WO2009084635A1 - Aqueous coating agent for electronic component - Google Patents
Aqueous coating agent for electronic component Download PDFInfo
- Publication number
- WO2009084635A1 WO2009084635A1 PCT/JP2008/073740 JP2008073740W WO2009084635A1 WO 2009084635 A1 WO2009084635 A1 WO 2009084635A1 JP 2008073740 W JP2008073740 W JP 2008073740W WO 2009084635 A1 WO2009084635 A1 WO 2009084635A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- atom
- fluorine
- carbon atoms
- coating agent
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
Definitions
- the present invention relates to an aqueous coating agent that imparts excellent moisture resistance, water / oil repellency and antifouling properties to electronic parts and electrical parts.
- the term “electronic component” means both an electronic component and an electrical component.
- the water and oil repellent is applied by dissolving low molecular weight silicone and fluorine compounds (perfluoropolyether oligomers, etc.) with poor film-forming ability in a solvent and spraying the circuit board (patent) Therefore, no coating is formed on the surface of the circuit board, and the effect of the coating decreases with time.
- Patent Document 2 Japanese Patent Laid-Open No. 61-189893 discloses that a coating solution in which a polyfluoroalkyl group-containing polymer is dissolved in a nonflammable low-boiling organic solvent is applied to an electronic component.
- the organic solvent has a problem from the viewpoint of the coating operation and the environment.
- telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups). We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. Yes.
- the Rf group carbon number of the fluorine-containing copolymer mentioned above is 8 or more, there is a problem that it contains PFOA and PFOA analogs having bioaccumulative properties, and the short carbon number is 6 or less. There is a need for fluorine-containing polymers with improved transition to chain Rf group-containing fluoroacrylate polymers and improved affinity with other materials and skin.
- this invention relates to the moisture-proof coating agent for electronic components which consists of a fluorine-containing compound (1) and an aqueous liquid medium (2).
- the fluorine-containing compound (1) is generally a fluorine-containing polymer.
- the fluorine-containing compound (1) is (A) A polymer having a repeating unit derived from a fluorine-containing acrylate monomer is preferred.
- the fluorine-containing compound (1) is A polymer having (A) a repeating unit derived from a fluorine-containing acrylate monomer and (B) a repeating unit derived from an amino group-containing monomer is particularly preferred.
- the fluoropolymer has sufficient solubility in the necessary water. When it has a short-chain fluoroalkyl group having 7 or less carbon atoms, especially 6 or less, higher solubility can be obtained.
- the fluorine-containing polymer of the present invention has sufficiently high water solubility, and gives high moisture resistance on the substrate.
- the coating agent of the present invention can be easily formed on the surface of an electronic component by drying at a low temperature in a short time.
- the coating has excellent moisture resistance, water / oil repellency and antifouling properties, and is excellent in sustainability of these properties.
- the film formed from the coating agent of the present invention has high moisture resistance, water / oil repellency and antifouling property even if the film thickness is thin. Furthermore, the coating is excellent in chemical resistance, electrical insulation, weather resistance, and durability.
- the “acrylate monomer” includes not only an acrylate having a hydrogen atom at the ⁇ -position but also an acrylate in which the hydrogen atom at the ⁇ -position is substituted with a substituent such as a methyl group or a halogen atom.
- examples of the fluorine-containing acrylate monomer (A) include at least one fluorine-containing group selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group and a fluoroether group (hereinafter referred to as “fluorine-containing group”).
- X is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (where X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine 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. ] It is a monomer which has an unsaturated group represented by these.
- R 1 represents an alkyl group having 1 to 4 carbon atoms
- Y 1 is a hydrogen atom or an acetyl group.
- Rf represents a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or repeating units: —C 3 F 6 O—, —C 2 F 4 O— and —
- a fluoroether group having a total number of 1 to 200 of at least one repeating unit selected from the group consisting of CF 2 O—.
- Rf group when the Rf group is a fluoroalkyl group, it is preferably a perfluoroalkyl group.
- Rf group include those having 1 to 7 carbon atoms, such as —CF 3 , —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —CF (CF 3 ) 2 , —CF 2 CF 2 CF 2.
- the number of carbons in the Rf group should be 1 to 7, for example 2 to 6, especially 4 to 6, especially 6 from the viewpoints of PFOA and functions described above. Is preferred.
- the Rf group is a fluoroalkenyl group
- the Rf group is a fluoroalkenyl group
- the Rf group preferably has 2 to 7 carbon atoms, particularly 3 to 6 carbon atoms, especially 6 carbon atoms.
- the fluoroether group is at least one repeating unit selected from the group consisting of —C 3 F 6 O—, —C 2 F 4 O—, and —CF 2 O— (oxypar group). Fluoroalkylene group).
- —C 3 F 6 O— is —CF 2 CF 2 CF 2 O— or —CF 2 C (CF 3 ) FO—.
- —C 2 F 4 O— is generally —CF 2 CF 2 O—.
- the total number of oxyperfluoroalkylene repeating units is 1 to 200, for example 1 to 100, in particular 5 to 50.
- the fluoroether group has a terminal group that is directly bonded to the oxyperfluoroalkylene repeat unit.
- the fluoroether group may have a C1-C10 fluoroalkylene group, particularly a perfluoroalkylene group, in addition to the oxyperfluoroalkylene repeating unit and the terminal group. Examples of the fluoroalkylene group having 1 to 10 carbon atoms are —CF 2 — and —CF 2 CF 2 —.
- fluoroether groups that are examples of Rf groups are as follows.
- F- (CF 2 CF 2 CF 2 O) n -CF 2 CF 2- (n is 1 to 200)
- F- (CF 2 C (CF 3 ) FO) n -CF 2 CF 2- (n is 1 to 200)
- F- (CF 2 C (CF 3 ) FO) n- (CF 2 O) m -CF 2 CF 2- (total of n and m is 1 to 200)
- F- (CF 2 CF 2 O) n- (CF 2 O) m -CF 2 CF 2- total of n and m is 1 to 200)
- Y represents a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group.
- An aliphatic group a —CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms) or a —CH 2 CH (OY 1 ) CH 2 — group ( However, Y ⁇ 1 > is a hydrogen atom or an acetyl group.).
- the aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, such as 1 or 2).
- the aromatic group and the cycloaliphatic group may be either substituted or unsubstituted.
- fluorine-containing acrylate monomer examples include as follows.
- 2 OCOCH CH 2 Rf-SO 2 N (C 2 H 5)
- Rf is preferably a linear or branched fluoroalkyl group having 1 to 7 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or a repeating unit: —C 3 F 6 O—, — A fluoroether group in which the total number of at least one repeating unit selected from the group consisting of C 2 F 4 O— and —CF 2 O— is 1 to 200.
- the amino group-containing monomer (B) is a compound having an amino group and a carbon-carbon double bond.
- the amino group-containing monomer (B) preferably does not contain a fluorine atom.
- Examples of amino group-containing monomers (B) have the formula: [Wherein R 11 , R 12 and R 21 are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y 11 is an oxygen atom or NH, and Z is 1 to 4 carbon atoms] 10 branched or straight chain alkylene groups. R 11 and R 12 may be bonded to each other to form a ring together with the adjacent nitrogen atom. ] It is shown by. Since the copolymer includes an amino group, for example, when a salt is formed with a protonic acid, the copolymer is dissociated when dissolved in water and becomes cationic.
- R 11 , R 12 and R 21 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl, etc.).
- R 21 is preferably a hydrogen atom or a methyl group.
- R 11 and R 12 When R 11 and R 12 are bonded to each other to form a ring with an adjacent nitrogen atom, R 11 and R 12 may be bonded through a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom.
- Examples of the ring formed by combining R 11 and R 12 together with the adjacent nitrogen atom include an aziridine ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
- Examples of the alkylene group represented by Z include linear or branched alkylene groups having 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms) such as methylene, ethylene, propylene, trimethylene, tetramethylene and hexamethylene groups. Can be mentioned.
- amino group-containing monomer (B) examples include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) )
- the compound etc. which are NH are mentioned.
- the amino group-containing monomer (B) can be used alone or in combination of two or more.
- the monomer constituting the fluoropolymer may contain a hydrophilic non-fluorine monomer (C) in addition to the monomers (A) and (B).
- the hydrophilic non-fluorine monomer (C) has hydrophilicity and does not contain a fluorine atom.
- An example of a hydrophilic group is an oxyalkylene group.
- the hydrophilic non-fluorine monomer (C) may be a monomer having a hydrophilic group which is an oxyalkylene group (2 to 6 carbon atoms of an alkylene group) and a carbon-carbon double bond.
- the hydrophilic group which is an oxyalkylene group is nonionic.
- the number of oxyalkylene groups in the hydrophilic non-fluorine monomer (C) may be 2 to 200, for example 3 to 50.
- the hydrophilic non-fluorine monomer (C) may be polyalkylene glycol mono (meth) acrylate and / or polyalkylene glycol di (meth) acrylate.
- the molecular weight of the hydrophilic non-fluorine monomer (C) may be 100 or more, such as 150 or more, particularly 200 or more, particularly 250 to 3000.
- R in the general formula (III) is preferably ethylene, propylene and butylene, particularly an ethylene group.
- R in the general formula (III) may be a combination of two or more alkylene groups. In that case, at least one of R is preferably an ethylene group. Examples of the combination of R include an ethylene group / propylene group combination and an ethylene group / butylene group combination.
- the hydrophilic non-fluorine monomer (C) may be a mixture of two or more. In that case, at least one of the hydrophilic non-fluorine monomers (C) preferably has R in the general formula (III) as an ethylene group.
- hydrophilic non-fluorine monomer (C) examples include, for example, the following, but are not limited thereto.
- C 4 H 9 CH 2 CX 1 COO- (CH 2 CH 2 O) 23 -OOC (
- the monomer constituting the fluoropolymer may contain another monomer (D) as required in addition to the monomers (A), (B), (C).
- the other monomer (D) is preferably a non-fluorine monomer.
- the other monomer (D) include hydrocarbon group-containing monomers, ethylene, vinyl acetate, vinyl halide (eg, vinyl chloride), vinylidene halide (eg, vinylidene chloride), acrylonitrile, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, vinyl alkyl ketone, vinyl alkyl Examples include, but are not limited to, ether, isoprene, chloroprene, butadiene and the like.
- the other monomer (D) includes a monomer having a silane group.
- the monomer having a silane group is preferably a compound having a silane group (particularly a terminal silane group) and a carbon-carbon double bond.
- the monomer having a silane group may be a terminal silane coupling agent or a monomer having a silane coupling agent in the side chain. Specific examples of the monomer having a silane group are as follows.
- the weight average molecular weight of the fluoropolymer may be, for example, from 1,000 to 1,000,000, in particular from 2,000 to 100,000, especially from 4,000 to 20,000.
- the weight average molecular weight of the fluoropolymer is determined by GPC (gel permeation chromatography) (polystyrene conversion).
- the fluoropolymer is soluble in water.
- the solubility of the fluoropolymer (the amount of the fluoropolymer that can be dissolved in 100 g of water at 25 ° C.) may be 5 g or more, for example, 10 g or more, particularly 20 g or more.
- the upper limit of solubility may be 500 g, for example 200 g.
- the fluorine-containing polymer may be composed of a combination of repeating units derived from the following monomers. (1) Monomer (A) + Monomer (B) (2) Monomer (A) + Monomer (B) + Monomer (C) (3) Monomer (A) + Monomer (B) + Monomer (D) (4) Monomer (A) + Monomer (B) + Monomer (C) + Monomer (D)
- the amount of monomer (B) is 1 to 500 parts by weight, for example 2 to 100 parts by weight, in particular 3 to 80 parts by weight, especially 5 to 70 parts by weight,
- the amount of the monomer (C) is 0 to 10 parts by weight, for example 1 to 5 parts by weight
- the amount of the monomer (D) is 0 to 10 parts by weight, for example 1 to 5 parts by weight, It may be.
- the fluoropolymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected.
- Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. In particular, solution polymerization is preferable.
- a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, for example, is heated and stirred in the range of 50 to 120 ° C. for 1 to 10 hours.
- the polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, Examples include diisopropyl peroxydicarbonate.
- the polymerization initiator may be used in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer.
- Organic solvents are those that are inert to the monomers and dissolve them, such as pentane, hexane, heptane, octane, isooctane, cyclohexane, benzene, toluene, xylene, petroleum ether, commercial petroleum solvents (ExxonMobil).
- EXXSOL D40, ISOPER E, etc. tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, t-butyl acetate, isopropanol, propylene glycol methyl ether acetate, p- Examples include chlorobenzotrifluoride, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like.
- the organic solvent may be used in the range of 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.
- an aqueous solution of the polymer can be obtained by adding water to the reaction mixture and removing the organic solvent (by distillation or the like).
- the coating agent (for example, water / oil repellent or antifouling agent) comprises (1) a fluoropolymer and (2) an aqueous liquid medium, that is, water or a mixture of water and a water-soluble organic solvent.
- a fluoropolymer for example, water / oil repellent or antifouling agent
- an aqueous liquid medium that is, water or a mixture of water and a water-soluble organic solvent.
- water-soluble organic solvents are alcohols such as methanol, ethanol, n-propanol, isopropanol; ketones such as acetone.
- the amount of the water-soluble organic solvent may be 50% by weight or less, for example, 1 to 30% by weight with respect to the mixture (the sum of water and the water-soluble organic solvent).
- the coating agent is in the form of a solution (aqueous solution) of a fluoropolymer.
- the amount of the fluorine-containing polymer is not particularly limited and may be appropriately selected from a range in which it can be uniformly dissolved. For example, it may be from 0.1 to 50% by weight, for example from 0.2 to 20% by weight, in particular from 0.5 to 10% by weight, based on the coating agent.
- the coating agent of the present invention may contain (3) an additive in addition to (1) the fluoropolymer and (2) the aqueous liquid medium.
- the additive (3) are silicon-containing compounds.
- the silicon-containing compound is preferably a compound having at least one siloxane bond.
- the silicon-containing compound is generally a compound excluding a monomer having a silane group.
- Examples of silicon-containing compounds include alkyl silicates and siliconates.
- alkyl silicates include the following general formula (I): [Wherein R 1n represents an alkyl group having 1 to 18 carbon atoms, and when nn is 2 or more, they may be the same or different.
- R 2n represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be the same or different when nn is 2 or more.
- nn represents an integer of 1 to 20.
- the alkyl group having 1 to 18 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and hexyl.
- the alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and these are linear. Alternatively, it may be branched.
- the nn is an integer of 1 to 20, for example, 1 to 10.
- the alkyl silicate includes, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethyl.
- dimers and the like of silicon-containing compounds can also be used as silicon-containing compounds, and examples thereof include those having nn of 2 or 3 in the above general formula (I). Furthermore, nn may be an integer up to 20.
- Siliconates are for example represented by the formula: R 1 a Si (OR 2 ) b (OM) c is a compound represented by c .
- a is an integer of 0 or more (preferably 1)
- b is an integer of 0 or more (preferably 2)
- R 1 may be the same or different and represents a hydrocarbon group having 1 to 18 carbon atoms.
- R 2 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
- M may be the same or different and represents an alkali metal.
- the hydrocarbon group is, for example, an aliphatic hydrocarbon group (for example, an alkyl group), an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group.
- R 1 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, and n-hexyl.
- a methyl group, an ethyl group, and a propyl group are preferable, and a methyl group is particularly preferable.
- R 2 include a hydrogen atom and the same group as R 1 . Among these, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom is particularly preferable.
- M include Li, Na, K and the like, and Na is particularly preferable.
- Specific examples of the alkyl siliconate are sodium methyl siliconate [CH 3 Si (OH) 2 (ONa)] and potassium ethyl siliconate [C 2 H 5 Si (OH) 2 (OK)].
- the amount of the additive (3) may be 0 to 200 parts by weight, for example 0 to 50 parts by weight, for example, 0.1 to 50 parts by weight with respect to 100 parts by weight of the fluoropolymer (1). .
- the coating agent may contain other water repellents, other oil repellents, fluorescent agents, drying rate adjusting agents, crosslinking agents, film-forming aids, Solubilizers, surfactants, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, antifoaming agents, slipperiness adjusters, antistatic agents, hydrophilic agents, antibacterial agents, antiseptics, You may contain an insect repellent, an aromatic agent, a flame retardant, a color tone regulator, etc.
- a coating agent is applied to a substrate to impart moisture resistance to the substrate.
- the substrate examples include electronic parts and electric parts.
- the term “electronic component” simply means an electrical component in addition to an electronic component.
- the base material is an electronic component and an electrical component that are disposed in a place exposed to moisture regardless of whether they are outdoors or indoors, and is an electronic component and an electrical component on which various elements are mounted.
- Examples of the substrate include a circuit board and a hard disk bearing. Electronic parts and electrical parts are used in articles such as telephones, traffic lights, air conditioner outdoor units, switchboards, pole capacitors, mobile phones, portable relay antennas, automotive electronic equipment, ship electronic equipment, vending machines, mobile personal computers, etc. Is done.
- Examples of electronic components include various printed wiring boards (electronic circuit boards) and hybrid ICs, but are not limited thereto.
- Epoxy resin, phenolic resin, BT resin, polyimide, glass base fabric (fiber), aluminum, etc. are used as substrate materials for such electronic components, and copper, silver, gold, platinum and other metals as circuit materials, Solder is scattered on the substrate.
- the coating composition of the present invention does not alter these materials.
- examples of electrical components include various electrical devices incorporating the above-described electronic components, as well as switchboards.
- outdoor units for air conditioners, mobile phones, car navigation systems, solar panels, lighting, traffic lights, mobile relay antennas, automotive electronics, vending machines, mobile PCs, unmanned antenna stations, radios, marine equipment An example is a watch.
- Coating the coating agent by brushing, dipping, spraying, roll coating, potting, casting, etc., and leaving it in the surrounding environment to volatilize the aqueous liquid medium to form a coating film.
- the coating film may be a film prepared from the coating composition, for example, a cast film. This film provides a moisture-proof effect by wrapping electronic / electrical parts.
- the substrate is treated (particularly applied) with the coating agent.
- the amount of the coating agent is 0.05 to 50 g / m 2 , for example 0.1 to 25 g / m 2 , preferably 0.5 to 5.0 g / m 2 in terms of the fluoropolymer in the coating agent.
- the application may be performed once but may be divided into a plurality of times.
- Treatment means that the treatment agent is applied to the substrate by dipping, spraying, coating, or the like.
- the fluoropolymer which is an active ingredient of the treatment agent adheres to the surface of the base material (and / or penetrates into the base material).
- Test methods and measurement methods employed in the present invention and the following examples are as follows.
- (1) Water / oil repellency The water / oil repellency of the copper foil portion of the test piece was evaluated using a contact angle meter (CONTACT-ANGLE METER CA-DT, manufactured by Kyowa Interface Science Co., Ltd.).
- High-temperature and high-humidity resistance Place the test piece in a high-temperature and high-humidity tank maintained at 85 RH% at 85 ° C for 48 hours and continuously apply a voltage of 16V. When measuring the resistance value, a voltage of 100 V was applied, and the change with time of the resistance value under high temperature and high humidity was examined.
- Production Example 2 [Rf (C4) Cl-DM] and Production Example 3 [Rf (C2) -DM]
- Rf (C6) methacrylate and DM are replaced with CF 3 CF 2 CF 2 CF 2 —CH 2 CH 2 OCOC (Cl) ⁇ CH 2 [Rf (C4) chloroacrylate] 63.00 g and DM 37.00 g, respectively.
- a product produced in exactly the same manner except for the above was designated Production Example 2.
- Production Example 3 was produced in exactly the same manner except that it was replaced with 59.62 g of CF 3 CF 2 —CH 2 OCOC (CH 3 ) ⁇ CH 2 [Rf (C2) methacrylate] and 40.38 g of DM.
- Example 1 Glass fiber reinforced epoxy resin plate with comb-shaped electrode substrate (material: CEM3, plate thickness: 1.6mm, copper foil thickness: 18 ⁇ m, pattern width: 0.75mm or 0.3mm), coating agent by brush coating method (Production Example 1) And a test piece having a coating thickness of 2.7 ⁇ m was prepared. About this test piece (test piece which apply
- Example 2 The same procedure as in Example 1 was repeated except that the film thickness of the coating was changed to 0.8 ⁇ m. The results are shown in Tables 1 to 4.
- Comparative Examples 1 and 2 The same procedure as in Example 1 was repeated except that the type of coating agent and the film thickness of the coating were changed.
- a urethane dispersion (“Takelac W-6020” manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) and an acrylic dispersion (“ViniBran Binibrand T0-453N” manufactured by Nissin Chemical Industry Co., Ltd.) were used. The results are shown in Tables 1 to 4.
- the coating agent of the present invention can be used for moisture-proof coating of electronic parts and electric parts.
- electronic components and electrical components are circuit boards, hard disk bearings, and the like.
- Electronic parts and electric parts are, for example, telephones, traffic lights, air conditioner outdoor units, switchboards, pole capacitors, mobile phones, portable relay antennas, automobile electronic devices, ship electronic devices, vending machines, mobile personal computers, and the like.
Abstract
Description
一方、Federal Register(FR Vol.68, No.73/April 16, 2003[FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf)やEPA Environmental News FOR RELEASE: MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID(http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf)やEPA OPPT FACT SHEET April 14, 2003(http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf)は、テロマーが分解または代謝によりPFOAを生成する可能性があると公表している(テロマーとは長鎖フルオロアルキル基のことを意味する)。また、テロマーが、撥水撥油性、防汚性を付与された泡消火剤、ケア製品、洗浄製品、カーペット、テキスタイル、紙、皮革などの多くの製品に使用されていることをも公表している。 Next, I will explain the environmental problems of PFOA. From recent research results [EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)] Concerns about the environmental impact of PFOA (perfluorooctanoic acid), a type of fluoroalkyl compound, have become apparent, and on April 14, 2003, EPA (US Environmental Protection Agency) will strengthen scientific research on PFOA Announced.
On the other hand, Federal Register (FR Vol.68, No.73 / April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) and EPA Environmental News FOR RELEASE : MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT SHEET April 14, 2003 (http: // www. epa.gov/opptintr/pfoa/pfoafacts.pdf) publishes that telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups). We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. Yes.
本発明の別の目的は、電子部品表面にコーティングが容易に形成され、しかも防湿性だけでなく、耐薬品性、電気絶縁性、耐候性、耐久性に優れた塗膜を形成できる防湿コーティング剤を提供することにもある。 An object of the present invention is to provide a moisture-proof coating agent (that is, an aqueous coating composition) that is excellent in coating workability and environmental properties (no organic solvent is used).
Another object of the present invention is to provide a moisture-proof coating agent that can easily form a coating on the surface of an electronic component and can form a coating film that is excellent not only in moisture resistance but also in chemical resistance, electrical insulation, weather resistance, and durability. There is also to provide.
含フッ素化合物(1)は、一般に、含フッ素重合体である。含フッ素化合物(1)は、
(A)含フッ素アクリレート単量体から誘導された繰り返し単位を有してなる重合体であることが好ましい。含フッ素化合物(1)は、
(A)含フッ素アクリレート単量体から誘導された繰り返し単位、および
(B)アミノ基含有単量体から誘導された繰り返し単位
を有してなる重合体であることが特に好ましい。 That is, this invention relates to the moisture-proof coating agent for electronic components which consists of a fluorine-containing compound (1) and an aqueous liquid medium (2).
The fluorine-containing compound (1) is generally a fluorine-containing polymer. The fluorine-containing compound (1) is
(A) A polymer having a repeating unit derived from a fluorine-containing acrylate monomer is preferred. The fluorine-containing compound (1) is
A polymer having (A) a repeating unit derived from a fluorine-containing acrylate monomer and (B) a repeating unit derived from an amino group-containing monomer is particularly preferred.
本発明のコーティング剤は、低温かつ短時間で乾燥して、電子部品表面上に被膜を容易に形成できる。被膜は、優れた防湿性、撥水撥油性および防汚性を有しており、これら性質の持続性に優れている。本発明のコーティング剤から形成された被膜は、膜厚が薄くても、防湿性、撥水撥油性および防汚性が高い。さらに、被膜は、耐薬品性、電気絶縁性、耐候性、耐久性に優れている。 In the present invention, the fluoropolymer has sufficient solubility in the necessary water. When it has a short-chain fluoroalkyl group having 7 or less carbon atoms, especially 6 or less, higher solubility can be obtained. The fluorine-containing polymer of the present invention has sufficiently high water solubility, and gives high moisture resistance on the substrate.
The coating agent of the present invention can be easily formed on the surface of an electronic component by drying at a low temperature in a short time. The coating has excellent moisture resistance, water / oil repellency and antifouling properties, and is excellent in sustainability of these properties. The film formed from the coating agent of the present invention has high moisture resistance, water / oil repellency and antifouling property even if the film thickness is thin. Furthermore, the coating is excellent in chemical resistance, electrical insulation, weather resistance, and durability.
含フッ素重合体において、含フッ素アクリレート単量体(A)の例は、フルオロアルキル基、フルオロアルケニル基およびフルオロエーテル基からなる群から選択された少なくとも一種のフッ素含有基(以下、「フッ素含有基」という)、および
式:-O-CO-CX=CH2
[式中、Xは、水素原子、炭素数1~6の直鎖状または分岐状のアルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX1X2基(但し、X1およびX2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。)、シアノ基、炭素数1~21の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基である。]
で表される不飽和基を有する単量体である。 In the present invention, the “acrylate monomer” includes not only an acrylate having a hydrogen atom at the α-position but also an acrylate in which the hydrogen atom at the α-position is substituted with a substituent such as a methyl group or a halogen atom. .
In the fluorine-containing polymer, examples of the fluorine-containing acrylate monomer (A) include at least one fluorine-containing group selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group and a fluoroether group (hereinafter referred to as “fluorine-containing group”). And the formula: —O—CO—CX═CH 2
[Wherein, X is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (where X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine 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. ]
It is a monomer which has an unsaturated group represented by these.
CH2=C(-X)-C(=O)-O-Y-Rf (I)
[式中、Xは、水素原子、炭素数1~6の直鎖状または分岐状のアルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX1X2基(但し、X1およびX2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。)、シアノ基、炭素数1~21の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基、
Yは、直接結合、酸素原子を有していてもよい炭素数1~10の脂肪族基、酸素原子を有していてもよい炭素数6~10の芳香族基、環状脂肪族基または芳香脂肪族基、-CH2CH2N(R1)SO2-基(但し、R1は炭素数1~4のアルキル基である。)または-CH2CH(OY1)CH2-基(但し、Y1は水素原子またはアセチル基である。)、
Rfは炭素数1~21の直鎖状または分岐状のフルオロアルキル基、炭素数2~7のフルオロアルケニル基または、繰り返し単位:-C3F6O-、-C2F4O-および-CF2O-からなる群から選択された少なくとも一種の繰り返し単位の合計数が1~200のフルオロエーテル基である。]
で示される。 Examples of the acrylate monomer having a fluorine-containing group include a formula:
CH 2 = C (-X) -C (= O) -OY-Rf (I)
[Wherein, X is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (where X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine 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,
Y represents a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms) or a —CH 2 CH (OY 1 ) CH 2 — group ( Y 1 is a hydrogen atom or an acetyl group.
Rf represents a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or repeating units: —C 3 F 6 O—, —C 2 F 4 O— and — A fluoroether group having a total number of 1 to 200 of at least one repeating unit selected from the group consisting of CF 2 O—. ]
Indicated by
Rf基がフルオロアルケニル基の場合、Rf基の例は、-CF=CF(CF3)、-CF=C(CF3)2、-CF=C(CF3)(CF2CF2CF3)、-CF=C(CF3)(CF(CF3)2)、-C(CF3)=CF(CF(CF3)2) 、-C(CF2CF3)=C(CF3)2等である。Rf基がフルオロアルケニル基である場合に、Rf基の炭素数は、2~7、特に3~6、特別には6であることが好ましい。 In the formula (I), when the Rf group is a fluoroalkyl group, it is preferably a perfluoroalkyl group. Specific examples of the Rf group include those having 1 to 7 carbon atoms, such as —CF 3 , —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —CF (CF 3 ) 2 , —CF 2 CF 2 CF 2. CF 3 , —CF 2 CF (CF 3 ) 2 , —C (CF 3 ) 3 , — (CF 2 ) 4 CF 3 , — (CF 2 ) 2 CF (CF 3 ) 2 , —CF 2 C (CF 3 ) 3 , -CF (CF 3 ) CF 2 CF 2 CF 3 ,-(CF 2 ) 5 CF 3 ,-(CF 2 ) 3 CF (CF 3 ) 2 ,-(CF 2 ) 4 CF (CF 3 ) 2 , — (CF 2 ) 2 H, —CF 2 CFHCF 3 , — (CF 2 ) 4 H, — (CF 2 ) 6 H, and the like. When the Rf group is a fluoroalkyl group, the number of carbons in the Rf group should be 1 to 7, for example 2 to 6, especially 4 to 6, especially 6 from the viewpoints of PFOA and functions described above. Is preferred.
When the Rf group is a fluoroalkenyl group, examples of the Rf group are -CF = CF (CF 3 ), -CF = C (CF 3 ) 2 , -CF = C (CF 3 ) (CF 2 CF 2 CF 3 ) , -CF = C (CF 3 ) (CF (CF 3 ) 2 ), -C (CF 3 ) = CF (CF (CF 3 ) 2 ), -C (CF 2 CF 3 ) = C (CF 3 ) 2 Etc. When the Rf group is a fluoroalkenyl group, the Rf group preferably has 2 to 7 carbon atoms, particularly 3 to 6 carbon atoms, especially 6 carbon atoms.
アミン基(例えば、H2N-)、カルボン酸基(例えば、HOOC-)、酸ハライド基(例えば、F(O=)C-)、クロロメチル基(ClH2C-)である。フルオロエーテル基は、オキシパーフルオロアルキレン繰り返し単位および末端基に加えて、炭素数1~10のフルオロアルキレン基、特にパーフルオロアルキレン基を有していてもよい。炭素数1~10のフルオロアルキレン基の例は、-CF2-および-CF2CF2-である。 When the Rf group is a fluoroether group, the fluoroether group is at least one repeating unit selected from the group consisting of —C 3 F 6 O—, —C 2 F 4 O—, and —CF 2 O— (oxypar group). Fluoroalkylene group). —C 3 F 6 O— is —CF 2 CF 2 CF 2 O— or —CF 2 C (CF 3 ) FO—. —C 2 F 4 O— is generally —CF 2 CF 2 O—. The total number of oxyperfluoroalkylene repeating units is 1 to 200, for example 1 to 100, in particular 5 to 50. The fluoroether group has a terminal group that is directly bonded to the oxyperfluoroalkylene repeat unit. Examples of the terminal group include a hydrogen atom, a halogen atom (for example, a fluorine atom), an alcohol group (for example, HOCH 2 —), an epoxy group (for example,
An amine group (for example, H 2 N-), a carboxylic acid group (for example, HOOC-), an acid halide group (for example, F (O =) C-), and a chloromethyl group (ClH 2 C-). The fluoroether group may have a C1-C10 fluoroalkylene group, particularly a perfluoroalkylene group, in addition to the oxyperfluoroalkylene repeating unit and the terminal group. Examples of the fluoroalkylene group having 1 to 10 carbon atoms are —CF 2 — and —CF 2 CF 2 —.
F-(CF2CF2CF2O)n-CF2CF2- (nは1~200)
F-(CF2C(CF3)FO)n-CF2CF2- (nは1~200)
F-(CF2C(CF3)FO)n-(CF2O)m-CF2CF2- (nとmの合計は1~200)
F-(CF2CF2O)n-(CF2O)m-CF2CF2- (nとmの合計は1~200) Examples of fluoroether groups (particularly perfluoroether groups) that are examples of Rf groups are as follows.
F- (CF 2 CF 2 CF 2 O) n -CF 2 CF 2- (n is 1 to 200)
F- (CF 2 C (CF 3 ) FO) n -CF 2 CF 2- (n is 1 to 200)
F- (CF 2 C (CF 3 ) FO) n- (CF 2 O) m -CF 2 CF 2- (total of n and m is 1 to 200)
F- (CF 2 CF 2 O) n- (CF 2 O) m -CF 2 CF 2- (total of n and m is 1 to 200)
Rf-(CH2)10OCOCH=CH2
Rf-(CH2)10OCOC(CH3)=CH2
Rf-CH2OCOCH=CH2
Rf-CH2OCOC(CH3)=CH2
Rf-(CH2)2OCOCH=CH2
Rf-(CH2)2OCOC(CH3)=CH2
Rf-SO2N(CH3)(CH2)2OCOCH=CH2
Rf-SO2N(C2H5)(CH2)2OCOCH=CH2
Rf-CH2CH(OCOCH3)CH2OCOC(CH3)=CH2
Rf-CH2CH(OH)CH2OCOCH=CH2
Rf- (CH 2 ) 10 OCOCH═CH 2
Rf- (CH 2) 10 OCOC ( CH 3) = CH 2
Rf—CH 2 OCOCH═CH 2
Rf-CH 2 OCOC (CH 3 ) = CH 2
Rf- (CH 2 ) 2 OCOCH═CH 2
Rf- (CH 2 ) 2 OCOC (CH 3 ) ═CH 2
Rf-SO 2 N (CH 3 ) (CH 2) 2 OCOCH = CH 2
Rf-SO 2 N (C 2 H 5) (CH 2) 2 OCOCH = CH 2
Rf-CH 2 CH (OCOCH 3 ) CH 2 OCOC (CH 3) = CH 2
Rf-CH 2 CH (OH) CH 2 OCOCH = CH 2
アミノ基含有単量体(B)の例は、式:
[式中、R11、R12、R21は、同一又は異なって、水素原子、又は炭素数1~4のアルキル基であり、Y11は酸素原子又はNHであり、Zは炭素数1~10の分岐または直鎖のアルキレン基である。R11とR12は互いに結合して隣接する窒素原子と共に環を形成してもよい。]
で示されるものである。
共重合体は、アミノ基を含むため、例えばプロトン酸により塩を形成すると、水に溶解したときに解離してカチオン性を呈する。 The amino group-containing monomer (B) is a compound having an amino group and a carbon-carbon double bond. The amino group-containing monomer (B) preferably does not contain a fluorine atom.
Examples of amino group-containing monomers (B) have the formula:
[Wherein R 11 , R 12 and R 21 are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y 11 is an oxygen atom or NH, and Z is 1 to 4 carbon atoms] 10 branched or straight chain alkylene groups. R 11 and R 12 may be bonded to each other to form a ring together with the adjacent nitrogen atom. ]
It is shown by.
Since the copolymer includes an amino group, for example, when a salt is formed with a protonic acid, the copolymer is dissociated when dissolved in water and becomes cationic.
Zであるアルキレン基としては、メチレン、エチレン、プロピレン、トリメチレン、テトラメチレン、ヘキサメチレン基などの直鎖状又は分岐鎖状の炭素数1~6(好ましくは炭素数1~4)のアルキレン基が挙げられる。 R 11 , R 12 and R 21 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl, etc.). R 21 is preferably a hydrogen atom or a methyl group. When R 11 and R 12 are bonded to each other to form a ring with an adjacent nitrogen atom, R 11 and R 12 may be bonded through a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom. Examples of the ring formed by combining R 11 and R 12 together with the adjacent nitrogen atom include an aziridine ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
Examples of the alkylene group represented by Z include linear or branched alkylene groups having 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms) such as methylene, ethylene, propylene, trimethylene, tetramethylene and hexamethylene groups. Can be mentioned.
親水性基の例は、オキシアルキレン基である。 The monomer constituting the fluoropolymer may contain a hydrophilic non-fluorine monomer (C) in addition to the monomers (A) and (B). The hydrophilic non-fluorine monomer (C) has hydrophilicity and does not contain a fluorine atom.
An example of a hydrophilic group is an oxyalkylene group.
オキシアルキレン基である親水性基は、ノニオン性である。親水性非フッ素単量体(C)におけるオキシアルキレン基の数は、2~200、例えば3~50であってよい。
親水性非フッ素単量体(C)は、ポリアルキレングリコールモノ(メタ)アクリレートおよび/またはポリアルキレングリコールジ(メタ)アクリレートであってよい。
親水性非フッ素単量体(C)の分子量は、100以上、例えば150以上、特に200以上、特に250~3000であってよい。 The hydrophilic non-fluorine monomer (C) may be a monomer having a hydrophilic group which is an oxyalkylene group (2 to 6 carbon atoms of an alkylene group) and a carbon-carbon double bond.
The hydrophilic group which is an oxyalkylene group is nonionic. The number of oxyalkylene groups in the hydrophilic non-fluorine monomer (C) may be 2 to 200, for example 3 to 50.
The hydrophilic non-fluorine monomer (C) may be polyalkylene glycol mono (meth) acrylate and / or polyalkylene glycol di (meth) acrylate.
The molecular weight of the hydrophilic non-fluorine monomer (C) may be 100 or more, such as 150 or more, particularly 200 or more, particularly 250 to 3000.
CH2=CX1C(=O)-O-(RO)n-X2 (III)
[式中、
X1は、水素原子またはメチル基、
X2は、水素原子または炭素数1~22の不飽和または飽和の炭化水素基
Rは、炭素数2~6のアルキレン基、
nは、2~90の整数、
である。]
で示されるものであることが好ましい。nは、特に3~30、例えば4~20であってよい。 The polyalkylene glycol mono (meth) acrylate has the general formula:
CH 2 = CX 1 C (= O) -O- (RO) n -X 2 (III)
[Where:
X 1 is a hydrogen atom or a methyl group,
X 2 is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms,
n is an integer of 2 to 90,
It is. ]
It is preferable that it is shown by these. n may in particular be 3 to 30, for example 4 to 20.
一般式(III)中のRは2種類以上のアルキレン基の組み合わせであっても良い。その場合、少なくともRのひとつはエチレン基であることが好ましい。Rの組合せとしては、エチレン基/プロピレン基の組合せ、エチレン基/ブチレン基の組合せが挙げられる。
親水性非フッ素単量体(C)は2種類以上の混合物であっても良い。その場合は少なくとも親水性非フッ素単量体(C)のひとつは一般式(III)中のRがエチレン基であることが好ましい。 R in the general formula (III) is preferably ethylene, propylene and butylene, particularly an ethylene group.
R in the general formula (III) may be a combination of two or more alkylene groups. In that case, at least one of R is preferably an ethylene group. Examples of the combination of R include an ethylene group / propylene group combination and an ethylene group / butylene group combination.
The hydrophilic non-fluorine monomer (C) may be a mixture of two or more. In that case, at least one of the hydrophilic non-fluorine monomers (C) preferably has R in the general formula (III) as an ethylene group.
CH2=CX1COO-(CH2CH2O)n-H
CH2=CX1-(CH2CH2O)n-CH3
CH2=CX1COO-(CH2CH(CH3)O)n-H
CH2=CX1COO-(CH2CH(CH3)O)n-CH3
CH2=CX1COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H
CH2=CX1COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3
CH2=CX1COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9
CH2=CX1COO-(CH2CH2O)23-OOC(CH3)C=CH2
CH2=CX1COO-(CH2CH2O)20-(CH2CH(CH3)O)5-CH2-CH=CH2 Specific examples of the hydrophilic non-fluorine monomer (C) include, for example, the following, but are not limited thereto.
CH 2 = CX 1 COO- (CH 2 CH 2 O) n -H
CH 2 = CX 1- (CH 2 CH 2 O) n -CH 3
CH 2 = CX 1 COO- (CH 2 CH (CH 3 ) O) n -H
CH 2 = CX 1 COO- (CH 2 CH (CH 3 ) O) n -CH 3
CH 2 = CX 1 COO- (CH 2 CH 2 O) 5- (CH 2 CH (CH 3 ) O) 2 -H
CH 2 = CX 1 COO- (CH 2 CH 2 O) 5- (CH 2 CH (CH 3 ) O) 3 -CH 3
CH 2 = CX 1 COO- (CH 2 CH 2 O) 8 - (CH 2 CH (CH 3) O) 6 -CH 2 CH (C 2 H 5) C 4 H 9
CH 2 = CX 1 COO- (CH 2 CH 2 O) 23 -OOC (CH 3 ) C = CH 2
CH 2 = CX 1 COO- (CH 2 CH 2 O) 20 - (CH 2 CH (CH 3) O) 5 -CH 2 -CH = CH 2
シラン基を有する単量体の具体例は、次のとおりである。
CH2=CHCO2(CH2)3Si(OCH3)3、
CH2=CHCO2(CH2)3Si(OC2H5)3、
CH2=C(CH3)CO2(CH2)3Si(OCH3)3
(γ-メタクリロキシプロピルトリメトキシシラン)、
CH2=C(CH3)CO2(CH2)3Si(OC2H5)3、
CH2=CHCO2(CH2)3SiCH3(OC2H5)2、
CH2=C(CH3)CO2(CH2)3SiC2H5(OCH3)2、
CH2=C(CH3)CO2(CH2)3Si(CH3)2(OC2H5)、
CH2=C(CH3)CO2(CH2)3Si(CH3)2OH、
CH2=CHCO2(CH2)3SiCH3〔ON(CH3)C2H5〕2、
CH2=C(CH3)CO2(CH2)3SiC6H5〔ON(CH3)C2H5〕2、
CH2=CHSi(OCH3)3、
CH2=CHSi(OC2H5)3、
CH2=CHSiCH3(OCH3)2、
CH2=CHSi(CH3)2(OC2H5)、
CH2=CHSi(CH3)2SiCH3(OCH3)2、
CH2=CHSiCH3〔ON(CH3)C2H5〕2
ビニルトリクロロシラン、
ビニルトリス(2-メトキシエトキシ)シラン。 Another example of the other monomer (D) includes a monomer having a silane group. The monomer having a silane group is preferably a compound having a silane group (particularly a terminal silane group) and a carbon-carbon double bond. The monomer having a silane group may be a terminal silane coupling agent or a monomer having a silane coupling agent in the side chain.
Specific examples of the monomer having a silane group are as follows.
CH 2 = CHCO 2 (CH 2 ) 3 Si (OCH 3 ) 3 ,
CH 2 = CHCO 2 (CH 2 ) 3 Si (OC 2 H 5 ) 3 ,
CH 2 = C (CH 3) CO 2 (CH 2) 3 Si (OCH 3) 3
(Γ-methacryloxypropyltrimethoxysilane),
CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 Si (OC 2 H 5 ) 3 ,
CH 2 = CHCO 2 (CH 2 ) 3 SiCH 3 (OC 2 H 5) 2,
CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 SiC 2 H 5 (OCH 3 ) 2 ,
CH 2 = C (CH 3) CO 2 (CH 2) 3 Si (CH 3) 2 (OC 2 H 5),
CH 2 = C (CH 3) CO 2 (CH 2) 3 Si (CH 3) 2 OH,
CH 2 = CHCO 2 (CH 2 ) 3 SiCH 3 [ON (CH 3 ) C 2 H 5 ] 2 ,
CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 SiC 6 H 5 [ON (CH 3 ) C 2 H 5 ] 2 ,
CH 2 = CHSi (OCH 3 ) 3 ,
CH 2 = CHSi (OC 2 H 5 ) 3 ,
CH 2 = CHSiCH 3 (OCH 3 ) 2 ,
CH 2 = CHSi (CH 3 ) 2 (OC 2 H 5 ),
CH 2 = CHSi (CH 3 ) 2 SiCH 3 (OCH 3 ) 2 ,
CH 2 = CHSiCH 3 [ON (CH 3 ) C 2 H 5 ] 2
Vinyltrichlorosilane,
Vinyltris (2-methoxyethoxy) silane.
含フッ素重合体は、水に溶解する。含フッ素重合体の溶解度(25℃で水100gに対して溶解可能な含フッ素重合体の量)は、5g以上、例えば10g以上、特に20g以上であってよい。溶解度の上限は、500g、例えば200gであってよい。 The weight average molecular weight of the fluoropolymer may be, for example, from 1,000 to 1,000,000, in particular from 2,000 to 100,000, especially from 4,000 to 20,000. The weight average molecular weight of the fluoropolymer is determined by GPC (gel permeation chromatography) (polystyrene conversion).
The fluoropolymer is soluble in water. The solubility of the fluoropolymer (the amount of the fluoropolymer that can be dissolved in 100 g of water at 25 ° C.) may be 5 g or more, for example, 10 g or more, particularly 20 g or more. The upper limit of solubility may be 500 g, for example 200 g.
(1) 単量体(A)+単量体(B)
(2) 単量体(A)+単量体(B)+単量体(C)
(3) 単量体(A)+単量体(B)+単量体(D)
(4) 単量体(A)+単量体(B)+単量体(C)+単量体(D) The fluorine-containing polymer may be composed of a combination of repeating units derived from the following monomers.
(1) Monomer (A) + Monomer (B)
(2) Monomer (A) + Monomer (B) + Monomer (C)
(3) Monomer (A) + Monomer (B) + Monomer (D)
(4) Monomer (A) + Monomer (B) + Monomer (C) + Monomer (D)
単量体(B)の量が1~500重量部、例えば2~100重量部、特に3~80重量部、特別に5~70重量部、
単量体(C)の量が0~10重量部、例えば1~5重量部、
単量体(D)の量が0~10重量部、例えば1~5重量部、
であってよい。 In the fluoropolymer, with respect to 100 parts by weight of the monomer (A),
The amount of monomer (B) is 1 to 500 parts by weight, for example 2 to 100 parts by weight, in particular 3 to 80 parts by weight, especially 5 to 70 parts by weight,
The amount of the monomer (C) is 0 to 10 parts by weight, for example 1 to 5 parts by weight,
The amount of the monomer (D) is 0 to 10 parts by weight, for example 1 to 5 parts by weight,
It may be.
コーティング剤は、含フッ素重合体の溶液(水溶液)の形態である。
コーティング剤において、含フッ素重合体の量は、特に限定はなく均一に溶解させることが可能な範囲内から適宜選択すればよい。例えばコーティング剤に対して、0.1~50重量%、例えば0.2~20重量%、特に0.5~10重量%であってよい。 In the present invention, the coating agent (for example, water / oil repellent or antifouling agent) comprises (1) a fluoropolymer and (2) an aqueous liquid medium, that is, water or a mixture of water and a water-soluble organic solvent. Comprising. Examples of water-soluble organic solvents are alcohols such as methanol, ethanol, n-propanol, isopropanol; ketones such as acetone. The amount of the water-soluble organic solvent may be 50% by weight or less, for example, 1 to 30% by weight with respect to the mixture (the sum of water and the water-soluble organic solvent).
The coating agent is in the form of a solution (aqueous solution) of a fluoropolymer.
In the coating agent, the amount of the fluorine-containing polymer is not particularly limited and may be appropriately selected from a range in which it can be uniformly dissolved. For example, it may be from 0.1 to 50% by weight, for example from 0.2 to 20% by weight, in particular from 0.5 to 10% by weight, based on the coating agent.
添加剤(3)の例は、含ケイ素化合物などである。
含ケイ素化合物は、少なくとも1つのシロキサン結合を有する化合物であることが好ましい。含ケイ素化合物は、一般に、シラン基を有する単量体を除く化合物である。 The coating agent of the present invention may contain (3) an additive in addition to (1) the fluoropolymer and (2) the aqueous liquid medium.
Examples of the additive (3) are silicon-containing compounds.
The silicon-containing compound is preferably a compound having at least one siloxane bond. The silicon-containing compound is generally a compound excluding a monomer having a silane group.
アルキルシリケートの例は、下記一般式(I):
[式中、R1nは炭素数1~18のアルキル基を表し、nnが2以上の場合には同一であっても異なっていてもよい。 R2nは、水素原子または炭素数1~5のアルキル基を表し、nnが2以上の場合には同一であっても異なっていてもよい。nnは、1~20の整数を表す。]
で示される化合物であってよい。 Examples of silicon-containing compounds include alkyl silicates and siliconates.
Examples of alkyl silicates include the following general formula (I):
[Wherein R 1n represents an alkyl group having 1 to 18 carbon atoms, and when nn is 2 or more, they may be the same or different. R 2n represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be the same or different when nn is 2 or more. nn represents an integer of 1 to 20. ]
It may be a compound shown by these.
上記nnは、1~20、例えば1~10の整数である。 Regarding R 2n , the alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and these are linear. Alternatively, it may be branched.
The nn is an integer of 1 to 20, for example, 1 to 10.
R1 aSi(OR2)b(OM)cで表される化合物である。
[式中、aは0以上の整数(好ましくは1)、bは0以上の整数(好ましくは2)、cは1以上の整数(好ましくは1)であり、a+b+c=4を満たす。R1は同一または異なるものであってよく、炭素数1~18の炭化水素基を表す。R2は同一または異なるものであってよく、水素原子または炭素数1~18の炭化水素基を表す。Mは同一または異なるものであってよく、アルカリ金属を表す。] Siliconates (especially alkyl siliconates) are for example represented by the formula:
R 1 a Si (OR 2 ) b (OM) c is a compound represented by c .
[Wherein, a is an integer of 0 or more (preferably 1), b is an integer of 0 or more (preferably 2), c is an integer of 1 or more (preferably 1), and satisfies a + b + c = 4. R 1 may be the same or different and represents a hydrocarbon group having 1 to 18 carbon atoms. R 2 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. M may be the same or different and represents an alkali metal. ]
R1としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、n-ペンチル基、イソペンチル基、ネオペンチル基、t-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、イソオクチル基、2,2,4-トリメチルペンチル基、n-ノニル基、n-デシル基、n-ドデシル基、n-オクタデシル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロヘキシル基、フェニル基、ナフチル基、アンスリル基、フェナンスリル基、トリル基、キシリル基、エチルフェニル基、ベンジル基、フェニルエチル基等が挙げられる。このうち、メチル基、エチル基、プロピル基が好ましく、特にメチル基が好ましい。
R2としては、水素原子の他、R1と同様の基が挙げられる。このうち、水素原子、メチル基、エチル基が好ましく、特に水素原子が好ましい。
Mとしては、Li、Na、K等が挙げられ、特にNaが好ましい。
アルキルシリコネートの具体例は、ナトリウムメチルシリコネート〔CH3Si(OH)2(ONa)〕やカリウムエチルシリコネート〔C2H5Si(OH)2(OK)〕である。 The hydrocarbon group is, for example, an aliphatic hydrocarbon group (for example, an alkyl group), an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group.
Examples of R 1 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, and n-hexyl. Group, n-heptyl group, n-octyl group, isooctyl group, 2,2,4-trimethylpentyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group, cyclopentyl group, cyclohexyl group , Cycloheptyl group, methylcyclohexyl group, phenyl group, naphthyl group, anthryl group, phenanthryl group, tolyl group, xylyl group, ethylphenyl group, benzyl group, phenylethyl group and the like. Among these, a methyl group, an ethyl group, and a propyl group are preferable, and a methyl group is particularly preferable.
Examples of R 2 include a hydrogen atom and the same group as R 1 . Among these, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom is particularly preferable.
Examples of M include Li, Na, K and the like, and Na is particularly preferable.
Specific examples of the alkyl siliconate are sodium methyl siliconate [CH 3 Si (OH) 2 (ONa)] and potassium ethyl siliconate [C 2 H 5 Si (OH) 2 (OK)].
基材は、屋外・屋内を問わず、湿気に曝される場所に配置される電子部品および電気部品であって、回路が設けられかつ各種の素子が装着された電子部品および電気部品である。基材の例は、回路基板、ハードディスクの軸受などである。電子部品および電気部品は、例えば、電話、信号機、エアコン室外機、配電盤、柱上コンデンサー、携帯電話、携帯中継アンテナ、自動車電子機器、船の電子機器、自動販売機、モバイルパソコンなどの物品において使用される。 Examples of the substrate include electronic parts and electric parts. In this specification, the term “electronic component” simply means an electrical component in addition to an electronic component.
The base material is an electronic component and an electrical component that are disposed in a place exposed to moisture regardless of whether they are outdoors or indoors, and is an electronic component and an electrical component on which various elements are mounted. Examples of the substrate include a circuit board and a hard disk bearing. Electronic parts and electrical parts are used in articles such as telephones, traffic lights, air conditioner outdoor units, switchboards, pole capacitors, mobile phones, portable relay antennas, automotive electronic equipment, ship electronic equipment, vending machines, mobile personal computers, etc. Is done.
(1)撥水撥油性
試験片の銅箔部の撥水撥油性を接触角計(協和界面科学(株)社製 CONTACT-ANGLE METER CA-DT)を用いて評価した。 Test methods and measurement methods employed in the present invention and the following examples are as follows.
(1) Water / oil repellency The water / oil repellency of the copper foil portion of the test piece was evaluated using a contact angle meter (CONTACT-ANGLE METER CA-DT, manufactured by Kyowa Interface Science Co., Ltd.).
試験片の表面抵抗を電気抵抗測定機((株)アドバンテスト社製 ULTRA HIGH RESISTANCE METER R8340A)にて測定した。 (2) Resistance Value The surface resistance of the test piece was measured with an electric resistance measuring device (ULTRA HIGH RESISTANCE METER R8340A manufactured by Advantest Corporation).
試験片を25度の脱イオン水の中に24時間浸漬させた。浸漬後の試験片の表面抵抗を電気抵抗測定機にて測定した。 (3) Water resistance The test piece was immersed in deionized water at 25 degrees for 24 hours. The surface resistance of the test piece after immersion was measured with an electric resistance measuring machine.
くし型電極基板を取り付けたガラス繊維補強エポキシ樹脂版に刷毛塗り法でコーティング剤を塗布し、室温で乾燥しながら試験片の表面抵抗を電気抵抗測定機にて測定した。 (4) Drying property A coating agent was applied to the glass fiber reinforced epoxy resin plate to which the comb electrode substrate was attached by a brush coating method, and the surface resistance of the test piece was measured with an electric resistance measuring device while drying at room temperature.
試験片を85℃で85RH%に維持された高温高湿槽に48時間入れ、常時16Vの電圧をかけ続ける。抵抗値を測定する際には100Vの電圧を印加し、高温高湿下での抵抗値の経時変化を調べた。 (5) High-temperature and high-humidity resistance Place the test piece in a high-temperature and high-humidity tank maintained at 85 RH% at 85 ° C for 48 hours and continuously apply a voltage of 16V. When measuring the resistance value, a voltage of 100 V was applied, and the change with time of the resistance value under high temperature and high humidity was examined.
CF3CF2-(CF2CF2)2-CH2CH2OCOC(CH3)=CH2 [Rf(C6)メタクリレート] 73.30g、ジメチルアミノエチルメタクリレート(DM)26.70g、イソプロパノール(IPA)150.00gを四つ口フラスコ内で撹拌溶解し、窒素置換しながら60℃で保持した後、t-ブチルパーオキシピバレート2gを添加し、60℃で6時間反応させポリマー溶液を得た。重合反応の終了はガスクロマトグラフィーにより単量体の転化率99%以上を確認した。さらにこのポリマー溶液を60℃で撹拌しながら、CH3COOH(酢酸)10.20gとイオン交換水300gとの混合液を滴下した。その後、IPAを減圧除去し、この溶液の固形分を130℃で1時間加熱した後の蒸発残分から求めて、固形分が25mass%となるようにイオン交換水で希釈し、透明で安定なポリマー水溶液を得た。 Production Example 1 (Preparation of aqueous solution of “Rf (C6) -DM” polymer)
CF 3 CF 2- (CF 2 CF 2 ) 2 -CH 2 CH 2 OCOC (CH 3 ) = CH 2 [Rf (C6) methacrylate] 73.30 g, dimethylaminoethyl methacrylate (DM) 26.70 g, isopropanol (IPA) 150.00 After stirring and dissolving g in a four-necked flask and maintaining at 60 ° C. while purging with nitrogen, 2 g of t-butyl peroxypivalate was added and reacted at 60 ° C. for 6 hours to obtain a polymer solution. The completion of the polymerization reaction was confirmed by gas chromatography to have a monomer conversion rate of 99% or more. Further, while this polymer solution was stirred at 60 ° C., a mixed solution of 10.20 g of CH 3 COOH (acetic acid) and 300 g of ion-exchanged water was added dropwise. Thereafter, the IPA is removed under reduced pressure, and the solid content of this solution is obtained from the evaporation residue after heating at 130 ° C. for 1 hour, diluted with ion-exchanged water so that the solid content becomes 25 mass%, and is a transparent and stable polymer. An aqueous solution was obtained.
製造例1においてRf(C6)メタクリレートおよびDMを、それぞれCF3CF2CF2CF2-CH2CH2OCOC(Cl)=CH2 [Rf(C4)クロロアクリレート] 63.00g、DM 37.00gに置き換える以外は全く同じ方法で製造したものを製造例2とした。また CF3CF2-CH2OCOC(CH3)=CH2 [Rf(C2)メタクリレート] 59.62g、DM 40.38gに置き換える以外は全く同じ方法で製造したものを製造例3とした。 Production Example 2 [Rf (C4) Cl-DM] and Production Example 3 [Rf (C2) -DM]
In Production Example 1, Rf (C6) methacrylate and DM are replaced with CF 3 CF 2 CF 2 CF 2 —CH 2 CH 2 OCOC (Cl) ═CH 2 [Rf (C4) chloroacrylate] 63.00 g and DM 37.00 g, respectively. A product produced in exactly the same manner except for the above was designated Production Example 2. Production Example 3 was produced in exactly the same manner except that it was replaced with 59.62 g of CF 3 CF 2 —CH 2 OCOC (CH 3 ) ═CH 2 [Rf (C2) methacrylate] and 40.38 g of DM.
くし型電極基板を取り付けたガラス繊維補強エポキシ樹脂版(材質:CEM3、板厚:1.6mm、銅箔厚:18μm、パターン幅:0.75mmまたは0.3mm)に刷毛塗り法でコーティング剤(製造例1~3のポリマー水溶液)を塗布し、乾燥させ、コーティングの膜厚2.7μmの試験片を作成した。この試験片(実施例1のポリマー水溶液を塗布した試験片)について、撥水撥油性、抵抗値、耐高温高湿性を測定した。結果を表1~表4に示す。 Example 1
Glass fiber reinforced epoxy resin plate with comb-shaped electrode substrate (material: CEM3, plate thickness: 1.6mm, copper foil thickness: 18μm, pattern width: 0.75mm or 0.3mm), coating agent by brush coating method (Production Example 1) And a test piece having a coating thickness of 2.7 μm was prepared. About this test piece (test piece which apply | coated the polymer aqueous solution of Example 1), water-and-oil repellency, resistance value, and high temperature-and-humidity resistance were measured. The results are shown in Tables 1 to 4.
コーティングの膜厚を0.8μmに変更する以外は実施例1と同様の手順を繰り返した。結果を表1~表4に示す。 Example 2
The same procedure as in Example 1 was repeated except that the film thickness of the coating was changed to 0.8 μm. The results are shown in Tables 1 to 4.
コーティング剤の種類およびコーティングの膜厚を変更する以外は実施例1と同様の手順を繰り返した。比較例として、ウレタン系ディスパージョン(三井化学ポリウレタン(株)製「タケラック W-6020」)とアクリル系ディスパージョン(日信化学工業(株)製「ビニブラン ビニブランT0-453N」)を用いた。結果を表1~表4に示す。 Comparative Examples 1 and 2
The same procedure as in Example 1 was repeated except that the type of coating agent and the film thickness of the coating were changed. As a comparative example, a urethane dispersion (“Takelac W-6020” manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) and an acrylic dispersion (“ViniBran Binibrand T0-453N” manufactured by Nissin Chemical Industry Co., Ltd.) were used. The results are shown in Tables 1 to 4.
Claims (13)
- 含フッ素化合物(1)と水性液状媒体(2)からなる電子部品用コーティング剤。 A coating agent for electronic parts comprising a fluorine-containing compound (1) and an aqueous liquid medium (2).
- 上記フッ素化合物(1)が、含フッ素アクリレート単量体から誘導された繰り返し単位を有してなる重合体である請求項1に記載の電子部品用コーティング剤。 The coating agent for electronic parts according to claim 1, wherein the fluorine compound (1) is a polymer having a repeating unit derived from a fluorine-containing acrylate monomer.
- 上記含フッ素化合物(1)が、
(A)含フッ素アクリレート単量体から誘導された繰り返し単位、および
(B)アミノ基含有単量体から誘導された繰り返し単位
を有してなる重合体である請求項2に記載の電子部品用コーティング剤。 The fluorine-containing compound (1) is
3. The electronic component according to claim 2, which is a polymer comprising (A) a repeating unit derived from a fluorine-containing acrylate monomer and (B) a repeating unit derived from an amino group-containing monomer. Coating agent. - 含フッ素アクリレート単量体(A)が、
フルオロアルキル基、フルオロアルケニル基およびフルオロエーテル基からなる群から選択された少なくとも一種のフッ素含有基(以下、「フッ素含有基」という)、および
式:-O-CO-CX=CH2
[式中、Xは、水素原子、炭素数1~6の直鎖状または分岐状のアルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX1X2基(但し、X1およびX2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。)、シアノ基、炭素数1~21の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基である。]
で表される不飽和基を有する単量体である請求項1~3に記載のコーティング剤。 The fluorine-containing acrylate monomer (A) is
At least one fluorine-containing group selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group and a fluoroether group (hereinafter referred to as “fluorine-containing group”), and a formula: —O—CO—CX═CH 2
[Wherein, X is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (where X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine 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. ]
The coating agent according to claims 1 to 3, which is a monomer having an unsaturated group represented by the formula: - 含フッ素アクリレート単量体(A)が
式:
CH2=C(-X)-C(=O)-O-Y-Rf (I)
[式中、Xは、水素原子、炭素数1~6の直鎖状または分岐状のアルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、CFX1X2基(但し、X1およびX2は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。)、シアノ基、炭素数1~21の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基、
Yは、直接結合、酸素原子を有していてもよい炭素数1~10の脂肪族基、酸素原子を有していてもよい炭素数6~10の芳香族基、環状脂肪族基または芳香脂肪族基、-CH2CH2N(R1)SO2-基(但し、R1は炭素数1~4のアルキル基である。)または-CH2CH(OY1)CH2-基(但し、Y1は水素原子またはアセチル基である。)、
Rfは、炭素数1~21の直鎖状または分岐状のフルオロアルキル基、炭素数2~21のフルオロアルケニル基または、繰り返し単位:-C3F6O-、-C2F4O-および-CF2O-からなる群から選択された少なくとも一種の繰り返し単位の合計数が1~200のフルオロエーテル基である。]
で示されるものである請求項1~4に記載のコーティング剤。 The fluorine-containing acrylate monomer (A) has the formula:
CH 2 = C (-X) -C (= O) -OY-Rf (I)
[Wherein, X is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (where X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine 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,
Y represents a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms) or a —CH 2 CH (OY 1 ) CH 2 — group ( Y 1 is a hydrogen atom or an acetyl group.
Rf represents a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a fluoroalkenyl group having 2 to 21 carbon atoms, or a repeating unit: —C 3 F 6 O—, —C 2 F 4 O— and A fluoroether group having a total number of 1 to 200 of at least one repeating unit selected from the group consisting of —CF 2 O—. ]
The coating agent according to claim 1, which is represented by the formula: - 含フッ素アクリレート単量体(A)のRfが、炭素数2~6のフルオロアルキル基または炭素数3~6のフルオロアルケニル基である請求項5に記載のコーティング剤。 6. The coating agent according to claim 5, wherein Rf of the fluorinated acrylate monomer (A) is a fluoroalkyl group having 2 to 6 carbon atoms or a fluoroalkenyl group having 3 to 6 carbon atoms.
- アミノ基含有単量体(B)が、式:
[式中、R11、R12、R21は、同一又は異なって、水素原子、又は炭素数1~4のアルキル基であり、Y11は酸素原子又はNHであり、Zは炭素数1~10の分岐または直鎖のアルキレン基である。R11とR12は互いに結合して隣接する窒素原子と共に環を形成してもよい。]
で示されるものである請求項1~6のいずれかに記載のコーティング剤。 The amino group-containing monomer (B) has the formula:
[Wherein R 11 , R 12 and R 21 are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y 11 is an oxygen atom or NH, and Z is 1 to 4 carbon atoms] 10 branched or straight chain alkylene groups. R 11 and R 12 may be bonded to each other to form a ring together with the adjacent nitrogen atom. ]
The coating agent according to any one of claims 1 to 6, which is represented by: - 水性液状媒体(2)が、(i)水、あるいは(ii)水と水溶性有機溶媒との混合物である請求項1~7のいずれかに記載のコーティング剤。 The coating agent according to any one of claims 1 to 7, wherein the aqueous liquid medium (2) is (i) water or (ii) a mixture of water and a water-soluble organic solvent.
- 含フッ素化合物(1)および水性液状媒体(2)、ならびに添加剤(3)からなる請求項1~8のいずれかに記載のコーティング剤。 The coating agent according to any one of claims 1 to 8, comprising a fluorine-containing compound (1), an aqueous liquid medium (2), and an additive (3).
- 添加剤(3)として蛍光剤あるいは色素を含有している請求項9記載のコーティング剤 The coating agent according to claim 9, which contains a fluorescent agent or a dye as the additive (3).
- 請求項1~10のいずれかに記載のコーティング剤で電子部品または電気部品を塗布することからなる処理電子部品の製造方法。 A method for producing a processed electronic component comprising applying an electronic component or an electrical component with the coating agent according to any one of claims 1 to 10.
- コーティング剤を電子部品または電気部品に適用した後、水性液状媒体を除去することからなる請求項11に記載の方法。 The method according to claim 11, comprising removing the aqueous liquid medium after applying the coating agent to the electronic component or the electrical component.
- 請求項11または12に記載の方法で製造された処理電子部品。 Processed electronic parts manufactured by the method according to claim 11 or 12.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008801226205A CN101910337A (en) | 2007-12-28 | 2008-12-26 | Aqueous coating agent for electronic component |
KR1020107014630A KR101132049B1 (en) | 2007-12-28 | 2008-12-26 | Aqueous coating agent for electronic component |
JP2009548091A JP5593698B2 (en) | 2007-12-28 | 2008-12-26 | Water-based coating agent for electronic parts |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007339669 | 2007-12-28 | ||
JP2007-339669 | 2007-12-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009084635A1 true WO2009084635A1 (en) | 2009-07-09 |
Family
ID=40824348
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2008/073740 WO2009084635A1 (en) | 2007-12-28 | 2008-12-26 | Aqueous coating agent for electronic component |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5593698B2 (en) |
KR (1) | KR101132049B1 (en) |
CN (2) | CN104592847B (en) |
TW (1) | TWI410466B (en) |
WO (1) | WO2009084635A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9063238B2 (en) * | 2012-08-08 | 2015-06-23 | General Electric Company | Complementary metal-oxide-semiconductor X-ray detector |
WO2015153627A1 (en) * | 2014-03-31 | 2015-10-08 | Peach State Labs, Inc. | Fluid-resistant electronic devices |
US9949377B2 (en) | 2012-01-10 | 2018-04-17 | Hzo, Inc. | Electronic devices with internal moisture-resistant coatings |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107675504A (en) * | 2016-08-02 | 2018-02-09 | 大金工业株式会社 | Non-woven fabrics |
CN107699099A (en) * | 2017-10-13 | 2018-02-16 | 浙江大学 | A kind of fluorescent visual type electronic protection coating composition and preparation method thereof |
CN107805434A (en) * | 2017-10-13 | 2018-03-16 | 浙江大学 | A kind of fluorescent type electronic protection coating and preparation method thereof |
CN108395497B (en) * | 2018-01-22 | 2021-03-30 | 中国科学院兰州化学物理研究所 | Ultraviolet fluorescent space lubricating oil creeping barrier material |
CN110484129B (en) * | 2019-07-02 | 2022-01-25 | 昆山联滔电子有限公司 | Product with protective coating and preparation method thereof |
CN116057136A (en) * | 2020-07-29 | 2023-05-02 | 兰达公司 | Inkjet ink formulation and use thereof |
CN112694569B (en) * | 2020-12-23 | 2021-08-17 | 东莞泰岳光学镀膜材料有限公司 | Fluorine-containing graft copolymer and preparation method and application thereof |
KR102424921B1 (en) * | 2021-08-12 | 2022-07-22 | 김소중 | Water-based paint on the outer wall of concrete structure with enhanced durability by reinforcing the ultraviolet performance of the outer wall of concrete structure |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000061697A1 (en) * | 1999-04-12 | 2000-10-19 | Daikin Industries, Ltd. | Powdery water-and-oil repellent, process for producing the same, and use thereof |
JP2001206919A (en) * | 1999-12-06 | 2001-07-31 | Atofina | New fluorocopolymer for treatment of several kind of substrate to obtain hydrophobic and lipophobic property |
JP2004352976A (en) * | 2003-05-02 | 2004-12-16 | Daikin Ind Ltd | Surface treating agent containing fluorine-containing polymer |
WO2006038493A1 (en) * | 2004-10-06 | 2006-04-13 | Daikin Industries, Ltd. | Fluorine-containing water- and oil-repellent composition |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61189693A (en) * | 1985-02-19 | 1986-08-23 | 旭硝子株式会社 | Moistureproof coating of electronic component |
JP2693822B2 (en) * | 1988-08-08 | 1997-12-24 | 花王株式会社 | Method for producing fluororesin aqueous dispersion |
AT392478B (en) * | 1989-09-01 | 1991-04-10 | Vianova Kunstharz Ag | USE OF ACRYLATE COPOLYMERISATES AS ADDITIVES FOR AQUEOUS CATIONIC LACQUER SYSTEMS |
JP4667564B2 (en) * | 2000-07-28 | 2011-04-13 | 株式会社シミズ | Cationic electrodeposition coating composition |
JP2002105433A (en) * | 2000-10-02 | 2002-04-10 | Lion Corp | Fluorine-containing, surface-treatment agent |
JP2005120198A (en) * | 2003-10-16 | 2005-05-12 | Jsr Corp | Hydrophilic polymer composition |
ATE540985T1 (en) * | 2004-03-26 | 2012-01-15 | Daikin Ind Ltd | FLUORINE CONTAINING MONOMER, FLUORINE CONTAINING POLYMER AND SURFACE TREATMENT AGENT |
CA2562593A1 (en) * | 2004-04-15 | 2005-10-27 | Daikin Industries, Ltd. | Fluorine-containing polymer and treating agent composition |
CN101065443A (en) * | 2004-10-29 | 2007-10-31 | 大金工业株式会社 | Fluorine-containing treatment composition |
-
2008
- 2008-12-26 JP JP2009548091A patent/JP5593698B2/en active Active
- 2008-12-26 CN CN201410817857.2A patent/CN104592847B/en active Active
- 2008-12-26 CN CN2008801226205A patent/CN101910337A/en active Pending
- 2008-12-26 KR KR1020107014630A patent/KR101132049B1/en active IP Right Grant
- 2008-12-26 TW TW97150818A patent/TWI410466B/en active
- 2008-12-26 WO PCT/JP2008/073740 patent/WO2009084635A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000061697A1 (en) * | 1999-04-12 | 2000-10-19 | Daikin Industries, Ltd. | Powdery water-and-oil repellent, process for producing the same, and use thereof |
JP2001206919A (en) * | 1999-12-06 | 2001-07-31 | Atofina | New fluorocopolymer for treatment of several kind of substrate to obtain hydrophobic and lipophobic property |
JP2004352976A (en) * | 2003-05-02 | 2004-12-16 | Daikin Ind Ltd | Surface treating agent containing fluorine-containing polymer |
WO2006038493A1 (en) * | 2004-10-06 | 2006-04-13 | Daikin Industries, Ltd. | Fluorine-containing water- and oil-repellent composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9949377B2 (en) | 2012-01-10 | 2018-04-17 | Hzo, Inc. | Electronic devices with internal moisture-resistant coatings |
US9063238B2 (en) * | 2012-08-08 | 2015-06-23 | General Electric Company | Complementary metal-oxide-semiconductor X-ray detector |
WO2015153627A1 (en) * | 2014-03-31 | 2015-10-08 | Peach State Labs, Inc. | Fluid-resistant electronic devices |
Also Published As
Publication number | Publication date |
---|---|
JP5593698B2 (en) | 2014-09-24 |
JPWO2009084635A1 (en) | 2011-05-19 |
CN104592847A (en) | 2015-05-06 |
CN101910337A (en) | 2010-12-08 |
CN104592847B (en) | 2019-07-23 |
KR101132049B1 (en) | 2012-04-02 |
KR20100092039A (en) | 2010-08-19 |
TWI410466B (en) | 2013-10-01 |
TW200936712A (en) | 2009-09-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5593698B2 (en) | Water-based coating agent for electronic parts | |
US11174349B2 (en) | Silane compound containing perfluoro(poly)ether group | |
JP5692272B2 (en) | Durable waterproof and moisture-proof coating composition | |
JP6166097B2 (en) | Water and oil repellent antifouling agent with good solvent solubility | |
EP2231730B1 (en) | Fluorine-containing polymer and aqueous treatment agent | |
EP2362883B1 (en) | Method of preparing water- and oil-repellent soil-resistant composition | |
KR101729823B1 (en) | Coating Composition for Water-Proofing and Moisture-Proofing | |
US9382363B2 (en) | Masonry-treating agent | |
CN108441056B (en) | Environment-friendly fluorine circuit board conformal coating composition and preparation method and application thereof | |
JP5133606B2 (en) | Surfactant | |
JP6350161B2 (en) | Waterproof and moisture-proof durable coating composition | |
WO2009119445A1 (en) | Release agent | |
KR20140018556A (en) | Antifouling coating agent and antifouling coating thereof | |
CN109971289B (en) | Water-proof and moisture-proof composition and application thereof | |
CN117659800A (en) | Protective coating agent for flexible circuit board | |
CN117447703A (en) | Multifunctional group modified silane compound and preparation method thereof, hardening coating and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880122620.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08865960 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2009548091 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20107014630 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 08865960 Country of ref document: EP Kind code of ref document: A1 |