Classifications

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  • 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
  • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
  • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
  • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
• • 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
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
  • C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
  • C08G65/3326—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic aromatic
• • 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
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
• • 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 relates to a fluoropolyether group-containing compound with excellent storage stability that can be crosslinked and cured by light irradiation, a photocrosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound, and a photocrosslinked product thereof. , an article having the photocrosslinked product, and a method for photocrosslinking the composition.
• fluorine compounds that can be cured by light irradiation such as ultraviolet rays
• polymerizable monomers having a perfluoroalkyl group in the side chain such as polymers containing fluorine-containing alkyl acrylic acid esters and fluorine-containing alkyl methacrylic acid esters
• fluorine-containing acrylic compounds are suitable for applications that take advantage of their excellent curing properties by ultraviolet irradiation and the water repellency, oil repellency, chemical resistance, solvent resistance, stain resistance, high transparency, and low refractive index of fluorine. Applications are being widely attempted.
• JP-A-6-136062 (Patent Document 1) describes the application of acrylic compounds containing fluorine in their side chains to anti-reflection coatings, and JP-A-5-32749 (Patent Document 2) , has been shown to be used as a coating for optical fibers.
• these fluorine-containing acrylic compounds can be used to increase the fluorine content for purposes such as improving water repellency, oil repellency, chemical resistance, stain resistance, and solvent resistance, and further lowering the refractive index.
• the solubility in non-fluorinated organic compounds decreases, and it becomes insoluble in general photopolymerization initiators, resulting in the inability to obtain a transparent cured product, or increased crystallinity and loss of transparency. There was a problem.
• Patent Document 3 Japanese Patent Laid-Open No. 2006-233172
• a fluorine acrylic compound Although these compounds can form a transparent cured product with a low refractive index, on the other hand, a photoinitiator modified with a perfluoropolyether group must be separately synthesized in a composition containing these compounds. I had to.
• the crosslinked structure of these compounds is a chain polymerization of acrylic groups, the crosslinked portion tends to become dense, making them suitable for applications that require hardness, but for example, gel-like crosslinked products that require flexibility. was difficult to obtain.
• a polymerization initiator causes chemical bond cleavage to generate a low-molecular component when it exhibits its function. Therefore, the low molecular weight components generated after curing can cause problems such as a decrease in the transparency of the cured product when used in optical components, and the generation of volatile components when used in electronic components.
• acrylic compounds are unstable not only to light but also to heat, so a polymerization inhibitor is required to obtain practical storage stability.
• Most of these polymerization inhibitors are non-fluorine compounds and have the same problem of solubility in fluorine compounds as polymerization initiators.
• due to its mechanism of action there are many products whose use has been restricted in recent years due to their toxicity to living organisms, such as the widely used 2,6-di-tert-butyl-p-cresol, and their release into the environment. are also being restricted.
• Japanese Patent Application Publication No. 6-136062 Japanese Patent Application Publication No. 5-32749 Japanese Patent Application Publication No. 2006-233172 JP2013-237824A Japanese Patent Application Publication No. 2015-189843 JP 2017-190429 Publication Japanese Patent Application Publication No. 2021-175782
• the present invention was developed in view of the above circumstances, and essentially does not require the addition of photopolymerization initiators or polymerization inhibitors, has excellent storage stability, and can form transparent crosslinked products (cured products) by light irradiation.
• a fluoropolyether group-containing compound a photocrosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound, a photocrosslinked product thereof, an article having the photocrosslinked product, and a method for photocrosslinking the composition.
• the purpose is to
• the present invention provides the following fluoropolyether group-containing compound, a photocrosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound, a photocrosslinked product thereof, an article having the photocrosslinked product, and the composition.
• the present invention provides a photocrosslinking method.
• the following general formula (1) is attached to one or both ends of a linear perfluoropolyether group having a number average molecular weight of 1,000 to 40,000 via a linking group.
• R is a phenyl group, which may have one or two same or different substituents.
• a fluoropolyether group-containing compound having a total of 1 to 20 monovalent groups shown in the molecule.
• V is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine, or a monovalent group represented by -Y[Q(R 1 -X) b ] c
• Rf is a divalent linear perfluoropolyether group having a number average molecular weight of 1,000 to 40,000 and composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom.
• Y is independently A c+1 valent organic group having 1 to 20 carbon atoms which may contain a single bond or an oxygen atom, nitrogen atom, fluorine atom or silicon atom.Q is independently a single bond or C, O, H, N , Si, S, F, Cl and Br, and may have a
• R 1 is independently a single bond, or A divalent organic group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom.
• X is independently a monovalent group represented by the above general formula (1) or a hydroxyl group, 1 to 20 X in the molecule are monovalent groups represented by the above general formula (1).
• b is independently an integer of 1 to 9, and c is independently an integer of 1 to 3.
• the linear perfluoropolyether group has the following general formula (In the formula, n is an integer from 1 to 6 independently for each unit.
• d, e, f, g, h, and i are each an integer from 0 to 200, and d+e+f+g+h+i is an integer from 4 to 200.
• Each unit may be linear or branched, and the repeating units shown in parentheses with d, e, f, g, h, and i are randomly bonded.
• n is an integer of 1 to 6 independently for each unit, d1, e1, f1, and f2 are each an integer of 1 or more, and the total of d1, e1, f1, and f2 is an integer of 4 to 200, respectively.
• eg1 is an integer from 2 to 99
• f3 is an integer from 4 to 200.
• j is an integer from 1 to 6
• C j F 2j O may be linear or branched, but when j is 3, it is linear.
• k is (Integers from 0 to 6, f4 and f5 are each integers from 1 to 100, f4+f5 is an integer from 2 to 200, k+f4+f5 is an integer from 4 to 200.
• the connecting group that connects the monovalent group represented by the above general formula (1) and the fluoropolyether group is a divalent to hexavalent group containing a cyclic structure, according to any one of [1] to [4]. Fluoropolyether group-containing compound.
• the fluoropolyether according to any one of [1] to [5], wherein the connecting group that connects the monovalent group represented by the above general formula (1) and the fluoropolyether group includes one of the following structures: Group-containing compounds.
• Ph is a phenylene group.
• a photocrosslinkable fluoropolyether composition comprising the fluoropolyether group-containing compound according to any one of [1] to [10].
• the photocrosslinkable fluoropolyether composition according to [11] which is diluted with a fluorinated solvent containing 0.001 to 99% by mass of a fluoropolyether group-containing compound.
• [16] A photocrosslinked product of the photocrosslinkable fluoropolyether composition according to any one of [11] to [15].
• [17] An article having the photocrosslinked product according to [16].
• [18] The article according to [17], wherein the photocrosslinked product is in the form of a film.
• [11] A method for photocrosslinking a photocrosslinkable fluoropolyether composition, comprising the step of irradiating the photocrosslinkable fluoropolyether composition according to any one of [15] with light containing ultraviolet light having a wavelength of 250 to 350 nm.
• the photocrosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound of the present invention is not crosslinked by heating, so it is thermally stable, has excellent long-term storage stability, and has photopolymerization initiators and polymerization inhibitors. Since it is not necessary to incorporate , a transparent photocrosslinked structure can be formed without containing a non-fluorine compound and without generating low-molecular volatile matter. Therefore, the photocrosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound of the present invention can be used as a coating agent for various optical components, a nanoimprint material, a potting agent for electronic components and various sensors, a photocurable 3D printer output material, etc. Useful.
• the fluoropolyether group-containing compound of the present invention has the following general formula (1) attached to one or both ends of a linear perfluoropolyether group having a number average molecular weight of 1,000 to 40,000 via a linking group.
• R is a phenyl group, and may have one or two same or different substituents.
• It is a fluoropolyether group-containing compound having a total of 1 to 20, preferably 1 to 12, more preferably 1 to 8 monovalent groups in the molecule.
• the monovalent groups represented by formula (1) may be different even if they are the same. It may be something.
• R is a phenyl group, and may have one or two same or different substituents on the phenyl group.
• Substituents on the phenyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, An alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as a 2-ethylhexyl group, nonyl group, or decyl group, and a part or all of the hydrogen atoms of the above alkyl group.
• Halogen-substituted alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as trifluoromethyl groups substituted with halogen atoms such as fluorine, methoxy groups, ethoxy groups, propoxy groups , isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, hexadecyloxy group, octadecyloxy group, etc.
• phenyl groups having 1 to 20 carbon atoms, preferably 1 to 16 carbon atoms, more preferably carbon number 1 to 4 alkoxy groups, thioalkoxy groups having 1 to 20 carbon atoms, preferably 1 to 16 carbon atoms, more preferably 1 to 4 carbon atoms, phenyl groups, hydroxyl groups in which the oxygen atom of the above alkoxy group is replaced with a sulfur atom , an amino group, a nitro group, a nitrile group, and halogen atoms such as fluorine, chlorine, bromine, and iodine.
• R an unsubstituted phenyl group is particularly preferred.
• the monovalent group represented by formula (1) is preferably a cinnamic acid residue represented by the following structural formula.
• fluoropolyether group-containing compound having a monovalent group represented by formula (1) of the present invention include fluoropolyether group-containing compounds represented by the following general formula (2).
• V-Rf-Y[Q(R 1 -X) b ] c (2) (In the formula, V is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with fluorine, or a monovalent group represented by -Y[Q(R 1 -X) b ] c )
• Rf is a divalent linear perfluoropolyether group having a number average molecular weight of 1,000 to 40,000 and composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom.
• Y is independently A c+1 valent organic group having 1 to 20 carbon atoms which may contain a single bond or an oxygen atom, nitrogen atom, fluorine atom or silicon atom.Q is independently a single bond or
• R 1 is independently a single bond, or A divalent organic group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom.
• X is independently a monovalent group represented by the above general formula (1) or a hydroxyl group, 1 to 20, preferably 1 to 12, more preferably 1 to 8 X in the molecule are monovalent groups represented by the above general formula (1).
• b is independently an integer of 1 to 9
• c is independently an integer from 1 to 3.
• V is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms in which all or some of the hydrogen atoms may be substituted with a fluorine atom, or -Y[Q(R 1 -X) b ] is a monovalent group represented by c .
• examples of the alkyl group having 1 to 6 carbon atoms in which all or some of the hydrogen atoms may be substituted with fluorine atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, difluoromethyl group (CF 2 H-), trifluoromethyl group (CF 3 -), 2,2,2-trifluoroethyl group (CF 3 CH 2 -), 1,1,2,2,2-pentafluoroethyl group (CF 3 CF 2 -), 3,3,3-trifluoropropyl group (CF 3 CH 2 CH 2 -), 1,1, 2,2,3,3,3-heptafluoropropyl group (CF 3 CF 2 CF 2 -), heptafluoroisopropyl group ((CF 3 ) 2 CF-), 1,1,2,2,3,3, Examples
• Rf is a divalent linear perfluoropolyether group having a number average molecular weight of 1,000 to 40,000 and composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom.
• a perfluorooxyalkylene structure having 1 to 6 carbon atoms particularly those having the following perfluorooxyalkylene structure having 1 to 4 carbon atoms as a main repeating unit are preferred.
• These structures may be any one homopolymer, or a random copolymer or block copolymer consisting of a plurality of structures, or an alternating copolymer with a certain arrangement rule.
• Rf having such a structure examples include the following structure.
• n is an integer of 1 to 6, preferably 1 to 4, independently for each unit.
• d, e, f, g, h, and i are each an integer of 0 to 200, preferably, d is an integer of 0 to 100, particularly an integer of 1 to 50, and e is an integer of 0 to 100, particularly an integer from 1 to 50, f is an integer from 0 to 100, particularly an integer from 1 to 50, g is an integer from 0 to 100, h is an integer from 0 to 100, i is an integer from 0 to 100, and d+e+f+g+h+i is an integer from 0 to 100; It is an integer of 4 to 200, preferably 10 to 150, more preferably 30 to 150.
• each unit may be linear or branched. Furthermore, the repeating units shown in parentheses with d, e, f, g, h, and i may be randomly combined.
• Rf is sufficient as long as the number average molecular weight of the relevant structural part is in the range of 1,000 to 40,000, preferably 2,000 to 25,000, and the molecular weight distribution (or degree of polymerization distribution) is not particularly limited. If the number average molecular weight is less than 1,000, it becomes difficult to obtain the desired properties as a fluorine compound due to a decrease in the fluorine atom content. If it exceeds 40,000, handling properties will be lowered due to increased viscosity and crosslinkability will be lowered due to lowered concentration of terminal functional groups.
• the molecular weight (or degree of polymerization or number of repeating units) is expressed as the number average molecular weight (or number average degree of polymerization) in terms of polystyrene by gel permeation chromatography (GPC) analysis using a fluorinated solvent as a developing solvent.
• GPC gel permeation chromatography
• the number average molecular weight (or number average degree of polymerization) calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure based on 1 H-NMR analysis and 19 F-NMR analysis may be used.
• Rf having such a structure include the following structure.
• n is an integer of 1 to 6 independently for each unit, d1, e1, f1, and f2 are each an integer of 1 or more, and the total of d1, e1, f1, and f2 is each 4 to 200, preferably is an integer from 10 to 150, eg1 is an integer from 2 to 99, and f3 is an integer from 4 to 200, preferably from 10 to 150.
• j is an integer of 1 to 6, preferably 2 to 4, and C j F 2j O may be linear or branched, but when j is 3, It is chain-like.
• k is an integer of 0 to 6, preferably 1 to 4
• f4 is an integer of 1 to 100, preferably 5 to 80
• f5 is an integer of 1 to 100, preferably 5 to 80.
• f4+f5 is an integer of 2 to 200, preferably 10 to 150
• k+f4+f5 is an integer of 4 to 200, preferably 10 to 150.
• m is an integer of 5 to 200, preferably 10 to 150. .
• Rf preferably has the following structure. (In the formula, d1, e1, f1, f2, the sum of d1, e1, and f1 or f2, f3, m, and eg1 are the same as above.)
• Rf preferably has the following structure.
• d1, e1, f1 the sum of d1, e1, and f1, f3 is the same as above.
• f4' is an integer of 1 to 100, preferably 5 to 80
• f5' is 1 to 100
• It is preferably an integer of 5 to 80
• the sum of f4' and f5' is an integer of 4 to 199, preferably 10 to 149.
• Y is independently a single bond, or has a C+1 valence of 1 to 20 carbon atoms (i.e., a valence of 2 to 4, preferably It is a divalent or trivalent) organic group (especially a hydrocarbon group).
• Examples of Y other than a single bond include the following.
• Ph is a phenylene group.
• it is preferable that the bond on the left side is bonded to Rf, and the other bonds are bonded to Q (or R 1 or X).
• Q is independently a single bond or a b+1 valent element consisting of one or more elements of C, O, H, N, Si, S, F, Cl, and Br (i.e., It is a linking group having a valence of 2 to 10, preferably 3 to 7, and may have a cyclic structure.
• Q other than a single bond can particularly include a carbon atom, a nitrogen atom, a silicon atom, and the following structures.
• the bond of each of the (b'+1) units, etc. is bonded to Y and any one of the b R 1 groups surrounded by ( ).
• b' is an integer of 2 to 9, preferably 2 to 6.
• T is a (b'+1)-valent linking group.
• T is a (b'+1)-valent linking group (ie, a 3- to 10-valent, preferably a 3- to 7-valent linking group), and examples thereof include the following.
• R 1 is independently a single bond or a divalent organic group (especially a hydrocarbon group) having 1 to 20 carbon atoms which may contain an oxygen atom, nitrogen atom or sulfur atom. , an ether bond, an ester bond, an amide bond, a urethane bond, or a sulfide bond, and may include a cyclic structure.
• suitable structures other than single bonds include the following.
• x and y are each independently an integer of 1 to 20, preferably x is an integer of 1 to 10, y is an integer of 2 to 10, and z is an integer of 1 to 6, preferably 1 to 3. (x+y and x+z ⁇ y are 20 or less. Ph is a phenylene group.
• X is independently a monovalent group or hydroxyl group represented by the above formula (1), and 1 to 20, preferably 1 to 12, more preferably 1 to 8 in the molecule.
• X is a monovalent group represented by the above formula (1). Further, it is preferable that X is only a monovalent organic group represented by formula (1).
• b is independently an integer of 1 to 9, preferably 1 to 6, and c is independently an integer of 1 to 3, preferably 1 or 2.
• the method for producing the fluoropolyether group-containing compound in the present invention is not particularly limited, but the following two methods can be mentioned as particularly specific examples.
• the first production method is a method in which a fluoropolyether group-containing alcohol compound is reacted with an acid halide represented by the following general formula (3) to form an ester bond.
• R is the same as above.
• Z is a halogen atom, particularly preferably a chlorine atom.
• Examples include cinnamoyl chloride, trans-3-bromo-4-hexadecyloxyc
• the structure of the fluoropolyether group-containing alcohol compound is not particularly limited, but for example, those having the structures shown by the following general formulas (4), (5), (6), and (7) are Can be mentioned.
• Rf is the same as above, and z1 is independently an integer from 1 to 6.
• Fomblin D series such as Fomblin D2, Fomblin D4000, Fomblin D6000 of Solvay Specialty Polymers, Fomblin T4, Fluorolink 5147X, Fluorolink 5148X can be mentioned.
• Patent Document 7 The following compounds exemplified in JP 2021-175782 (Patent Document 7) etc. can be used.
• the first production method involves reacting a fluoropolyether group-containing alcohol compound with an acid halide represented by formula (3) to form an ester bond.
• an acid halide represented by formula (3) it is preferable to charge the acid halide represented by formula (3) in an amount equal to or more than the same mole based on the total amount of hydroxyl groups in the fluoropolyether group-containing alcohol compound, and to react all the hydroxyl groups.
• the polyether group-containing alcohol compound has a plurality of hydroxyl groups, the amount may be sufficient as long as the monovalent group represented by formula (1) can be introduced into at least one hydroxyl group.
• the amount of the acid halide represented by formula (3) is 0.5 to 6 times, particularly 0.7 to 4 times, the amount of hydroxyl groups in the fluoropolyether group-containing alcohol compound in the reaction system. It is desirable to use moles for the reaction. If the amount is too large, it will be difficult to remove the excess acid halide represented by formula (3), and if it is too small, the fluoropolyether group-containing alcohol compound will not introduce any monovalent group represented by formula (1). more likely to remain.
• an acid acceptor in the ester production reaction in which a fluoropolyether group-containing alcohol compound is reacted with an acid halide represented by formula (3).
• the acid halide represented by formula (3) and the acid acceptor are mixed and stirred.
• known compounds such as triethylamine, various tertiary amines, diazabicycloundecene, diazabicyclononene, pyridine, and urea can be used.
• the amount of acid acceptor used is preferably about 0.9 to 3 times the mole of the acid halide represented by formula (3). If it is too small, a large amount of untrapped acid will remain, and if it is too large, it may become difficult to remove excess acid acceptor.
• the reaction may be carried out after diluting with an appropriate solvent as necessary.
• a solvent any solvent can be used without particular limitation as long as it does not react with the hydroxyl group of the fluoropolyether group-containing alcohol compound or the halogen atom of the acid halide represented by formula (3).
• hydrocarbon solvents such as toluene, xylene, isooctane, ether solvents such as tetrahydrofuran (THF), diisopropyl ether, dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, m-
• fluorine-modified aromatic hydrocarbon solvents such as xylene hexafluoride (also known as hexafluorometa-xylene) and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether.
• This solvent may be removed by a known method such as distillation under reduced pressure after the reaction, or may be used as it is as a diluted solution depending on the intended use.
• the amount of solvent used is not particularly limited, but is preferably 10 times or less based on the total mass of the reaction components. If too much solvent is used, the reaction rate may be significantly reduced.
• the above reaction is carried out at a temperature of 0 to 150°C, preferably 10 to 90°C, for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be too slow; if the reaction temperature is too high, problems such as difficulty in trapping the generated acid occur.
• the unreacted acid halide represented by formula (3), solvent, acid acceptor, etc. are removed and purified by methods such as distillation, adsorption, filtration, washing, etc. to obtain the fluoropolyether of the present invention.
• Group-containing compounds can be obtained.
• fluoropolyether group-containing compound having a monovalent group represented by the above formula (1) of the present invention obtained by the first production method include those shown below.
• Rf is the same as above
• z1 is independently the same as above
• X a is the following group.
• Rf 1 is -CF 2 O(CF 2 O) d1 (CF 2 CF 2 O) e1 CF 2 - or -CF 2 O(CF 2 O) d1 (CF 2 CF 2 O) e1 (CF 2 CF 2 CF 2 O) f1 CF 2 -.
• X a , d1, e1 are the same as above.
• Rf 2 is a group represented by the following formula. (f4', f5', the sum of f4' and f5' is the same as above.)]
• X a and m are the same as above.
• z2 is independently an integer from 1 to 6.
• R is as described above.
• R 4 is a divalent organic group, preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, and may contain an oxygen atom, nitrogen atom or sulfur atom, preferably a methylene group, ethylene group, propylene group. group, butylene group, pentene group, hexylene group, or a divalent ether structure composed of these groups and ether-bonding oxygen.
• a methylene group is particularly preferred.
• R 5 is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or a methyl group.
• Examples of the compound represented by formula (8) include those shown below.
• the structure is not particularly limited, but for example, the following fluoropolyether compounds (9) to (19) having an olefin at the end ( i) to (In the formula, Rf is the same as above.)
• a compound having a SiH group at the end of a fluoropolyether group can be obtained by carrying out an addition reaction in the presence of a platinum group metal-based addition reaction catalyst.
• the polyfunctional SiH compound (ii) reacts with one terminal olefin structure of one molecule of the fluoropolyether compound (i), and the allyl group of the fluoropolyether compound (i), etc.
• unreacted polyfunctional SiH compound (ii) is removed by distillation under reduced pressure or the like. It is desirable that the polyfunctional SiH compound (ii) be reacted in the presence of 1 to 10 equivalents, particularly 2 to 6 equivalents, per equivalent of a terminal olefin group such as an allyl group of the fluoropolyether compound (i). .
• the addition reaction catalyst for example, a compound containing platinum, rhodium, or palladium can be used.
• compounds containing platinum are preferred, such as hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde/octanol complex, Alternatively, platinum supported on activated carbon can be used.
• the amount of the addition reaction catalyst is preferably such that the amount of metal contained is 0.1 to 5,000 ppm by mass, more preferably 1 to 1,000 mass ppm, based on the polyfunctional SiH compound (ii). The amount is ppm.
• the above addition reaction can be carried out in the absence of a solvent, it may be diluted with a solvent if necessary.
• organic solvents such as toluene, xylene, isooctane, etc.
• it is soluble at the reaction temperature.
• partially fluorine-modified solvents such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether are preferable, and particularly m-xylene Hexafluoride is preferred.
• the amount of solvent used is not particularly limited, but is preferably 10 times or less based on the total mass of the reaction components. If too much solvent is used, the reaction rate may be significantly reduced.
• the order of charging each component is not particularly limited, but for example, the mixture of the fluoropolyether compound (i), the polyfunctional SiH compound (ii), and the addition reaction catalyst is gradually added from room temperature (23 ⁇ 15°C, the same applies hereinafter).
• a method such as dropping a mixture of the ether compound (i) and the addition reaction catalyst may be used.
• the above reaction is carried out in a dry atmosphere in air or inert gas (N 2 , Ar, etc.) at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 0.5 to 96 hours, preferably 1 to It is desirable to do this for 48 hours.
• air or inert gas N 2 , Ar, etc.
• Known compounds having a SiH group at the end of the fluoropolyether group obtained in this way include the following compounds exemplified in JP-A No. 2015-189843 (Patent Document 5).
• Patent Document 5 Patent Document 5
• g' is an integer from 2 to 100, preferably from 2 to 50.
• g' is the same as above.
• a compound having an SiH group at the end of the fluoropolyether group and a compound represented by formula (8) are combined in the presence of a platinum group metal-based addition reaction catalyst. It can be obtained by performing the following addition reaction.
• the SiH group of the compound having an SiH group at the end of the fluoropolyether group reacts only with the terminal olefin structure of one molecule of the compound represented by formula (8), and the compound represented by formula (8) It is desirable that the internal olefins do not react.
• an addition reaction is carried out using an excess amount of the compound represented by formula (8) on a compound having a SiH group at the end of a fluoropolyether group, and then the unreacted compound represented by formula (8) is It is desirable to remove the compound by distillation under reduced pressure, etc., and the compound represented by formula (8) is added in an amount of 1 to 10 equivalents, particularly 1.05 to 10 equivalents per equivalent of the SiH group of the compound having an SiH group at the end of the fluoropolyether group.
• the reaction is carried out in the presence of 2 equivalents.
• the addition reaction catalyst for example, a compound containing platinum, rhodium or palladium can be used.
• compounds containing platinum are preferred, such as hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde/octanol complex, Alternatively, platinum supported on activated carbon can be used.
• the amount of addition reaction catalyst to be added is preferably such that the amount of metal contained is 0.1 to 5,000 ppm by mass, more preferably 1 The amount is ⁇ 1,000 ppm by mass.
• the above addition reaction can be carried out in the absence of a solvent, it may be diluted with a solvent if necessary.
• organic solvents such as toluene, xylene, isooctane, etc.
• it is soluble at the reaction temperature.
• partially fluorine-modified solvents such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether are preferable, and particularly m-xylene Hexafluoride is preferred.
• the amount of solvent used is not particularly limited, but is preferably 10 times or less based on the total mass of the reaction components. If too much solvent is used, the reaction rate may be significantly reduced.
• each component is not particularly limited, but for example, a mixture of a compound represented by formula (8), a compound having a SiH group at the end of a fluoropolyether group, and an addition reaction catalyst is added gradually from room temperature.
• a method in which a compound represented by formula (8) is dropped into a mixture of a compound having a SiH group at the end of a fluoropolyether group and an addition reaction catalyst heated to the desired reaction temperature a method in which a compound represented by formula (8) is dropped into a mixture of a compound having a SiH group at the end of a fluoropolyether group and an addition reaction catalyst heated to the desired reaction temperature;
• a method such as dropping a mixture of a compound having an SiH group at the end of a fluoropolyether group and an addition reaction catalyst to the compound represented by (8) can be used.
• a method of adding an addition reaction catalyst after heating a mixture of a compound represented by formula (8), a compound having a SiH group at the end of a fluoropolyether group, and a diluting solvent to a desired reaction temperature is particularly preferred.
• the above reaction is carried out in a dry atmosphere in air or inert gas (N 2 , Ar, etc.) at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 0.5 to 96 hours, preferably 1 to It is desirable to do this for 48 hours.
• air or inert gas N 2 , Ar, etc.
• the unreacted compound represented by formula (8), solvent, addition reaction catalyst, etc. are removed and purified by methods such as distillation, adsorption, filtration, washing, etc. to obtain the fluoropolyether group-containing product of the present invention. compound can be obtained.
• fluoropolyether group-containing compound having a monovalent group represented by the above formula (1) of the present invention obtained by the second production method include those shown below. (In the formula, Rf 1 , m, and X a are the same as above.)
• the fluoropolyether group-containing compound having a monovalent group represented by the above formula (1) obtained as described above can be used as a component of a photocrosslinkable fluoropolyether composition.
• a photocrosslinkable fluoropolyether composition which is one of the embodiments of the present invention, is characterized by containing a fluoropolyether group-containing compound having a monovalent group represented by the above formula (1).
• the content of the fluoropolyether group-containing compound having a monovalent group represented by formula (1) in the photocrosslinkable fluoropolyether composition is preferably 20 to 100% by mass, more preferably It is 60 to 100% by mass.
• a fluoropolyether group-containing compound having a monovalent group represented by the above formula (1) can be irradiated with light having a wavelength in the range of 250 to 350 nm to form a compound represented by the above formula (1) as shown below.
• a dimerization reaction of a monovalent group causes a crosslinking reaction between molecules, forming a crosslinked structure and curing.
• This reaction essentially does not require the addition of photopolymerization initiators, and is relatively stable against heat if stored in a light-shielded condition, allowing for long-term storage without adding stabilizers such as polymerization inhibitors. .
• the photocrosslinkable fluoropolyether composition of the present invention contains a fluoropolyether group-containing compound having three or more monovalent groups represented by the above formula (1) in the molecule alone or in combination with the fluoropolyether group-containing compound.
• the use of a fluoropolyether group-containing compound having one or two monovalent groups represented by the above formula (1) in combination can improve the viscosity of the composition before crosslinking and the density of the desired crosslinked structure. , is preferable for controlling the physical properties of the crosslinked product.
• the photocrosslinkable fluoropolyether composition which is one of the embodiments of the present invention, is formed into a coating film layer, a sealing layer, a three-dimensional object, etc. by coating, potting, various molding methods, etc., and is repelled by light irradiation. It forms a crosslinked product that has various properties derived from the fluoropolyether structure, such as water resistance, oil repellency, chemical resistance, solvent resistance, low refractive index, and transparency, and does not harm the desired properties. Any component can be blended within the range.
• coating or potting can be performed after diluting with various solvents (organic solvents, etc.) at an arbitrary ratio.
• organic solvents include alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol, and diacetone alcohol; methylpropyl ketone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK).
• ketones such as cyclohexanone
• ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate; ethyl acetate
• esters such as propyl acetate, butyl acetate, and cyclohexyl acetate.
• the organic solvent may be fluorinated, such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride, benzotrifluoride, and hexafluorobenzene, and fluorine-modified ether solvents such as methyl perfluorobutyl ether.
• fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride, benzotrifluoride, and hexafluorobenzene
• fluorine-modified ether solvents such as methyl perfluorobutyl ether.
• fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride, benzotrifluoride, and hexafluorobenzene
• fluorine-modified ether solvents such as methyl perfluorobutyl ether.
• examples include partially fluorine-modified solvents, perfluoropolyethers, perflu
• ASAHIKULN AE-3000 and AMOLEA AS-300 from AGC Bartrel and Opteon from Chemours, Fluorinert from 3M, Cellfin from Central Glass, and Galden from Solvay.
• the above organic solvents may be used alone or in combination of two or more, regardless of whether or not they contain fluorine.
• the light irradiation for crosslinking may be performed after the solvent is removed by heating, blowing air, reduced pressure, or the like, or may be performed while a portion of the solvent remains.
• particles with various structures made of metal oxides, metal nitrides, metal sulfides, metal halides, etc. can be blended.
• the composition of the particles can be exemplified by NaF, KF, CaF 2 , MgF 2 and SiO 2 , and the shape can be spherical, amorphous, hollow structure, mesoporous structure, etc. with a space that retains air. Structures such as particles can be used.
• particles with various structures made of these metal oxides, metal nitrides, metal sulfides, metal halides, etc. have a surface containing a fluoropolyether compound or a monovalent group represented by the above formula (1). It may be chemically modified with a fluoropolyether group-containing compound.
• inorganic fillers can be used to adjust physical properties other than optical properties of the crosslinked material, such as gel-like or rubber-like properties.
• specific examples of inorganic fillers include silica powder such as fumed silica (fumed silica or dry silica), precipitated silica (wet silica), spherical silica (fused silica), sol-gel silica, silica aerogel, or the like.
• Silica powder obtained by treating the surface of the powder with various types of organochlorosilane, organodisilazane, cyclic organopolysilazane, etc., and further reusing the surface-treated silica powder with organosilane or organosiloxane having a fluoroalkyl group or fluoropolyether group.
• organosilane or organosiloxane having a fluoroalkyl group or fluoropolyether group.
• silica-based reinforcing fillers such as treated silica powder, reinforcing or semi-reinforcing fillers such as quartz powder, fused quartz powder, diatomaceous earth, and calcium carbonate.
• inorganic pigments such as titanium oxide, iron oxide, carbon black, and cobalt aluminate
• heat resistance improvers such as titanium oxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, and manganese carbonate.
• thermal conductivity imparting agents such as alumina, boron nitride, silicon carbide, metal powder, etc.
• electrical conductivity imparting agents such as carbon black, silver powder, conductive zinc white, etc.
• the surfaces of these components may be chemically modified with a fluoropolyether compound or a fluoropolyether group-containing compound having a monovalent group represented by the above formula (1).
• fluoropolyether group-containing compounds that do not have a monovalent group represented by the above formula (1), specifically, the above formula (2), can be used as plasticizers, viscosity modifiers, and flexibility imparting agents.
• all X is a hydroxyl group, specifically, the fluoropolyether group-containing alcohol compounds shown by the above formulas (4) to (7), and the Rf in the above formula (2).
• a compound or the like having fluorine atoms bonded to both ends of the group may be added.
• raw material impurities, unreacted intermediates, and terminal double bonds contained in the synthesis of the fluoropolyether group-containing compound of the present invention may be removed as long as the physical properties of the final target crosslinked product are met. It may also include a transition compound, a compound in which the trans structure of the monovalent group represented by the above formula (1) is partially or completely a cis structure, and the like.
• the concentration of the fluoropolyether group-containing compound may be adjusted depending on the purpose and is not particularly limited. It is desirable that the concentration of the monovalent group represented by the above formula (1) bonded to is 0.0001 to 0.002 mol/g, preferably 0.0002 to 0.0015 mol/g. If the number of monovalent groups represented by formula (1) is less than this, the crosslinking reaction by photodimerization may not proceed sufficiently, and if the number of monovalent groups represented by formula (1) is more than this, Due to the aggregation of the monovalent groups represented by formula (1), crosslinking due to the photodimerization reaction may not proceed sufficiently as a result.
• the concentration of the monovalent group represented by formula (1) in the fluoropolyether group-containing compound can be measured by means such as 1 H-NMR and infrared absorption spectroscopy.
• the concentration of the monovalent group represented by formula (1) in the fluoropolyether group-containing compound is calculated based on the concentration and blending ratio of the monovalent group represented by formula (1) in each component determined individually. be able to.
• the photocrosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound of the present invention can be used depending on the intended use.
• the compound can be diluted with a fluorine-based solvent or a non-fluorine-based solvent to a concentration of, for example, 0.001 to 99% by mass. It is desirable that the solvent or non-fluorinated solvent (volatile component) be removed.
• the photocrosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound of the present invention is used to prevent volatile components from contaminating the surrounding area. It is preferable to install it in a position where crosslinking is carried out with a composition that does not contain components.
• the photocrosslinkable fluoropolyether composition as a whole is equipped with components (such as solvent components) that have a boiling point of less than 200°C under atmospheric pressure. ) is desirably controlled to 1% by mass or less, particularly 0.1% by mass or less.
• a method for photocrosslinking a photocrosslinkable fluoropolyether composition containing a fluoropolyether group-containing compound of the present invention includes a step of irradiating the composition with light containing ultraviolet rays having a wavelength of 250 to 350 nm.
• the photocrosslinking method of the photocrosslinkable fluoropolyether composition of the present invention when irradiating light containing ultraviolet rays, there is no particular limitation as long as ultraviolet rays in the wavelength range of 250 to 350 nm are included; It may also include light outside the wavelength range. Specific light sources include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, ultraviolet LEDs, xenon lamps, and the like.
• a filter may be used to cut out light and heat in wavelength ranges other than necessary, and any light source installation method such as a spot light source, line light source, or surface light source can be used.
• the composition may be continuously irradiated with light using a conveyor type or linear winding type substrate moving device, or an irradiation device using a mobile light source.
• heating may be performed during ultraviolet irradiation to improve reactivity, leveling properties, and the like.
• the photocrosslinked product of the photocrosslinkable fluoropolyether composition is preferably in the form of a film.
• the film-like photocrosslinked material is a photocrosslinkable fluoropolyether composition diluted with a fluorinated solvent or a non-fluorinated solvent as described above, or a liquid photocrosslinkable fluoropolyether that is not diluted with a solvent. It is obtained by coating the composition, leveling it if necessary to obtain a predetermined thickness, and then irradiating it with light.
• the film thickness of the photocrosslinked film is usually about 2 nm to 500 ⁇ m.
• the film thickness is measured using a micrometer, calculation based on the coating mass relative to the coated area and the specific gravity of the composition after drying, and calculation based on the interlayer fluorine content in the film and the fluorine content in the composition using fluorescent X-rays. It can be measured by a method such as a method of measuring the cross section of the coating using an AFM.
• the photocrosslinkable fluoropolyether composition containing the fluoropolyether group-containing compound of the present invention is not crosslinked by heating, so it is thermally stable, has excellent long-term storage stability, and has a photopolymerization initiator. Because it does not require the addition of polymerization inhibitors or polymerization inhibitors, it can form transparent photocrosslinked structures without containing non-fluorine compounds or generating low-molecular volatile matter, making it suitable for coating agents for various optical components, nanoimprint materials, It is useful as a potting agent for electronic parts and various sensors, a photocurable 3D printer output material, etc. Examples of articles having a film of the photocrosslinked product of the photocrosslinkable fluoropolyether composition of the present invention include various optical parts, nanoimprint members, electronic parts, various sensors, 3D printer output members, and the like.
• the number average molecular weight of the perfluoropolyether group is a value calculated from the characteristic peak intensity ratio of the terminal structure and main chain structure based on 19 F-NMR analysis. Further, the room temperature was 23°C. Further, the thickness was measured by calculating the mass of the coating relative to the coated area and the specific gravity of the composition excluding the solvent.
• reaction solution was heated and stirred for 2 hours at a bath temperature of 50°C, then cooled to room temperature, washed twice with 100g of ethanol in a separating funnel, and the collected lower layer was heated in an evaporator at 120°C/133Pa (1 Torr). Distillation was carried out under reduced pressure for 1 hour to obtain 48.1 g of a colorless and transparent liquid substance. It was confirmed by 1 H-NMR, 19 F-NMR, and IR that the obtained compound had a structure represented by the following formula (F-1).
• Examples 1 to 9 and Comparative Example 1 A composition was prepared using the compounds of Synthesis Examples 1 to 6 (compounds represented by formulas (F-1) to (F-6)) and compounds represented by the following formulas (F-7) and (F-8). The coating film formation and curability were confirmed.
• Compound represented by the following formula (F-7) HOCH 2 CF 2 (OCF 2 CF 2 ) 9.1 (OCF 2 ) 9.7 OCF 2 CH 2 OH (F-7)
• Compound represented by the following formula (F-8) R x :-(CO)-NH-CH 2 CH 2 O(CO)-CH CH 2 (Rf y is as mentioned above)
• compositions were prepared by blending the compounds represented by formulas (F-1) to (F-8) in the proportions shown in Table 1, and diluting with a solvent if necessary.
• a composition layer was formed on an aluminum petri dish to a thickness of 20 ⁇ m using any of the following methods (1) to (4), and leveling was performed. All work was done in the dark.
• (1) A solution (composition) in which the compound or mixture was diluted to 30% by mass with hexafluorometa-xylene was charged, dried at 120°C for 30 minutes, and then returned to room temperature.
• a solution (composition) in which the compound or mixture was diluted to 30% by mass with isobutyl acetate was applied and dried at 120° C. for 30 minutes.
• Table 1 shows the concentration of cinnamic acid residue in the composition and the coating film forming method.
• the concentration of cinnamic acid residue in the composition is determined by the peak appearing at a chemical shift of 7 to 8 ppm in the NMR spectrum obtained by 1 H-NMR using tetramethylsilane as an internal standard in the state of the compound or mixture before dilution with the solvent.
• Formulas (F-1) to (F-6 ) was calculated by measuring the concentration of cinnamic acid residue in each compound.

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