Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

• the present invention relates to a composition for forming a fluorine-containing sealant.
• a sealing material for filling the gap is provided.
• the sealing material is required to have waterproofness for protecting members included in the electronic device.
• Patent Document 1 discloses an acrylic acid ester having a fluoroalkyl group ester-bonded to a carboxyl group directly or via a divalent organic group and having a substituent at the ⁇ -position, and high softening Waterproofing and / or moisture-proof coating compositions containing point monomers are described. In such a waterproof and / or moisture-proof coating composition, a thin film having a thickness of several ⁇ m is usually formed.
• JP 2013-253240 A JP 2009-46575 A JP2013-231168A
• the present inventor has tried to use a coating composition containing a fluorine-containing compound in order to fill a gap such as an electronic member.
• a coating composition containing a fluorine-containing compound in order to fill a gap such as an electronic member.
• An object of the present invention is to provide a composition containing a fluorine-containing compound, which is suitable for filling voids such as electronic members.
• the present inventor tried to fill the voids with a coating composition having a high concentration of fluorine-containing compound.
• a coating composition having a high concentration of fluorine-containing compound it has been found that the coating compositions that have been studied in the past have a small film thickness after curing and it is difficult to sufficiently fill the voids.
• the above-mentioned voids can be sufficiently filled by using a composition containing a specific polymer at a specific concentration.
• a branched alkyl group; Y is a direct bond or a divalent organic group.
• the Si atom-containing polymerizable monomer and the Si atom-containing mercaptan each independently contain at least one Si atom bonded to one or more hydroxyl groups or hydrolyzable groups, Provided is a
• an article including a sealing material formed using the above-mentioned composition for forming a fluorine-containing sealing material.
• composition for forming a fluorine-containing sealing material suitable for filling a gap such as an electronic member it is possible to obtain a composition for forming a fluorine-containing sealing material suitable for filling a gap such as an electronic member.
• divalent organic group means a divalent group containing carbon. Such a divalent organic group is not particularly limited, and examples thereof include a divalent group obtained by further removing one hydrogen atom from a hydrocarbon group.
• hydrocarbon group means a group containing carbon and hydrogen.
• Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned.
• the “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated.
• the hydrocarbon group may also contain one or more ring structures.
• Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like in the terminal or molecular chain.
• the substituent of the “hydrocarbon group” is not particularly limited.
• a halogen atom a C 1-6 alkyl group which may be substituted with one or more halogen atoms, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group, C Examples include 6-10 aryl group, 5- to 10-membered heteroaryl group, and the like.
• an alkyl group and a phenyl group may be unsubstituted or substituted.
• the substituent of such a group is not particularly limited, and examples thereof include one or more groups selected from a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. Can be mentioned.
• the “hydrolyzable group” means a group that can undergo a hydrolysis reaction, that is, a group that can be removed from the main skeleton of the compound by the hydrolysis reaction.
• the hydrolyzable group include —OR, —OCOR, —O—N ⁇ CR 2 , —NR 2 , —NHR, halogen (in these formulas, R represents a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms). And the like, preferably —OR (that is, an alkoxy group).
• R examples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
• an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
• the “hydroxyl group” written together with the “hydrolyzable group” is not particularly limited, but may be generated by hydrolysis of a hydrolyzable group.
• composition for forming fluorine-containing sealant is a composition for forming a fluorine-containing sealing material suitable for filling a gap (gap) of, for example, an electronic member or an electronic device including the electronic member.
• a gap of, for example, an electronic member or an electronic device including the electronic member.
• the fact that the gap filling property is good may be described as being suitable for filling the gap as described above.
• the composition for forming a fluorine-containing sealing material of the present invention contains a fluorine-containing polymer and a fluorine-based solvent, and the concentration of the fluorine-containing polymer is 7 to 33% by mass with respect to 100% by mass of the composition for forming a fluorine-containing sealing material. is there.
• the fluorine-containing polymer contained in the composition for forming a fluorine-containing sealant of the present invention has the formula (1): [Where: Rf is a fluoroalkyl group; X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (provided that X 1 and X 2 are the same or different and are a hydrogen atom, a fluorine atom, or a chlorine atom).
• a branched alkyl group; Y is a direct bond or a divalent organic group.
• B A fluorine-containing polymer comprising a component derived from a Si atom-containing mercaptan and a component derived from a monomer component containing the fluoroalkyl group-containing (meth) acrylic acid ester.
• the Si atom-containing polymerizable monomer and the Si atom-containing mercaptan each independently contain Si atoms bonded to at least one hydroxyl group or hydrolyzable group.
• the fluoroalkyl group-containing (meth) acrylic acid ester is one in which a fluoroalkyl group is ester-bonded directly or via a divalent organic group to acrylic acid that may have a substituent at the ⁇ -position.
• the fluoroalkyl group-containing acrylic acid ester and the fluoroalkyl group-containing methacrylic acid ester are also collectively referred to as “fluoroalkyl group-containing (meth) acrylic acid ester”.
• the fluoroalkyl group-containing (meth) acrylic acid ester is a chemical resistance (for example, salt water, acid or basic aqueous solution, acetone) of a fluorine-containing sealant formed using the composition for forming a fluorine-containing sealant of the present invention.
• a chemical resistance for example, salt water, acid or basic aqueous solution, acetone
• Oleic acid or hexane particularly resistance to salt water
• the fluoroalkyl group-containing (meth) acrylic acid ester is represented by the following formula (1): It is represented by
• X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (provided that X 1 and X 2 are the same or different, and a hydrogen atom, a fluorine atom Or a chlorine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a carbon number of 1 to 20 straight-chain or branched alkyl groups.
• X is preferably a hydrogen atom, a fluorine atom, a chlorine atom, or a methyl group.
• X is preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (X 1 and X 2 are as defined above), a cyano group, a carbon number of 1 to 21 is a linear or branched fluoroalkyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms, preferably Is a fluorine atom, a chlorine atom, or a methyl group.
• Y is a direct bond or a divalent organic group.
• the divalent organic group is as defined above.
• Y is preferably a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom or a sulfur atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, A cyclic aliphatic group having 6 to 10 carbon atoms which may have an oxygen atom, an araliphatic group having 6 to 10 carbon atoms which may have an oxygen atom, —CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms), —CH 2 CH (OY 1 ) CH 2 — group (where Y 1 is a hydrogen atom or an acetyl group) ), Or — (CH 2 ) n SO 2 — group (n is 1 to 10), more preferably a direct bond, an aliphatic group having 1 to 10 carbon atoms,
• Examples of the aliphatic group include an alkylene group having 1 to 10 carbon atoms.
• the aliphatic group is preferably, for example, an alkylene group having 1 to 4 carbon atoms.
• Examples of the aromatic group include a phenylene group.
• cycloaliphatic group examples include a cycloalkylene ring.
• araliphatic group examples include —Y 21 —Ar—Y 22 —.
• Y 21 and Y 22 are each independently a direct bond or an alkylene group having 1 to 12 carbon atoms, and Ar can be a substituted or unsubstituted arylene group (more specifically, a phenylene group). .
• Rf is a fluoroalkyl group, preferably a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, more preferably at least one hydrogen atom. It is an alkyl group substituted with a fluorine atom, and includes a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
• the fluoroalkyl group-containing (meth) acrylic acid ester represented by the above formula (1) has a good solubility in a fluorinated solvent described below, particularly hydrofluoroether, and Rf has 4 to 6 carbon atoms. It is preferably a linear or branched fluoroalkyl group.
• the fluoroalkyl group-containing (meth) acrylic acid ester represented by the above formula (1) is further in the ⁇ position represented by X. Is preferably an ⁇ -substituted acrylate ester in which the substituent is a group or atom other than a hydrogen atom.
• the ⁇ -position substituent X is preferably a methyl group, a chlorine atom or a fluorine atom. From the viewpoint of improving the film formability, the ⁇ -position substituent X is particularly preferably a methyl group.
• the fluoroalkyl group-containing (meth) acrylic acid ester represented by the above formula (1) is a fluorine-based solvent described later, for example, at least one hydrogen atom is a fluorine atom and at least one hydrogen Rf is preferably a linear or branched fluoroalkyl group having 4 to 6 carbon atoms from the viewpoint of good solubility in an olefin substituted with a chlorine atom.
• the fluoroalkyl group-containing (meth) acrylic acid ester represented by the above formula (1) further has an ⁇ -position substituent represented by X.
• an ⁇ -substituted acrylate ester that is a group or atom other than a hydrogen atom is preferable.
• the ⁇ -position substituent X is preferably a methyl group, a chlorine atom or a fluorine atom.
• the ⁇ -position substituent X is particularly preferably a methyl group.
• Rf is a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms, and more preferably a linear or branched perfluoroalkyl group having 4 to 6 carbon atoms.
• fluoroalkyl group-containing (meth) acrylic acid ester represented by the above general formula (1) are as follows.
• the fluoroalkyl group-containing (meth) acrylic acid ester may be used alone or in combination of two or more.
• the Si atom-containing polymerizable monomer contains at least one Si atom bonded to one or more hydroxyl groups or hydrolyzable groups.
• the Si atom-containing polymerizable monomer preferably contains at least one Si atom bonded to at least one hydroxyl group or hydrolyzable group and at least one polymerizable functional group in the molecule.
• the Si atom-containing polymerizable monomer contributes to improvement in adhesion to the wall surface of the gap or a member previously filled in the gap, and improvement in wear resistance of the fluorine-containing sealing material.
• the polymerizable functional group is preferably a group containing a polymerizable unsaturated bond, more preferably a group containing a polymerizable ethylenically unsaturated bond.
• One polymerizable functional group is preferably present in the molecule of the Si atom-containing polymerizable monomer.
• the Si atom is preferably bonded to 1 to 3 hydroxyl groups or hydrolyzable groups, and more preferably bonded to 3 hydroxyl groups or hydrolyzable groups.
• the hydrolyzable group is as defined above.
• the Si atom-containing polymerizable monomer is preferably the following formula (2): It is represented by
• R 2 , R 3 and R 4 are the same or different and are a hydroxyl group, a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms, and R 2 , R 3 and R 4 At least one is a hydroxyl group or a hydrolyzable group.
• the hydrolyzable group is as defined above. More preferably, R 2 , R 3 and R 4 are the same or different and are an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms (—OR), and R 2 , R 3 and R 4 At least one of 4 is an alkoxy group having 1 to 4 carbon atoms.
• R is as defined above.
• R 2 , R 3 and R 4 are each independently more preferably an alkoxy group, more preferably each independently a methoxy group or an ethoxy group.
• R 2 , R 3 and R 4 can all be methoxy groups.
• R 5 is a group containing a polymerizable unsaturated bond, and preferably a group containing a polymerizable ethylenically unsaturated bond.
• the compound represented by the formula (2) can be represented by the following formula (2 ′).
• R 2 , R 3 and R 4 are as defined above.
• R 14 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom, a chlorine atom, or a methyl group.
• Y 2 represents a direct bond or a divalent organic group, and is preferably a direct bond, an alkylene group having 1 to 10 carbon atoms, or an araliphatic group having 6 to 15 carbon atoms. The araliphatic group has the same meaning as described above.
• Si atom-containing polymerizable monomer examples include monomers represented by the following formula.
• R 2 , R 3 and R 4 are as defined above, R 6 is a hydrogen atom, a methyl group, or a chlorine atom, and h is 1 to 12 (eg, 1 to 10). It is an integer.
• R 2 , R 3 and R 4 are a methoxy group or an ethoxy group, preferably a methoxy group, R 6 is a methyl group, and h is an integer of 1-12.
• Si atom-containing polymerizable monomers may be used alone or in combination of two or more.
• the monomer component may contain a high softening point monomer or other monomer as necessary.
• the high softening point monomer is a monomer having a glass transition point or melting point of a homopolymer composed of a high softening point monomer of 100 ° C. or higher, preferably 120 ° C. or higher.
• the polymer having a glass transition point needs to have a glass transition point of 100 ° C. or higher, preferably 120 ° C. or higher, and the polymer having no glass transition point has a melting point of 100 ° C. or higher, preferably Needs to be 120 ° C. or higher.
• the glass transition point and melting point are the extrapolated glass transition end temperature (T eg ) and melting peak temperature (T pm ) defined in JIS K7121-1987 “Method for Measuring Plastic Transition Temperature”, respectively.
• the above high softening point monomer can contribute to the improvement of waterproofing and / or moisture-proof performance of the fluorine-containing sealing material formed from the fluorine-containing sealing material forming composition. Furthermore, by including a high softening point monomer, the fluorine-containing sealant can have improved hardness and better durability such as wear resistance.
• the sealing material has very good dynamic water repellency that serves as an index indicating the removal performance of water droplets attached to the surface.
• the dynamic water repellency can be evaluated by the falling angle of water.
• the high softening point monomer is preferably a (meth) acrylic acid ester represented by the general formula (4).
• bridged hydrocarbon rings may be directly bonded to the carboxyl group, or may be bonded to the carboxyl group via a linear or branched alkylene group having 1 to 5 carbon atoms. . These bridged hydrocarbon rings may be further substituted with a hydroxyl group or an alkyl group (carbon number, for example, 1 to 5).
• the ratio of carbon atoms to hydrogen atoms represents the ratio of the number of carbon atoms to the number of hydrogen atoms.
• Examples of the (meth) acrylic acid ester represented by the general formula (4) include (meth) acrylate having an isobornyl group, (meth) acrylate having a norbornyl group, (meth) acrylate having an adamantyl group, and the like. it can.
• the (meth) acrylate having a norbornyl group 3-methyl-norbornylmethyl (meth) acrylate, norbornylmethyl (meth) acrylate, norbornyl (meth) acrylate, 1,3,3- Trimethyl-norbornyl (meth) acrylate, miltanylmethyl (meth) acrylate, isopinocamphanyl (meth) acrylate, 2- ⁇ [5- (1 ′, 1 ′, 1′-trifluoro-2′-trifluoromethyl-2) '-Hydroxy) propyl] norbornyl ⁇ (meth) acrylate and the like.
• Examples of the (meth) acrylate having an adamantyl group include 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) Acrylate, 3-hydroxy-1-adamantyl (me ) Acrylate can be exemplified by 1-adamantyl - ⁇ - trifluoromethyl (meth) acrylate.
• the other monomer may be any monomer that can be copolymerized with a fluoroalkyl group-containing (meth) acrylic acid ester, and can be selected from a wide range as long as it does not adversely affect the performance of the resulting fluoropolymer.
• aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen-containing unsaturated compound, silicon-containing unsaturated compound, unsaturated dicarboxylic acid compound, vinyl ester compound, allyl ester compound, unsaturated group-containing ether compound, maleimide examples include, but are not limited to, compounds, (meth) acrylic acid esters, acrolein, methacrolein, cyclopolymerizable monomers, N-vinyl compounds, and the like.
• the Si atom-containing mercaptan contains at least one Si atom bonded to at least one hydroxyl group or hydrolyzable group.
• the Si atom-containing mercaptan functions as a chain transfer agent, and the degree of polymerization of the fluoropolymer can be adjusted by adding it. Furthermore, a part of Si atom-containing mercaptan, specifically, a hydroxyl group or hydrolyzable group bonded to an Si atom contained in the Si atom-containing mercaptan is contained in the fluorine-based polymer. This improves the adhesion between the formed fluorine-containing sealing material and the elastomer (for example, silicone) and / or the wall surface of the void. Therefore, the Si atom-containing mercaptan can contribute to the formation of a fluorine-containing sealing material excellent in wear resistance.
• Si atom containing mercaptan if it is a compound which has a Si atom couple
• Preferred examples of the Si atom-containing mercaptan include compounds represented by the following formula (3).
• R 7 , R 8 and R 9 are the same or different and are a hydroxyl group, a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms, and R 7 , R 8 and R 9 At least one is a hydroxyl group or a hydrolyzable group.
• the hydrolyzable group is as defined above.
• R 7 , R 8 and R 9 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms (—OR), and at least one of R 7 , R 8 and R 9 More preferably, it is an alkoxy group having 1 to 4 carbon atoms.
• R 7 , R 8 and R 9 are each independently more preferably an alkoxy group, particularly preferably each independently a methoxy group or an ethoxy group.
• R 7 , R 8 and R 9 can all be methoxy groups.
• R 10 is an alkylene group having 1 to 12 carbon atoms.
• the alkylene group is linear or branched, and is preferably a linear alkylene group.
• R 7 , R 8 and R 9 are each independently a methoxy group or an ethoxy group, preferably a methoxy group, and R 10 is an alkylene group having 1 to 5 carbon atoms.
• R 10 is preferably a linear alkylene group having 1 to 4 carbon atoms from the viewpoint of solubility in a fluorine-based solvent described later.
• Si atom-containing mercaptans may be used alone or in combination of two or more.
• the Si atom-containing polymerizable monomer and the Si atom-containing mercaptan each independently contain at least one Si atom bonded to one or more hydroxyl groups or hydrolyzable groups. Including.
• the fluoropolymer 1 can be obtained by polymerizing a monomer component containing a fluoroalkyl group-containing (meth) acrylic acid ester and a Si atom-containing polymerizable monomer as essential components. That is, the fluorine-containing polymer 1 is a fluorine-containing polymer obtained by polymerizing a monomer component containing a fluoroalkyl group-containing (meth) acrylic acid ester and a Si atom-containing polymerizable monomer.
• the fluoropolymer 1 is a copolymer having a structural unit derived from a fluoroalkyl group-containing (meth) acrylic acid ester and a structural unit derived from a Si atom-containing polymerizable monomer.
• the weight average molecular weight of the fluoropolymer 1 is preferably 3,000 to 500,000, more preferably 5,000 to 300,000, still more preferably 20,000 to 100,000.
• the weight average molecular weight of the fluoropolymer 1 can be determined by GPC (gel permeation chromatography).
• the fluoroalkyl group-containing (meth) acrylic acid ester and the Si atom-containing polymerizable monomer have the same meanings as described above.
• the fluorine-containing polymer 1 comprises a structural unit derived from the fluoroalkyl group-containing (meth) acrylic ester and a structural unit derived from the Si atom-containing polymerizable monomer in a mass ratio of 99.9: 0.1 to 50 : 50, preferably 96: 4 to 70:30, more preferably 96: 4 to 90:10.
• the fluoroalkyl group-containing (meth) acrylic ester is represented by the following formula (1)
• the Si atom-containing polymerizable monomer is represented by the following formula (2).
• Rf, X, Y, and R 2 to R 5 are as defined above.
• the obtained fluoropolymer 1 is a copolymer having a structural portion represented by the following chemical formula (5).
• the terminal of the fluoropolymer 1 may be a group derived from a terminator, a group derived from an initiator, or a group derived from a monomer.
• the composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 1 can contribute to the formation of a fluorine-containing sealing material having a large thickness.
• the composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 1 is excellent in abrasion resistance, has good waterproof and / or moisture-proof performance, can contribute to the formation of a sealing material having excellent water repellency and good water drainage.
• the composition for forming a fluorine-containing sealant containing the fluorine-containing polymer 1 has chemical resistance, for example, against salt water (for example, 5% salt water), acid or basic aqueous solution, acetone, oleic acid or hexane, particularly salt water. It can contribute to the formation of a sealing material with good resistance.
• R 5 ′ is a trivalent group derived from the group R 5 in the formula (2), that is, a trivalent group derived from a group containing a polymerizable unsaturated bond.
• the structural unit enclosed in parentheses with l is a structural unit derived from a fluoroalkyl group-containing (meth) acrylic acid ester, and a structural unit enclosed in m with m
• the unit is a structural unit derived from the Si atom-containing polymerizable monomer. Note that the order of presence of each repeating unit with l and m in parentheses is arbitrary in the formula.
• l and m are each independently an integer of 1 or more.
• the sum of l and m is preferably a numerical value with a weight average molecular weight of 3,000 to 500,000.
• l: m is preferably in the range of 99.9: 0.5 to 50:50, and more preferably in the range of 95: 5 to 70:30. Preferably, it is in the range of 95: 5 to 80:20, more preferably in the range of 95: 5 to 85:15.
• l: m may be in the range of 93: 7 to 80:20, or may be in the range of 90:10 to 80:20.
• the monomer component includes a high softening point monomer in addition to the fluoroalkyl group-containing acrylic ester and the Si atom-containing polymerizable monomer.
• the fluorine-containing polymer 1 is a copolymer further containing a structural unit based on a high softening point monomer.
• the high softening point monomer has the same meaning as described above.
• composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer obtained in this embodiment has good waterproof and moistureproof properties and can contribute to the formation of a sealing material with good hardness.
• the fluoroalkyl group-containing (meth) acrylic acid ester is represented by the following formula (1);
• the Si atom-containing polymerizable monomer is represented by the following formula (2);
• Rf, X, Y, R 2 to R 5 , R 11 and R 12 are as defined above.
• the obtained fluoropolymer 1 is a copolymer having a structural portion represented by the following chemical formula (5 ′).
• the composition for forming a fluorine-containing sealant containing this copolymer is excellent in abrasion resistance, has good waterproof and / or moisture-proof performance, and further has excellent water repellency and excellent water drainage. Can contribute.
• the terminal of the fluoropolymer 1 may be a group derived from a terminator, a group derived from an initiator, or a group derived from a monomer.
• R 5 ′ is a trivalent group derived from the group R 5 in the formula (2), that is, a trivalent group derived from a group containing a polymerizable unsaturated bond.
• the structural unit enclosed in parentheses with l ′ is a structural unit derived from a fluoroalkyl group-containing (meth) acrylic acid ester, and is enclosed in parentheses with m ′.
• the structural unit is a structural unit derived from a Si atom-containing polymerizable monomer
• the structural unit in parentheses with n ′ is a structural unit derived from a high softening point monomer.
• the order of presence of each repeating unit with l ', m', and n 'enclosed in parentheses is arbitrary in the formula.
• l', m 'and n' are each independently an integer of 1 or more.
• the sum of l ′, m ′ and n ′ is preferably a numerical value having a weight average molecular weight of 3,000 to 500,000.
• the ratio of l ′, m ′, and n ′ is such that l ′ is in the range of 50 to 99.8 and m ′ is 0.1 to 49.5.
• n ′ is preferably in the range of 0.1 to 49.9. More preferably, the ratio of l ′, m ′, and n ′ is such that l ′ is in the range of 65-99.8, m ′ is in the range of 5-29.5, and n ′ is in the range of 0.2-30. Is in range.
• the ratio of l ', m' and n ' is preferably such that l' is in the range of 65 to 75, m 'is in the range of 3 to 15, and n' is in the range of 20 to 30.
• the monomer component may further contain other monomers as necessary.
• Other monomers are as defined above.
• the above-mentioned other monomers are preferably contained in an amount of 0.1 to 20% by mass with respect to 100% by mass of the entire fluoropolymer 1.
• the polymerization method of the fluoropolymer 1 is not particularly limited, but for example, solution polymerization can be performed in a fluorine-based solvent. According to this method, since the formed fluoropolymer 1 has good solubility in a fluorine-based solvent, the polymerization reaction can proceed smoothly without forming a precipitate.
• the fluorine-based solvent used in the above solution polymerization (hereinafter sometimes referred to as “polymerizing fluorine-based solvent”) has fluorine atoms in the molecule, and the solubility of the formed fluorine-containing polymer is good.
• it is a simple solvent, it may be any of hydrocarbon compounds, alcohols, ethers, etc., and may be either aliphatic or aromatic.
• chlorinated fluorinated hydrocarbons particularly 2 to 5 carbon atoms
• HCFC225 diichloropentafluoropropane
• HCFC141b diichlorofluoroethane
• CFC316 (2,2,3,3-tetrachlorohexafluorobutane)
• Vertrel XF chemical formula C 5 H 2 F 10
• hexafluoro-m-xylene pentafluoropropanol
• fluorinated ether and the like
• hydrofluoroether is used as the fluorinated solvent contained in the composition for forming a fluorinated sealant of the present invention
• hydrofluoroether is used as the fluorinated solvent contained in the composition for forming a fluorinated sealant of the present invention
• hydrofluoroether is used as the fluorinated solvent for polymerization.
• the above-mentioned polymerization fluorinated solvents may be used alone or in combination of two or more.
• the polymerization reaction is performed by dissolving the monomer component in the fluorinated solvent and adding a polymerization initiator while stirring the obtained solution. Can be advanced.
• the polymerization initiator is not particularly limited as long as it is a known polymerization initiator for a polymerization reaction.
• the polymerization initiator include azo initiators such as azobisisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile; benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivatives, phosphine oxide derivatives, benzoketones Derivatives, phenylthioether derivatives, azide derivatives, diazo derivatives, disulfide derivatives and the like can be used. These polymerization initiators may be used alone or in combination of two or more.
• the amount of the polymerization initiator used is not particularly limited, but is usually preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the fluoroalkyl group-containing (meth) acrylic acid ester used as the monomer component. More preferably, the content is 0.1 to 1 part by mass.
• the polymerization conditions such as the polymerization temperature and the polymerization time may be appropriately adjusted according to the type of monomer component, the amount used, the type of polymerization initiator, the amount used, etc. Usually, it is about 50 to 100 ° C.
• the polymerization reaction may be performed at a temperature for 4 to 10 hours.
• the concentration of the monomer component in the fluorinated solvent for polymerization is not particularly limited, but is usually preferably 10 to 50% by mass, and more preferably 20 to 40% by mass.
• the amount of the Si atom-containing polymerizable monomer used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the fluoroalkyl group-containing (meth) acrylic acid ester.
• the amount of the high softening point monomer used is 0.1 to 49.9 parts by mass with respect to 100 parts by mass of the fluoroalkyl group-containing (meth) acrylic acid ester. Yes, preferably 1 to 25 parts by mass.
• the content of other monomers is preferably about 20% by mass or less, more preferably 10% by mass or less, based on the total amount of monomer components used for obtaining the fluoropolymer 1.
• the fluoropolymer 2 can be obtained by polymerizing a monomer component containing a fluoroalkyl group-containing (meth) acrylic acid ester in the presence of a Si atom-containing mercaptan. That is, the fluorine-containing polymer 2 is a fluorine-containing polymer obtained by polymerizing a monomer component containing a fluoroalkyl group-containing (meth) acrylic acid ester in the presence of a Si atom-containing mercaptan.
• the fluoroalkyl group-containing (meth) acrylic acid ester and the Si atom-containing mercaptan have the same meanings as described above.
• the monomer component can contain a high softening point monomer and other monomers in addition to the fluoroalkyl group-containing (meth) acrylic acid ester.
• the high softening point monomer and other monomers have the same meanings as described above.
• the weight average molecular weight of the fluoropolymer 2 is preferably 3,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 20,000 to 100,000.
• the weight average molecular weight of the fluoropolymer 2 can be determined by GPC.
• the fluorine-containing polymer 2 comprises a component derived from a fluoroalkyl group-containing (meth) acrylic acid ester and a component derived from a Si atom-containing mercaptan in a mass ratio of 100: 0.01 to 100: 25. Preferably, it is included in the range of 100: 0.1 to 100: 5.
• the fluorinated polymer 2 comprises a component derived from a fluoroalkyl group-containing (meth) acrylic acid ester and a component derived from a Si atom-containing mercaptan in a mass ratio of 100: 0.01 to 100: 1. It may be included, and may be included in the range of 100: 0.1 to 100: 1.
• a fluoroalkyl group-containing (meth) acrylic acid ester represented by the above formula (1) is used as a monomer, and a Si atom-containing mercaptan represented by the above formula (3) is used.
• the fluoropolymer 2 has the following general formula (6): It is represented by The fluorine-containing polymer 2 represented by the formula (6) is derived from a polymer chain of a polymer having a structural unit derived from a fluoroalkyl group-containing (meth) acrylic ester and a Si atom-containing mercaptan represented by the formula (3). It is combined with the structure.
• the fluoropolymer 2 represented by the formula (6) may have a Si atom bonded to a hydroxyl group or a hydrolyzable group at at least one end.
• k is preferably a numerical value corresponding to the above-mentioned weight average molecular weight, that is, a numerical value such that the weight average molecular weight of the polymer of the general formula (6) is 3,000 to 500,000, and 3,000 to 500,000. Is more preferable, and a numerical value of 20,000 to 100,000 is even more preferable.
• the composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 2 can contribute to the formation of a fluorine-containing sealing material having a large thickness.
• the composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 2 is excellent in abrasion resistance, has good waterproof and / or moisture-proof performance, can contribute to the formation of a sealing material having excellent water repellency and good drainage.
• the composition for forming a fluorine-containing sealant containing the fluorine-containing polymer 2 is used to form a sealant having good chemical resistance, for example, salt water, acid or basic aqueous solution, acetone, oleic acid or hexane, particularly salt water. Can contribute.
• a high softening point monomer can be further used as a monomer component together with a fluoroalkyl group-containing (meth) acrylic acid ester when the fluoropolymer 2 is produced.
• Specific examples of the high softening point monomer are the same as described above.
• the fluorine-containing polymer 2 includes a structural unit based on a high softening point monomer. More specifically, in addition to the structure represented by the general formula (6), a structural unit based on a high softening point monomer is included.
• the fluorinated polymer 2 preferably contains 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass of the constituent component derived from the high softening point monomer with respect to 100 parts by mass of the entire fluorinated polymer 2. More preferably, the content is 1 to 20 parts by mass.
• fluoropolymer 2 when the fluoropolymer 2 is produced, other monomers can be further used as a monomer component together with the fluoroalkyl group-containing (meth) acrylic acid ester. Specific examples of other monomers are the same as described above.
• a Si atom-containing polymerizable monomer when the fluorine-containing polymer 2 is produced, a Si atom-containing polymerizable monomer can be further used as a monomer component.
• the Si atom-containing polymerizable monomer has the same meaning as described above.
• the fluorine-containing polymer 2 further has a structural unit based on the Si atom-containing polymerizable monomer.
• the composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 2 can further contribute to improvement in adhesion to an elastomer (for example, silicone).
• the fluorine-containing polymer 2 contains at least one selected from the group consisting of a high softening point monomer, other monomers, and a Si atom-containing polymerizable monomer together with a fluoroalkyl group-containing (meth) acrylic acid ester as a monomer component. be able to.
• the said General formula (6) is obtained using a low-priced raw material, and has high usefulness which can form the gap fill material which has favorable waterproofness. It is a polymer.
• the type and amount of the polymerization initiator are the same as those of the fluoropolymer 1.
• the amount of Si atom-containing mercaptan used is 0.01 to 25 parts by mass with respect to 100 parts by mass of the fluoroalkyl group-containing (meth) acrylic acid ester used as the monomer component.
• the content is preferably 0.1 to 5 parts by mass.
• the amount of the high softening point monomer in the monomer component and the amount of the Si atom-containing polymerizable monomer used are the same as described in the fluoropolymer 1.
• the polymerization of the fluoropolymer 2 can be performed under the same conditions as the fluoropolymer 1.
• (II) Solvent As the fluorine-based solvent contained in the composition for forming a fluorine-containing sealing material of the present invention, a solvent having a fluorine atom in the molecule and good solubility of the formed fluorine-containing polymer may be used. It is preferable to use a hydrocarbon compound, alcohol or ether having a fluorine atom in the molecular structure.
• the fluorinated solvent may be aliphatic or aromatic.
• the fluorine-based solvent is selected from the group consisting of hydrofluoroether, hydrofluorocarbon, perfluorocarbon, and an olefin in which at least one hydrogen atom is substituted with a fluorine atom and at least one hydrogen atom is substituted with a chlorine atom. It is preferable to use at least 1.
• fluorinated solvent examples include chlorinated fluorinated hydrocarbons (particularly 2 to 5 carbon atoms), particularly HCFC225 (dichloropentafluoropropane), HCFC141b (dichlorofluoroethane), CFC316 (2, 2, 3, 3).
• hydrofluoroether is a solvent that has low chemical erosion with respect to various materials, and is a particularly suitable solvent as a solvent for the composition for forming a fluorine-containing sealant for electronic components that are strongly required to eliminate the adverse effects of the solvent. is there. Further, hydrofluoroether is an ideal solvent having excellent performance such as quick drying, low environmental pollution, nonflammability, and low toxicity.
• hydrofluoroether Formula: C y F 2y + 1 —O—C z H 2z + 1 [Wherein y is a number from 1 to 6, and z is a number from 1 to 6. ] It is preferable to use the compound shown by these.
• Such hydrofluoroethers include, for example, Novec HFE7100 (Chemical Formula C 4 F 9 OCH 3 ), 7200 (Chemical Formula C 4 F 9 OC 2 H 5 ), 7300 (Chemical Formula C 2 F 5 CF (OCH) manufactured by 3M Corporation, USA. 3 ) C 3 F 7 ) or the like can be used.
• an olefin in which at least one hydrogen atom is substituted with a fluorine atom and at least one hydrogen atom is substituted with a chlorine atom can be used as the fluorine-based solvent.
• the olefin is preferable from the viewpoint of preventing global warming.
• the olefin in which at least one hydrogen atom is substituted with a fluorine atom and at least one hydrogen atom is substituted with a chlorine atom is, for example, a compound having 2 to 5 carbon atoms, more specifically, having 3 carbon atoms. ⁇ 4 compounds.
• hydrochlorofluoroolefin or chlorofluoroolefin which has been recently developed as a low GWP solvent, is used.
• the chlorofluoroolefin means an olefin in which at least one of the substituents is substituted with a chlorine atom and the rest are substituted with a fluorine atom.
• hydrochlorofluoroolefin at least one of the substituents is substituted with a hydrogen atom, at least one with a chlorine atom, and the rest with a fluorine atom.
• hydrochlorofluoroolefin examples include 1-chloro-3,3,3-trifluoro-1-propene, 1-chloro-2,3,3-trifluoro-1-propene, and the like; 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,1,3-trichloro-2,3,3-trifluoro-1-propene, 1,1-dichloro-2, 3,3,3-tetrafluoro-1-propene and the like can be mentioned.
• the fluorine-containing polymer is 7% by mass or more, preferably 10% by mass or more, preferably 33% by mass or less, and 30% by mass with respect to the entire composition. % Or less, and more preferably 25% by mass or less.
• the fluorine-containing polymer is 7 to 33% by mass, preferably 10 to 30% by mass, and preferably 10 to 25% by mass with respect to the entire composition. It is more preferable.
• the composition for forming a fluorinated sealant of the present invention has a fluorinated polymer concentration as described above, so that the voids of the electronic member, particularly small voids (micro voids, for example, width 0.1 to 1 mm, depth 0. 1 to 3 mm) can be effectively filled.
• the composition for forming a fluorine-containing sealing material of the present invention is less likely to cause problems such as clogging of voids during filling, and can uniformly fill the voids.
• the composition for forming a fluorine-containing sealing material of the present invention has a fluorine-containing polymer concentration as described above, so that there is little volume reduction due to volatilization of the solvent, and it is easy to form a fluorine-containing sealing material with a large film thickness. Become. Therefore, the gap fill property is improved by using the composition for forming a fluorine-containing sealant of the present invention.
• the composition for forming a fluorine-containing sealant of the present invention contains a fluorine-containing polymer 1 and / or a fluorine-containing polymer 2, and since these polymers all contain a fluoroalkyl group, they are formed using the above composition.
• the fluorine sealant exhibits good waterproof performance.
• the composition for forming a fluorine-containing sealant of the present invention is excellent in abrasion resistance, has good waterproof and / or moisture-proof performance, can contribute to the formation of a sealant having excellent water repellency and good drainage.
• the fluorine-containing polymer 1 and the fluorine-containing polymer 2 are excellent in chemical resistance, for example, salt water, acid or basic aqueous solution, acetone, oleic acid or hexane, particularly salt water, and therefore the fluorine-containing sealing material of the present invention.
• the forming composition can contribute to the formation of a fluorine-containing sealing material having good chemical resistance.
• a member such as an electrode or a resin material may be formed in advance.
• the electrode or the resin is formed from water or the like. It becomes possible to protect members such as materials.
• the adhesion of the sealing material formed from the fluorine-containing sealing material-forming composition of the present invention to the object to be treated is good.
• the object to be treated include a wall surface of a gap of an electronic member, or a member (for example, glass; metal or metal oxide (for example, metal wiring)) filled in the gap; an elastomer such as silicone; polyethylene or epoxy; Resin materials) or display peripheral materials (optical adhesive, OCA, polarizing plate, etc.).
• the composition for forming a fluorine-containing sealing material contains the fluorine-containing polymer 1 as the fluorine-containing polymer.
• Fluoropolymer 1 is good for various treatment objects (the same is true for various treatment objects) due to hydroxyl groups or hydrolyzable groups bonded to Si atoms present in the side chain. It exhibits excellent adhesiveness and crosslinkability. Therefore, the fluorine-containing sealant formed using the fluorine-containing sealant-forming composition of this embodiment has good adhesion to the treatment object, abrasion resistance, and waterproof and / or moisture-proof performance.
• the composition for forming a fluorine-containing sealant contains the fluorine-containing polymer 2 as the fluorine-containing polymer.
• the fluorine-containing polymer 2 at least a part of the Si atom-containing mercaptan existing during the polymerization reaction is bonded to the polymer chain, and various treatments are performed depending on the hydroxyl group or hydrolyzable group bonded to the Si atom existing at the terminal. In addition to exhibiting good adhesiveness to an object (for various treatment objects, the same meaning as described above), it has crosslinkability.
• the fluorine-containing sealing material formed by using the composition for forming a fluorine-containing sealing material according to this aspect has excellent adhesion to the treatment object and abrasion resistance, and is further waterproof and / or moisture-proof. The performance is also good.
• the fluorine-containing polymer 1 or the fluorine-containing polymer 2 is formed using a monomer component further containing a high softening point monomer.
• both the fluorine-containing polymer 1 and the fluorine-containing polymer 2 improve the water repellency of the fluorine-containing sealing material to be formed, and improve water drainage.
• the composition for forming a fluorine-containing sealant of the present invention preferably has a viscosity in the range of 10 to 1000 mPa ⁇ s, more preferably in the range of 10 to 100 mPa ⁇ s, and in the range of 10 to 60 mPa ⁇ s. More preferably, it is in the range of 10 to 50 mPa ⁇ s.
• the viscosity is a B-type viscometer at 25 ° C. and can be measured according to JIS K7117-1: 1999.
• the composition for forming a fluorine-containing sealant of the present invention has the above-described viscosity, so that it is difficult for clogging of voids at the time of filling, and even for voids between electronic members, particularly minute voids having a narrow width. Can be filled uniformly. Since the composition for forming a fluorine-containing sealant of the present invention has the above-described viscosity, it is difficult for bubbles to be formed when filling the gaps, or even if bubbles are generated, the generated bubbles Disappears naturally (without special manipulation). Furthermore, the fluorine-containing sealing material-forming composition of the present invention having the above-described viscosity can form a sealing material having a sufficient film thickness after curing.
• the composition for forming a fluorine-containing sealing material is an ⁇ -substituted fluoroalkyl group-containing (meth) acrylic acid ester in which the fluoroalkyl group-containing (meth) acrylic acid ester is represented by the formula (1)
• Rf is a linear or branched fluoroalkyl group having 4 to 6 carbon atoms
• X is a group or atom other than a hydrogen atom, preferably a fluorine atom, a chlorine atom, Or it is a methyl group.
• the fluorine-based solvent is a hydrofluoroether.
• the fluorine-containing polymer formed from an ⁇ -substituted fluoroalkyl group-containing acrylic ester in which Rf is a fluoroalkyl group having 4 to 6 carbon atoms has good solubility in hydrofluoroether, and the fluorine-containing polymer formed
• the sealant has good waterproofness and moistureproofness and good wear resistance.
• Y is preferably a direct bond, an aliphatic group having 1 to 10 carbon atoms (for example, an alkylene group), or a —CH 2 CH (OH) CH 2 — group, more preferably 1 to 4 aliphatic groups (for example, an alkylene group), or a —CH 2 CH (OY 1 ) CH 2 — group.
• Y 1 is a hydrogen atom or an acetyl group.
• composition for forming a fluorine-containing sealing material of the present invention by using a fluorine-based solvent, the above-mentioned fluorine-containing polymer can be stably dissolved, and formation of a fluorine-containing sealing material having good stability that hardly causes precipitation or the like. Composition.
• the composition for forming a fluorine-containing sealing material of the present invention may be used as a composition for forming a fluorine-containing sealing material as it is after the polymerization reaction is carried out in a fluorine-based solvent for polymerization, and then the concentration of the polymer is adjusted as necessary.
• the fluorine-containing polymer may be separated, and a composition for forming a fluorine-containing sealing material containing the separated fluorine-containing polymer and a fluorine-based solvent may be used.
• the polymer concentration is adjusted using hydrofluoroether to obtain a composition for forming a fluorine-containing sealing material. .
• a target fluorine-containing sealing material-forming composition can be obtained efficiently.
• the composition for forming a fluorine-containing sealing material of the present invention may contain other components in addition to the fluorine-containing polymer and the fluorine-based solvent.
• Other components include catalysts (metal catalysts such as tin or titanium, or organic catalysts such as acid bases, stabilizers (dehydrating agents, molecular sieves, magnesium sulfate or methyl orthoformate), viscosity modifiers, fillers ( Inorganic materials such as silica, mica, and clay), colorants, and fluorescent agents.
• composition for forming a fluorine-containing sealing material of the present invention is not particularly limited, but can be used for electronic members such as displays or printed boards, for example, and materials contained in these members such as elastomers, plastics, Applicable to metals, ceramics, etc.
• electronic devices including the electronic member include a personal computer, a tablet personal computer, a smart phone, a digital camera, and a car navigation system.
• composition for forming a fluorine-containing sealing material of the present invention it is possible to form a fluorine-containing sealing material having water resistance and moisture resistance excellent in wear resistance.
• hydrofluoroether is used as a solvent
• a fluorine-containing sealing material having good waterproof and moisture resistance can be formed without causing chemical erosion and without adversely affecting the environment.
• a fluorine-containing sealing material having good chemical resistance and a large film thickness can be formed.
• composition for forming a fluorine-containing sealing material of the present invention it is not necessary to separately provide an adhesive layer, and it becomes possible to adhere to the wall surface of a member or a gap, thereby simplifying the process of forming the fluorine-containing sealing material. Is possible.
• the treatment method is not particularly limited.
• the composition for forming a fluorine-containing sealing material according to the present invention is used to form a void in an electronic member (for example, a bonded portion of a housing and a printed board, or a resin-molded metal terminal portion and a mold). It can be carried out by filling a gap between the resin and the like, and drying after filling.
• the hydroxyl group or hydrolyzable group bonded to the Si atom introduced into the polymer terminal or side chain of the fluorine-containing polymer contained in the composition for forming a fluorine-containing sealing material of the present invention is hydrolyzed by moisture in the atmosphere.
• the wall surface of the gap of the electronic member, or a member for example, glass, metal wiring, or elastomer such as silicone, resin material such as polyethylene or epoxy
• Silanol groups that have not reacted with the wall surfaces of the voids or the above members are condensed to form a strong film by crosslinking two-dimensionally or three-dimensionally.
• the temperature during the treatment there is no particular limitation on the temperature during the treatment, and the treatment may be usually performed at room temperature.
• the treatment time is not particularly limited, and can be, for example, 5 minutes to 1 hour.
• the composition for forming a fluorine-containing sealant of the present invention prior to the treatment with the composition for forming a fluorine-containing sealant of the present invention, it is formed from the composition for forming a fluorine-containing sealant by applying a primer treatment to the wall surfaces of the voids as necessary.
• the adhesion of the fluorine-containing sealant can be improved, and the wear resistance can be further improved.
• the primer treatment may be performed under the same conditions as the primer treatment in the case of using a silane coupling agent according to a conventional method.
• the obtained polymer coating film was subjected to water contact angle measurement for evaluation of repellency and cross-cut test for adhesion evaluation under the following conditions.
• Compound 5 was subjected to GPC measurement in the same manner as in Synthesis Example 1. Moreover, the polymer coating film was formed and the coating film was evaluated similarly to the synthesis example 1.
• Examples 1 to 12 and Comparative Examples 1 to 14> The reaction compositions obtained in Synthesis Examples 1 to 5 were adjusted in concentration using HFE7200, and solutions having polymer concentrations shown in Tables 1 and 2 were prepared. Evaluation of gap fill property and chemical resistance of each obtained sample was performed under the following conditions, respectively.
• a copper plate having a thickness of 0.5 mm was sandwiched between two slide glasses to form a gap having a thickness of 0.5 mm and a depth of 2 mm.
• the solution was put into a syringe equipped with a needle having an outer diameter of 0.2 mm and poured into the gap.
• the gap fill property was evaluated as follows. A: The solution enters the gap smoothly and spreads. Even if it does not bite bubbles or bites bubbles, the bubbles disappear naturally. B: The solution enters the gap smoothly and spreads, but foaming occurs. If the sample is shaken immediately after injection, the bubbles disappear. C: No solution enters the gap.
• the present invention can be suitably used for forming a fluorine-containing sealing material for filling a gap between electronic members such as a display or a printed board (for example, a gap at the end face of a display) in an electronic device or the like.

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