WO2023112714A1 - 含フッ素活性エネルギー線硬化性組成物、硬化物、並びに物品 - Google Patents
含フッ素活性エネルギー線硬化性組成物、硬化物、並びに物品 Download PDFInfo
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- WO2023112714A1 WO2023112714A1 PCT/JP2022/044497 JP2022044497W WO2023112714A1 WO 2023112714 A1 WO2023112714 A1 WO 2023112714A1 JP 2022044497 W JP2022044497 W JP 2022044497W WO 2023112714 A1 WO2023112714 A1 WO 2023112714A1
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- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- TYNRPOFACABVSI-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F TYNRPOFACABVSI-UHFFFAOYSA-N 0.000 description 1
- VPKQPPJQTZJZDB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C VPKQPPJQTZJZDB-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- RASBDVLERRNNLJ-UHFFFAOYSA-N CCCCO[Ti] Chemical compound CCCCO[Ti] RASBDVLERRNNLJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- URFLCXSTNZSALZ-UHFFFAOYSA-N [F].C(C(=C)C)(=O)O Chemical compound [F].C(C(=C)C)(=O)O URFLCXSTNZSALZ-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000002862 amidating effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000005710 tetrahydropyranylene group Chemical group 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
Definitions
- the present invention provides a fluorine-containing active energy ray-curable composition capable of forming a transparent cured product having a low refractive index and excellent water vapor resistance and having excellent handleability, a cured product of the composition, and the It relates to an article having a cured product.
- fluorine compound that can be cured by light irradiation such as ultraviolet rays
- polymerizable monomers having perfluoroalkyl groups in side chains such as polymers containing fluorine-containing acrylic acid alkyl esters and methacrylic acid fluorine-containing alkyl esters
- fluorine-containing acrylic compounds have been widely attempted to be used in optical materials utilizing their excellent curing properties, high transparency, and low refractive index when irradiated with ultraviolet rays.
- Patent Document 1 describes the application of a fluorine-containing acrylic compound in a side chain to an antireflection coating
- Patent Document 2 Japanese Patent Application Laid-Open No. 5-32749
- Patent Document 2 describes , as a coating material for optical fibers.
- a fluorine-containing curable composition capable of forming a transparent cured product having a refractive index is proposed.
- compositions can form a transparent cured product with a low refractive index, there is a problem that the mechanical properties of the cured product are significantly reduced by exposure to water vapor. Moreover, these compositions also have the problem that a photopolymerization initiator modified with a perfluoropolyether group must be separately synthesized.
- the present invention has been made in view of the above circumstances, can be cured by active energy rays such as ultraviolet rays and electron beams, can form a transparent cured product having a low refractive index and excellent water vapor resistance, and
- An object of the present invention is to provide a fluorine-containing active energy ray-curable composition excellent in handleability, a cured product of the composition, and an article comprising the cured product.
- Rf 1 is a divalent perfluoropolyether group composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom and having a number average molecular weight of 500 to 40,000.
- Z is a divalent organic may contain a cyclic structure in the middle Y is a (b+1)-valent organic group having 1 to 20 carbon atoms
- X is independently a monovalent organic group containing an acryl group or an ⁇ -substituted acryl group and contains at least one acryl group or ⁇ -substituted acryl group on average per molecule
- V 1 is represented by a hydrogen atom, a fluorine atom, or —Z—Y(X) b is a monovalent group, b is an integer of 1 to 10.
- (B) Acrylic compounds having a viscosity at 23° C.
- the viscosity at 23 ° C. is in the range of 10 to 100,000 mPa s
- the temperature is 25 ° C.
- a fluorine-containing active energy ray-curable composition having a refractive index of 1.390 or less at 589 nm is curable by active energy rays such as ultraviolet rays and electron beams, and has a low refractive index and excellent water vapor resistance.
- the inventors have found that a fluorine-containing active energy ray-curable composition that can form a transparent cured product and that is excellent in handleability can be obtained, and have completed the present invention.
- the present invention provides the following fluorine-containing active energy ray-curable composition, a cured product of the composition, and an article comprising the cured product.
- A 100 parts by mass of a fluoropolyether group-containing acrylic compound represented by the following general formula (1), V 1 -Rf 1 -ZY(X) b (1)
- Rf 1 is a divalent perfluoropolyether group composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom and having a number average molecular weight of 500 to 40,000.
- Z is a divalent organic may contain a cyclic structure in the middle Y is a (b+1)-valent organic group having 1 to 20 carbon atoms
- X is independently a monovalent organic group containing an acryl group or an ⁇ -substituted acryl group and contains at least one acryl group or ⁇ -substituted acryl group on average per molecule
- V 1 is represented by a hydrogen atom, a fluorine atom, or —Z—Y(X) b is a monovalent group, b is an integer of 1 to 10.
- (B) Acrylic compounds having a viscosity at 23° C.
- the viscosity at 23 ° C. is in the range of 10 to 100,000 mPa s
- the temperature is 25 ° C.
- a fluorine-containing active energy ray-curable composition having a refractive index of 1.390 or less at 589 nm.
- Rf 2 is a divalent perfluoropolyether group composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom and having a number average molecular weight of 500 to 40,000.
- Y 2 is independently a carbon is a (b'+1)-valent organic group having a number of 1 to 20.
- Rf 2 is the following formula (Wherein, c is an integer of 2 to 6 independently for each unit.
- Each of these units may be linear or branched, and each repeating unit shown in parentheses labeled d, e, f, g, h, i may be randomly linked.
- Rf 2 has the following structural formula -CF 2 CF 2 O-(CF 2 CF 2 CF 2 O) q -CF 2 CF 2 - (Wherein, q is an integer of 4 to 200.) (wherein r is an integer of 1 to 6, C r F 2r O may be linear or branched, s is an integer of 0 to 6, t and u are each 1 to 200 , t + u is an integer of 2 to 200, s + t + u is an integer of 4 to 200, and v is an integer of 5 to 200.)
- n 1 or 2.
- component (A) is a fluoropolyether group-containing acrylic compound represented by any of the following formulas.
- the fluorine-containing active energy ray-curable composition of the present invention can be cured by active energy rays such as ultraviolet rays and electron beams, and can form a transparent cured product having a low refractive index and excellent water vapor resistance. and excellent handling. Therefore, the fluorine-containing active energy ray-curable composition of the present invention is useful as a material for various optical components such as antireflection agents, optical fiber coating agents, and lenses.
- the fluorine-containing active energy ray-curable composition of the present invention is (A) 100 parts by mass of a fluoropolyether group-containing acrylic compound represented by the following general formula (1), V 1 -Rf 1 -ZY(X) b (1) (In the formula, Rf 1 is a divalent perfluoropolyether group composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom and having a number average molecular weight of 500 to 40,000.
- Z is a divalent organic may contain a cyclic structure in the middle Y is a (b+1)-valent organic group having 1 to 20 carbon atoms
- X is independently a monovalent organic group containing an acryl group or an ⁇ -substituted acryl group and contains at least one acryl group or ⁇ -substituted acryl group on average per molecule
- V 1 is represented by a hydrogen atom, a fluorine atom, or —Z—Y(X) b is a monovalent group, b is an integer of 1 to 10.
- (B) Acrylic compounds having a viscosity at 23° C.
- the viscosity at 23 ° C. is in the range of 10 to 100,000 mPa s
- the temperature is 25 ° C.
- the wavelength It is characterized by having a refractive index of 1.390 or less at 589 nm.
- the fluoropolyether group-containing acrylic compound of component (A) comprises a perfluoropolyether group as a group having low refractive index and water vapor resistance, and an acrylic group.
- a perfluoropolyether group as a group having low refractive index and water vapor resistance
- an acrylic group since it has an ⁇ -substituted acrylic group, it can be cured by active energy rays such as ultraviolet rays and electron beams, and can form a transparent cured product having a low refractive index and excellent water vapor resistance.
- the fluoropolyether group-containing acrylic compound of component (A), which is the first essential component in the fluorine-containing active energy ray-curable composition of the present invention, is represented by the following general formula (1).
- V 1 -Rf 1 -ZY(X) b (1)
- "acrylic compound” is a general term for compounds having an acrylic group or an ⁇ -substituted acrylic group, and two or more acrylic groups or ⁇ -substituted acrylic It also includes compounds into which groups have been introduced.
- (meth)acrylate refers to one or both of acrylate and methacrylate
- (meth)acrylic group refers to one or both of acrylic group and methacrylic group
- (meth)acrylic “Acid” refers to one or both of acrylic acid and methacrylic acid.
- Rf 1 is a divalent perfluoropolyether group having a number average molecular weight of 500 to 40,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf 1 is , C 1-6, particularly those having the following C 1-3 perfluorooxyalkylene structure as a main repeating unit.
- c is an integer of 2 to 6 independently for each unit.
- These units may be linear or branched, and each repeating unit shown in parentheses labeled d, e, f, g, h, i may be randomly linked.
- c is an integer of 2 to 6, preferably 2 to 4, independently for each unit.
- c is 1, the water vapor resistance decreases, so c is preferably an integer of 2 to 6 independently for each unit.
- each unit may be linear or branched.
- each repeating unit shown in parentheses with d, e, f, g, h and i may be randomly combined.
- the number average molecular weight of the corresponding structural portion of Rf 1 is in the range of 500 to 40,000, preferably 2,000 to 25,000. It is not particularly limited. If the number average molecular weight is less than 500, the refractive index increases due to the decrease in the fluorine atom content. The decrease in solubility becomes a non-negligible degree.
- the molecular weight (or the degree of polymerization or the number of repeating units) is the number average molecular weight (or the number average degree of polymerization) in terms of polystyrene by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. number - average molecular weight (or number-average polymerization degrees).
- Z is a divalent organic group and may contain a cyclic structure in the middle.
- Z include the structures shown below.
- R is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms.
- Y and X are the same as Y and X described later.
- * is bonded to Rf 1 is a bond, and ** is a bond that bonds with Y.
- Y is a (b+1)-valent organic group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms.
- Examples of Y include the following. (Wherein, * is a bond that bonds to Z, and ** is a bond that bonds to X.)
- X is independently a monovalent organic group containing an acryl group or an ⁇ -substituted acryl group, and on average at least one acryl group or ⁇ -substituted acryl group per molecule. contains.
- X preferably has a structure represented by the following formula.
- V 1 is a hydrogen atom, a fluorine atom, or a monovalent group represented by -Z-Y(X) b , preferably represented by -Z-Y(X) b It is a monovalent group.
- V 1 is a monovalent group represented by —Z—Y(X) b
- the composition contains at least two acryl groups or ⁇ -substituted acryl groups on average per molecule. forms a mesh-like network and gives a cured product with excellent mechanical properties.
- a plurality of Z, Y, X, and b present in formula (1) may be the same or different. may be
- b is an integer of 1-10, preferably 1 or 2.
- the fluoropolyether group-containing acrylic compound of component (A) is represented by general formula (2)
- at least one of the terminals of Rf 2 is bonded to an amide structure.
- the terminal portion of Rf 2 is highly reactive due to the electron-withdrawing property of the fluorine atom, and is likely to undergo hydrolysis.
- the cured product of the composition of the present invention is exposed to steam, hydrolysis is unlikely to occur due to the high bond energy of the amide bond, and as a result, the steam resistance is particularly excellent, which is preferable.
- the fluoropolyether group-containing acrylic compound of component (A) has an amide bond
- the amide structure acts as a hydrogen bond acceptor, thereby interacting with a hydrogen atom in the photopolymerization initiator. It is preferable because the compatibility with is improved, and as a result, a transparent composition can be formed.
- Rf 2 is a divalent perfluoropolyether group having a number average molecular weight of 500 to 40,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom
- Rf 1 is , C 1-6, particularly those having the following C 1-3 perfluorooxyalkylene structure as a main repeating unit.
- c is an integer of 2 to 6 independently for each unit.
- These units may be linear or branched, and each repeating unit shown in parentheses labeled d, e, f, g, h, i may be randomly linked.
- c is an integer of 2 to 6, preferably 2 to 4, independently for each unit.
- c is 1, the water vapor resistance is lowered, so c is preferably an integer of 2 to 6 independently for each unit.
- each unit may be linear or branched.
- each repeating unit shown in parentheses with d, e, f, g, h and i may be randomly combined.
- the number average molecular weight of the corresponding structural portion of Rf 2 should be in the range of 500 to 40,000, preferably 2,000 to 25,000. It is not particularly limited. If the number average molecular weight is less than 500, the refractive index increases due to the decrease in the fluorine atom content. The decrease in solubility becomes a non-negligible degree.
- the molecular weight (or the degree of polymerization or the number of repeating units) is the number average molecular weight (or the number average degree of polymerization) in terms of polystyrene by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. number - average molecular weight (or number-average polymerization degrees).
- Rf 2 having such a structure include the following structures. -CF2CF2O- ( CF2CF2CF2O ) q -CF2CF2- _ _ (Wherein, q is an integer of 4 to 200, preferably 10 to 150.)
- r is an integer of 1 to 6, preferably 2 to 4
- C r F 2r O may be linear or branched
- s is an integer of 0 to 6 , preferably an integer of 1 to 4
- t is an integer of 1 to 100, preferably an integer of 5 to 80
- u is an integer of 1 to 100, preferably an integer of 5 to 80
- t+u is 2
- An integer of ⁇ 200, preferably an integer of 10 to 150, s + t + u is an integer of 4 to 200, preferably an integer of 10 to 150.
- v is an integer of 5 to 200, preferably an integer of 10 to 150.
- Rf 2 The most preferred example of Rf 2 is the structure below.
- the terminal portion of Rf 2 is highly reactive due to the electron- withdrawing property of the fluorine atom, and hydrolysis is likely to occur.
- CF (CF 3 ) groups are shielded, so hydrolysis is unlikely to occur, resulting in excellent steam resistance, which is particularly preferred.
- r, s, t, u, and v are the same as above.
- R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms.
- monovalent hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and octyl group.
- R 1 is preferably a hydrogen atom, a methyl group or an ethyl group, particularly preferably a hydrogen atom.
- Y 2 is independently a (b'+1)-valent organic group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, preferably 1 to 1 carbon atoms optionally containing an ether bond. 20, preferably 1 to 8 (b'+1) valent hydrocarbon groups.
- Particularly preferred structures for Y 2 include the following. (Wherein, * is a bond that bonds to N, and ** is a bond that bonds to X2 .)
- X 2 is independently a monovalent organic group containing an acrylic group or an ⁇ -substituted acrylic group, and on average at least one acrylic group or ⁇ -substituted acrylic group per molecule.
- X 2 preferably has a structure represented by the following formula. (Wherein, R 2 is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and W is a single bond, or one or more selected from an ether bond, an ester bond and a urethane bond. It is a divalent or trivalent hydrocarbon group that may be contained, and n is 1 or 2.)
- W is a single bond, or a divalent or trivalent hydrocarbon group that may contain one or more selected from ether bonds, ester bonds and urethane bonds
- hydrocarbon group of can be exemplified by groups represented by the following formulas. (Wherein, * is a bond that bonds to Y 2 in general formula (2), and ** is a bond that bonds to an oxygen atom.)
- X 2 is more preferably a structure represented by the following formula.
- V 2 is a monovalent group represented by —C( ⁇ O)—NR 1 a [Y 2 (X 2 ) b′ ] 2 -a , at least two or more Since it contains an acryl group or an ⁇ -substituted acryl group, a composition using this compound forms a mesh-like network, and a cured product having excellent mechanical properties can be obtained.
- V 2 is a monovalent group represented by —C( ⁇ O)—NR 1 a [Y 2 (X 2 ) b′ ] 2-a
- multiple R 1 , Y 2 , X 2 , b' and a may be the same or different.
- a is 0 or 1, preferably 1.
- b' is an integer of 1 to 10, preferably 1 or 2.
- fluoropolyether group-containing acrylic compound represented by the above formula (2) those represented by the following formula are preferable. (Wherein, X 2 , q, r, s, t and u are the same as above.)
- fluoropolyether group-containing acrylic compound represented by the above formula (2) those represented by the following formula are particularly preferable. (Wherein, X 2 , r, s, t and u are the same as above.)
- X 3 in the above formula (4) is a halogen atom or preferably an unsubstituted or fluorine-substituted alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. , chlorine, halogen atoms such as bromine, alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, hexyloxy group, octyloxy group, hydrogen of these groups Fluorine such as a trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,1,3,3,3-hexafluoroisopropoxy group, in which some or all of the atoms are substituted with fluorine atoms Substituted alkoxy groups are included.
- fluoropolyether group-containing compound having an acid halide or ester at the molecular chain end represented by the above formula (4) include those shown below.
- Rf 2 [C( O)-Cl] 2
- Rf 2 [C( O)-F] 2
- Rf 2 [C( O)-O-CH 3 ] 2
- Rf 2 [C( O)--O--C 2 H 5 ] 2
- Rf 2 [C( O)-O-C 3 H 7 ] 2
- Rf 2 [C( O)--O--C 4 H 9 ] 2
- Rf 2 [C( O)-OC 5 H 11 ] 2
- Rf 2 [C( O)--O--C 6 H 13 ] 2
- Rf 2 [C( O)-O-CF 3 ] 2
- Rf 2 [C( O)-O-C 2 F 5 ] 2
- Rf 2 [C( O)--O--CH(CF 3 ) 2 ] 2
- examples of the aminoalcohol compound represented by the above formula (5) include those shown below.
- the reaction ratio between the fluoropolyether group-containing compound having an acid halide or ester at the molecular chain end represented by formula (4) and the amino alcohol compound represented by formula (5) is represented by formula (4). 1 to 12 times the moles of the aminoalcohol compound represented by the formula (5), particularly It is desirable to use 1.2 to 6 times the molar amount for the reaction. If the amount of the aminoalcohol compound represented by formula (5) is too small, it may be difficult to obtain the target fluoropolyether group-containing alcohol compound.
- a fluoropolyether group-containing compound having an acid halide or ester at the molecular chain end represented by the above formula (4) and an amino alcohol compound represented by the formula (5) are mixed, and the reaction temperature is It is desirable to carry out the reaction at 0 to 100° C., preferably 0 to 80° C., for 1 minute to 48 hours, particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop before the reaction proceeds sufficiently.
- the above amidation reaction can be carried out without the presence of a solvent, it may be diluted with a solvent if necessary.
- a solvent widely used organic solvents can be used, but those having a boiling point higher than the target reaction temperature and not inhibiting the reaction are preferable.
- solvents include fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and partially fluorine-modified solvents such as fluorine-modified ether solvents such as methyl perfluorobutyl ether. is desirable, and m-xylene hexafluoride is particularly preferred.
- the amount used is preferably 5 to 2,000 mass parts per 100 parts by mass of the fluoropolyether group-containing compound having an acid halide or ester at the molecular chain end represented by formula (4). parts, more preferably 50 to 500 parts by mass. If it is less than this, the effect of dilution with the solvent will be weak, and if it is more than this, the degree of dilution will become too high, which may lead to a decrease in the reaction rate.
- the fluoropolyether group-containing alcohol compound represented by the formula (6) is converted into a (meth)acrylic group.
- a method of reacting with an isocyanate compound contained can be mentioned.
- (Meth)acrylic group-containing isocyanate compound may be reacted in an equimolar amount or more with respect to the total amount of hydroxyl groups of the fluoropolyether group-containing alcohol compound, and all hydroxyl groups may be reacted, but the fluoropolyether group-containing It suffices to introduce an average of 1 mol or more (meth)acrylic groups per 1 mol of the alcohol compound, and by making the hydroxyl groups excessive, the isocyanate compound containing unreacted (meth)acrylic groups does not remain. You may do so.
- an isocyanate compound containing a (meth)acrylic group is preferably x mol or more and 2 y mol or less, particularly preferably x mol or more and 0.6 y mol or more and 1.4 y mol or less. If the amount is too small, there is a high possibility that the fluoropolyether group-containing alcohol compound with no (meth)acrylic groups will remain, and if it is too large, it will be difficult to remove the unreacted (meth)acryl group-containing isocyanate compound. becomes.
- any solvent that does not react with the hydroxyl group of the fluoropolyether group-containing alcohol compound and the isocyanate group of the isocyanate compound containing the (meth)acrylic group can be used without particular limitation.
- Hydrocarbon solvents such as toluene, xylene and isooctane; ether solvents such as tetrahydrofuran (THF), diisopropyl ether and dibutyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone; Hexafluoride [alias: hexafluorometaxylene], fluorine-modified aromatic hydrocarbon-based solvents such as benzotrifluoride, and fluorine-modified ether-based solvents such as methyl perfluorobutyl ether can be used.
- ether solvents such as tetrahydrofuran (THF), diisopropyl ether and dibutyl ether
- ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl iso
- This solvent may be removed by a known technique such as distillation under reduced pressure after the reaction.
- the amount of the solvent to be used is not particularly limited, but is preferably 10 times or less of the total mass of the reaction components. If too much solvent is used, the reaction rate may drop significantly.
- a polymerization inhibitor may be added during the reaction, if necessary.
- the polymerization inhibitor is not particularly limited, but those commonly used as polymerization inhibitors for acrylic compounds can be used. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene and the like.
- the amount of the polymerization inhibitor to be used may be determined from the reaction conditions, post-reaction purification conditions, and final use conditions, and is not particularly limited, but is usually 0.01 to 5,000,000,000,000,000,000,000, or 000 ppm, particularly preferably 0.1 to 500 ppm.
- a suitable catalyst may be added to increase the rate of reaction.
- catalysts include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctoate, tetraisopropoxytitanium, tetraisopropoxytitanium, and tetraisopropoxytitanium.
- n-butoxytitanium tetrakis(2-ethylhexoxy)titanium [also known as tetrakis(2-ethylhexyl)orthotitanate], dipropoxybis(acetylacetona)titanium, titanium isopropoxyoctylene glycol, and other titanate esters or titanium chelates compounds, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), zirconium tetraacetylacetonate, zirconium chelates, carboxylic acids A bismuth compound etc.
- reaction rate can be increased by adding 0.01 to 2% by weight, preferably 0.05 to 1% by weight, of these catalysts relative to the total weight of the reaction components.
- the above reaction is carried out at a temperature of 0 to 120°C, preferably 10 to 100°C, for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may become too slow, and if the reaction temperature is too high, polymerization of (meth)acrylic groups may occur as a side reaction.
- an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound.
- the produced urethane (meth)acrylates can be removed in the same manner as the unreacted isocyanate compound, but they can also be used as they remain.
- the fluoropolyether group-containing alcohol compound represented by formula (6) is added to (meth) ) reaction with an acrylic acid halide to form an ester.
- (Meth)acrylic acid halides include those shown below.
- X4 is a halogen atom such as fluorine, chlorine, or bromine.
- Acrylic acid chloride and methacrylic acid chloride are particularly preferred.
- (Meth)acrylic acid halide is desirably charged in an equimolar amount or more with respect to the total amount of hydroxyl groups in the fluoropolyether group-containing alcohol compound and reacted so that all the hydroxyl groups are reacted.
- the amount of (meth)acrylic acid halide is 1 to 6 mol, particularly 1.2 to 4 mol, relative to the amount of hydroxyl groups in the fluoropolyether group-containing alcohol compound in the reaction system, and the reaction is carried out. is desirable. If the amount is too small, there is a high possibility that the fluoropolyether group-containing alcohol compound to which the (meth)acrylic group has not been introduced will remain.
- an acid acceptor in the ester formation reaction of reacting a fluoropolyether group-containing alcohol compound with a (meth)acrylic acid halide, and the fluoropolyether group-containing alcohol compound represented by the above formula (6), ( A meth)acrylic acid halide and an acid acceptor are mixed and stirred.
- Usable acid acceptors include triethylamine, pyridine, and urea.
- the amount of the acid acceptor used is desirably about 0.9 to 3 times the number of moles of the (meth)acrylic acid halide. If it is too small, a large amount of untrapped acid will remain, and if it is too large, it will be difficult to remove the surplus acid acceptor.
- any solvent that does not react with the hydroxyl group of the fluoropolyether group-containing alcohol compound and the halogen atom of the (meth)acrylic acid halide can be used without particular limitation.
- Hydrocarbon solvents such as isooctane, ether solvents such as tetrahydrofuran (THF), diisopropyl ether and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone, m-xylene hexafluoride [ alias: hexafluorometaxylene], fluorine-modified aromatic hydrocarbon-based solvents such as benzotrifluoride, fluorine-modified ether-based solvents such as methyl perfluorobutyl ether, and the like.
- ether solvents such as tetrahydrofuran (THF)
- THF tetrahydrofuran
- ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone
- This solvent may be removed by a known technique such as distillation under reduced pressure after the reaction.
- the amount of the solvent to be used is not particularly limited, but is preferably 10 times or less with respect to the total mass of the reaction components. If too much solvent is used, the reaction rate may drop significantly.
- the above reaction is carried out at a temperature of 0 to 120°C, preferably 10 to 100°C, for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may become too slow, and if the reaction temperature is too high, polymerization of (meth)acrylic groups may occur as a side reaction.
- the fluoropolyether group-containing acrylic compound thus obtained does not contain volatile organic compounds (volatile organic solvents).
- the fluoropolyether group-containing acrylic compound may be used alone or in combination of two or more.
- the second essential component in the fluorine-containing active energy ray-curable composition of the present invention is (B) a viscosity at 23° C. of 5,000 mPa ⁇ s or less, and one acrylic group or ⁇ -substituted acrylic group per molecule. It is an acrylic compound containing one or two, excluding the component (A).
- the (B) component acrylic compound may contain oxygen atoms and nitrogen atoms other than the acrylic structure, and specifically may contain ether bonds, urethane bonds, isocyanate groups and hydroxyl groups.
- the component (B) has a viscosity at 23°C of 5,000 mPa ⁇ s or less, preferably 0.4 to 2,000 mPa ⁇ s, because of its solubility with the component (A). If the viscosity at 23° C. exceeds 5,000 mPa ⁇ s, it becomes difficult to mix with the component (A) and the handleability is poor.
- the viscosity can be measured by a rotational viscometer (eg, BL type, GH type, BS type, cone plate type, rheometer, etc.) (same below).
- Preferred examples of the compound (B) having one (meth)acrylic group in the molecule include those represented by the following general formula (7).
- R 4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group or a hydroxyl group, and some of the hydrogen atoms bonded to the carbon atoms are fluorine and R 5 is a hydrogen atom, a methyl group, a fluorine atom or a fluoroalkyl group having 1 to 6 carbon atoms.
- R 4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group or a hydroxyl group, and has 1 to 20 carbon atoms, preferably 1 to 10 alkyl groups, 6 to 20 carbon atoms, preferably 6 to 10 aryl groups, or 7 to 20 carbon atoms, preferably 7 to 10 aralkyl groups, which are branched or cyclic. or may contain an aliphatic unsaturated (double) bond, a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group.
- R 4 examples include methyl group, ethyl group, propyl group, butyl group, isobutyl group, hexyl group, cyclohexyl group, octyl group, 2-ethyl-hexyl group, isodecyl group, tridecyl group and isostearyl.
- R 4 some of the hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms.
- R 5 is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group, a trifluoropropyl group, a nonafluorobutyl group, A hydrogen atom, a methyl group, a fluorine atom and a trifluoromethyl group are particularly preferred.
- Such compounds represented by formula (7) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
- the compounds in which some of the hydrogen atoms bonded to the carbon atoms of R 4 are substituted with fluorine atoms include, specifically, ethyl 2-fluoro(meth)acrylate, phenyl 2-fluoro (meth) acrylate, 3-fluoropropyl (meth) acrylate, 2,2-difluoroethyl (meth) acrylate, methyl 3,3-difluoro (meth) acrylate, 2-fluoroethyl (meth) acrylate, methyl 2-fluoro ( meth)acrylate, 1H,1H-perfluorononyl (meth)acrylate, methyl 2,3,3-trifluoro(meth)acrylate, pentafluorobenzyl (meth)acrylate, pentafluorophenyl (meth)acrylate, tert-butyl 2 -fluoro (meth)acrylate, methyl 2-fluoro (meth)acrylate,
- methoxypolyethylene glycol (meth)acrylates such as acrylate compounds having repeating unit structures such as ethylene oxide, propylene oxide, tetramethylene oxide, and lactone and having various alkoxy terminals , phenoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, nonylphenol EO adduct acrylate, etc.
- (meth)acrylic compounds have a viscosity of 5,000 mPa s at 23°C. It can be used if:
- R 6 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group or a hydroxyl group, and some of the hydrogen atoms bonded to the carbon atoms are fluorine each R 7 is independently a hydrogen atom, a methyl group, a fluorine atom or a fluoroalkyl group having 1 to 6 carbon atoms.
- R 6 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group or a hydroxyl group, and has 1 to 20 carbon atoms, preferably 1 to 10 alkylene groups, 6 to 20 carbon atoms, preferably 6 to 10 arylene groups, or 7 to 20 carbon atoms, preferably 7 to 10 aralkylene groups. or may contain aliphatic unsaturated (double) bonds, urethane bonds, ether bonds, isocyanate groups, and hydroxyl groups.
- R6 examples include methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexylene group (hexamethylene group), cyclohexylene group, octamethylene group, nonamethylene group, decamethylene group, —CH 2 CH 2 —O—CH 2 CH 2 —, —C 3 H 6 —O—C 3 H 6 —, phenylene group, dicyclopentanylene group, di A cyclopentenylene group, a furfurylene group, a tetrahydrofurrylene group, a tetrahydropyranylene group and the like can be mentioned. Also, in R 6 , some of the hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms.
- Each R 7 is independently a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a trifluoropropyl group, or a fluoroalkyl group having 1 to 6 carbon atoms such as a nonafluorobutyl group, particularly a hydrogen atom. , a methyl group, a fluorine atom and a trifluoromethyl group are preferred.
- such compounds represented by formula (8) include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, dipropylene glycol di(meth) ) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, nonanediol di (Meth)acrylate, 10-decanediol di(meth)acrylate and the like can be mentioned.
- the component (B) contains a fluoroalkyl group and also contains one or two acrylic groups or ⁇ -substituted acrylic groups.
- the component (B) contains a fluoroalkyl group, the compatibility with the fluoropolyether group-containing acrylic compound of the component (A) is improved, and the transparency of the cured product is improved.
- the component (B) contains one or more perfluoroalkyl groups having 1 to 8 carbon atoms and one or two acrylic groups or ⁇ -substituted acrylic groups.
- Component (B) may be a single component or a mixture of a plurality of compounds that meet the above definition. In the case of a mixture, the total content of compounds corresponding to component (B) is calculated as the content of component (B). good.
- Compounds corresponding to component (B) can be synthesized by known methods as necessary, and various products are commercially available from reagent manufacturers and the like, and these can be used as they are.
- the content of component (B) is 0.1 to 300 parts by mass, preferably 1 to 100 parts by mass, per 100 parts by mass of component (A). If it is less than 0.1 parts by mass, it becomes difficult to adjust the viscosity of the fluorine-containing active energy ray-curable composition to a range that exhibits excellent handling properties, and if it exceeds 300 parts by mass, the fluorine-containing active energy ray-curable composition is It becomes difficult to develop the low refractive index property of
- the third essential component in the fluorine-containing active energy ray-curable composition of the present invention is (C) a photopolymerization initiator.
- the photopolymerization initiator of component (C) is not particularly limited as long as it can cure the acrylic compound by irradiation with active energy rays.
- Examples include acetophenone, benzophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxy ethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1-(4-morpholinophenyl)butanone-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]- 1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octane
- the photopolymerization initiator of component (C) does not contain a fluorine atom in its structure.
- Photopolymerization initiators that do not contain fluorine atoms in the structure are excellent in terms of availability, and by using various commercially available photopolymerization initiators, the absorption wavelength and curing of fluorine-containing active energy ray-curable compositions You can control the properties.
- component (C) is 0.01 to 20 parts by mass, preferably 0.1 to 6 parts by mass, per 100 parts by mass of component (A). If the amount added is less than this range, the curability will be lowered, and if the amount added is greater than this range, the physical properties after curing will be greatly affected.
- the fluorine-containing active energy ray-curable composition of the present invention is a volatile organic compound that does not have a group that reacts with an acrylic group (in particular, a non-reactive volatile organic compound that does not contain a (meth)acrylic group in the molecule). (or a volatile organic solvent)) (that is, a solvent-free fluorine-containing active energy ray-curable composition) is particularly preferred.
- an acrylic group in particular, a non-reactive volatile organic compound that does not contain a (meth)acrylic group in the molecule.
- a volatile organic solvent that is, a solvent-free fluorine-containing active energy ray-curable composition
- the fluorine-containing active-energy-ray-curable composition of the present invention also contains active-energy-ray-reactive compounds other than acrylic groups, such as thiol compounds and maleimide compounds, polymerization inhibitors, antistatic agents, antifoaming agents, and viscosity adjusters.
- active-energy-ray-reactive compounds other than acrylic groups such as thiol compounds and maleimide compounds, polymerization inhibitors, antistatic agents, antifoaming agents, and viscosity adjusters.
- Agents, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, fillers of polymers and inorganic substances, and the like can also be blended. These are not particularly limited in their structure, and known ones can be used as long as they do not impair the object of the present invention.
- the fluorine-containing active energy ray-curable composition of the present invention can be produced by a conventionally known method.
- components (A) to (C) and, if necessary, other components are blended in predetermined amounts, and mixed using a mixing means such as a mixer at a temperature of preferably 10° C. or higher and 70° C. or lower, preferably It can be produced by mixing for 0.1 hour or more and 5 hours or less.
- a mixing means such as a mixer at a temperature of preferably 10° C. or higher and 70° C. or lower, preferably It can be produced by mixing for 0.1 hour or more and 5 hours or less.
- the viscosity of the fluorine-containing active energy ray-curable composition of the present invention at 23° C. is 10 to 100,000 mPa ⁇ s, preferably 10 to 70,000 mPa ⁇ s, more preferably 10 to 40,000 mPa ⁇ s. is. With such a viscosity, a curable composition with good handleability (workability) can be obtained.
- the handleability (workability) referred to here means, for example, when the fluorine-containing active energy ray-curable composition of the present invention is handled, phenomena such as dripping and set-off due to low viscosity during operations such as coating. In other words, phenomena such as poor sortability and deterioration of leveling properties due to high viscosity hardly occur.
- the refractive index of the fluorine-containing active energy ray-curable composition of the present invention at a temperature of 25° C. and a wavelength of 589 nm is preferably 1.390 or less, more preferably 1.380 or less, and still more preferably 1.380 or less. 370 or less. When it has such a refractive index, it is possible to form a cured product with a low refractive index that is useful in optical component applications.
- the refractive index can be measured with a refractometer such as an Abbe refractometer. In the present invention, in order to set the refractive index to 1.390 or less under conditions of a temperature of 25° C.
- the fluoropolyether group-containing acrylic compound (A) is a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen It must have a divalent perfluoropolyether group with a number average molecular weight of 500 to 40,000 composed of atoms.
- the fluorine-containing active energy ray-curable composition of the present invention obtained as described above has an acrylic group or an ⁇ -substituted acrylic group as an active energy ray-curable group, it can be cured by an active energy ray such as an ultraviolet ray or an electron beam. Since it has a perfluoropolyether group as a curable group having a low refractive index and water vapor resistance, it is possible to form a transparent cured product having a low refractive index and excellent water vapor resistance.
- the present invention provides a cured product of the above fluorine-containing active energy ray-curable composition of the present invention.
- This cured product is obtained by irradiating the fluorine-containing active energy ray-curable composition of the present invention described above with light such as electron beams, ultraviolet rays, and visible light, and the light source is not particularly limited.
- Ultraviolet rays are particularly preferable as light
- mercury lamps, metal halide lamps, and LED lamps are preferable as ultraviolet light sources.
- the amount of light irradiation is preferably in the range of 10 to 10,000 mJ/cm 2 , particularly 100 to 4,000 mJ/cm 2 from the viewpoint of the properties of the cured product. If it is too small, uncured components will remain, and if it is too large, the cured product may deteriorate.
- the irradiation atmosphere is replaced with an inert gas that does not contain oxygen molecules, such as nitrogen, carbon dioxide, argon, etc., or the surface of the cured product is treated with a mold-releasing UV-transmitting agent.
- UV rays are irradiated from above, or if the substrate has UV transparency, the surface of the cured product is covered with a protective layer that has release properties and UV rays are applied from the side of the substrate. may be irradiated.
- the cured product and substrate are heated by any method such as infrared rays or a hot air drying oven before and during UV irradiation. good too.
- the cured product obtained by curing the fluorine-containing active energy ray-curable composition of the present invention exhibits a low refractive index and excellent water vapor resistance.
- the cured product preferably has a refractive index of 1.400 or less, more preferably 1.390 or less, and still more preferably 1.380 or less at a temperature of 25°C and a wavelength of 589 nm.
- the fluoropolyether group-containing acrylic compound in order to set the refractive index under the above conditions to 1.400 or less, is composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and has a number average molecular weight of 500 to 40. ,000 divalent perfluoropolyether groups.
- the cured product preferably has a hardness change value after heating for 12 hours at 95 ° C. and 100% RH within ⁇ 10 points of the initial value, more preferably within ⁇ 7 points of the initial value. preferable. If the change value is within ⁇ 10 points of the initial value, the water vapor resistance is excellent.
- the hardness can be measured according to JIS K6253.
- Rf 1 or Rf 2 which is a divalent perfluoropolyether group contained in component (A), is represented by the following formula A structure is preferred.
- each of these units may be linear or branched, and d, e , f, g, h, and i may be randomly combined.
- the present invention provides an article having a cured product of the fluorine-containing active energy ray-curable composition of the present invention described above in all or at least part of its structure.
- the use of the fluorine-containing active energy ray-curable composition of the present invention can impart low refractive index properties and water vapor resistance to articles.
- the fluorine-containing active energy ray-curable composition of the present invention can be suitably used for optical parts, and specifically can be used as an antireflection agent, an optical fiber coating agent, a lens, and the like.
- the coating method of the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, but examples include knife coating, roll coating, gravure coating, flow coating, dip coating, spray coating and spin coating. , bar coating, screen printing, and other known coating methods can be used.
- the coating film is irradiated with active energy rays to cure it.
- the active energy ray can be cured by irradiation with any light such as an electron beam, ultraviolet light, visible light, etc.
- the light source is not particularly limited.
- Halogen lamps, xenon lamps, LED lamps, fluorescent lamps, sunlight, electron beam irradiation devices and the like can be mentioned.
- Ultraviolet rays are particularly preferable as light, and mercury lamps, metal halide lamps, and LED lamps are preferable as ultraviolet light sources.
- the amount of light irradiation is preferably in the range of 10 to 10,000 mJ/cm 2 , particularly 100 to 4,000 mJ/cm 2 from the viewpoint of the properties of the cured product. If it is too small, uncured components will remain, and if it is too large, the cured product may deteriorate.
- the irradiation atmosphere is replaced with an inert gas that does not contain oxygen molecules, such as nitrogen, carbon dioxide, argon, etc., or the surface of the cured product is treated with a mold-releasing UV-transmitting agent.
- UV rays are irradiated from above, or if the substrate has UV transparency, the surface of the cured product is covered with a protective layer that has release properties and UV rays are applied from the side of the substrate. may be irradiated.
- the cured product and substrate are heated by any method such as infrared rays or a hot air drying oven before and during UV irradiation. good too.
- the number average molecular weight of the perfluoropolyether group is a value calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoropolyether group-containing acrylic compound based on 19 F-NMR analysis.
- the viscosity of component (B) is a value measured at 23°C according to JIS K7117.
- the fluoropolyether group-containing acrylic compounds (A-1) to (A-7) obtained in Synthesis Examples 1 to 7 above do not contain volatile organic compounds.
- fluorine-containing active energy ray-curable composition [Examples 1 to 15, Comparative Example 1]
- the fluoropolyether group-containing acrylic compounds (A-1) to (A-7) obtained in Synthesis Examples 1 to 7 above, the following acrylic compounds (B-1) to (B-5), and the following photopolymerization Using the initiators (C-1) and (C-2), fluorine-containing active energy ray-curable compositions (F-1) to (F-16) were prepared by blending them in the proportions shown in Table 1 below. bottom.
- Viscosity of Composition The viscosity of each fluorine-containing active energy ray-curable composition of Examples and Comparative Examples was measured at 23° C. in accordance with JIS K7117-1, Z8803. Table 2 shows the results.
- Hardness, tensile Strength, and Elongation at Break were measured according to JIS K6250, 6251, and 6253. bottom. The hardness was measured using a durometer A hardness tester. Table 3 shows the results.
- Examples 1 to 15 exhibited a low refractive index, small change in hardness, change in tensile strength, and change in elongation at break after the water vapor resistance test, confirming excellent water vapor resistance.
- Comparative Example 1 the acrylic compound (B) containing one or two acrylic groups or ⁇ -substituted acrylic groups in one molecule was not blended, and the fluoropolyether group-containing acrylic compound as the component (A) was used.
- a fluorine-containing active energy ray-curable composition (F-16) was prepared by blending only the photopolymerization initiator (C). In Comparative Example 1, the viscosity of the composition was remarkably high and the handleability was poor.
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Abstract
Description
(A)下記一般式(1)で表されるフルオロポリエーテル基含有アクリル化合物 100質量部、
V1-Rf1-Z-Y(X)b (1)
(式中、Rf1は炭素数1~6のパーフルオロアルキレン基と酸素原子によって構成される数平均分子量500~40,000の2価のパーフルオロポリエーテル基である。Zは2価の有機基であり、途中環状構造を含んでいてもよい。Yは炭素数1~20の(b+1)価の有機基である。Xは独立にアクリル基又はα置換アクリル基を含有する1価の有機基であり、かつ1分子中に平均して少なくとも1個の前記アクリル基もしくはα置換アクリル基を含有する。V1は水素原子、フッ素原子、又は-Z-Y(X)bで表される1価の基である。bは1~10の整数である。)
(B)23℃における粘度が5,000mPa・s以下であり、1分子中にアクリル基又はα置換アクリル基を1個又は2個含有するアクリル化合物(但し、(A)成分を除く) 0.1~300質量部、及び
(C)光重合開始剤 0.01~20質量部
を必須成分として含有し、23℃における粘度が10~100,000mPa・sの範囲であり、温度25℃、波長589nmの条件における屈折率が1.390以下である含フッ素活性エネルギー線硬化性組成物が、紫外線や電子線等の活性エネルギー線により硬化可能であり、低い屈折率及び優れた耐水蒸気性を有する透明な硬化物を形成可能であり、かつハンドリング性に優れた含フッ素活性エネルギー線硬化性組成物となり得ることを見出し、本発明をなすに至った。
[1]
(A)下記一般式(1)で表されるフルオロポリエーテル基含有アクリル化合物 100質量部、
V1-Rf1-Z-Y(X)b (1)
(式中、Rf1は炭素数1~6のパーフルオロアルキレン基と酸素原子によって構成される数平均分子量500~40,000の2価のパーフルオロポリエーテル基である。Zは2価の有機基であり、途中環状構造を含んでいてもよい。Yは炭素数1~20の(b+1)価の有機基である。Xは独立にアクリル基又はα置換アクリル基を含有する1価の有機基であり、かつ1分子中に平均して少なくとも1個の前記アクリル基もしくはα置換アクリル基を含有する。V1は水素原子、フッ素原子、又は-Z-Y(X)bで表される1価の基である。bは1~10の整数である。)
(B)23℃における粘度が5,000mPa・s以下であり、1分子中にアクリル基又はα置換アクリル基を1個又は2個含有するアクリル化合物(但し、(A)成分を除く) 0.1~300質量部、及び
(C)光重合開始剤 0.01~20質量部
を必須成分として含有し、23℃における粘度が10~100,000mPa・sの範囲であり、温度25℃、波長589nmの条件における屈折率が1.390以下である含フッ素活性エネルギー線硬化性組成物。
[2]
アクリル基と反応する基を持たない揮発性有機化合物が配合されていないものである[1]に記載の含フッ素活性エネルギー線硬化性組成物。
[3]
一般式(1)において、Rf1が下記式
で表される2価のパーフルオロポリエーテル基である[1]又は[2]に記載の含フッ素活性エネルギー線硬化性組成物。
[4]
(A)成分が、下記一般式(2)で表されるフルオロポリエーテル基含有アクリル化合物である[1]~[3]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
V2-Rf2-C(=O)-NR1 a[Y2(X2)b’]2-a (2)
(式中、Rf2は炭素数1~6のパーフルオロアルキレン基と酸素原子によって構成される数平均分子量500~40,000の2価のパーフルオロポリエーテル基である。Y2は独立に炭素数1~20の(b’+1)価の有機基である。X2は独立にアクリル基又はα置換アクリル基を含有する1価の有機基であり、かつ1分子中に平均して少なくとも1個の前記アクリル基もしくはα置換アクリル基を含有する。R1は水素原子又は炭素数1~8の1価の炭化水素基である。V2は水素原子、フッ素原子、又は-C(=O)-NR1 a[Y2(X2)b’]2-aで表される1価の基である。aは0又は1である。b’は1~10の整数である。)
[5]
一般式(2)において、Rf2が下記式
で表される2価のパーフルオロポリエーテル基である[4]に記載の含フッ素活性エネルギー線硬化性組成物。
[6]
一般式(2)において、Rf2が下記構造式
-CF2CF2O-(CF2CF2CF2O)q-CF2CF2-
(式中、qは4~200の整数である。)
で表される2価のパーフルオロポリエーテル基から選ばれるものである[4]又は[5]に記載の含フッ素活性エネルギー線硬化性組成物。
[7]
一般式(2)において、R1が水素原子であり、aが1である[4]~[6]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
[8]
一般式(2)において、Y2が下記のいずれかで表されるものである[4]~[7]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
[9]
一般式(2)において、X2が下記構造式
で表されるものである[4]~[8]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
[10]
一般式(2)において、X2が下記のいずれかで表されるものである[4]~[9]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
(A)成分が、下記式のいずれかで表されるフルオロポリエーテル基含有アクリル化合物である[4]~[10]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
[12]
(B)成分が、フルオロアルキル基を含有し、かつアクリル基又はα置換アクリル基を1個又は2個含有するものである[1]~[11]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
[13]
(B)成分が、下記式のいずれかで表されるアクリル化合物である[1]~[12]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
(B)成分が、炭素数1~8のパーフルオロアルキル基を1個以上含有し、かつアクリル基又はα置換アクリル基を1個又は2個含有するものである[1]~[13]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
[15]
(B)成分が、下記式のいずれかで表されるアクリル化合物である[1]~[14]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
(C)成分の光重合開始剤が、構造中にフッ素原子を含有しないものである[1]~[15]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
[17]
反射防止剤用又は光ファイバーのコーティング剤用である[1]~[16]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物。
[18]
[1]~[17]のいずれかに記載の含フッ素活性エネルギー線硬化性組成物を硬化してなる硬化物。
[19]
温度25℃、波長589nmの条件における屈折率が1.400以下である[18]に記載の硬化物。
[20]
95℃、100%RH条件で12時間加熱した後の硬さの変化値が初期値±10ポイント以内である[18]又は[19]に記載の硬化物。
[21]
[18]~[20]のいずれかに記載の硬化物が、構成の全て又は少なくともその構成の一部であることを特徴とする物品。
[22]
光学部品である[21]に記載の物品。
[23]
レンズ、反射防止膜及び光ファイバーのいずれかである[21]又は[22]に記載の物品。
(A)下記一般式(1)で表されるフルオロポリエーテル基含有アクリル化合物 100質量部、
V1-Rf1-Z-Y(X)b (1)
(式中、Rf1は炭素数1~6のパーフルオロアルキレン基と酸素原子によって構成される数平均分子量500~40,000の2価のパーフルオロポリエーテル基である。Zは2価の有機基であり、途中環状構造を含んでいてもよい。Yは炭素数1~20の(b+1)価の有機基である。Xは独立にアクリル基又はα置換アクリル基を含有する1価の有機基であり、かつ1分子中に平均して少なくとも1個の前記アクリル基もしくはα置換アクリル基を含有する。V1は水素原子、フッ素原子、又は-Z-Y(X)bで表される1価の基である。bは1~10の整数である。)
(B)23℃における粘度が5,000mPa・s以下であり、1分子中にアクリル基又はα置換アクリル基を1個又は2個含有するアクリル化合物(但し、(A)成分を除く) 0.1~300質量部、及び
(C)光重合開始剤 0.01~20質量部
を必須成分として含有し、23℃における粘度が10~100,000mPa・sの範囲であり、温度25℃、波長589nmの条件における屈折率が1.390以下であることを特徴とする。
V1-Rf1-Z-Y(X)b (1)
なお、本発明において「アクリル化合物」とは、アクリル基、α置換アクリル基を有する化合物の総称であり、各種重合体の側鎖や末端に任意の方法で2個以上のアクリル基、α置換アクリル基を導入した化合物も含む。また本発明において「(メタ)アクリレート」とは、アクリレートとメタクリレートの一方又は両方を示し、「(メタ)アクリル基」とは、アクリル基とメタクリル基の一方又は両方を示し、「(メタ)アクリル酸」とは、アクリル酸とメタクリル酸の一方又は両方を示す。
-CF2O-
-CF2CF2O-
-CF(CF3)CF2O-
-CF2CF2CF2O-
これらの構造は、いずれか一つの単独重合体、あるいは複数の構造からなるランダム、ブロック重合体でもよい。
また、d、e、f、g、h、iはそれぞれ0~200の整数、好ましくは、dは0~100の整数、eは5~100の整数、fは5~100の整数、gは0~100の整数、hは0~100の整数、iは0~100の整数であり、d+e+f+g+h+i=4~200であり、好ましくは10~150であり、より好ましくは30~150である。
上記式において、各単位は直鎖状であっても分岐状であってもよい。また、d、e、f、g、h、iが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。
V1が-Z-Y(X)bで表される1価の基である場合、1分子中に平均して少なくとも2個以上のアクリル基もしくはα置換アクリル基を含有するため、該組成物は網目状のネットワークを形成し、力学特性に優れる硬化物が得られる。なお、V1が-Z-Y(X)bで表される1価の基である場合、式(1)中に存在する複数のZ、Y、X、bはそれぞれ同一であっても異なっていてもよい。
V2-Rf2-C(=O)-NR1 a[Y2(X2)b’]2-a (2)
-CF2O-
-CF2CF2O-
-CF(CF3)CF2O-
-CF2CF2CF2O-
これらの構造は、いずれか一つの単独重合体、あるいは複数の構造からなるランダム、ブロック重合体でもよい。
また、d、e、f、g、h、iはそれぞれ0~200の整数、好ましくは、dは0~100の整数、eは5~100の整数、fは5~100の整数、gは0~100の整数、hは0~100の整数、iは0~100の整数であり、d+e+f+g+h+i=4~200であり、好ましくは10~150であり、より好ましくは30~150である。
上記式において、各単位は直鎖状であっても分岐状であってもよい。また、d、e、f、g、h、iが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。
-CF2CF2O-(CF2CF2CF2O)q-CF2CF2-
(式中、qは4~200、好ましくは10~150の整数である。)
V2が-C(=O)-NR1 a[Y2(X2)b’]2-aで表される1価の基である場合、1分子中に平均して少なくとも2個以上のアクリル基もしくはα置換アクリル基を含有するため、該化合物を用いた組成物は網目状のネットワークを形成し、力学特性に優れる硬化物が得られる。なお、V2が-C(=O)-NR1 a[Y2(X2)b’]2-aで表される1価の基である場合、式(2)中に存在する複数のR1、Y2、X2、b’、aはそれぞれ同一であっても異なっていてもよい。
上記式(2)において、b’は1~10の整数であり、好ましくは1又は2である。
Rf2[C(=O)-NR1 a[Y2(X2)b’]2-a]2 (3)
(式中、Rf2、R1、Y2、X2、a、b’は上記と同じである。)
で表されるフルオロポリエーテル基含有アクリル化合物の好適な合成方法としては、例えば、先ず下記一般式(4)
Rf2[C(=O)-X3]2 (4)
(式中、Rf2は上記と同じであり、X3はハロゲン原子又は非置換もしくはフッ素置換アルコキシ基である。)
で表される分子鎖末端に酸ハライド又はエステルを有するフルオロポリエーテル基含有化合物に、下記一般式(5)
H-NR1 a[Y2[OH]b’]2-a (5)
(式中、R1、Y2、a、b’は上記と同じである。)
で表されるアミノアルコール化合物をアミド化反応させることにより、中間体であるフルオロポリエーテル基含有アルコール化合物を得る。
Rf2[C(=O)-Cl]2
Rf2[C(=O)-F]2
Rf2[C(=O)-O-CH3]2
Rf2[C(=O)-O-C2H5]2
Rf2[C(=O)-O-C3H7]2
Rf2[C(=O)-O-C4H9]2
Rf2[C(=O)-O-C5H11]2
Rf2[C(=O)-O-C6H13]2
Rf2[C(=O)-O-CF3]2
Rf2[C(=O)-O-C2F5]2
Rf2[C(=O)-O-CH(CF3)2]2
(式中、Rf2は上記と同じである。)
溶剤を使用する場合、その使用量は、式(4)で表される分子鎖末端に酸ハライド又はエステルを有するフルオロポリエーテル基含有化合物100質量部に対して、好ましくは5~2,000質量部であり、より好ましくは50~500質量部である。これより少なければ溶剤による希釈の効果が薄くなり、多ければ希釈度が高くなりすぎて反応速度の低下を招く場合がある。
Rf2[C(=O)-NR1 a[Y2[OH]b’]2-a]2 (6)
(式中、Rf2、R1、Y2、a、b’は上記と同じである。)
溶剤の使用量は特に限定されないが、反応成分の全合計質量に対して10倍以下が好ましい。溶剤の使用量が多すぎると、反応速度が大幅に低下する場合がある。
重合禁止剤の使用量は反応条件、反応後の精製条件、最終的な使用条件から決定すればよく、特に制限はされないが、通常、反応成分の全合計質量に対して0.01~5,000ppm、特に好ましくは0.1~500ppmである。
これらの触媒を反応成分の全合計質量に対して、0.01~2質量%、好ましくは0.05~1質量%加えることにより、反応速度を増加させることができる。
受酸剤の使用量は、(メタ)アクリル酸ハライドのモル数に対して0.9~3倍程度が望ましい。少なすぎるとトラップされない酸が多く残存することになり、多すぎると余剰となる受酸剤の除去が困難になる。
溶剤の使用量は特に限定されないが、反応成分の全合計質量に対して10倍以下が好ましい。溶剤の使用量が多すぎると、反応速度が大幅に低下する場合がある。
CH2=C(R5)C(=O)OR4 (7)
(式中、R4はウレタン結合、エーテル結合、イソシアネート基又は水酸基を含んでいてもよい炭素数1~20の1価の炭化水素基であり、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。R5は水素原子、メチル基、フッ素原子又は炭素数1~6のフルオロアルキル基である。)
また、R4は炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。
CH2=C(R7)C(=O)O-R6-O(O=)C(R7)C=CH2 (8)
(式中、R6はウレタン結合、エーテル結合、イソシアネート基又は水酸基を含んでいてもよい炭素数1~20の2価の炭化水素基であり、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。R7はそれぞれ独立に水素原子、メチル基、フッ素原子又は炭素数1~6のフルオロアルキル基である。)
また、R6は炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。
(C)成分の光重合開始剤は、活性エネルギー線照射によりアクリル化合物を硬化させることができるものであれば特に限定されないが、例えば、アセトフェノン、ベンゾフェノン、2-ヒドロキシ-2-メチルプロピオフェノン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)ブタノン-1-オン、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、1,2-オクタンジオン-1-[4-(フェニルチオ)-2-(o-ベンゾイルオキシム)]、エタノン-1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-1-(O-アセチルオキシム)、2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチルプロピオニル)ベンジル]フェニル}-2-メチルプロパン-1-オン等が挙げられ、1種単独でも2種以上を併用してもよい。これらの中でも、光硬化性に優れるという観点から、アルキルフェノン系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤が好ましい。
[合成例1]フルオロポリエーテル基含有アクリル化合物(A-1)の合成
乾燥窒素雰囲気下で、反応容器に、平均構造が下記式
で表される化合物(I)100g(0.025モル)、下記式
乾燥窒素雰囲気下で、反応容器に、平均構造が下記式
で表される化合物(III)100g(0.017モル)、下記式
乾燥空気雰囲気下、反応容器中で、合成例2と同様にして得られたフルオロポリエーテル基含有アルコール化合物(IV)50.0g(水酸基量0.017モル)に、THF50.0gと、メタクリロイルオキシエチルイソシアネート2.6g(0.017モル)を混合し、50℃に加熱した。そこにカルボン酸ビスマス触媒(楠本化成製XK-640)0.15gを添加し、50℃下24時間攪拌した。加熱終了後、減圧留去を行い、液状高粘調物質48.3gを得た。1H-NMR及びIRの結果から下記式で示されるフルオロポリエーテル基含有アクリル化合物(A-3)であることを確認した。
乾燥空気雰囲気下、反応容器中で、合成例2と同様にして得られたフルオロポリエーテル基含有アルコール化合物(IV)50.0g(水酸基量0.017モル)に、THF50.0gと、1,1-(ビスアクリロイルオキシメチル)エチルイソシアネート4.1g(0.017モル)を混合し、50℃に加熱した。そこにカルボン酸ビスマス触媒(楠本化成製XK-640)0.15gを添加し、50℃下24時間攪拌した。加熱終了後、減圧留去を行い、液状高粘調物質37.3gを得た。1H-NMR及びIRの結果から下記式で示されるフルオロポリエーテル基含有アクリル化合物(A-4)であることを確認した。
乾燥窒素雰囲気下で、反応容器に、平均構造が下記式
で表される化合物(V)100g(0.0063モル)、下記式
乾燥窒素雰囲気下で、反応容器に、平均構造が下記式
で表される化合物(III)100g(0.017モル)、下記式
乾燥窒素雰囲気下で、反応容器に、平均構造が下記式
で表される化合物(VIII)100g(0.027モル)、下記式
[実施例1~15、比較例1]
上記合成例1~7で得られたフルオロポリエーテル基含有アクリル化合物(A-1)~(A-7)、以下のアクリル化合物(B-1)~(B-5)、及び以下の光重合開始剤(C-1)及び(C-2)を用いて、各々、下記表1に示す割合で配合した含フッ素活性エネルギー線硬化性組成物(F-1)~(F-16)を調製した。
(B-2)2-ヒドロキシエチルメタクリレート(粘度:6.1mPa・s)
(B-3)1,6-ヘキサンジオールジアクリレート(粘度:6.5mPa・s)
(B-4)2-(パーフルオロヘキシル)エチルメタクリレート(粘度:3.3mPa・s)
(B-5)1H,1H,5H-オクタフルオロペンチルメタクリレート(粘度:4.1mPa・s)
(C-2)2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド
実施例及び比較例の各含フッ素活性エネルギー線硬化性組成物の外観を目視観察により下記基準で評価した。結果を表2に示す。
○(良) :均一である。
×(不良):不均一である。
実施例及び比較例の各含フッ素活性エネルギー線硬化性組成物の粘度は、23℃条件においてJIS K7117-1、Z8803に準拠して測定した。結果を表2に示す。
実施例及び比較例の各含フッ素活性エネルギー線硬化性組成物の屈折率は、アッベ屈折計(アタゴ社製:DR-A1)を用い、温度:25℃、波長:589nmにおいて測定した。結果を表2に示す。
実施例及び比較例の各含フッ素活性エネルギー線硬化性組成物をガラス上にナイフコートした(スペーサー厚2.0mm)。真空脱泡を行った後、コンベヤ式UV-LED照射装置(アイグラフィックス製、波長365nm)を使用し、窒素雰囲気中で、ピーク強度490mW/cm2、積算照射量1,000mJ/cm2の紫外線を塗工面及びガラス面から計2回照射して組成物を硬化させ、厚み約2mmの硬化物を得た。
上記で作製した実施例及び比較例の硬化物の屈折率は、アッベ屈折計(アタゴ社製:DR-A1)を用い、温度:25℃、波長:589nmにおいて測定した。結果を表3に示す。
上記で作製した実施例及び比較例の硬化物の硬さ、引張強さ、切断時伸びは、JIS K6250、6251、6253に準じて測定した。なお、硬さは、デュロメーターA硬度計を用いて測定した。結果を表3に示す。
上記で作製した実施例及び比較例の硬化物を空気雰囲気下95℃、100%RHで12時間加熱した。試験後の硬化物について硬さ、引張強さ、切断時伸びを測定した。これらの結果を表3に示す。
一方、比較例1では、1分子中にアクリル基又はα置換アクリル基を1個又は2個含有するアクリル化合物(B)を配合せず、(A)成分であるフルオロポリエーテル基含有アクリル化合物と光重合開始剤(C)のみを配合することにより含フッ素活性エネルギー線硬化性組成物(F-16)を調製した。比較例1は、組成物の粘度が著しく高く、ハンドリング性に劣っていた。
Claims (23)
- (A)下記一般式(1)で表されるフルオロポリエーテル基含有アクリル化合物 100質量部、
V1-Rf1-Z-Y(X)b (1)
(式中、Rf1は炭素数1~6のパーフルオロアルキレン基と酸素原子によって構成される数平均分子量500~40,000の2価のパーフルオロポリエーテル基である。Zは2価の有機基であり、途中環状構造を含んでいてもよい。Yは炭素数1~20の(b+1)価の有機基である。Xは独立にアクリル基又はα置換アクリル基を含有する1価の有機基であり、かつ1分子中に平均して少なくとも1個の前記アクリル基もしくはα置換アクリル基を含有する。V1は水素原子、フッ素原子、又は-Z-Y(X)bで表される1価の基である。bは1~10の整数である。)
(B)23℃における粘度が5,000mPa・s以下であり、1分子中にアクリル基又はα置換アクリル基を1個又は2個含有するアクリル化合物(但し、(A)成分を除く) 0.1~300質量部、及び
(C)光重合開始剤 0.01~20質量部
を必須成分として含有し、23℃における粘度が10~100,000mPa・sの範囲であり、温度25℃、波長589nmの条件における屈折率が1.390以下である含フッ素活性エネルギー線硬化性組成物。 - アクリル基と反応する基を持たない揮発性有機化合物が配合されていないものである請求項1に記載の含フッ素活性エネルギー線硬化性組成物。
- (A)成分が、下記一般式(2)で表されるフルオロポリエーテル基含有アクリル化合物である請求項1~3のいずれか1項に記載の含フッ素活性エネルギー線硬化性組成物。
V2-Rf2-C(=O)-NR1 a[Y2(X2)b’]2-a (2)
(式中、Rf2は炭素数1~6のパーフルオロアルキレン基と酸素原子によって構成される数平均分子量500~40,000の2価のパーフルオロポリエーテル基である。Y2は独立に炭素数1~20の(b’+1)価の有機基である。X2は独立にアクリル基又はα置換アクリル基を含有する1価の有機基であり、かつ1分子中に平均して少なくとも1個の前記アクリル基もしくはα置換アクリル基を含有する。R1は水素原子又は炭素数1~8の1価の炭化水素基である。V2は水素原子、フッ素原子、又は-C(=O)-NR1 a[Y2(X2)b’]2-aで表される1価の基である。aは0又は1である。b’は1~10の整数である。) - 一般式(2)において、R1が水素原子であり、aが1である請求項4~6のいずれか1項に記載の含フッ素活性エネルギー線硬化性組成物。
- (B)成分が、フルオロアルキル基を含有し、かつアクリル基又はα置換アクリル基を1個又は2個含有するものである請求項1~11のいずれか1項に記載の含フッ素活性エネルギー線硬化性組成物。
- (B)成分が、炭素数1~8のパーフルオロアルキル基を1個以上含有し、かつアクリル基又はα置換アクリル基を1個又は2個含有するものである請求項1~13のいずれか1項に記載の含フッ素活性エネルギー線硬化性組成物。
- (C)成分の光重合開始剤が、構造中にフッ素原子を含有しないものである請求項1~15のいずれか1項に記載の含フッ素活性エネルギー線硬化性組成物。
- 反射防止剤用又は光ファイバーのコーティング剤用である請求項1~16のいずれか1項に記載の含フッ素活性エネルギー線硬化性組成物。
- 請求項1~17のいずれか1項に記載の含フッ素活性エネルギー線硬化性組成物を硬化してなる硬化物。
- 温度25℃、波長589nmの条件における屈折率が1.400以下である請求項18に記載の硬化物。
- 95℃、100%RH条件で12時間加熱した後の硬さの変化値が初期値±10ポイント以内である請求項18又は19に記載の硬化物。
- 請求項18~20のいずれか1項に記載の硬化物が、構成の全て又は少なくともその構成の一部であることを特徴とする物品。
- 光学部品である請求項21に記載の物品。
- レンズ、反射防止膜及び光ファイバーのいずれかである請求項21又は22に記載の物品。
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TW202334277A (zh) | 2023-09-01 |
JPWO2023112714A1 (ja) | 2023-06-22 |
CN118369362A (zh) | 2024-07-19 |
KR20240121289A (ko) | 2024-08-08 |
IL313421A (en) | 2024-08-01 |
EP4450528A1 (en) | 2024-10-23 |
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