this compound is by methylene radical (CH
2-) form, as the major portion of main chain, main chain comprises unsaturated link(age) and the unsaturated group that hangs on the main chain as side chain.Because along with the reduction of degree of unsaturation, the permanent stability of curing optical fiber coating increase, so preferably complete saturated compound, for example hydrogenate hydrocarbon.As hydrocarbon glycol example, can provide end and have the polymkeric substance of hydroxyl and hydrogenant polymkeric substance wholly or in part, for example 1,2-polyhutadiene, 1,4-or 1,2-polybutadiene copolymer, 1,2-polyhutadiene-ethene or-third rare multipolymer, polyisobutene polyol, these mixture of polymers.As the hydrocarbon glycol, hydrogenant 1 almost completely preferably, 2-polyhutadiene or 1,2-polyhutadiene/ethylene copolymer.
When but the ring opening copolymer of the ionic polymerization ring compound by polyethers alkene glycol or two or more types obtained polyether glycol, this polyether glycol preferably on average had two or more hydroxyls.This oligopolymer main chain polyvalent alcohol on average has the hydroxyl more than two.As the oligomer diol example, can provide the mixture of polyether glycol, polyolefin diols, polyester glycol, polycarbonate diol and these glycol.The preferably combination of polyether glycol, polyolefin diols and these glycol.When using polyether glycol, it is desirable to polyethers is non-crystalline state basically.This polyethers preferably comprises one or more repeating units that are selected from following monomeric groups:
-O-CH
2-CH(CH
3)-
-O-CH
2-CH
2-CH
2-
-O-CH(CH
3)-CH
2-CH
2-
-O-CH
2-CH(CH
3)-CH
2-
-O-CH
2-CH
2-CH
2-CH
2-
-O-CH
2-CH(CH
3)-CH
2-CH
2-
-O-CH(CH
3)-CH
2-CH
2-CH
2
As available polyether glycol example, can provide the reaction product of the tetrahydrofuran (THF) of the 3-methyltetrahydrofuran of 20wt% and 80wt%.This copolyether has the oxyalkylene repeating unit of branching and the oxyalkylene repeating unit of non-branching, and this multipolymer commerce can be PTGL1000 (by Hodogaya Chemical Co., Ltd produces).Another polyethers example of available is PTGL2000 (by Hodogaya Chemical Co., Ltd produces) in these are a series of.
Commerce as these polyether glycols can get product example, can provide PTMG650, PTMG1000, PTMG2000 (producing) by Mitsubishi Chemical Corp., EXCENOL1020,2020,3020, PREMINOL PML-4002, PML-5005 is (by Asahi GlassCo., Ltd produces), UNISAFE DC1100, DC1800, DCB1000 is (by Nippon Oiland Fats Co., Ltd. produce), PPTG1000, PPTG2000, PPTG4000, PTG400, PTG650, PTG 1000, PTG2000, PTG-L1000, PTG-L2000 is (by HodogayaChemical Co., Ltd produces), Z-3001-4, Z-3001-5, PBG2000 (by DaiichiKogyo Seiyaku Co., Ltd. produces), ACCLAIM 2200,2220,3201,3205,4200,4220,8200,12000 (producing) etc. by Lyondell.
The polycarbonate diol example comprises the compound by carbonic acid two ethyls and glycol alcoholysis preparation.This glycol can be the aklylene glycol with 2-12 carbon atom, for example 1, and 4-butyleneglycol, 1,6-hexylene glycol or 1,12-dodecyl glycol.Also can use the mixture of these glycol.Except carbonate group, can comprise ehter bond in the main chain of polycarbonate diol.Therefore, can use for example Copolycarbonate of alkylene oxide monomer and above-mentioned aklylene glycol.As alkylene oxide monomer, can provide oxyethane and tetrahydrofuran (THF).Compare with polycarbonate homopolymer, these multipolymers can prepare the solidified coating with low modulus, and can restrain the crystallization of liquid coating composition.Also can use the mixture of polycarbonate diol and Copolycarbonate.
As the specific examples of polycarbonate diol, can provide Duracarb 122 (producing) and Permanol KM10-1733 (Permuthane by U.S. Massachusetts produces) by PPGIndustries.Duracarb 122 produces by diethyl carbonate and hexylene glycol alcoholysis.As the polyether glycol example, can provide the reaction product of saturated polycarboxylic acid or its acid anhydrides and glycol.Saturated polycarboxylic acid or its acid anhydrides example comprise phthalic acid, m-phthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, tetrahydrophthalic acid, hexahydro-phthalic acid, tetrachloro phthalic acid, hexanodioic acid, nonane diacid, sebacic acid, Succinic Acid, pentanedioic acid, propanedioic acid, pimelic acid, suberic acid, 2,2-dimethyl succinic acid, 3,3-dimethylated pentanedioic acid, 2,2-dimethylated pentanedioic acid, these sour acid anhydrides and mixtures.As the glycol example, can provide 1,4-butyleneglycol, 1,8-ethohexadiol, Diethylene Glycol, 1,6-hexylene glycol and hydroxymethyl-cyclohexane.Polycaprolactone is included in this class and can be Tone Polyol series product from Union Carbide Corp. commerce, and for example Tone 0200,0221,0301,0310,2201 and 2221.Tone 0301 and 0310 is the trifunctional compound.
Example as the polyisocyanates (b) that is used for synthesis of polyurethane (methyl) acrylate (A) can provide aromatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate etc.As long as polyisocyanates (b) can be used in the resin combination that is used for optical fiber, this compound just is not specifically limited.In these, preferably aromatic diisocyanate and alicyclic diisocyanate, also more preferably 2,4 toluene diisocyanate and isophorone diisocyanate.These diisocyanate cpds can use separately or two or more are used in combination.
Any polyisocyanates can use separately or use as mixture, as polyisocyanates (b).
Preferred vulcabond is as the polyisocyanates that is used for synthesis of polyurethane (methyl) acrylate (A).The example of polyisocyanates (b) comprises isophorone diisocyanate, tetramethylxylene diisocyanate, tolylene diisocyanate, MDI, hexamethylene diisocyanate, the cyclohexylidene vulcabond, methylene radical bicyclohexane vulcabond, 2,2, the 4-trimethyl hexamethylene diisocyanate, the metaphenylene vulcabond, 4-chloro-1, the 3-phenylene vulcabond, 4,4 '-biphenylene vulcabond, 1, the 5-naphthalene diisocyanate, 1, the 4-tetramethylene diisocyanate, 1, the 6-hexamethylene diisocyanate, 1,10-decamethylene vulcabond, 1,4 cyclohexalene diisocyanate and have the compound that the vulcabond of tolylene diisocyanate for example is bonded to polyalkylene oxide or polyester glycol two ends.In these vulcabond, preferably isophorone diisocyanate and tolylene diisocyanate.
As the hydroxy functional group ethylenically unsaturated monomers (c) that is used for synthesis of polyurethane (methyl) acrylate (A), can provide (methyl) acrylate of hydroxyl, the vinyl ether of hydroxyl, the maleic acid ester of hydroxyl and the fumarate of hydroxyl.Consider the reactivity with the isocyanate groups of polyisocyanates, preferably hydroxyl bond is incorporated into hydroxyl (methyl) acrylate (after this be called as and contain primary hydroxyl (methyl) acrylate) on the primary carbon atom and hydroxyl bond and is incorporated into hydroxyl (methyl) acrylate (after this be called as and contain secondary hydroxyl (methyl) acrylate) on the secondary carbon(atom).
As the example that contains primary hydroxyl (methyl) acrylate, can provide (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 4-hydroxyl butyl ester, 1,6-hexylene glycol list (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, neopentyl glycol single (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolethane two (methyl) acrylate etc.
As the example that contains secondary hydroxyl (methyl) acrylate, can provide (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid 4-hydroxyl cyclohexyl, by (methyl) vinylformic acid with contain the compound of glycidyl, the compound that obtains of the addition reaction of alkyl glycidyl base ether, allyl glycidyl ether and (methyl) glycidyl acrylate etc. for example.These hydroxy functional group ethylenically unsaturated monomers can use separately or two or more are used in combination.
Preferably, be identified for the ratio of polyvalent alcohol (a), polyisocyanate compound (b) and the hydroxy functional group ethylenically unsaturated monomers (c) of synthesis of polyurethane (methyl) acrylate, make that for the 1 equivalent hydroxyl that is included in the polyvalent alcohol isocyanate groups that is included in the polyisocyanate compound is respectively 1.1-2 equivalent and 0.1-1 equivalent with the hydroxyl that is included in the hydroxy functional group ethylenically unsaturated monomers.
In addition, diamine can be used for synthesis of polyurethane (methyl) acrylate with the polyvalent alcohol combination.As the diamine example, can provide for example quadrol, tetramethylene-diamine, hexamethylene-diamine, P-pHENYLENE dI AMINE and 4, the diamines of 4 '-diaminodiphenyl-methane, contain heteroatomic diamines, polyether diamine etc.
Can use and have and to substitute part of hydroxyl functional group ethylenically unsaturated monomers with the compound of the functional group of isocyanate group addition.As this examples of compounds, can provide γ-An Jibingjisanyiyangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan etc.Use these compounds further to improve adhesivity to the base material of for example glass.
In urethane (methyl) acrylate (A) synthetic, preferably use for example copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyl tin laurate, dibutyltin diacetate, two lauric acid dioctyl tins, oxalic acid dioctyl tin, methyl ethyl diketone zirconium, 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 is the 0.01-1wt% of reaction-ure mixture.Usually temperature of reaction is 5-90 ℃, preferably 10-80 ℃.
Without polyol compound (a), promptly only by polyisocyanate compound (b) and hydroxy functional group ethylenically unsaturated monomers (c) reaction can be obtained urethane (methyl) acrylate (A).In an embodiment of invention, urethane (methyl) origoester acrylate (A) also comprises at least a without the resulting urethane of polyvalent alcohol (methyl) acrylate except by urethane (methyl) origoester acrylate that polyol compound (a), polyisocyanates (b) and hydroxyl (methyl) acrylate (c) reaction are obtained.Obtain the Young's modulus of cured product and the viewpoint of surface adhesive from minimizing, can preferred this combination.The amount of urethane (methyl) acrylate that obtains without polyol compound (a) preferably component (A) total amount 10 to 80wt%, more preferably 25 to 55wt%, 10-50wt% more preferably also, most preferably 30 to 50wt%.
Particular instance as the polymkeric substance that only forms by polyisocyanate compound (b) and hydroxy functional group ethylenically unsaturated monomers (c), can provide by (methyl) vinylformic acid 2-hydroxyl ethyl ester and 2,4 toluene diisocyanate are reacted urethane (methyl) acrylate that obtains.Preferably about 2: 1 of the reaction molar ratio of (methyl) vinylformic acid 2-hydroxyl ethyl ester and 2,4 toluene diisocyanate.
The content of the urethane in radiation-curable liquid resin composition of the present invention (methyl) acrylate (A) is 20 to 90wt%, 40-90wt% preferably, 65-90wt% more preferably, particularly preferably be 70-90wt%, so that guarantee cured product for example Young's modulus and the superior mechanical properties of elongation at break and the proper viscosity of radiation-curable liquid resin composition of the present invention.If content surpasses 90wt%, so because the Young's modulus of cured product greater than 1200MPa, so said composition is not suitable for the resin of coated fiber.And the viscosity of radiation-curable resin composition surpasses 10Pas, thereby causes workability to reduce.And, the water tolerance variation of cured product.If less than 20wt%, be difficult to obtain to have elastic Young's modulus so and be suitable for cured product as optical fiber secondary layer and belt.As the Young's modulus of the cured product of the secondary layer of optical fiber or belt 50-1200MPa preferably.The viscosity of radiation-curable liquid resin composition is 1.0-6.0Pas preferably, more preferably 1.0-5.0Pas.If be (methyl) acrylate monomer of hydroxyl (B), particularly preferably be so, the content of the urethane in the radiation-curable liquid resin composition of the present invention (methyl) acrylate (A) is 65 to 90wt%, more preferably 40 arrives 90wt%.
Component used in this invention (B) is (methyl) acrylate monomer of monomer shown in the following formula (1) or hydroxyl.As R in the following formula (1)
2And R
3Represented examples of alkyl can provide methyl, ethyl and n-propyl.N is 1-4 preferably, particularly preferably is 1-3.Specific examples is (methyl) vinylformic acid 2-(2 '-vinyl oxygen oxyethyl group) ethyl ester and (methyl) vinylformic acid 2-vinyl 2-ethoxyethyl acetate.Commerce as component (B) can get product, can propose VEEA, VEEM, VEA (by NIPPON SHOKUBAI Co., Ltd. produces) etc.
(methyl) acrylate monomer that comprises hydroxyl preferably includes aliphatic series or alicyclic substituting group, and this substituting group comprises hydroxyl.Specific examples is the compound that provides as the example that is used for the component (c) of synthesis of polyurethane (methyl) origoester acrylate (A).Component (c) is used as the reactive component of preparation urethane (methyl) origoester acrylate (A).Yet component of the present invention (B) is not added into as the raw material of component (A), but is added into as reactive thinner.As component (B), preferred examples is hydroxy functional group aliphatic series (methyl) acrylate and hydroxy functional group alicyclic (methyl) acrylate that provides as component (c) example.In these, particularly preferably be (methyl) vinylformic acid hydroxyl C
2-C
8Alkane ester and (methyl) vinylformic acid hydroxyl C
2-C
8Cycloalkanes ester, for example (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester and (methyl) vinylformic acid 4-hydroxyl cyclohexyl.
Not adding nitrogenous vinyl monomer by the component (B) of adding specified quantitative can obtain high solidification rate and can restrain the cured product yellowing.
Component (B) can be used separately also and can two or more be used in combination.If be the monomer shown in the following formula (1) (B), the ratio that is used in the component (B) in the radiation-curable liquid resin composition of the present invention so is 1-35wt%, preferably 5-35wt%, more preferably 10-30wt% normally.If (B) be (methyl) acrylate monomer of hydroxyl, the ratio that is used in the component (B) in the radiation-curable liquid resin composition of the present invention so normally 1 arrives 35wt%, preferably 1 to 30wt%, also more preferably 2-20wt%, most preferably 5-15wt%.Consider viscosity, etiolation and the solidification rate of liquid resin composition, preferred above scope.
Composition of the present invention can randomly comprise reactive diluent (C), (C) is not included in the definition of component (B).This reactive thinner (C) be can with the vinyl monomer of component (A) copolymerization, do not comprise component (B) compound.This reactive thinner can be used to regulate the viscosity of coating composition.Therefore, this reactive thinner is to have at least one when the low viscosity monomer that is exposed to chemical radiation polymerisable functional group of following time.
As component (C) example, can provide polymerizable monofunctional group's compound (C1) and polymerizable polyfunctional compound (C2).As the example of polymerizable monofunctional group compound (C1), can provide and contain vinyl lactam, for example N-vinyl pyrrolidone and N-caprolactam; (methyl) acrylate with alicyclic structure, for example (methyl) isobornyl acrylate, (methyl) vinylformic acid norbornene ester, (methyl) vinylformic acid three ring esters in the last of the ten Heavenly stems, (methyl) vinylformic acid two ring pentyl esters, methacrylic acid 4-butyl cyclohexyl; (methyl) acrylate with aryl structure, for example (methyl) vinylformic acid benzene methyl; Acryloyl morpholine, vinyl imidazole, vinyl pyridine, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy 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 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 and 2-ethylhexyl vinyl ether.
From dilution properties, in these polymerizable monofunctional group's compounds (C1), preferably contain simple function group (methyl) acrylate of aliphatic hydrocarbyl with 10 or more a plurality of carbon atoms.Aliphatic group with 10 or more a plurality of carbon atoms can be linear, branching or alicyclic ring.Carbonatoms is 10-24 preferably.In these simple function group monomers, particularly preferably be (methyl) isobornyl acrylate, (methyl) isodecyl acrylate and (methyl) lauryl acrylate.Can get the example of product as the commerce of these polymerizable monofunctional group's compounds (C1), can provide IBXA (by Osaka Organic Chemical Industry Co., Ltd. production), Aronix M-110, M-111, M-113, M-114, M-117 and TO-1210 (by Toagosei Co., Ltd. produces).
From curing performance, preferably have acrylate-functional part or vinyl ether functional part and have the alkyl of 4-20 carbon atom or the monomer of polyether moiety is rolled into a ball compound (C1) as polymerizable monofunctional.This reactive thinner example comprises Ethyl acrylate, 2-EHA, isobornyl acrylate, decyl acrylate, lauryl acrylate, vinylformic acid stearyl, vinylformic acid ethoxy ethoxy ethyl ester, lauryl vinyl ether, 2-ethylhexyl vinyl ether, N-vinyl formamide, isodecyl acrylate, Isooctyl acrylate monomer, caprolactam and N-vinyl pyrrolidone.
And from Young's modulus, preferred reactive thinner is the compound that contains aryl.As reactive thinner example with aryl, can provide ethylene glycol phenyl ether acrylate, polyoxyethylene glycol phenyl ether acrylate, polypropylene glycol phenyl ether acrylate and these monomeric alkyl substituted benzene radical derivative, for example polyethylene glycol nonylphenyl ether acrylate.
On the other hand, for example the vinyl lactam that contains of N-vinyl pyrrolidone and N-caprolactam helps increasing solidification rate, but has the shortcoming of etiolation, promptly causes the character of cured product flavescence.Therefore, radiation-hardenable composition preferably of the present invention does not contain this lactan, if the change that perhaps has, the amount that comprises is less than 10wt%, preferably less than 5wt%.
Example as polymerizable polyfunctional compound (C2), can provide trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris oxyethyl group (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 obtains by diglycidylether addition with (methyl) acrylate and dihydroxyphenyl propane, triethylene glycol divinyl ether etc.
The example that above polyfunctional compound commerce can get product comprises: Light Acrylate 9EG-A and Light Acrylate 4EG-A are (by Kyoeisha Chemical Co., Ltd. produce), YupimerUV SA1002, SA2007 (producing) by Mitsubishi Chemical Corp., Viscoat 700 (producing) by Osaka Organic Chemical Industry Ltd., KAYARAD R-604, DPCA-20, DPCA-30, DPCA-60, DPCA-120, HX-620, D-310, D-330 is (by Nippon Kayaku Co., Ltd. produce), ARONIX M-210, M-215, M-315, M-325 (by Toagosei Co., Ltd. produces) etc.
As polymerizable polyfunctional compound (C2), preferably have the hydrocarbon omega-diol diacrylate of 2-18 carbon atom, hydrocarbon divinyl ether, hydrocarbon triol triacrylate and the analogue of these polyethers with 3-18 carbon atom with 4-18 carbon atom, for example 1,6 hexanediol diacrylate, Viscoat 295, hexylene glycol divinyl ether, triethylene glycol diacrylate, pentaerythritol triacrylate and tripropylene glycol diacrylate.Particularly preferred polymerizable polyfunctional compound (C2) is alkoxylated alkyl phenol (methyl) acrylate, and most preferred reactive thinner is ethoxylated nonylphenol (methyl) acrylate.Preferably contain acrylate group as radiation curable group for oligopolymer and reactive thinner.
Polymerizable monofunctional group's compound (C1) and polymerizable polyfunctional compound (C2) can be used singly or in combination.
When (B) was monomer according to formula (1), the add-on of component in the radiation-curable liquid resin composition of the present invention (C) is 1-33wt%, more preferably 2-30wt% preferably.If add-on less than 1wt%, can be damaged curing performance so.Surpass 33wt% if added,, apply instability thereby cause so because viscosity is low, and it is inhomogeneous that coating may become.When (B) is hydroxyl (methyl) acrylate monomer, the add-on of the component in the radiation-curable liquid resin composition of the present invention (C) preferably total composition 5 to 75wt%, also will be more preferably 10 to 70wt%.If add-on is less than 5wt%, the solidification rate of composition may be lowered so.If add-on surpasses 75wt%, so because viscosity is low, thereby apply shape can change cause applying unstable.
Solidify radiation-curable liquid resin composition of the present invention by applying radiation.The radiation of Shi Yonging herein refers to ir radiation, visible light, ultraviolet ray, X-ray, α-ray, beta-rays, gamma-radiation, electron beam etc.In these, particularly preferably be ultraviolet ray and electron beam.
For example, the ordinary light source such as the UV lamp that obtains from Fusion System Corp. can be used as UV source.Other suitable light source is low pressure, medium-pressure or high pressure mercury lamp, efficient chemical ray fluorescence pipe and flashlight.
When using the UV photocuring, polymerization starter (D) can randomly be added in the radiation-curable liquid resin composition of the present invention.As component (D), use light trigger (D1) usually.If necessary, thermal polymerization (D2) can and light trigger (D1) be used in combination.
As light trigger (D1), can provide benzophenone; Acetophenone derivs, for example Alpha-hydroxy alkyl phenyl ketone, benzoin alkylether and phenmethyl ketal; Acylphosphine oxide; Other diacyl phosphine oxide; With two luxuriant titaniums.
Specific examples as Photoepolymerizationinitiater initiater (D1), 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-1-acetone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, thioxanthone, diethyl thioxanthone, the 2-isopropyl thioxanthone, the 2-clopenthixal ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino-1-acetone, 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.Can get the example of product as the commerce of Photoepolymerizationinitiater initiater, can provide Irgacure 184,369,651,500,907,819, CGI1700, CGI1750, CGI1850, CGI1870, CG2461, Darocur1116,1173 (by Ciba Specialty Chemicals Co., Ltd. produces), Lucirin TPO (producing), Ubecryl P36 (producing) etc. by UCB by BASF.
As the example of thermal polymerization (D2), can provide superoxide, azo-compound etc.Specific examples comprises benzoyl peroxide, peroxidized t-butyl perbenzoate, Diisopropyl azodicarboxylate etc.
The consumption of the polymerization starter in the radiation-curable liquid resin composition of the present invention (D) is 0.1-10wt% preferably, particularly preferably is 0.5-5wt%.
And, photosensitizers, photostabilizer etc. can be added in the radiation-curable liquid resin composition of the present invention.Example as photosensitizers, can provide secondary amine and/or tertiary amine, for example thanomin, methyldiethanolamine, dimethylethanolamine, triethylamine, trolamine, to ethyl dimethylaminobenzoic acid ester, to methyl dimethoxy base Aminobenzoate, to ethyl dimethylaminobenzoic acid ester, to isopentyl dimethylaminobenzoic acid ester, phenmethyl dimethylamine, dimethylaminoethyl acrylate, N-phenylglycine, N-methyl-N-phenylglycine.For example the compound of for example superoxide of the aliphatic series of 2-chloromethyl naphthalene and 1-chloro-2-chloromethyl naphthalene or aromatic halide and formation free radical and azo-compound also can be used for quickening to solidify.The example of product can be got as the commerce of photosensitizers, Ubecryl P102,103,104,105 (producing) etc. can be provided by UCB.
As photostabilizer, can add a small amount of UV absorption agent, be generally benzotriazole UV absorbers, benzophenone UV absorption agent or N, N '-oxalyl absorbers.Also can add and have sterically hindered hindered amine as light stabilizer (HALS).Specific examples as photostabilizer, can provide Tinuvin 292,144,622LD (by Ciba Specialty Chemicals Co., Ltd. production), Sanol LS770 is (by Sankyo Co., Ltd. produce), TM-061 (by SumitomoChemical Industries Co., Ltd. produces) etc.As the silane coupling agent example, can provide γ-An Jibingjisanyiyangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan, γ-methacryloxypropyl trimethoxy silane, commerce can get product for example SH6062, SZ6030 (by Toray-DowCorning Silicone Co., Ltd. produce), KBE903,603,403 (by Shin-EtsuChemical Co., Ltd. produces) etc.
As other example additives, what pay special attention to is hot stopper, and it suppresses the initial stage polymerization during various components are mixed with composition.Can provide quinhydrones, hydroquinone derivatives, p methoxy phenol, 2-Naphthol and have sterically hindered phenol, for example 1,6-two (tertiary butyl)-p-cresol is as an example.
When composition is used for the painting optic fibre band, can adds releasing agent and make and remove coating and become easy.Siloxanes, fluorocarbon oil and resin are suitable for as releasing agent.When using, suitable releasing agent adds the amount 0.5-20wt% preferably in the composition to.
Except above component, for example the additive of pigment, silane coupling agent, levelling agent, tensio-active agent, sanitas, softening agent, lubricant, solvent, filler, protective agent, wettability improving agent and coatingsurface improving agent and so on can be added in the radiation-curable liquid resin composition.
The viscosity of radiation-curable liquid resin composition of the present invention is 0.3-6.0Pas at 25 ℃ preferably, is 1.0-6.0Pas at 25 ℃ more preferably, particularly preferably is at 25 ℃ to be 1.0-5.0Pas.Solidification rate is 0.6-0.9 preferably, particularly preferably is 0.7-0.9.
The Young's modulus of the cured product that is obtained by resin combination of the present invention is 50-1200MPa preferably, particularly preferably is 500-1200MPa.
Yellowness index (Δ Y.I.) preferably 2.0 or littler, more preferably 1.5 or littler, most preferably 1.3 or littler.
Adhesivity is 8N/m or littler preferably.
Dynamic friction coefficient preferably 0.4 or littler.
The present invention is described by the following examples in more detail.Yet, the invention is not restricted to these embodiment.Except as otherwise noted, among the embodiment, umber refers to parts by weight.
Embodiment and Comparative Examples
Synthetic embodiment 1. urethane acrylate oligomer UA-1
Adding 134.8g 2,4 toluene diisocyanate, 774.2g molecular weight are 2000 poly(propylene oxide), 0.24g 2,6 ditertiary butyl p cresol and 0.08g thiodiphenylamine in the reactor of agitator is housed.After adding the 0.8g dibutyl tin laurate, this mixture stirring was controlled at temperature 25-35 ℃ in 1 hour simultaneously.Then, add the 89.9g Hydroxyethyl Acrylate and under 50-60 ℃ with mixture restir 1 hour.When remaining isocyanate content is 0.1wt% or more hour, termination reaction.The urethane acrylate that obtains is called as " UA-1 ".
Synthetic embodiment 2. urethane acrylate oligomer UA-2
In being housed, the reactor of agitator adds 413.8g 2,4 toluene diisocyanate, 0.24g 2,6 ditertiary butyl p cresol, 0.08g thiodiphenylamine and 0.8g dibutyl tin laurate.After adding 309.2g vinylformic acid hydroxy propyl ester, this mixture stirring was controlled at temperature 25-35 ℃ in 1 hour simultaneously.Then, add the 275.9g Hydroxyethyl Acrylate and under 50-60 ℃ with mixture restir 1 hour.When remaining isocyanate content is 0.1wt% or more hour, termination reaction.The urethane acrylate that obtains is called as " UA-2 ".
Synthetic embodiment 3. urethane acrylate oligomer UA-3
In being housed, the reactor of agitator adds 428.1g 2,4 toluene diisocyanate, 0.24g 2,6 ditertiary butyl p cresol, 0.08g thiodiphenylamine and 0.8g dibutyl tin laurate.Then, add the 570.8g Hydroxyethyl Acrylate and under 50-60 ℃ with mixture restir 1 hour.When remaining isocyanate content is 0.1wt% or more hour, termination reaction.The urethane acrylate that obtains is called as " UA-3 ".
Embodiment 1-9 and Comparative Examples 1-3
In being housed, the reactor of agitator adds compound according to component shown in table 1 and the table 2 (weight part).Under 50 ℃, stir this mixture and obtain composition.
Testing method
(1) solidification rate: adopt the coating instrument that fluid composition is coated on the quartz glass plate, thickness is 200 μ m.(dosage is 0.1J/cm to adopt the 3.5kW metal halide lamp
2And 1.0J/cm
2) composition that in air, applies with ultraviolet radiation, obtain cured film.Cured article was placed 24 hours under the relative humidity of 23 ℃ temperature and 50%, be cut into the width of 1cm, obtain specimen.Adopt tester for elongation to measure the Young's modulus (MPa) of specimen.The Young's modulus that measures (MPa) is divided by UV radiation dose (J/cm
2) obtain solidification rate.
(2) viscosity: in composition being placed on 25 ℃ water bath with thermostatic control, after 30 minutes, adopt B-type viscosity apparatus to measure viscosity.
(3) yellowness index: adopt applicator that composition is coated on the clean sheet glass, thickness is 200 μ m.(dosage is 0.1J/cm to adopt the 3.5kW metal halide lamp
2) composition that in nitrogen atmosphere, applies with ultraviolet radiation, obtain cured film.Cured article was placed 24 hours under the relative humidity of 23 ℃ temperature and 50%, then adopted the chromatism measurement instrument to measure Δ Y.I.
(4) surface properties: (dosage is 0.1J/cm to adopt the 3.5kW metal halide lamp
2) in air with ultraviolet radiation thickness be the film of 70 μ m to obtain cured film, be used to measure adhesivity.Cured film and another film sticks together and placed under predetermined load 24 hours then adopts Instron digital testing system (being made by Instron Japan Inc.) to peel off method by 180 ℃ and measures adhesivity.(dosage is 0.1J/cm to adopt the 3.5kW metal halide lamp
2) in air, adopt ultraviolet radiation thickness be the film of 200 μ m to obtain cured film, be used to measure dynamic friction coefficient.Film is divided into two and be made into cylinder.Adopt surface properties measuring engine (by Shinto Scientific Co., Ltd. makes) to make the load lower slip of this cylinder, determine dynamic friction coefficient to measure resistance coefficient at 100g.
(5) Young's modulus: adopt the coating instrument that composition is coated on the sheet glass, thickness is 250 μ m.(dosage is 1J/cm to adopt the 3.5kW metal halide lamp
2) composition that in air, applies with ultraviolet radiation, obtain cured film.Film is cut into the band shape sample of the long 25mm of wide 6mm (treating the tensile part).Under the humidity of 23 ℃ temperature and 50%, to the sample measurement that stretches.Calculate Young's modulus by the tensile strength under the strain of the rate of extension of 1mm/min and 2.5%.
Above various performances to the composition for preparing among the embodiment are assessed.The results are shown in table 1 and the table 2.
Table 1
| Embodiment | The contrast experiment | ||||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | |
| UA-1 | 55 | 55 | 55 | 70 | 55 | 55 | 70 |
| UA-2 | 15 | 15 | 15 | 15 | 15 | ||
| UA-3 | 10 | 10 | 10 | 10 | 10 | ||
| Lauryl acrylate | 10 | 10 | 10 | 10 | 10 | 20 | 10 |
| The N-caprolactam | 10 | 20 | |||||
| Vinylformic acid 2-vinyl oxygen base ethyl ester | 10 | ||||||
| Isobornyl acrylate | |||||||
| Vinylformic acid 2-(2 '-vinyloxy group oxyethyl group) ethyl ester | 10 | 20 | |||||
| Methacrylic acid 2-(2 '-vinyloxy group oxyethyl group) ethyl ester | 10 | ||||||
| Iragcure 184 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Viscosity (Pas) | 3.8 | 4.3 | 4.4 | 3.3 | 7.4 | 6.1 | 6.0 |
| Young's modulus (MPa) | 810 | 770 | 800 | 85 | 830 | 540 | 100 |
| Solidification rate | 0.83 | 0.86 | 0.76 | 0.85 | 0.86 | 0.75 | 0.85 |
| Yellowness index (Δ Y.I) | 1.3 | 1.1 | 1.0 | 1.2 | 2.1 | 0.9 | 2.9 |
| Surface properties adhesivity (N/m) | 6.0 | 7.4 | 3.4 | 7.0 | 7.7 | 17 | 8.5 |
| Dynamic friction coefficient | 0.36 | 0.33 | 0.17 | 0.35 | 0.40 | 1.5 | 0.55 |
Vinylformic acid 2-vinyloxy group ethyl ester: VEA is by Nippon Shokubai Co., and Ltd. produces
Vinylformic acid 2-(2 '-vinyloxy group oxyethyl group) ethyl ester: VEEA is by Nippon Shokubai Co., and Ltd. produces
Methacrylic acid 2-(2 '-vinyloxy group oxyethyl group) ethyl ester: VEEM is by Nippon Shokubai Co., and Ltd. produces
Irgacure 184:1-hydroxy-cyclohexyl phenyl ketone is by Ciba Specialty Chemicals Co., and Ltd produces
Table 2
| The contrast experiment | Embodiment | |||||||
| 1 | 2 | 3 | 5 | 6 | 7 | 8 | 9 | |
| UA-1 | 55 | 55 | 70 | 55 | 55 | 55 | 70 | 55 |
| UA-2 | 15 | 15 | 15 | 15 | 15 | 15 | ||
| UA-3 | 10 | 10 | 10 | 10 | 10 | 10 | ||
| Lauryl acrylate | 10 | 20 | 10 | 10 | 10 | 10 | 10 | 10 |
| The N-caprolactam | 10 | 20 | ||||||
| Vinylformic acid 2-hydroxyl ethyl ester | 10 | 20 | ||||||
| Vinylformic acid 2-hydroxypropyl acrylate | 10 | 20 | ||||||
| Vinylformic acid 4-hydroxy butyl ester | 10 | |||||||
| Irgacure 184 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Viscosity (Pas) | 7.4 | 6.1 | 6.0 | 3.8 | 4.3 | 4.4 | 3.5 | 2.8 |
| Young's modulus (MPa) | 830 | 540 | 100 | 810 | 770 | 750 | 830 | 690 |
| Solidification rate | 0.86 | 0.75 | 0.85 | 0.85 | 0.88 | 0.89 | 0.88 | 0.89 |
| The yellowness factor of solidifying product (Δ Y.I) | 2.5 | 0.9 | 2.9 | 0.8 | 0.8 | 0.9 | 0.9 | 0.8 |
| Surface properties adhesivity (N/m) | 8 | 17 | 9 | 6 | 5 | 3 | 7 | 4 |
| Dynamic friction coefficient | 0.4 | 1.5 | 0.6 | 0.4 | 0.3 | 0.2 | 0.4 | 0.3 |
From table 1 and table 2 as can be seen, the resin combination that comprises 20-90wt% component (A) and 1-35wt% component (B) has low viscosity, excellent operability, and Young's modulus is 50-1200MPa when cured.Said composition has high solidification rate, low yellowness index and excellent surface property.
Claims (15)
1. radiation-curable liquid resin composition, described composition comprises:
(A) 20-90wt% urethane (methyl) origoester acrylate and
(B)1-35wt％
Monomer shown in the-following formula (1)
Wherein, R
1Expression hydrogen atom or methyl, R
2And R
3Represent hydrogen atom respectively or have the alkyl of 1-4 carbon atom, R
4Expression hydrogen atom or methyl, and n represents the integer of 1-6, or
The monomer of-hydroxyl.
2. radiation-curable liquid resin composition as claimed in claim 1, wherein, described urethane (methyl) origoester acrylate passes through polyol compound (a), and polyisocyanates (b) and hydroxy functional group ethylenically unsaturated monomers (c) reaction obtain.
3. radiation-curable liquid resin composition as claimed in claim 1, wherein, described urethane (methyl) origoester acrylate of 10-80wt% is by obtaining polyisocyanate compound (b) and hydroxy functional group ethylenically unsaturated monomers (c) reaction.
4. radiation-curable liquid resin composition as claimed in claim 3, described composition also comprise urethane (methyl) origoester acrylate that obtains by with polyol compound (a), polyisocyanates (b) and hydroxy functional group ethylenically unsaturated monomers (c) reaction.
5. as claim 3 or the described radiation-curable liquid resin composition of claim 4, wherein, described is by (methyl) vinylformic acid 2-hydroxy methacrylate and 2,4 toluene diisocyanate are reacted the oligopolymer that obtains by the oligopolymer that polyisocyanate compound (b) and hydroxy functional group ethylenically unsaturated monomers (c) reaction are obtained.
6. as any described radiation-curable liquid resin composition among the claim 1-5, wherein, described monomer (B) is selected from the group of being made up of (methyl) vinylformic acid 2-(2 '-vinyloxy group oxyethyl group) ethyl ester and (methyl) vinylformic acid 2-vinyloxy group ethyl ester.
7. as any described radiation-curable liquid resin composition among the claim 1-5, wherein, described monomer (B) is selected from the group of being made up of (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester and (methyl) vinylformic acid 4-hydroxyl cyclohexyl.
8. as any described radiation-curable liquid resin composition among the claim 1-7, also comprise reactive thinner (C), wherein (C) is not included in the definition of component (B).
9. radiation-curable liquid resin composition as claimed in claim 8 comprises the reactive thinner of 1-33wt%.
10. as any described radiation-curable liquid resin composition among the claim 1-9, wherein, the viscosity of described composition under 25 ℃ is 1.0-6.0Pas.
11. purposes according to primary coating, secondary coating, ink composite or the substrate material of any described radiation-curable liquid resin composition conduct on optical glass fibre among the claim 1-10.
12. 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 big envelope 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 big envelope 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, at least a in wherein said coating or the composition derives from any described radiation-hardenable composition among the claim 1-10.
13. through that apply and optional through being coated with the optical fiber of China ink, comprise glass optical fiber, described glass optical fiber has the primary coating that is coated on it, secondary coating and optional ink composite, wherein, described coating or ink composite derives from according to radiation-hardenable composition any among the claim 1-10 one of at least.
14. a fibre ribbon, described fibre ribbon comprise many by substrate material keep together according to claim 12 or claim 13 through that apply and optional through being coated with the optical fiber of ink-jet.
15. a fibre ribbon, described fibre ribbon comprise many by substrate material keep together through that apply and optional through being coated with the optical fiber of ink-jet, wherein, described substrate material derives from radiation-curable resin composition any among the claim 1-10.
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| CN103380181A (en) * | 2010-12-28 | 2013-10-30 | 阿克佐诺贝尔国际涂料股份有限公司 | Radiation curable coating compositions for metal |
| CN104449541A (en) * | 2013-09-25 | 2015-03-25 | 奇美实业股份有限公司 | Photocurable releasable adhesive composition and use thereof |
| CN109071753A (en) * | 2016-03-04 | 2018-12-21 | 陶氏环球技术有限责任公司 | The reactive diluent without styrene for urethane acrylate resin composition |
| CN114555736A (en) * | 2020-09-25 | 2022-05-27 | 住友电气工业株式会社 | Resin composition, method for producing resin composition, optical fiber, and method for producing optical fiber |
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| JP4568516B2 (en) * | 2004-03-18 | 2010-10-27 | Ｊｓｒ株式会社 | Liquid curable resin composition |
| JP4763244B2 (en) * | 2004-03-15 | 2011-08-31 | Ｊｓｒ株式会社 | Liquid curable resin composition |
| JP5162525B2 (en) * | 2009-06-09 | 2013-03-13 | Ｊｓｒ株式会社 | Liquid curable resin composition |
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2003
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2004
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| CN102770496A (en) * | 2010-02-11 | 2012-11-07 | 帝斯曼知识产权资产管理有限公司 | Radiation curable liquid composition for low gloss coatings |
| CN102770496B (en) * | 2010-02-11 | 2014-12-31 | 帝斯曼知识产权资产管理有限公司 | Radiation curable liquid composition for low gloss coatings |
| CN103380181A (en) * | 2010-12-28 | 2013-10-30 | 阿克佐诺贝尔国际涂料股份有限公司 | Radiation curable coating compositions for metal |
| CN104449541A (en) * | 2013-09-25 | 2015-03-25 | 奇美实业股份有限公司 | Photocurable releasable adhesive composition and use thereof |
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| CN109071753B (en) * | 2016-03-04 | 2021-09-14 | 陶氏环球技术有限责任公司 | Styrene-free reactive diluents for urethane acrylate resin compositions |
| CN114555736A (en) * | 2020-09-25 | 2022-05-27 | 住友电气工业株式会社 | Resin composition, method for producing resin composition, optical fiber, and method for producing optical fiber |
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