WO2010110149A1 - Surface treatment agent - Google Patents
Surface treatment agent Download PDFInfo
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- WO2010110149A1 WO2010110149A1 PCT/JP2010/054576 JP2010054576W WO2010110149A1 WO 2010110149 A1 WO2010110149 A1 WO 2010110149A1 JP 2010054576 W JP2010054576 W JP 2010054576W WO 2010110149 A1 WO2010110149 A1 WO 2010110149A1
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Classifications
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- 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
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
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- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1173—Differences in wettability, e.g. hydrophilic or hydrophobic areas
Definitions
- the present invention relates to a surface treatment agent that imparts water repellency, oil repellency and IPA repellency to various substrates.
- a polymer of (meth) acrylic acid ester having a linear or terminally branched perfluoroalkyl group having a carbon chain length of 8 or more has been used as a fluorine-based surface treatment agent.
- the crystallinity of the side chain (CF 2 ) 8 F group is high water repellency, oil repellency, and the ability to repel 2-propanol (also referred to as IPA) used as a solvent such as flux. This was to show IPA performance.
- a polymer obtained from an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms exhibits high oil repellency and IPA performance, but Tg is It has been found to have a low and unique tack.
- the methacrylic acid ester having a linear perfluoroalkyl group having 6 carbon atoms has a slight decrease in oil repellency and IPA performance due to the influence of the methyl group in the main chain.
- the present invention relates to a polymer obtained from an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms and a linear perfluoroalkyl group having 6 carbon atoms, which has little influence on the living body and the environment.
- An object of the present invention is to provide a surface treatment agent that uses a polymer obtained from a methacrylic acid ester and has excellent water repellency, oil repellency and IPA repellency. Furthermore, it aims at reducing the adhesiveness of a film, maintaining these performances.
- a polymer obtained from an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms and a linear structure having 6 carbon atoms By mixing a polymer obtained from an acrylate ester having a perfluoroalkyl group, it is possible to provide a surface treatment agent having better water repellency, oil repellency and IPA repellency than those used alone. I found out.
- the present invention provides the following surface treatment agent.
- the surface treating agent of the present invention comprises an acrylic polymer (1) containing a polymer unit (A) derived from a compound represented by the following formula (a) at a content of 80% by mass or more, and the following formula (b): And a methacrylic polymer (2) containing a polymerization unit (B) derived from the compound represented by formula (B) in a content of 80% by mass or more.
- CH 2 CH-COO- (CH 2 ) n1- (CF 2 ) 6 F
- n 1 is an integer of 0-4.
- Formula (b) In the formula (b), n 2 is an integer of 0-4.
- At least one of the acrylic polymer (1) and the methacrylic polymer (2) further contains a polymer unit (C) derived from a compound represented by the following formula (c).
- a polymer unit (C) derived from a compound represented by the following formula (c).
- R a hydrogen atom or a methyl group
- Q a divalent linking group
- Y a monovalent functional group.
- the mass ratio (1) / (2) between the acrylic polymer (1) and the methacrylic polymer (2) is preferably 50/50 to 5/95.
- Y in the formula (c) is preferably a hydroxyl group, a carboxyl group or an alkoxysilyl group.
- the weight average molecular weight (in terms of polymethyl methacrylate) of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 100,000 or more.
- the surface treatment agent of the present invention can be used as a solder flux creep-up preventive agent, a lubricant oozing-out preventive agent, a waterproof / moisture-proof coating agent, and an electronic component resin adhesion preventive agent.
- the present invention also provides a substrate coated with the surface treating agent of the present invention.
- the surface treatment agent of the present invention comprises a polymer obtained from an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms, while suppressing the carbon number of the perfluoroalkyl group to 6 or less,
- a polymer obtained from an acrylate ester having a linear perfluoroalkyl group of 6 it is possible to have better water repellency, oil repellency and IPA repellency than those used alone. did it. In particular, high IPA repellency could be achieved even at low concentrations.
- an acrylic ester having a linear perfluoroalkyl group having 6 carbon atoms while maintaining water repellency, oil repellency and IPA repellency It was also possible to improve the tackiness of the coating, which occurs when the polymer obtained from the above is used alone.
- (meth) acrylate represents both or one of acrylic ester and methacrylic ester.
- the acrylic polymer (1) (hereinafter also referred to as “the acrylic polymer (1) of the present invention”), which is an essential component of the surface treating agent of the present invention, is derived from a compound represented by the following formula (a).
- a polymerization unit (A) is contained and the content is 80 mass% or more.
- the methacrylic polymer (2) (hereinafter also referred to as “the methacrylic polymer (2) of the present invention”), which is an essential component of the surface treating agent of the present invention, is derived from a compound represented by the following formula (b).
- a polymerization unit (B) is contained, and the content thereof is 80% by mass or more.
- n 1 is an integer of 0-4.
- n 2 is an integer of 0-4.
- n 1 and n 2 are both preferably 0 to 3, more preferably 1 or 2.
- the compound (a) and the compound (b) may be one kind or plural kinds respectively.
- the mass ratio of each polymer unit in each polymer is a value that is considered that all the raw materials used in each polymerization constitute a polymer unit. Therefore, for example, the mass ratio of the polymerized units (A) in the acrylic polymer (1) (percentage of the mass of the polymerized units (A) contained therein with respect to the total polymerized unit mass of the acrylic polymer (1)) is substantially equal to And the ratio of the mass of the compound (a) used for the polymerization of the acrylic polymer (1) to the total mass of the polymerization raw material compound of the acrylic polymer (1).
- the mass ratio of other polymer units in the polymer can be obtained in the same manner.
- the mass ratio of the polymer units (B) in the methacrylic polymer (2) is the same as that of the polymerization raw material compound of the methacrylic polymer (2) in the mass of the compound (b) used for the polymerization of the methacrylic polymer (2). It is determined as a percentage of the total mass.
- the content of the polymerization unit (A) is 80% by mass or more, and preferably 90% by mass or more.
- the content of the polymer unit (B) is also 80% by mass or more, and preferably 90% by mass. This is because the water-repellent performance, oil-repellent performance and IPA-repellent performance of the surface treatment agent of the present invention are good when the content is in the above range.
- the water repellency, oil repellency and IPA performance are collectively referred to as water repellency, oil repellency and IPA performance.
- the acrylic polymer (1) and methacrylic polymer (2) of the present invention preferably contain a polymer unit (C) derived from a compound represented by the following formula (c).
- the content of the polymer unit (C) is usually 10% by mass or less in both the acrylic polymer (1) and the methacrylic polymer (2). Among these, 0.1 to 10% by mass is preferable, 0.5 to 5% by mass is more preferable, and 1 to 2% by mass is particularly preferable.
- the polymerization unit (C) is contained, the adhesion to the substrate is improved. However, when the content is too large, the water / oil / oil repellency / IPA performance is lowered.
- R is preferably a methyl group because it does not increase the adhesion of the film and does not decrease the hardness of the film.
- Y can be appropriately selected as long as it is a monovalent functional group.
- a hydroxyl group, a carboxy group, or an alkoxysilyl group is preferable because it improves adhesion to the substrate.
- Q in the formula is a divalent linking group.
- Q can be appropriately selected as long as it is a divalent linking group.
- divalent linking group examples include linear or branched alkylene groups or alkenylene groups, oxyalkylene groups, 6-membered aromatic groups, 4- to 6-membered saturated or unsaturated aliphatic groups, and 5-6. And a divalent linking group represented by the formula -X 1 -ZX 2- . These divalent linking groups may be combined, and a plurality of cyclic groups may be condensed. You may do it.
- the symbols in the above formula have the following meanings.
- X 1 and X 2 each independently a linear or branched alkylene group or oxyalkylene group, a 6-membered aromatic group, a 4- to 6-membered saturated or unsaturated aliphatic group, 5 to 6 A membered heterocyclic group or a condensed ring group thereof; Z: —O—, —S—, —CO—, —COO—, —COS—, —N (R 1 ) —, —SO 2 —, —PO (OR 1 ) —, —N (R 1 ) — COO—, —N (R 1 ) —CO—, —N (R 1 ) —SO 2 — or —N (R 1 ) —PO (OR 1 ) —.
- R 1 a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- the above linking group may have a substituent.
- substituents include a halogen atom (F, Cl, Br, I), a hydroxyl group, a cyano group, an alkoxy group (methoxy, ethoxy, butoxy, octyl).
- the compound (c) is preferably a compound represented by the following formula when Y is a hydroxyl group.
- R has the same meaning as described above.
- Q 1 is a linear or branched alkylene group, — (C 2 H 4 O) n —, — (C 3 H 6 O) n —, or a combination thereof (where n is 1 to 30). Is an integer). These groups may have a substituent.
- the compound (c) is preferably a compound represented by the following formula when Y is a carboxy group. CH 2 ⁇ C (R) —COO—Q 2 —COOH Formula (c2)
- R has the same meaning as described above.
- Q 2 represents a linear or branched alkylene group, phenylene group, cyclohexylene group, — (C 2 H 4 O) n —, — (C 3 H 6 O) n —, or the above formula —X 1 —Z—.
- X 1 and X 2 each independently a linear or branched alkylene group, phenylene group, cyclohexylene group, — (C 2 H 4 O) n— or — (C 3 H 6 O) n— Yes, Z: —O—, —S—, —CO—, —COO—, —N (R 1 ) —, —N (R 1 ) —COO—, —N (R 1 ) —CO— (R 1 Is the same as above).
- the compound (c) is preferably a compound represented by the following formula when Y is an alkoxysilyl group.
- CH 2 C (R) —C (O) OQ 3 —Si (OAk) 3 formula (c3)
- R has the same meaning as described above.
- Q 3 is a linear or branched alkylene group, and the alkylene group may have a substituent.
- Ak is a linear or branched alkyl group having 1 to 3 carbon atoms.
- the acrylic polymer (1) of the present invention may contain other polymer units (D) in addition to the polymer units (A) and polymer units (C) as described above.
- the methacrylic polymer (2) of the present invention may contain other polymer units (D) in addition to the polymer units (B) and polymer units (C) as described above.
- the other polymer unit (D) is not particularly limited as long as it is a polymer unit derived from a compound that can be copolymerized with the compound that forms the polymer units (A), (B), and (C).
- the compound (d) which has a polymeric group is mentioned normally, Specifically, other than the compound illustrated about the styrene-type compound (d1) and the said polymerization unit (A), (B) and (C). And a compound (d3) having an unsaturated group such as the (meth) acrylic acid compound (d2) and a compound (d3) which is another polymerizable compound. Specific examples of such compound (d) are shown below, but are not limited thereto.
- Compound (d) is not particularly limited as long as it is another compound capable of forming a polymer with (meth) acrylate. Specifically, a styrenic compound (d1), a compound (a) other than the above compound (a), a compound (b), a (meth) acrylic acid compound (d2) other than the compound (c), and other polymerizable compounds ( d3). Specific examples of such compound (d) are shown below, but are not limited thereto.
- R 2 —H, CH 3 , —Cl, —CHO, —COOH, —CH 2 Cl, —CH 2 NH 2 , —CH 2 N (CH 3 ) 2 , —CH 2 N + (CH 3 ) 3 Cl ⁇ , —CH 2 N + H 3 Cl ⁇ , —CH 2 CN, —CH 2 COOH, —CH 2 N (CH 2 COOH) 2 , —CH 2 SH, —CH 2 SO 3 Na or —CH it is a 2 OCOCH 3.
- Examples of the compound (d2) include acrylic acid, methacrylic acid, ⁇ -chloroacrylic acid, and (meth) acrylate represented by the following formula.
- Examples of the compound (d2) include (meth) acrylamide represented by the following formula.
- CH 2 C (R 1 ) -CONH-R 4
- R 1 is H or CH 3
- Examples of the compound (d2) further include (meth) acrylic acid diesters, and (meth) acrylic acid polyesters such as compounds represented by the following formulas.
- R in the above formula is a (meth) acryloyloxy group.
- vinyl compounds other than the above (d1) and (d2) for example, vinyl chloride (CH 2 ⁇ CHCl), acrylonitrile (CH 2 ⁇ CHCN), or a compound having the following epoxy group: Can be mentioned.
- the compound (d) may be a compound having a plurality of polymerizable functional groups.
- the specific example which has 3 or more of vinyl groups or an epoxy group is shown below, it is not limited to these.
- the mass of the total amount of these other polymer units in the acrylic polymer (1) is different depending on the type. Is preferably 20% by mass or less, and more preferably 10% by mass or less.
- the methacrylic polymer (2) of the present invention contains other polymerized units (D) as described above, the total amount of these other polymerized units in the methacrylic polymer (2) varies depending on the type. Is preferably 20% by mass or less, and more preferably 10% by mass or less.
- the polymerization unit (D) is excessively contained, the water / oil repellency / IPA performance is lowered.
- the mass ratio (1) / (2) of the acrylic polymer (1) and the methacrylic polymer (2) of the present invention reduces the tackiness and improves the film properties while achieving high repellency.
- a range of 50/50 to 5/95 is preferable. More preferably, it is in the range of 30/70 to 10/90.
- the molecular weight of the acrylic polymer of the present invention (1) and methacrylic polymer (2) is not particularly limited, is preferably 1 ⁇ 10 3 ⁇ 1 ⁇ 10 7 in terms of weight-average molecular weight (Mw), 1 ⁇ 10 5 More preferably, it is ⁇ 1 ⁇ 10 6 .
- Mw weight-average molecular weight
- the molecular weight is within such a range, high water / oil repellency / IPA performance can be exhibited even at a low concentration.
- the solubility of the polymer of the present invention in a solvent tends to be poor.
- the acrylic polymer (1) and the methacrylic polymer (2) of the present invention are not particularly limited in the form of polymerization.
- the form of polymerization in the case of a copolymer is not particularly limited and may be any of random, block, graft and the like, but is preferably a random polymer.
- the method for producing the polymer is not particularly limited, and various known methods can be adopted.
- addition polymerization can be performed based on an unsaturated group in each compound.
- the polymerization can be carried out by appropriately adopting known addition polymerization conditions for unsaturated compounds.
- a normal initiator such as an organic peroxide, an azo compound, or a persulfate can be used as a polymerization initiation source.
- the surface treating agent of the present invention is a liquid form containing the specific acrylic polymer (1) and methacrylic polymer (2) as described above as a film component, and containing the polymer in a solvent.
- the method for producing the surface treatment agent of the present invention is not limited. For example, it can be obtained by dissolving the acrylic polymer (1) and methacrylic polymer (2) of the present invention in a known solvent. Further, for example, the acrylic polymer (1) of the present invention is produced by solution polymerization using the solvent as a polymerization medium by adding the compound (a), and the methacrylic polymer (2) is similarly produced from the compound (b).
- the surface treatment agent of the present invention is prepared by mixing the solution containing the acrylic polymer (1) of the present invention in the solvent and the solvent containing the methacrylic polymer (2). It can also be.
- a solution containing the acrylic polymer (1) of the present invention and a solution containing the methacrylic polymer (2) can be obtained by emulsion polymerization, and these can be mixed to obtain the surface treating agent of the present invention.
- the polymerization raw material compound is a gas such as vinyl chloride, it may be continuously supplied under pressure using a pressure vessel.
- the solvent for forming the surface treating agent of the present invention is not particularly limited as long as it can dissolve or disperse the acrylic polymer (1) and methacrylic polymer (2) of the present invention, and various organic solvents, water or These mixed media etc. are mentioned.
- a fluorine-based solvent is preferable.
- the fluorine-based solvent include hydrofluorocarbon (HFC) or hydrofluoroether (HFE). Specific examples of usable fluorinated solvents are shown below, but are not limited thereto.
- m-Xylene hexafluoride (hereinafter referred to as m-XHF) p-Xylene hexafluoride CF 3 CH 2 CF 2 CH 3 CF 3 CH 2 CF 2 H C 6 F 13 OCH 3 C 6 F 13 OC 2 H 5 C 6 F 13 CH 2 CH 3 C 3 F 7 OCH 3 C 3 F 7 OC 2 H 5 C 6 F 13 H CF 2 HCF 2 CH 2 OCF 2 CF 2 H CF 3 CFHCHFHCF 2 CH 3 CF 3 (OCF 2 CF 2 ) n (OCF 2 ) m OCF 2 H C 8 F 17 OCH 3 C 7 F 15 OCH 3 C 4 F 9 OCH 3 C 4 F 9 OC 2 H 5 C 4 F 9 CH 2 CH 3 CF 3 CH 2 OCF 2 CF 2 H (In the above examples, the subscripts m and n each independently represent an integer of 1 to 20) And mixtures of these.
- a hydrofluoroether mixture of CF 3 (CF 2 ) 3 OC 2 H 5 and (CF 3 ) 2 CFCF 2 OC 2 H 5 is available under the trade name Novec HFE 7200 (manufactured by 3M).
- the concentration of the surface treatment agent of the present invention is properly used depending on the application.
- the total concentration of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 1 to 20% by mass.
- the total concentration of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 1 to 5% by mass.
- the total concentration of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 0.01 to 1% by mass.
- the total concentration of the acrylic polymer (1) and the methacrylic polymer (2) of the present invention in the surface treatment agent of the present invention may be a final concentration.
- the solder flux creep-up preventing agent of the present invention is directly prepared.
- the polymer concentration (solid content concentration) in the solution containing the polymer immediately after polymerization may exceed 1% by mass.
- a solution containing a high-concentration polymer can be appropriately diluted so that the final desired concentration is obtained.
- the diluted solution can be used as a surface treatment agent as it is.
- the surface treatment agent of the present invention may contain components other than those described above as long as the stability, performance, appearance, etc. are not adversely affected.
- Such other components include, for example, the purpose of controlling the concentration of the polymer in the liquid when diluting a pH adjuster, a rust inhibitor, and a surface treatment agent to prevent corrosion of the coating surface.
- examples thereof include dyes for distinguishing from untreated parts, dye stabilizers, flame retardants, antifoaming agents and antistatic agents.
- the surface treatment agent of the present invention can be used by forming a film by coating it on a portion where water / oil / oil repellency / IPA performance is desired.
- the coating is formed by removing the solvent from the surface treatment agent of the present invention, and mainly comprises the acrylic polymer (1) and the methacrylic polymer (2) of the present invention.
- the coating film may be formed only from the acrylic polymer (1) and the methacrylic polymer (2) of the present invention, and other components are included within a range not adversely affecting as described above. It means that it may contain.
- a coating method a general coating method can be adopted. For example, there are methods such as dip coating, spray coating, and roller coating.
- the surface treatment agent of the present invention After applying the surface treatment agent of the present invention, it is preferable to perform drying at a temperature not lower than the boiling point of the solvent.
- a temperature not lower than the boiling point of the solvent For course, when it is difficult to heat and dry due to the material of the part to be processed, it should be dried while avoiding heating.
- what is necessary is just to select the conditions of heat processing according to the composition of the surface treating agent to apply
- the surface treatment agent of the present invention can be applied to the treatment of various materials, and in particular, for the treatment of precision equipment parts, sliding parts (motors, watches, HDDs), and electrical parts (electronic circuits, substrates, electronic parts, etc.). It is preferable to use it.
- the surface treatment agent of the present invention is preferably used as a solder flux creeping-up inhibitor, a lubricant oozing-out preventing agent, a waterproof coating agent, a moisture-proof coating agent and an electronic component resin adhesion preventing agent.
- it since it has a high IPA repellency even at a low concentration, it is preferably used as a solder flux creep-up preventing agent.
- Example 1 [Polymers 1 and 2] Each compound, polymerization solvent (m-XHF) and initiator (V-601) were charged in a sealed container so that the charging ratio (parts by mass) and concentration shown in Table 5 were obtained, and the reaction was carried out at 70 ° C. for 18 hours or more. And polymers 1 and 2 were obtained. Table 5 shows the results of measuring the weight average molecular weight (Mw) of the obtained polymer.
- a glass plate was immersed in each of the surface treatment agents 1 to 9 and the comparative surface treatment agents 1 and 2 having the polymer concentration adjusted to 0.1% by mass and 0.01% by mass at room temperature. And it took out after 1 minute and was made to dry at room temperature, and each glass plate which has a film of each processing agent was obtained. Next, IPA was dropped on the coating of each glass plate on which each type of coating was formed, and the contact angle was measured. For the measurement of each contact angle, an automatic contact angle meter OCA-20 (manufactured by dataphysics) was used.
- the surface treatment agent of the present invention is equivalent to or higher in water repellency and oil repellency than the comparative surface treatment agent containing only one of the acrylic polymer (1) and the methacrylic polymer (2).
- IPA repellency especially high IPA repellency at low concentrations.
- the mass ratio which is the mixing ratio of the acrylic polymer (1) and the methacrylic polymer (2), the adhesiveness of the coating is reduced without reducing the water repellency, oil repellency and IPA repellency. It has been found that the surface treatment agent has excellent performance with improved properties.
- Example 2 Next, other polymers were prepared as other acrylic polymer (1) and methacrylic polymer (2), and a surface treatment agent and a comparative surface treatment agent were prepared using the other polymers.
- Polymers 3-5 In the same manner as the polymers 1 and 2, polymers 3 to 5 were obtained. Table 7 shows the results obtained by measuring the Mw of the obtained polymer in the same manner as in polymers 1 and 2.
- the surface treatment agent of the present invention is superior to the comparative surface treatment agent containing only one of the acrylic polymer (1) or the methacrylic polymer (2). It turned out that it becomes the surface treating agent which has performance.
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Abstract
Provided is a surface treatment agent which uses a polymer formed of a compound having a linear perfluoroalkyl group having 6 carbon atoms and having less effect on living organisms and environment, and has excellent water repellency, oil repellency, and IPA repellency. The surface treatment agent comprises (1) an acrylic polymer containing a polymerization unit (A) derived from a compound represented by formula (a) at a content of 80% by mass or more and (2) a methacrylic polymer containing a polymerization unit (B) derived from a compound represented by formula (b) at a content of 80% by mass or more in a solvent.
CH2=CH-COO-(CH2)n1-(CF2)6F Formula (a)
In formula (a), n1 is an integer of 0 to 4.
CH2=C(CH3)-COO-(CH2)n2-(CF2)6F Formula (b)
In formula (b), n2 is an integer of 0 to 4.
Description
本発明は、各種基材に撥水性、撥油性および撥IPA性を付与する表面処理剤に関する。
The present invention relates to a surface treatment agent that imparts water repellency, oil repellency and IPA repellency to various substrates.
従来、フッ素系の表面処理剤として、炭素鎖長が8以上の直鎖状または末端分岐のパーフルオロアルキル基を有する(メタ)アクリル酸エステルの重合物が使用されてきた。これは、側鎖の(CF2)8F基の持つ結晶性が、高い撥水性能、撥油性能およびフラックス等の溶媒として用いられる2-プロパノール(IPAとも記す。)をはじく性能である撥IPA性能を示すためであった。
Conventionally, a polymer of (meth) acrylic acid ester having a linear or terminally branched perfluoroalkyl group having a carbon chain length of 8 or more has been used as a fluorine-based surface treatment agent. This is because the crystallinity of the side chain (CF 2 ) 8 F group is high water repellency, oil repellency, and the ability to repel 2-propanol (also referred to as IPA) used as a solvent such as flux. This was to show IPA performance.
米国環境保護庁(USEPA)が、野生動物や人の血液を含め、種々の環境から検出されるパーフロオロオクタン酸(PFOA)の安全性に関する予備リスク調査報告書を2003年3月に公開した。報告書では、PFOA発生の恐れのあるパーフルオロアルキル基の炭素数が8であるものについて、生体および環境への影響が指摘された。そして、2006年1月には、PFOAおよびその類縁物質ならびにこれらの前駆体物質の環境中への排出削減と製品中の含有量削減計画への参加をフッ素樹脂メーカー等に提唱している。
ここで対象になる構造としては、下記に示される炭素数が8の直鎖状のパーフルオロアルキル基を有する化合物などが挙げられる(特許文献1参照)。
CH2=CH-COO-(CH2)2-(CF2)8F
CH2=C(CH3)-COO-(CH2)2-(CF2)8F The US Environmental Protection Agency (USEPA) published a preliminary risk study report on the safety of perfluorooctanoic acid (PFOA) detected in various environments, including wild animals and human blood, in March 2003. In the report, it was pointed out that the perfluoroalkyl group that has the possibility of generating PFOA has 8 carbon atoms and has an impact on the living body and the environment. In January 2006, PFOA, its related substances, and their precursor substances were proposed to fluororesin manufacturers and others to participate in a reduction plan in the environment and a content reduction plan in products.
Examples of the structure to be used here include compounds having a linear perfluoroalkyl group having 8 carbon atoms shown below (see Patent Document 1).
CH 2 ═CH—COO— (CH 2 ) 2 — (CF 2 ) 8 F
CH 2 ═C (CH 3 ) —COO— (CH 2 ) 2 — (CF 2 ) 8 F
ここで対象になる構造としては、下記に示される炭素数が8の直鎖状のパーフルオロアルキル基を有する化合物などが挙げられる(特許文献1参照)。
CH2=CH-COO-(CH2)2-(CF2)8F
CH2=C(CH3)-COO-(CH2)2-(CF2)8F The US Environmental Protection Agency (USEPA) published a preliminary risk study report on the safety of perfluorooctanoic acid (PFOA) detected in various environments, including wild animals and human blood, in March 2003. In the report, it was pointed out that the perfluoroalkyl group that has the possibility of generating PFOA has 8 carbon atoms and has an impact on the living body and the environment. In January 2006, PFOA, its related substances, and their precursor substances were proposed to fluororesin manufacturers and others to participate in a reduction plan in the environment and a content reduction plan in products.
Examples of the structure to be used here include compounds having a linear perfluoroalkyl group having 8 carbon atoms shown below (see Patent Document 1).
CH 2 ═CH—COO— (CH 2 ) 2 — (CF 2 ) 8 F
CH 2 ═C (CH 3 ) —COO— (CH 2 ) 2 — (CF 2 ) 8 F
このような状況において、PFOAの発生の恐れを減らすために、パーフルオロアルキル基の炭素数を6以下に短くしたもの、具体的には、前記式中の(CF2)8Fを、(CF2)6Fまたは(CF2)4Fなどに置換した化合物を代替品として用いることが考えられる。しかし、炭素数が8の直鎖状のパーフルオロアルキル基を、そのまま6以下にしただけの場合は、重合体中のパーフルオロアルキル基に起因する撥水性、撥油性などの性能が低下する。
In such a situation, in order to reduce the possibility of the occurrence of PFOA, the carbon number of the perfluoroalkyl group is shortened to 6 or less, specifically, (CF 2 ) 8 F in the above formula is changed to (CF It is conceivable to use a compound substituted with 2 ) 6 F or (CF 2 ) 4 F as an alternative. However, when the straight-chain perfluoroalkyl group having 8 carbon atoms is simply reduced to 6 or less, the performance such as water repellency and oil repellency due to the perfluoroalkyl group in the polymer is lowered.
また、本発明者等の検討によると、炭素数が6の直鎖状のパーフルオロアルキル基を有するアクリル酸エステルから得られる重合体は、高い撥油性能と撥IPA性能を示すが、Tgが低くかつ独特の粘着性を有することが分った。一方、炭素数が6の直鎖状のパーフルオロアルキル基を有するメタクリル酸エステルは、主鎖のメチル基の影響により、撥油性能と撥IPA性能がやや低下することが分った。
Further, according to the study by the present inventors, a polymer obtained from an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms exhibits high oil repellency and IPA performance, but Tg is It has been found to have a low and unique tack. On the other hand, it was found that the methacrylic acid ester having a linear perfluoroalkyl group having 6 carbon atoms has a slight decrease in oil repellency and IPA performance due to the influence of the methyl group in the main chain.
本発明は、生体および環境への影響が少ない炭素数が6の直鎖状のパーフルオロアルキル基を有するアクリル酸エステルから得られる重合体および炭素数が6の直鎖状のパーフルオロアルキル基を有するメタクリル酸エステルから得られる重合体を使用し、かつ撥水性能、撥油性能および撥IPA性能に優れた表面処理剤の提供を目的とする。
更には、これらの性能を維持しつつ、被膜の粘着性を低減することも目的とする。 The present invention relates to a polymer obtained from an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms and a linear perfluoroalkyl group having 6 carbon atoms, which has little influence on the living body and the environment. An object of the present invention is to provide a surface treatment agent that uses a polymer obtained from a methacrylic acid ester and has excellent water repellency, oil repellency and IPA repellency.
Furthermore, it aims at reducing the adhesiveness of a film, maintaining these performances.
更には、これらの性能を維持しつつ、被膜の粘着性を低減することも目的とする。 The present invention relates to a polymer obtained from an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms and a linear perfluoroalkyl group having 6 carbon atoms, which has little influence on the living body and the environment. An object of the present invention is to provide a surface treatment agent that uses a polymer obtained from a methacrylic acid ester and has excellent water repellency, oil repellency and IPA repellency.
Furthermore, it aims at reducing the adhesiveness of a film, maintaining these performances.
本発明者は上記の課題を解決するために鋭意検討した結果、炭素数が6の直鎖状のパーフルオロアルキル基を有するアクリル酸エステルから得られる重合体と、炭素数が6の直鎖状のパーフルオロアルキル基を有するアクリル酸エステルから得られる重合体を混合することにより、単独で使用するより性能の良い撥水性能、撥油性能および撥IPA性能を有する表面処理剤の提供が可能であることを見出した。
As a result of intensive studies to solve the above problems, the present inventors have found that a polymer obtained from an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms and a linear structure having 6 carbon atoms. By mixing a polymer obtained from an acrylate ester having a perfluoroalkyl group, it is possible to provide a surface treatment agent having better water repellency, oil repellency and IPA repellency than those used alone. I found out.
すなわち、本発明は以下の表面処理剤を提供する。
本発明の表面処理剤は、下記式(a)で表される化合物から導かれる重合単位(A)を80質量%以上の含有量で含有するアクリル重合体(1)と、下記式(b)で表される化合物から導かれる重合単位(B)を80質量%以上の含有量で含有するメタクリル重合体(2)とを溶媒中に含む。
CH2=CH-COO-(CH2)n1-(CF2)6F 式(a)
式(a)中、n1は0~4の整数である。
CH2=C(CH3)-COO-(CH2)n2-(CF2)6F 式(b)
式(b)中、n2は0~4の整数である。 That is, the present invention provides the following surface treatment agent.
The surface treating agent of the present invention comprises an acrylic polymer (1) containing a polymer unit (A) derived from a compound represented by the following formula (a) at a content of 80% by mass or more, and the following formula (b): And a methacrylic polymer (2) containing a polymerization unit (B) derived from the compound represented by formula (B) in a content of 80% by mass or more.
CH 2 = CH-COO- (CH 2 ) n1- (CF 2 ) 6 F Formula (a)
In the formula (a), n 1 is an integer of 0-4.
CH 2 ═C (CH 3 ) —COO— (CH 2 ) n2 — (CF 2 ) 6 F Formula (b)
In the formula (b), n 2 is an integer of 0-4.
本発明の表面処理剤は、下記式(a)で表される化合物から導かれる重合単位(A)を80質量%以上の含有量で含有するアクリル重合体(1)と、下記式(b)で表される化合物から導かれる重合単位(B)を80質量%以上の含有量で含有するメタクリル重合体(2)とを溶媒中に含む。
CH2=CH-COO-(CH2)n1-(CF2)6F 式(a)
式(a)中、n1は0~4の整数である。
CH2=C(CH3)-COO-(CH2)n2-(CF2)6F 式(b)
式(b)中、n2は0~4の整数である。 That is, the present invention provides the following surface treatment agent.
The surface treating agent of the present invention comprises an acrylic polymer (1) containing a polymer unit (A) derived from a compound represented by the following formula (a) at a content of 80% by mass or more, and the following formula (b): And a methacrylic polymer (2) containing a polymerization unit (B) derived from the compound represented by formula (B) in a content of 80% by mass or more.
CH 2 = CH-COO- (CH 2 ) n1- (CF 2 ) 6 F Formula (a)
In the formula (a), n 1 is an integer of 0-4.
CH 2 ═C (CH 3 ) —COO— (CH 2 ) n2 — (CF 2 ) 6 F Formula (b)
In the formula (b), n 2 is an integer of 0-4.
また、前記アクリル重合体(1)およびメタクリル重合体(2)の少なくとも一方は、下記式(c)で表される化合物から導かれる重合単位(C)をさらに含有することが好ましい。
CH2=C(R)-C(O)O-Q-Y 式(c)
式(c)中、
R:水素原子またはメチル基、
Q:2価の連結基、
Y:1価の官能基。 Moreover, it is preferable that at least one of the acrylic polymer (1) and the methacrylic polymer (2) further contains a polymer unit (C) derived from a compound represented by the following formula (c).
CH 2 ═C (R) —C (O) OQY Formula (c)
In formula (c),
R: a hydrogen atom or a methyl group,
Q: a divalent linking group,
Y: a monovalent functional group.
CH2=C(R)-C(O)O-Q-Y 式(c)
式(c)中、
R:水素原子またはメチル基、
Q:2価の連結基、
Y:1価の官能基。 Moreover, it is preferable that at least one of the acrylic polymer (1) and the methacrylic polymer (2) further contains a polymer unit (C) derived from a compound represented by the following formula (c).
CH 2 ═C (R) —C (O) OQY Formula (c)
In formula (c),
R: a hydrogen atom or a methyl group,
Q: a divalent linking group,
Y: a monovalent functional group.
前記アクリル重合体(1)とメタクリル重合体(2)の質量比(1)/(2)は、50/50~5/95であることが好ましい。
The mass ratio (1) / (2) between the acrylic polymer (1) and the methacrylic polymer (2) is preferably 50/50 to 5/95.
前記式(c)におけるYは、水酸基、カルボキシル基またはアルコキシシリル基であることが好ましい。
Y in the formula (c) is preferably a hydroxyl group, a carboxyl group or an alkoxysilyl group.
前記アクリル重合体(1)およびメタクリル重合体(2)の重量平均分子量(ポリメチルメタクリレート換算)は、10万以上であることが好ましい。
The weight average molecular weight (in terms of polymethyl methacrylate) of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 100,000 or more.
本発明の表面処理剤は、はんだ用フラックス這い上がり防止剤、潤滑オイルの染み出し防止剤、防水・防湿コーティング剤および電子部品用樹脂付着防止剤に使用することが出来る。
The surface treatment agent of the present invention can be used as a solder flux creep-up preventive agent, a lubricant oozing-out preventive agent, a waterproof / moisture-proof coating agent, and an electronic component resin adhesion preventive agent.
また、本発明は、本発明の表面処理剤で被覆された基材を提供する。
The present invention also provides a substrate coated with the surface treating agent of the present invention.
本発明の表面処理剤は、パーフルオロアルキル基の炭素数を6以下に抑えながらも、炭素数が6の直鎖状のパーフルオロアルキル基を有するアクリル酸エステルから得られる重合体と、炭素数が6の直鎖状のパーフルオロアルキル基を有するアクリル酸エステルから得られる重合体を混合することにより、単独で使用するより性能の良い撥水性能、撥油性能および撥IPA性能を併せ持つことができた。特に、低濃度でも高い撥IPA性を有することができた。また前記2種の重合体の質量比を調整することで、撥水性能、撥油性能および撥IPA性能を維持しつつ、炭素数が6の直鎖状のパーフルオロアルキル基を有するアクリル酸エステルから得られる重合体を単独で使用する際に発生する、被膜の粘着性に関しても改善できた。
The surface treatment agent of the present invention comprises a polymer obtained from an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms, while suppressing the carbon number of the perfluoroalkyl group to 6 or less, By mixing a polymer obtained from an acrylate ester having a linear perfluoroalkyl group of 6, it is possible to have better water repellency, oil repellency and IPA repellency than those used alone. did it. In particular, high IPA repellency could be achieved even at low concentrations. Further, by adjusting the mass ratio of the two polymers, an acrylic ester having a linear perfluoroalkyl group having 6 carbon atoms while maintaining water repellency, oil repellency and IPA repellency. It was also possible to improve the tackiness of the coating, which occurs when the polymer obtained from the above is used alone.
本明細書において、式(a)で表される化合物を化合物(a)とも記す。他の式で表される化合物も同様に表記することがある。
なお本明細書中、(メタ)アクリレートとは、アクリル酸エステルおよびメタクリル酸エステルの両方またはどちらか一方を表す。 In the present specification, the compound represented by the formula (a) is also referred to as a compound (a). The compounds represented by other formulas may be expressed similarly.
In addition, in this specification, (meth) acrylate represents both or one of acrylic ester and methacrylic ester.
なお本明細書中、(メタ)アクリレートとは、アクリル酸エステルおよびメタクリル酸エステルの両方またはどちらか一方を表す。 In the present specification, the compound represented by the formula (a) is also referred to as a compound (a). The compounds represented by other formulas may be expressed similarly.
In addition, in this specification, (meth) acrylate represents both or one of acrylic ester and methacrylic ester.
本発明の表面処理剤の必須成分であるアクリル重合体(1)(以下、「本発明のアクリル重合体(1)」ともいう。)は、下記式(a)で表される化合物から導かれる重合単位(A)を含有し、その含有量が80質量%以上である。本発明の表面処理剤の必須成分であるメタクリル重合体(2)(以下、「本発明のメタクリル重合体(2)」ともいう。)は、下記式(b)で表される化合物から導かれる重合単位(B)を含有し、その含有量が80質量%以上である。
CH2=CH-COO-(CH2)n1-(CF2)6F 式(a)
式(a)中、n1は0~4の整数である。
CH2=C(CH3)-COO-(CH2)n2-(CF2)6F 式(b)
式(b)中、n2は0~4の整数である。 The acrylic polymer (1) (hereinafter also referred to as “the acrylic polymer (1) of the present invention”), which is an essential component of the surface treating agent of the present invention, is derived from a compound represented by the following formula (a). A polymerization unit (A) is contained and the content is 80 mass% or more. The methacrylic polymer (2) (hereinafter also referred to as “the methacrylic polymer (2) of the present invention”), which is an essential component of the surface treating agent of the present invention, is derived from a compound represented by the following formula (b). A polymerization unit (B) is contained, and the content thereof is 80% by mass or more.
CH 2 = CH-COO- (CH 2 ) n1- (CF 2 ) 6 F Formula (a)
In the formula (a), n 1 is an integer of 0-4.
CH 2 ═C (CH 3 ) —COO— (CH 2 ) n2 — (CF 2 ) 6 F Formula (b)
In the formula (b), n 2 is an integer of 0-4.
CH2=CH-COO-(CH2)n1-(CF2)6F 式(a)
式(a)中、n1は0~4の整数である。
CH2=C(CH3)-COO-(CH2)n2-(CF2)6F 式(b)
式(b)中、n2は0~4の整数である。 The acrylic polymer (1) (hereinafter also referred to as “the acrylic polymer (1) of the present invention”), which is an essential component of the surface treating agent of the present invention, is derived from a compound represented by the following formula (a). A polymerization unit (A) is contained and the content is 80 mass% or more. The methacrylic polymer (2) (hereinafter also referred to as “the methacrylic polymer (2) of the present invention”), which is an essential component of the surface treating agent of the present invention, is derived from a compound represented by the following formula (b). A polymerization unit (B) is contained, and the content thereof is 80% by mass or more.
CH 2 = CH-COO- (CH 2 ) n1- (CF 2 ) 6 F Formula (a)
In the formula (a), n 1 is an integer of 0-4.
CH 2 ═C (CH 3 ) —COO— (CH 2 ) n2 — (CF 2 ) 6 F Formula (b)
In the formula (b), n 2 is an integer of 0-4.
化合物(a)および化合物(b)において、n1およびn2はいずれも0~3であることが好ましく、1または2であることがより好ましい。
In the compounds (a) and (b), n 1 and n 2 are both preferably 0 to 3, more preferably 1 or 2.
化合物(a)および化合物(b)はそれぞれ1種でも複数種であってもよい。なお本発明において、各重合体における各重合単位の質量比率は、各重合に使用した原料がすべて重合単位を構成するとみなした値である。したがって、たとえばアクリル重合体(1)における重合単位(A)の質量比率(アクリル重合体(1)の全重合単位質量に対する、そこに含まれる重合単位(A)の質量の百分率)は、実質的に、アクリル重合体(1)の重合に使用した化合物(a)質量の、アクリル重合体(1)の重合原料化合物の全質量に対する割合として求められる。重合体における他の重合単位の質量比率も同様に求められる。また、メタクリル重合体(2)における重合単位(B)の質量比率も同様に、メタクリル重合体(2)の重合に使用した化合物(b)質量の、メタクリル重合体(2)の重合原料化合物の全質量に対する割合として求められる。
The compound (a) and the compound (b) may be one kind or plural kinds respectively. In the present invention, the mass ratio of each polymer unit in each polymer is a value that is considered that all the raw materials used in each polymerization constitute a polymer unit. Therefore, for example, the mass ratio of the polymerized units (A) in the acrylic polymer (1) (percentage of the mass of the polymerized units (A) contained therein with respect to the total polymerized unit mass of the acrylic polymer (1)) is substantially equal to And the ratio of the mass of the compound (a) used for the polymerization of the acrylic polymer (1) to the total mass of the polymerization raw material compound of the acrylic polymer (1). The mass ratio of other polymer units in the polymer can be obtained in the same manner. Similarly, the mass ratio of the polymer units (B) in the methacrylic polymer (2) is the same as that of the polymerization raw material compound of the methacrylic polymer (2) in the mass of the compound (b) used for the polymerization of the methacrylic polymer (2). It is determined as a percentage of the total mass.
本発明のアクリル重合体(1)において、重合単位(A)の含有量は80質量%以上であり、90質量%以上であることが好ましい。
同様に、本発明のメタクリル重合体(2)において、重合単位(B)の含有量も、80質量%以上であり、90質量%であることが好ましい。含有量が上記範囲内であると、本発明の表面処理剤の撥水性能、撥油性能および撥IPA性能が良好であるためである。なお、以下において、撥水性能、撥油性能および撥IPA性能をまとめて、撥水撥油撥IPA性能とも記す。 In the acrylic polymer (1) of the present invention, the content of the polymerization unit (A) is 80% by mass or more, and preferably 90% by mass or more.
Similarly, in the methacrylic polymer (2) of the present invention, the content of the polymer unit (B) is also 80% by mass or more, and preferably 90% by mass. This is because the water-repellent performance, oil-repellent performance and IPA-repellent performance of the surface treatment agent of the present invention are good when the content is in the above range. Hereinafter, the water repellency, oil repellency and IPA performance are collectively referred to as water repellency, oil repellency and IPA performance.
同様に、本発明のメタクリル重合体(2)において、重合単位(B)の含有量も、80質量%以上であり、90質量%であることが好ましい。含有量が上記範囲内であると、本発明の表面処理剤の撥水性能、撥油性能および撥IPA性能が良好であるためである。なお、以下において、撥水性能、撥油性能および撥IPA性能をまとめて、撥水撥油撥IPA性能とも記す。 In the acrylic polymer (1) of the present invention, the content of the polymerization unit (A) is 80% by mass or more, and preferably 90% by mass or more.
Similarly, in the methacrylic polymer (2) of the present invention, the content of the polymer unit (B) is also 80% by mass or more, and preferably 90% by mass. This is because the water-repellent performance, oil-repellent performance and IPA-repellent performance of the surface treatment agent of the present invention are good when the content is in the above range. Hereinafter, the water repellency, oil repellency and IPA performance are collectively referred to as water repellency, oil repellency and IPA performance.
本発明のアクリル重合体(1)およびメタクリル重合体(2)は、下記式(c)で表される化合物から導かれる重合単位(C)を含有していることが好ましい。重合単位(C)の含有量は、アクリル重合体(1)およびメタクリル重合体(2)のいずれにおいても通常10質量%以下である。中でも、0.1~10質量%が好ましく、0.5~5質量%がより好ましく、1~2質量%が特に好ましい。重合単位(C)を含有すると基材への密着性が向上するが、含有量が多すぎると撥水撥油撥IPA性能の低下につながる。
CH2=C(R)-COO-Q-Y 式(c)
式(c)中の記号は以下の意味を示す。
R:水素原子またはメチル基、
Q:2価の連結基、
Y:1価の官能基。 The acrylic polymer (1) and methacrylic polymer (2) of the present invention preferably contain a polymer unit (C) derived from a compound represented by the following formula (c). The content of the polymer unit (C) is usually 10% by mass or less in both the acrylic polymer (1) and the methacrylic polymer (2). Among these, 0.1 to 10% by mass is preferable, 0.5 to 5% by mass is more preferable, and 1 to 2% by mass is particularly preferable. When the polymerization unit (C) is contained, the adhesion to the substrate is improved. However, when the content is too large, the water / oil / oil repellency / IPA performance is lowered.
CH 2 ═C (R) —COO—QY Formula (c)
Symbols in the formula (c) have the following meanings.
R: a hydrogen atom or a methyl group,
Q: a divalent linking group,
Y: a monovalent functional group.
CH2=C(R)-COO-Q-Y 式(c)
式(c)中の記号は以下の意味を示す。
R:水素原子またはメチル基、
Q:2価の連結基、
Y:1価の官能基。 The acrylic polymer (1) and methacrylic polymer (2) of the present invention preferably contain a polymer unit (C) derived from a compound represented by the following formula (c). The content of the polymer unit (C) is usually 10% by mass or less in both the acrylic polymer (1) and the methacrylic polymer (2). Among these, 0.1 to 10% by mass is preferable, 0.5 to 5% by mass is more preferable, and 1 to 2% by mass is particularly preferable. When the polymerization unit (C) is contained, the adhesion to the substrate is improved. However, when the content is too large, the water / oil / oil repellency / IPA performance is lowered.
CH 2 ═C (R) —COO—QY Formula (c)
Symbols in the formula (c) have the following meanings.
R: a hydrogen atom or a methyl group,
Q: a divalent linking group,
Y: a monovalent functional group.
Rとしては、被膜の粘着性を増加させないとともに、被膜の硬度を低下させないことからメチル基が好ましい。
R is preferably a methyl group because it does not increase the adhesion of the film and does not decrease the hardness of the film.
Yは1価の官能基であれば適宜選択可能である。中でも、基材への密着性を向上させることから、水酸基、カルボキシ基またはアルコキシシリル基が好ましい。
Y can be appropriately selected as long as it is a monovalent functional group. Among these, a hydroxyl group, a carboxy group, or an alkoxysilyl group is preferable because it improves adhesion to the substrate.
式中のQは2価の連結基である。Qは2価の連結基であれば適宜選択可能である。
Q in the formula is a divalent linking group. Q can be appropriately selected as long as it is a divalent linking group.
2価の連結基としては、直鎖状もしくは分岐状のアルキレン基もしくはアルケニレン基、オキシアルキレン基、6員環芳香族基、4~6員環の飽和もしくは不飽和の脂肪族基、5~6員環の複素環基または式-X1-Z-X2-で表される2価の連結基が挙げられ、これら2価の連結基は組み合わされていても良く、複数の環基は縮合していても良い。
上記式中の記号は以下の意味を示す。
X1、X2:それぞれ独立して、直鎖状もしくは分岐状のアルキレン基もしくはオキシアルキレン基、6員環芳香族基、4~6員環の飽和もしくは不飽和の脂肪族基、5~6員環の複素環基またはこれらの縮合した環基。
Z:-O-、-S-、-CO-、-COO-、-COS-、-N(R1)-、-SO2-、-PO(OR1)-、-N(R1)-COO-、-N(R1)-CO-、-N(R1)-SO2-または-N(R1)-PO(OR1)-。
R1:水素原子または炭素数1~3のアルキル基。 Examples of the divalent linking group include linear or branched alkylene groups or alkenylene groups, oxyalkylene groups, 6-membered aromatic groups, 4- to 6-membered saturated or unsaturated aliphatic groups, and 5-6. And a divalent linking group represented by the formula -X 1 -ZX 2- . These divalent linking groups may be combined, and a plurality of cyclic groups may be condensed. You may do it.
The symbols in the above formula have the following meanings.
X 1 and X 2 : each independently a linear or branched alkylene group or oxyalkylene group, a 6-membered aromatic group, a 4- to 6-membered saturated or unsaturated aliphatic group, 5 to 6 A membered heterocyclic group or a condensed ring group thereof;
Z: —O—, —S—, —CO—, —COO—, —COS—, —N (R 1 ) —, —SO 2 —, —PO (OR 1 ) —, —N (R 1 ) — COO—, —N (R 1 ) —CO—, —N (R 1 ) —SO 2 — or —N (R 1 ) —PO (OR 1 ) —.
R 1 : a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
上記式中の記号は以下の意味を示す。
X1、X2:それぞれ独立して、直鎖状もしくは分岐状のアルキレン基もしくはオキシアルキレン基、6員環芳香族基、4~6員環の飽和もしくは不飽和の脂肪族基、5~6員環の複素環基またはこれらの縮合した環基。
Z:-O-、-S-、-CO-、-COO-、-COS-、-N(R1)-、-SO2-、-PO(OR1)-、-N(R1)-COO-、-N(R1)-CO-、-N(R1)-SO2-または-N(R1)-PO(OR1)-。
R1:水素原子または炭素数1~3のアルキル基。 Examples of the divalent linking group include linear or branched alkylene groups or alkenylene groups, oxyalkylene groups, 6-membered aromatic groups, 4- to 6-membered saturated or unsaturated aliphatic groups, and 5-6. And a divalent linking group represented by the formula -X 1 -ZX 2- . These divalent linking groups may be combined, and a plurality of cyclic groups may be condensed. You may do it.
The symbols in the above formula have the following meanings.
X 1 and X 2 : each independently a linear or branched alkylene group or oxyalkylene group, a 6-membered aromatic group, a 4- to 6-membered saturated or unsaturated aliphatic group, 5 to 6 A membered heterocyclic group or a condensed ring group thereof;
Z: —O—, —S—, —CO—, —COO—, —COS—, —N (R 1 ) —, —SO 2 —, —PO (OR 1 ) —, —N (R 1 ) — COO—, —N (R 1 ) —CO—, —N (R 1 ) —SO 2 — or —N (R 1 ) —PO (OR 1 ) —.
R 1 : a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
上記の連結基は、置換基を有していてもよく、置換基の例としては、ハロゲン原子(F、Cl、Br、I)、水酸基、シアノ基、アルコキシ基(メトキシ、エトキシ、ブトキシ、オクチルオキシ、メトキシエトキシなど)、アリールオキシ基(フェノキシなど)、アルキルチオ基(メチルチオ、エチルチオなど)、アシル基(アセチル、プロピオニル、ベンゾイルなど)、スルホニル基(メタンスルホニル、ベンゼンスルホニルなど)、アシルオキシ基(アセトキシ、ベンゾイルオキシなど)、スルホニルオキシ基(メタンスルホニルオキシ、トルエンスルホニルオキシなど)、ホスホニル基(ジエチルホスホニルなど)、アミド基(アセチルアミノ、ベンゾイルアミノなど)、カルバモイル基(N,N-ジメチルカルバモイル、N-フェニルカルバモイルなど)、アルキル基(メチル、エチル、プロピル、イソプロピル、シクロプロピル、ブチルなど)、アリール基(フェニル、トルイルなど)、複素環基(ピリジル、イミダゾリル、フラニルなど)、アルケニル基(ビニル、1-プロペニルなど)、アルコキシアシルオキシ基(アセチルオキシなど)、アルコキシカルボニル基(メトキシカルボニル、エトキシカルボニルなど)および重合性基(ビニル基、アクリロイル基、メタクリロイル基、シリル基、桂皮酸残基など)などが挙げられる。
The above linking group may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxyl group, a cyano group, an alkoxy group (methoxy, ethoxy, butoxy, octyl). Oxy, methoxyethoxy, etc.), aryloxy groups (phenoxy, etc.), alkylthio groups (methylthio, ethylthio, etc.), acyl groups (acetyl, propionyl, benzoyl, etc.), sulfonyl groups (methanesulfonyl, benzenesulfonyl, etc.), acyloxy groups (acetoxy, etc.) , Benzoyloxy etc.), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy etc.), phosphonyl group (diethylphosphonyl etc.), amide group (acetylamino, benzoylamino etc.), carbamoyl group (N, N-dimethylcarbamoyl, N-Fe Rucarbamoyl etc.), alkyl groups (methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl etc.), aryl groups (phenyl, toluyl etc.), heterocyclic groups (pyridyl, imidazolyl, furanyl etc.), alkenyl groups (vinyl, 1- Propenyl etc.), alkoxyacyloxy groups (acetyloxy etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl etc.) and polymerizable groups (vinyl group, acryloyl group, methacryloyl group, silyl group, cinnamic acid residue etc.) etc. It is done.
化合物(c)は、上記Yが水酸基である場合、下記式で表される化合物であるのが好ましい。
CH2=C(R)-COO-Q1-OH 式(c1)
式(c1)中、Rは前記と同じ意味を示す。Q1は、直鎖状または分岐状のアルキレン基、-(C2H4O)n-、-(C3H6O)n-またはこれらの組合せである(ここで、nは1~30の整数である)。これらの基は置換基を有していてもよい。 The compound (c) is preferably a compound represented by the following formula when Y is a hydroxyl group.
CH 2 ═C (R) —COO—Q 1 —OH Formula (c1)
In the formula (c1), R has the same meaning as described above. Q 1 is a linear or branched alkylene group, — (C 2 H 4 O) n —, — (C 3 H 6 O) n —, or a combination thereof (where n is 1 to 30). Is an integer). These groups may have a substituent.
CH2=C(R)-COO-Q1-OH 式(c1)
式(c1)中、Rは前記と同じ意味を示す。Q1は、直鎖状または分岐状のアルキレン基、-(C2H4O)n-、-(C3H6O)n-またはこれらの組合せである(ここで、nは1~30の整数である)。これらの基は置換基を有していてもよい。 The compound (c) is preferably a compound represented by the following formula when Y is a hydroxyl group.
CH 2 ═C (R) —COO—Q 1 —OH Formula (c1)
In the formula (c1), R has the same meaning as described above. Q 1 is a linear or branched alkylene group, — (C 2 H 4 O) n —, — (C 3 H 6 O) n —, or a combination thereof (where n is 1 to 30). Is an integer). These groups may have a substituent.
化合物(c)は、上記Yがカルボキシ基である場合、下記式で表される化合物であるのが好ましい。
CH2=C(R)-COO-Q2-COOH 式(c2)
式(c2)中、Rは前記と同じ意味を示す。Q2は直鎖状または分岐状のアルキレン基、フェニレン基、シクロヘキシレン基、-(C2H4O)n-、-(C3H6O)n-または上記式-X1-Z-X2-で表される2価の連結基である(ここで、nは1~30の整数である)。これらの基は置換基を有していてもよい。
上記式-X1-Z-X2-のうちでも、好ましくは、
X1、X2:それぞれ独立して、直鎖状もしくは分岐状のアルキレン基、フェニレン基、シクロヘキシレン基、-(C2H4O)n-または-(C3H6O)n-であり、
Z:-O-、-S-、-CO-、-COO-、-N(R1)-、-N(R1)-COO-、-N(R1)-CO-である(R1は上記と同じ)。 The compound (c) is preferably a compound represented by the following formula when Y is a carboxy group.
CH 2 ═C (R) —COO—Q 2 —COOH Formula (c2)
In the formula (c2), R has the same meaning as described above. Q 2 represents a linear or branched alkylene group, phenylene group, cyclohexylene group, — (C 2 H 4 O) n —, — (C 3 H 6 O) n —, or the above formula —X 1 —Z—. A divalent linking group represented by X 2 — (where n is an integer of 1 to 30). These groups may have a substituent.
Among the above formulas -X 1 -ZX 2- , preferably
X 1 and X 2 : each independently a linear or branched alkylene group, phenylene group, cyclohexylene group, — (C 2 H 4 O) n— or — (C 3 H 6 O) n— Yes,
Z: —O—, —S—, —CO—, —COO—, —N (R 1 ) —, —N (R 1 ) —COO—, —N (R 1 ) —CO— (R 1 Is the same as above).
CH2=C(R)-COO-Q2-COOH 式(c2)
式(c2)中、Rは前記と同じ意味を示す。Q2は直鎖状または分岐状のアルキレン基、フェニレン基、シクロヘキシレン基、-(C2H4O)n-、-(C3H6O)n-または上記式-X1-Z-X2-で表される2価の連結基である(ここで、nは1~30の整数である)。これらの基は置換基を有していてもよい。
上記式-X1-Z-X2-のうちでも、好ましくは、
X1、X2:それぞれ独立して、直鎖状もしくは分岐状のアルキレン基、フェニレン基、シクロヘキシレン基、-(C2H4O)n-または-(C3H6O)n-であり、
Z:-O-、-S-、-CO-、-COO-、-N(R1)-、-N(R1)-COO-、-N(R1)-CO-である(R1は上記と同じ)。 The compound (c) is preferably a compound represented by the following formula when Y is a carboxy group.
CH 2 ═C (R) —COO—Q 2 —COOH Formula (c2)
In the formula (c2), R has the same meaning as described above. Q 2 represents a linear or branched alkylene group, phenylene group, cyclohexylene group, — (C 2 H 4 O) n —, — (C 3 H 6 O) n —, or the above formula —X 1 —Z—. A divalent linking group represented by X 2 — (where n is an integer of 1 to 30). These groups may have a substituent.
Among the above formulas -X 1 -ZX 2- , preferably
X 1 and X 2 : each independently a linear or branched alkylene group, phenylene group, cyclohexylene group, — (C 2 H 4 O) n— or — (C 3 H 6 O) n— Yes,
Z: —O—, —S—, —CO—, —COO—, —N (R 1 ) —, —N (R 1 ) —COO—, —N (R 1 ) —CO— (R 1 Is the same as above).
化合物(c)は、上記Yがアルコキシシリル基である場合、下記式で表される化合物であるのが好ましい。
CH2=C(R)-C(O)O-Q3-Si(OAk)3 式(c3)
式(c3)中、Rは前記と同じ意味を示す。Q3は、直鎖状または分岐状のアルキレン基であり、アルキレン基は置換基を有していてもよい。 Akは炭素数1~3の直鎖状または分岐状のアルキル基である。 The compound (c) is preferably a compound represented by the following formula when Y is an alkoxysilyl group.
CH 2 = C (R) —C (O) OQ 3 —Si (OAk) 3 formula (c3)
In the formula (c3), R has the same meaning as described above. Q 3 is a linear or branched alkylene group, and the alkylene group may have a substituent. Ak is a linear or branched alkyl group having 1 to 3 carbon atoms.
CH2=C(R)-C(O)O-Q3-Si(OAk)3 式(c3)
式(c3)中、Rは前記と同じ意味を示す。Q3は、直鎖状または分岐状のアルキレン基であり、アルキレン基は置換基を有していてもよい。 Akは炭素数1~3の直鎖状または分岐状のアルキル基である。 The compound (c) is preferably a compound represented by the following formula when Y is an alkoxysilyl group.
CH 2 = C (R) —C (O) OQ 3 —Si (OAk) 3 formula (c3)
In the formula (c3), R has the same meaning as described above. Q 3 is a linear or branched alkylene group, and the alkylene group may have a substituent. Ak is a linear or branched alkyl group having 1 to 3 carbon atoms.
化合物(c)の具体例を、表1~3に示すが、これに限定されるものではない。
なお、表1、表2におけるmおよびnは、それぞれ独立に、1~10の整数を表す。 Specific examples of the compound (c) are shown in Tables 1 to 3, but are not limited thereto.
In Tables 1 and 2, m and n each independently represent an integer of 1 to 10.
なお、表1、表2におけるmおよびnは、それぞれ独立に、1~10の整数を表す。 Specific examples of the compound (c) are shown in Tables 1 to 3, but are not limited thereto.
In Tables 1 and 2, m and n each independently represent an integer of 1 to 10.
本発明のアクリル重合体(1)は、上記のような重合単位(A)および重合単位(C)以外に、他の重合単位(D)を含んでいてもよい。同様に、本発明のメタクリル重合体(2)は、上記のような重合単位(B)および重合単位(C)以外に、他の重合単位(D)を含んでいてもよい。他の重合単位(D)は、上記重合単位(A)、(B)および(C)を形成する化合物と共重合しうる化合物から導かれる重合単位であれば特に限定されない。この化合物として、通常、重合性基を有する化合物(d)が挙げられ、具体的には、スチレン系化合物(d1)、上記重合単位(A)、(B)および(C)について例示した化合物以外の(メタ)アクリル酸系化合物(d2)などの不飽和基を有する化合物(d)およびさらに他の重合性化合物である化合物(d3)が挙げられる。このような化合物(d)の具体例を以下に示すが、これらに限定されるものではない。
The acrylic polymer (1) of the present invention may contain other polymer units (D) in addition to the polymer units (A) and polymer units (C) as described above. Similarly, the methacrylic polymer (2) of the present invention may contain other polymer units (D) in addition to the polymer units (B) and polymer units (C) as described above. The other polymer unit (D) is not particularly limited as long as it is a polymer unit derived from a compound that can be copolymerized with the compound that forms the polymer units (A), (B), and (C). As this compound, the compound (d) which has a polymeric group is mentioned normally, Specifically, other than the compound illustrated about the styrene-type compound (d1) and the said polymerization unit (A), (B) and (C). And a compound (d3) having an unsaturated group such as the (meth) acrylic acid compound (d2) and a compound (d3) which is another polymerizable compound. Specific examples of such compound (d) are shown below, but are not limited thereto.
化合物(d)は、(メタ)アクリレートと重合体を形成し得る他の化合物であれば特に限定されない。具体的には、スチレン系化合物(d1)、上記化合物(a)、化合物(b)および化合物(c)以外の(メタ)アクリル酸系化合物(d2)およびさらに他の重合性化合物である化合物(d3)が挙げられる。このような化合物(d)の具体例を以下に示すが、これらに限定されるものではない。
Compound (d) is not particularly limited as long as it is another compound capable of forming a polymer with (meth) acrylate. Specifically, a styrenic compound (d1), a compound (a) other than the above compound (a), a compound (b), a (meth) acrylic acid compound (d2) other than the compound (c), and other polymerizable compounds ( d3). Specific examples of such compound (d) are shown below, but are not limited thereto.
上記(d1)としては、下記式で表わされるスチレン系化合物が挙げられる。
式中、R2:-H、CH3、-Cl、-CHO、-COOH、-CH2Cl、-CH2NH2、-CH2N(CH3)2、-CH2N+(CH3)3Cl-、-CH2N+H3Cl-、-CH2CN、-CH2COOH、-CH2N(CH2COOH)2、-CH2SH、-CH2SO3Na又は-CH2OCOCH3である。 As said (d1), the styrene-type compound represented by a following formula is mentioned.
In the formula, R 2 : —H, CH 3 , —Cl, —CHO, —COOH, —CH 2 Cl, —CH 2 NH 2 , —CH 2 N (CH 3 ) 2 , —CH 2 N + (CH 3 ) 3 Cl − , —CH 2 N + H 3 Cl − , —CH 2 CN, —CH 2 COOH, —CH 2 N (CH 2 COOH) 2 , —CH 2 SH, —CH 2 SO 3 Na or —CH it is a 2 OCOCH 3.
式中、R2:-H、CH3、-Cl、-CHO、-COOH、-CH2Cl、-CH2NH2、-CH2N(CH3)2、-CH2N+(CH3)3Cl-、-CH2N+H3Cl-、-CH2CN、-CH2COOH、-CH2N(CH2COOH)2、-CH2SH、-CH2SO3Na又は-CH2OCOCH3である。 As said (d1), the styrene-type compound represented by a following formula is mentioned.
In the formula, R 2 : —H, CH 3 , —Cl, —CHO, —COOH, —CH 2 Cl, —CH 2 NH 2 , —CH 2 N (CH 3 ) 2 , —CH 2 N + (CH 3 ) 3 Cl − , —CH 2 N + H 3 Cl − , —CH 2 CN, —CH 2 COOH, —CH 2 N (CH 2 COOH) 2 , —CH 2 SH, —CH 2 SO 3 Na or —CH it is a 2 OCOCH 3.
上記化合物(d2)としては、アクリル酸、メタクリル酸、α-クロロアクリル酸および下記式で表わされる(メタ)アクリレートが挙げられる。
CH2=C(R1)-COO-R3
式中、R1:H又はCH3、R3:-CH3、-CH2CH2N(CH3)2、-(CH2)mH(m=2~20の整数)、-CH2CH(CH3)2、-CH2-C(CH3)2-OCO-Ph(「Ph」はフェニル基を意味する。以下同様である。)、-CH2Ph、-CH2CH2OPh、-CH2N+(CH3)3Cl-、-(CH2CH2O)mCH3(m=2~20の整数)、-(CH2)2-NCO、又は以下の基である。 Examples of the compound (d2) include acrylic acid, methacrylic acid, α-chloroacrylic acid, and (meth) acrylate represented by the following formula.
CH 2 ═C (R 1 ) —COO—R 3
In the formula, R 1 : H or CH 3 , R 3 : —CH 3 , —CH 2 CH 2 N (CH 3 ) 2 , — (CH 2 ) m H (m = 2 to 20), —CH 2 CH (CH 3) 2, -CH 2 -C (CH 3) 2 -OCO-Ph, ( "Ph" and so on means a phenyl group..) - CH 2 Ph, -CH 2 CH 2 OPh , —CH 2 N + (CH 3 ) 3 Cl − , — (CH 2 CH 2 O) m CH 3 (m = 2 to 20), — (CH 2 ) 2 —NCO, or the following group .
CH2=C(R1)-COO-R3
式中、R1:H又はCH3、R3:-CH3、-CH2CH2N(CH3)2、-(CH2)mH(m=2~20の整数)、-CH2CH(CH3)2、-CH2-C(CH3)2-OCO-Ph(「Ph」はフェニル基を意味する。以下同様である。)、-CH2Ph、-CH2CH2OPh、-CH2N+(CH3)3Cl-、-(CH2CH2O)mCH3(m=2~20の整数)、-(CH2)2-NCO、又は以下の基である。 Examples of the compound (d2) include acrylic acid, methacrylic acid, α-chloroacrylic acid, and (meth) acrylate represented by the following formula.
CH 2 ═C (R 1 ) —COO—R 3
In the formula, R 1 : H or CH 3 , R 3 : —CH 3 , —CH 2 CH 2 N (CH 3 ) 2 , — (CH 2 ) m H (m = 2 to 20), —CH 2 CH (CH 3) 2, -CH 2 -C (CH 3) 2 -OCO-Ph, ( "Ph" and so on means a phenyl group..) - CH 2 Ph, -CH 2 CH 2 OPh , —CH 2 N + (CH 3 ) 3 Cl − , — (CH 2 CH 2 O) m CH 3 (m = 2 to 20), — (CH 2 ) 2 —NCO, or the following group .
化合物(d2)としては、下記式で表わされる(メタ)アクリルアミドも挙げられる。
CH2=C(R1)-CONH-R4
式中、R1:H又はCH3、R4:-CmH2m+1(m=2~20の整数)又は-Hである。 Examples of the compound (d2) include (meth) acrylamide represented by the following formula.
CH 2 = C (R 1 ) -CONH-R 4
In the formula, R 1 is H or CH 3 , R 4 is —C m H 2m + 1 (m = 2 is an integer of 2 to 20) or —H.
CH2=C(R1)-CONH-R4
式中、R1:H又はCH3、R4:-CmH2m+1(m=2~20の整数)又は-Hである。 Examples of the compound (d2) include (meth) acrylamide represented by the following formula.
CH 2 = C (R 1 ) -CONH-R 4
In the formula, R 1 is H or CH 3 , R 4 is —C m H 2m + 1 (m = 2 is an integer of 2 to 20) or —H.
化合物(d2)としては、さらに、(メタ)アクリル酸ジエステル、さらに下記各式で示される化合物等の(メタ)アクリル酸ポリエステルなどが挙げられる。
上記式中のRは、(メタ)アクリロイルオキシ基である。 Examples of the compound (d2) further include (meth) acrylic acid diesters, and (meth) acrylic acid polyesters such as compounds represented by the following formulas.
R in the above formula is a (meth) acryloyloxy group.
上記式中のRは、(メタ)アクリロイルオキシ基である。 Examples of the compound (d2) further include (meth) acrylic acid diesters, and (meth) acrylic acid polyesters such as compounds represented by the following formulas.
R in the above formula is a (meth) acryloyloxy group.
また、化合物(d3)としては、上記(d1)および(d2)以外のビニル化合物、例えば塩化ビニル(CH2=CHCl)、アクリロニトリル(CH2=CHCN)または以下のようなエポキシ基を有する化合物が挙げられる。
Further, as the compound (d3), vinyl compounds other than the above (d1) and (d2), for example, vinyl chloride (CH 2 ═CHCl), acrylonitrile (CH 2 ═CHCN), or a compound having the following epoxy group: Can be mentioned.
化合物(d)としては、上記以外にも、重合性の官能基を複数有する化合物であっても構わない。以下には、ビニル基またはエポキシ基を3以上有する具体例を示すが、これらに限定されるものではない。
In addition to the above, the compound (d) may be a compound having a plurality of polymerizable functional groups. Although the specific example which has 3 or more of vinyl groups or an epoxy group is shown below, it is not limited to these.
本発明のアクリル重合体(1)が、上記のような他の重合単位(D)を含有する場合、その種類によっても異なるが、アクリル重合体(1)におけるこれら他の重合単位全量での質量が20質量%以下であることが好ましく、10質量%以下であることがより好ましい。同様に、本発明のメタクリル重合体(2)が、上記のような他の重合単位(D)を含有する場合、その種類によっても異なるが、メタクリル重合体(2)におけるこれら他の重合単位全量での質量が20質量%以下であることが好ましく、10質量%以下であることがより好ましい。重合単位(D)を過剰に含有すると、撥水撥油撥IPA性能が低下する。
When the acrylic polymer (1) of the present invention contains other polymer units (D) as described above, the mass of the total amount of these other polymer units in the acrylic polymer (1) is different depending on the type. Is preferably 20% by mass or less, and more preferably 10% by mass or less. Similarly, when the methacrylic polymer (2) of the present invention contains other polymerized units (D) as described above, the total amount of these other polymerized units in the methacrylic polymer (2) varies depending on the type. Is preferably 20% by mass or less, and more preferably 10% by mass or less. When the polymerization unit (D) is excessively contained, the water / oil repellency / IPA performance is lowered.
本発明の表面処理剤における、本発明のアクリル重合体(1)およびメタクリル重合体(2)の質量比(1)/(2)は、粘着性を低減させ被膜特性を良好にしつつ、高い撥水撥油撥IPA性能を有すると言う観点から、50/50~5/95の範囲が好ましい。より好ましくは、30/70~10/90の範囲である。
In the surface treatment agent of the present invention, the mass ratio (1) / (2) of the acrylic polymer (1) and the methacrylic polymer (2) of the present invention reduces the tackiness and improves the film properties while achieving high repellency. From the viewpoint of having water / oil repellency and IPA performance, a range of 50/50 to 5/95 is preferable. More preferably, it is in the range of 30/70 to 10/90.
本発明のアクリル重合体(1)およびメタクリル重合体(2)の分子量は特に限定されないが、重量平均分子量(Mw)で1×103~1×107であることが好ましく、1×105~1×106であることがより好ましい。分子量がこのような範囲であると、低濃度においても高い撥水撥油撥IPA性能を示すことが出来る。一方、分子量が大きすぎると本発明の重合体の溶媒への溶解性が悪くなる傾向がある。
The molecular weight of the acrylic polymer of the present invention (1) and methacrylic polymer (2) is not particularly limited, is preferably 1 × 10 3 ~ 1 × 10 7 in terms of weight-average molecular weight (Mw), 1 × 10 5 More preferably, it is ˜1 × 10 6 . When the molecular weight is within such a range, high water / oil repellency / IPA performance can be exhibited even at a low concentration. On the other hand, if the molecular weight is too large, the solubility of the polymer of the present invention in a solvent tends to be poor.
本発明のアクリル重合体(1)およびメタクリル重合体(2)は、重合形態など特に制限されない。共重合体である場合の重合形態は特に制限されず、ランダム、ブロック、グラフトなどのいずれでもよいがランダム重合体であることが好ましい。
The acrylic polymer (1) and the methacrylic polymer (2) of the present invention are not particularly limited in the form of polymerization. The form of polymerization in the case of a copolymer is not particularly limited and may be any of random, block, graft and the like, but is preferably a random polymer.
重合体の製造方法も特に限定されず、各種の公知の方法を採用し得る。例えば、各化合物中の不飽和基に基づき付加重合させることができる。重合に際しては、公知の不飽和化合物の付加重合条件を適宜に採択して行うことができる。例えば重合開始源として有機過酸化物、アゾ化合物、過硫酸塩等の通常の開始剤が利用できる。
The method for producing the polymer is not particularly limited, and various known methods can be adopted. For example, addition polymerization can be performed based on an unsaturated group in each compound. The polymerization can be carried out by appropriately adopting known addition polymerization conditions for unsaturated compounds. For example, a normal initiator such as an organic peroxide, an azo compound, or a persulfate can be used as a polymerization initiation source.
本発明の表面処理剤は、被膜成分として上記のような特定のアクリル重合体(1)およびメタクリル重合体(2)を含み、該重合体を溶媒中に含む液状形態である。
本発明の表面処理剤の製造方法も限定されない。例えば本発明のアクリル重合体(1)およびメタクリル重合体(2)を公知の溶媒に溶解させて得ることができる。また、例えば化合物(a)を溶媒に添加し、この溶媒を重合媒体とする溶液重合によって本発明のアクリル重合体(1)を製造し、同様に化合物(b)からメタクリル重合体(2)を製造し、本発明のアクリル重合体(1)を前記溶媒中に含む溶液およびメタクリル重合体(2)を含む前記溶媒中に含む溶液を得て、これらを混合して、本発明の表面処理剤とすることもできる。乳化重合させることで本発明のアクリル重合体(1)を含む溶液およびメタクリル重合体(2)を含む溶液を得て、これらを混合させて本発明の表面処理剤とすることもできる。また、ここで得られた本発明のアクリル重合体(1)を分離し、他の溶媒に溶解させてもよい。本発明のメタクリル重合体(2)においても同様である。また、重合原料の化合物が、塩化ビニルなどのガスである場合には、圧力容器を用いて、加圧下に連続供給してもよい。 The surface treating agent of the present invention is a liquid form containing the specific acrylic polymer (1) and methacrylic polymer (2) as described above as a film component, and containing the polymer in a solvent.
The method for producing the surface treatment agent of the present invention is not limited. For example, it can be obtained by dissolving the acrylic polymer (1) and methacrylic polymer (2) of the present invention in a known solvent. Further, for example, the acrylic polymer (1) of the present invention is produced by solution polymerization using the solvent as a polymerization medium by adding the compound (a), and the methacrylic polymer (2) is similarly produced from the compound (b). The surface treatment agent of the present invention is prepared by mixing the solution containing the acrylic polymer (1) of the present invention in the solvent and the solvent containing the methacrylic polymer (2). It can also be. A solution containing the acrylic polymer (1) of the present invention and a solution containing the methacrylic polymer (2) can be obtained by emulsion polymerization, and these can be mixed to obtain the surface treating agent of the present invention. Moreover, you may isolate | separate the acrylic polymer (1) of this invention obtained here and dissolve it in another solvent. The same applies to the methacrylic polymer (2) of the present invention. Further, when the polymerization raw material compound is a gas such as vinyl chloride, it may be continuously supplied under pressure using a pressure vessel.
本発明の表面処理剤の製造方法も限定されない。例えば本発明のアクリル重合体(1)およびメタクリル重合体(2)を公知の溶媒に溶解させて得ることができる。また、例えば化合物(a)を溶媒に添加し、この溶媒を重合媒体とする溶液重合によって本発明のアクリル重合体(1)を製造し、同様に化合物(b)からメタクリル重合体(2)を製造し、本発明のアクリル重合体(1)を前記溶媒中に含む溶液およびメタクリル重合体(2)を含む前記溶媒中に含む溶液を得て、これらを混合して、本発明の表面処理剤とすることもできる。乳化重合させることで本発明のアクリル重合体(1)を含む溶液およびメタクリル重合体(2)を含む溶液を得て、これらを混合させて本発明の表面処理剤とすることもできる。また、ここで得られた本発明のアクリル重合体(1)を分離し、他の溶媒に溶解させてもよい。本発明のメタクリル重合体(2)においても同様である。また、重合原料の化合物が、塩化ビニルなどのガスである場合には、圧力容器を用いて、加圧下に連続供給してもよい。 The surface treating agent of the present invention is a liquid form containing the specific acrylic polymer (1) and methacrylic polymer (2) as described above as a film component, and containing the polymer in a solvent.
The method for producing the surface treatment agent of the present invention is not limited. For example, it can be obtained by dissolving the acrylic polymer (1) and methacrylic polymer (2) of the present invention in a known solvent. Further, for example, the acrylic polymer (1) of the present invention is produced by solution polymerization using the solvent as a polymerization medium by adding the compound (a), and the methacrylic polymer (2) is similarly produced from the compound (b). The surface treatment agent of the present invention is prepared by mixing the solution containing the acrylic polymer (1) of the present invention in the solvent and the solvent containing the methacrylic polymer (2). It can also be. A solution containing the acrylic polymer (1) of the present invention and a solution containing the methacrylic polymer (2) can be obtained by emulsion polymerization, and these can be mixed to obtain the surface treating agent of the present invention. Moreover, you may isolate | separate the acrylic polymer (1) of this invention obtained here and dissolve it in another solvent. The same applies to the methacrylic polymer (2) of the present invention. Further, when the polymerization raw material compound is a gas such as vinyl chloride, it may be continuously supplied under pressure using a pressure vessel.
本発明の表面処理剤を形成する溶媒は、本発明のアクリル重合体(1)およびメタクリル重合体(2)を溶解又は分散できるものであればよく、特に限定されず、各種有機溶剤、水またはこれらの混合媒体などが挙げられる。有機溶剤としては、フッ素系溶剤が好ましい。フッ素系溶剤としては、ハイドロフルオロカーボン(HFC)又はハイドロフルオロエーテル(HFE)が挙げられる。使用可能なフッ素系溶剤の具体例を以下に示すが、これらに限定されるものではない。
The solvent for forming the surface treating agent of the present invention is not particularly limited as long as it can dissolve or disperse the acrylic polymer (1) and methacrylic polymer (2) of the present invention, and various organic solvents, water or These mixed media etc. are mentioned. As the organic solvent, a fluorine-based solvent is preferable. Examples of the fluorine-based solvent include hydrofluorocarbon (HFC) or hydrofluoroether (HFE). Specific examples of usable fluorinated solvents are shown below, but are not limited thereto.
m-キシレンヘキサフルオリド(以下、m-XHFと記す。)
p-キシレンヘキサフルオリド
CF3CH2CF2CH3
CF3CH2CF2H
C6F13OCH3
C6F13OC2H5
C6F13CH2CH3
C3F7OCH3
C3F7OC2H5
C6F13H
CF2HCF2CH2OCF2CF2H
CF3CFHCFHCF2CH3
CF3(OCF2CF2)n(OCF2)mOCF2H
C8F17OCH3
C7F15OCH3
C4F9OCH3
C4F9OC2H5
C4F9CH2CH3
CF3CH2OCF2CF2CF2H
(上記例示中、添字mおよびnは、それぞれ独立に1~20の整数を表す。)
およびこれらの混合物。
たとえばCF3(CF2)3OC2H5と(CF3)2CFCF2OC2H5とのハイドロフルオロエーテル混合物がノベックHFE7200(3M社製)の商品名で入手可能である。 m-Xylene hexafluoride (hereinafter referred to as m-XHF)
p-Xylene hexafluoride CF 3 CH 2 CF 2 CH 3
CF 3 CH 2 CF 2 H
C 6 F 13 OCH 3
C 6 F 13 OC 2 H 5
C 6 F 13 CH 2 CH 3
C 3 F 7 OCH 3
C 3 F 7 OC 2 H 5
C 6 F 13 H
CF 2 HCF 2 CH 2 OCF 2 CF 2 H
CF 3 CFHCHFHCF 2 CH 3
CF 3 (OCF 2 CF 2 ) n (OCF 2 ) m OCF 2 H
C 8 F 17 OCH 3
C 7 F 15 OCH 3
C 4 F 9 OCH 3
C 4 F 9 OC 2 H 5
C 4 F 9 CH 2 CH 3
CF 3 CH 2 OCF 2 CF 2 CF 2 H
(In the above examples, the subscripts m and n each independently represent an integer of 1 to 20)
And mixtures of these.
For example, a hydrofluoroether mixture of CF 3 (CF 2 ) 3 OC 2 H 5 and (CF 3 ) 2 CFCF 2 OC 2 H 5 is available under the trade name Novec HFE 7200 (manufactured by 3M).
p-キシレンヘキサフルオリド
CF3CH2CF2CH3
CF3CH2CF2H
C6F13OCH3
C6F13OC2H5
C6F13CH2CH3
C3F7OCH3
C3F7OC2H5
C6F13H
CF2HCF2CH2OCF2CF2H
CF3CFHCFHCF2CH3
CF3(OCF2CF2)n(OCF2)mOCF2H
C8F17OCH3
C7F15OCH3
C4F9OCH3
C4F9OC2H5
C4F9CH2CH3
CF3CH2OCF2CF2CF2H
(上記例示中、添字mおよびnは、それぞれ独立に1~20の整数を表す。)
およびこれらの混合物。
たとえばCF3(CF2)3OC2H5と(CF3)2CFCF2OC2H5とのハイドロフルオロエーテル混合物がノベックHFE7200(3M社製)の商品名で入手可能である。 m-Xylene hexafluoride (hereinafter referred to as m-XHF)
p-Xylene hexafluoride CF 3 CH 2 CF 2 CH 3
CF 3 CH 2 CF 2 H
C 6 F 13 OCH 3
C 6 F 13 OC 2 H 5
C 6 F 13 CH 2 CH 3
C 3 F 7 OCH 3
C 3 F 7 OC 2 H 5
C 6 F 13 H
CF 2 HCF 2 CH 2 OCF 2 CF 2 H
CF 3 CFHCHFHCF 2 CH 3
CF 3 (OCF 2 CF 2 ) n (OCF 2 ) m OCF 2 H
C 8 F 17 OCH 3
C 7 F 15 OCH 3
C 4 F 9 OCH 3
C 4 F 9 OC 2 H 5
C 4 F 9 CH 2 CH 3
CF 3 CH 2 OCF 2 CF 2 CF 2 H
(In the above examples, the subscripts m and n each independently represent an integer of 1 to 20)
And mixtures of these.
For example, a hydrofluoroether mixture of CF 3 (CF 2 ) 3 OC 2 H 5 and (CF 3 ) 2 CFCF 2 OC 2 H 5 is available under the trade name Novec HFE 7200 (manufactured by 3M).
本発明の表面処理剤の濃度は、用途により使い分けることが好ましい。防水・防湿コート剤では、アクリル重合体(1)およびメタクリル重合体(2)の合計の濃度が1~20質量%であるのが好ましい。潤滑オイルの染み出し防止剤や電子部品用樹脂付着防止剤では、アクリル重合体(1)およびメタクリル重合体(2)の合計の濃度が1~5質量%であるのが好ましい。はんだ用フラックス這い上がり防止剤では、アクリル重合体(1)およびメタクリル重合体(2)の合計の濃度が0.01~1質量%であるのが好ましい。
本発明の表面処理剤における本発明のアクリル重合体(1)およびメタクリル重合体(2)の合計の濃度は最終的濃度であればよく、例えば本発明のはんだ用フラックス這い上がり防止剤を直接調製する場合には、重合直後の重合体を含む溶液中の重合体濃度(固形分濃度)が1質量%を超えていてもなんら差し支えない。高濃度の重合体を含む溶液は、最終的に上記好ましい濃度となるように適宜に希釈することができる。希釈した溶液は、そのまま表面処理剤とすることができる。 It is preferable that the concentration of the surface treatment agent of the present invention is properly used depending on the application. In the waterproof / moisture-proof coating agent, the total concentration of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 1 to 20% by mass. In the lubricant preventing seepage agent and the resin component adhesion preventing agent for electronic parts, the total concentration of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 1 to 5% by mass. In the solder flux creep-up preventing agent, the total concentration of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 0.01 to 1% by mass.
The total concentration of the acrylic polymer (1) and the methacrylic polymer (2) of the present invention in the surface treatment agent of the present invention may be a final concentration. For example, the solder flux creep-up preventing agent of the present invention is directly prepared. In this case, the polymer concentration (solid content concentration) in the solution containing the polymer immediately after polymerization may exceed 1% by mass. A solution containing a high-concentration polymer can be appropriately diluted so that the final desired concentration is obtained. The diluted solution can be used as a surface treatment agent as it is.
本発明の表面処理剤における本発明のアクリル重合体(1)およびメタクリル重合体(2)の合計の濃度は最終的濃度であればよく、例えば本発明のはんだ用フラックス這い上がり防止剤を直接調製する場合には、重合直後の重合体を含む溶液中の重合体濃度(固形分濃度)が1質量%を超えていてもなんら差し支えない。高濃度の重合体を含む溶液は、最終的に上記好ましい濃度となるように適宜に希釈することができる。希釈した溶液は、そのまま表面処理剤とすることができる。 It is preferable that the concentration of the surface treatment agent of the present invention is properly used depending on the application. In the waterproof / moisture-proof coating agent, the total concentration of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 1 to 20% by mass. In the lubricant preventing seepage agent and the resin component adhesion preventing agent for electronic parts, the total concentration of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 1 to 5% by mass. In the solder flux creep-up preventing agent, the total concentration of the acrylic polymer (1) and the methacrylic polymer (2) is preferably 0.01 to 1% by mass.
The total concentration of the acrylic polymer (1) and the methacrylic polymer (2) of the present invention in the surface treatment agent of the present invention may be a final concentration. For example, the solder flux creep-up preventing agent of the present invention is directly prepared. In this case, the polymer concentration (solid content concentration) in the solution containing the polymer immediately after polymerization may exceed 1% by mass. A solution containing a high-concentration polymer can be appropriately diluted so that the final desired concentration is obtained. The diluted solution can be used as a surface treatment agent as it is.
本発明の表面処理剤は、安定性、性能および外観等に悪影響を与えない範囲であれば、前記した以外の他の成分を含んでいてもよい。このような他の成分としては、例えば被膜表面の腐食を防止するためのpH調整剤、防錆剤、表面処理剤を希釈して使用する場合に液中の重合体の濃度管理をする目的や未処理部品との区別をするための染料、染料の安定剤、難燃剤、消泡剤および帯電防止剤等が挙げられる。
The surface treatment agent of the present invention may contain components other than those described above as long as the stability, performance, appearance, etc. are not adversely affected. Such other components include, for example, the purpose of controlling the concentration of the polymer in the liquid when diluting a pH adjuster, a rust inhibitor, and a surface treatment agent to prevent corrosion of the coating surface. Examples thereof include dyes for distinguishing from untreated parts, dye stabilizers, flame retardants, antifoaming agents and antistatic agents.
本発明の表面処理剤は、撥水撥油撥IPA性能を付与したい部分に塗布して被膜を形成して利用することができる。該被膜は、本発明の表面処理剤から溶媒が除去されて形成されるものであり、主として、本発明のアクリル重合体(1)およびメタクリル重合体(2)からなるものである。ここで、主としてとは、該被膜が、本発明のアクリル重合体(1)およびメタクリル重合体(2)のみから形成されていてもよく、前記のように悪影響を与えない範囲で他の成分を含んでいてもよいことを意味する。被覆方法としては一般的な被覆加工方法が採用できる。例えば浸漬塗布、スプレー塗布、ローラー塗布等による塗布等の方法がある。
The surface treatment agent of the present invention can be used by forming a film by coating it on a portion where water / oil / oil repellency / IPA performance is desired. The coating is formed by removing the solvent from the surface treatment agent of the present invention, and mainly comprises the acrylic polymer (1) and the methacrylic polymer (2) of the present invention. Here, mainly means that the coating film may be formed only from the acrylic polymer (1) and the methacrylic polymer (2) of the present invention, and other components are included within a range not adversely affecting as described above. It means that it may contain. As a coating method, a general coating method can be adopted. For example, there are methods such as dip coating, spray coating, and roller coating.
本発明の表面処理剤の塗布後は、溶媒の沸点以上の温度で乾燥を行うことが好ましい。無論、被処理部品の材質などにより加熱乾燥が困難な場合には、加熱を回避して乾燥すべきである。なお、熱処理の条件は、塗布する表面処理剤の組成や、塗布面積等に応じて選択すればよい。
After applying the surface treatment agent of the present invention, it is preferable to perform drying at a temperature not lower than the boiling point of the solvent. Of course, when it is difficult to heat and dry due to the material of the part to be processed, it should be dried while avoiding heating. In addition, what is necessary is just to select the conditions of heat processing according to the composition of the surface treating agent to apply | coat, an application area, etc.
本発明の表面処理剤は、各種材料の処理に適用可能であるが、中でも精密機器部品や摺動部品(モーター、時計、HDD)、電気部品(電子回路や基板、電子部品等)の処理に用いるのが好ましい。中でも、本発明の表面処理剤を、はんだ用フラックス這い上がり防止剤、潤滑オイルのにじみ出し防止剤、防水コート剤、防湿コート剤および電子部品用樹脂付着防止剤として用いることが好ましい。特に、低濃度でも高い撥IPA性を有することから、はんだ用フラックス這い上がり防止剤として用いることが好ましい。
The surface treatment agent of the present invention can be applied to the treatment of various materials, and in particular, for the treatment of precision equipment parts, sliding parts (motors, watches, HDDs), and electrical parts (electronic circuits, substrates, electronic parts, etc.). It is preferable to use it. Among these, the surface treatment agent of the present invention is preferably used as a solder flux creeping-up inhibitor, a lubricant oozing-out preventing agent, a waterproof coating agent, a moisture-proof coating agent and an electronic component resin adhesion preventing agent. In particular, since it has a high IPA repellency even at a low concentration, it is preferably used as a solder flux creep-up preventing agent.
以下に本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、特に断わりのない限り、以下の実施例の記載において「%」で表示されるものは「質量%」を表すものとする。
以下の実施例で使用する化合物を表4に示す。使用した化合物は、市場から試薬として入手することができるものまたは、既知の合成法によって容易に合成できるものである。 The present invention will be specifically described below, but the present invention is not limited to the following examples. Unless otherwise specified, what is indicated by “%” in the description of the following examples represents “mass%”.
The compounds used in the following examples are shown in Table 4. The compound used can be obtained as a reagent from the market or can be easily synthesized by a known synthesis method.
以下の実施例で使用する化合物を表4に示す。使用した化合物は、市場から試薬として入手することができるものまたは、既知の合成法によって容易に合成できるものである。 The present invention will be specifically described below, but the present invention is not limited to the following examples. Unless otherwise specified, what is indicated by “%” in the description of the following examples represents “mass%”.
The compounds used in the following examples are shown in Table 4. The compound used can be obtained as a reagent from the market or can be easily synthesized by a known synthesis method.
(実施例1)
〔重合体1および2〕
密閉容器に、表5に記載の仕込み比(質量部)および濃度となるように各化合物、重合溶剤(m-XHF)および開始剤(V-601)をそれぞれ仕込み、70℃で18時間以上反応を行い、重合体1および2を得た。得られた重合体の重量平均分子量(Mw)を測定した結果を表5に示す。 Example 1
[Polymers 1 and 2]
Each compound, polymerization solvent (m-XHF) and initiator (V-601) were charged in a sealed container so that the charging ratio (parts by mass) and concentration shown in Table 5 were obtained, and the reaction was carried out at 70 ° C. for 18 hours or more. And polymers 1 and 2 were obtained. Table 5 shows the results of measuring the weight average molecular weight (Mw) of the obtained polymer.
〔重合体1および2〕
密閉容器に、表5に記載の仕込み比(質量部)および濃度となるように各化合物、重合溶剤(m-XHF)および開始剤(V-601)をそれぞれ仕込み、70℃で18時間以上反応を行い、重合体1および2を得た。得られた重合体の重量平均分子量(Mw)を測定した結果を表5に示す。 Example 1
[Polymers 1 and 2]
Each compound, polymerization solvent (m-XHF) and initiator (V-601) were charged in a sealed container so that the charging ratio (parts by mass) and concentration shown in Table 5 were obtained, and the reaction was carried out at 70 ° C. for 18 hours or more. And polymers 1 and 2 were obtained. Table 5 shows the results of measuring the weight average molecular weight (Mw) of the obtained polymer.
[重量平均分子量の測定]
重合後、各重合体を含む溶液中の重合体の濃度が約1%になるように、アサヒクリンAK-225SEC1(旭硝子(株)製)を用いて希釈し、測定サンプルとした。昭和電工株式会社製Shodex GPC-104を用いて、以下の条件でGPCを測定した。
<GPC測定条件>
分析カラム:LF-604(充填剤:スチレンジビニルベンゼン共重合体,昭和電工株式会社製)×2
リファレンスカラム:KF600RH(充填剤:なし,昭和電工株式会社製)×2
移動層:AK-225SEC1
流量:0.3ml/min
カラム温度:40℃
標準物質:ポリメチルメタクリレート [Measurement of weight average molecular weight]
After the polymerization, the sample was diluted with Asahi Clin AK-225SEC1 (manufactured by Asahi Glass Co., Ltd.) so that the concentration of the polymer in the solution containing each polymer was about 1%, and used as a measurement sample. GPC was measured under the following conditions using Shodex GPC-104 manufactured by Showa Denko K.K.
<GPC measurement conditions>
Analysis column: LF-604 (filler: styrene divinylbenzene copolymer, manufactured by Showa Denko KK) x 2
Reference column: KF600RH (filler: none, Showa Denko KK) x 2
Moving layer: AK-225SEC1
Flow rate: 0.3 ml / min
Column temperature: 40 ° C
Reference material: Polymethylmethacrylate
重合後、各重合体を含む溶液中の重合体の濃度が約1%になるように、アサヒクリンAK-225SEC1(旭硝子(株)製)を用いて希釈し、測定サンプルとした。昭和電工株式会社製Shodex GPC-104を用いて、以下の条件でGPCを測定した。
<GPC測定条件>
分析カラム:LF-604(充填剤:スチレンジビニルベンゼン共重合体,昭和電工株式会社製)×2
リファレンスカラム:KF600RH(充填剤:なし,昭和電工株式会社製)×2
移動層:AK-225SEC1
流量:0.3ml/min
カラム温度:40℃
標準物質:ポリメチルメタクリレート [Measurement of weight average molecular weight]
After the polymerization, the sample was diluted with Asahi Clin AK-225SEC1 (manufactured by Asahi Glass Co., Ltd.) so that the concentration of the polymer in the solution containing each polymer was about 1%, and used as a measurement sample. GPC was measured under the following conditions using Shodex GPC-104 manufactured by Showa Denko K.K.
<GPC measurement conditions>
Analysis column: LF-604 (filler: styrene divinylbenzene copolymer, manufactured by Showa Denko KK) x 2
Reference column: KF600RH (filler: none, Showa Denko KK) x 2
Moving layer: AK-225SEC1
Flow rate: 0.3 ml / min
Column temperature: 40 ° C
Reference material: Polymethylmethacrylate
〔表面処理剤1~9および比較表面処理剤1、2〕
表6に記載の重合体の含有比率になるように、各重合体を混合したのち、m-XHFまたはHFE-7200(3M社)で希釈して、各濃度(15%、1%、0.1%、0.01%)の表面処理剤1~9および比較表面処理剤1、2を得た。なお、濃度15%の処理剤が重合溶剤と同じm-XHFで希釈したものであり、濃度1%、0.1%および0.01%の処理剤が、HFE-7200で希釈したものである。また、濃度は各処理剤における、アクリル重合体(1)とメタクリル重合体(2)との合計質量の百分率を重合体濃度とした。 [Surface treatment agents 1 to 9 and comparative surface treatment agents 1 and 2]
Each polymer was mixed so that the content ratio of the polymer described in Table 6 was obtained, and then diluted with m-XHF or HFE-7200 (3M company) to obtain each concentration (15%, 1%,. 1% and 0.01%) of surface treatment agents 1 to 9 and comparative surface treatment agents 1 and 2 were obtained. The treatment agent with a concentration of 15% was diluted with m-XHF which is the same as the polymerization solvent, and the treatment agents with concentrations of 1%, 0.1% and 0.01% were diluted with HFE-7200. . Moreover, the density | concentration made the polymer concentration the percentage of the total mass of an acrylic polymer (1) and a methacryl polymer (2) in each processing agent.
表6に記載の重合体の含有比率になるように、各重合体を混合したのち、m-XHFまたはHFE-7200(3M社)で希釈して、各濃度(15%、1%、0.1%、0.01%)の表面処理剤1~9および比較表面処理剤1、2を得た。なお、濃度15%の処理剤が重合溶剤と同じm-XHFで希釈したものであり、濃度1%、0.1%および0.01%の処理剤が、HFE-7200で希釈したものである。また、濃度は各処理剤における、アクリル重合体(1)とメタクリル重合体(2)との合計質量の百分率を重合体濃度とした。 [Surface treatment agents 1 to 9 and comparative surface treatment agents 1 and 2]
Each polymer was mixed so that the content ratio of the polymer described in Table 6 was obtained, and then diluted with m-XHF or HFE-7200 (3M company) to obtain each concentration (15%, 1%,. 1% and 0.01%) of surface treatment agents 1 to 9 and comparative surface treatment agents 1 and 2 were obtained. The treatment agent with a concentration of 15% was diluted with m-XHF which is the same as the polymerization solvent, and the treatment agents with concentrations of 1%, 0.1% and 0.01% were diluted with HFE-7200. . Moreover, the density | concentration made the polymer concentration the percentage of the total mass of an acrylic polymer (1) and a methacryl polymer (2) in each processing agent.
上記で得られた表面処理剤1~9および比較表面処理剤1、2について、以下の性能を評価した。評価結果を表6に示す。
[接触角の測定]
重合体濃度を1質量%に調整した表面処理剤1~9および比較表面処理剤1、2の各々に、室温下で、ガラス板を浸漬した。そして1分後に取り出し室温で乾燥させ、各処理剤の被膜を有する各ガラス板を得た。
次に各々の種類の被膜を形成した各ガラス板の被膜上に、水またはn-ヘキサデカン(HD)を滴下し、接触角を測定した。
重合体濃度を0.1質量%および0.01質量%に調整した表面処理剤1~9および比較表面処理剤1、2の各々に、室温下で、ガラス板を浸漬した。そして1分後に取り出し室温で乾燥させ、各処理剤の被膜を有する各ガラス板を得た。次に各々の種類の被膜を形成した各ガラス板の被膜上に、IPAを滴下し、接触角を測定した。
各接触角の測定には、自動接触角計OCA-20[dataphysics社製]を用いた。 The following performance was evaluated for the surface treatment agents 1 to 9 and comparative surface treatment agents 1 and 2 obtained above. The evaluation results are shown in Table 6.
[Measurement of contact angle]
A glass plate was immersed in each of surface treatment agents 1 to 9 and comparative surface treatment agents 1 and 2 having a polymer concentration adjusted to 1% by mass at room temperature. And it took out after 1 minute and was made to dry at room temperature, and each glass plate which has a film of each processing agent was obtained.
Next, water or n-hexadecane (HD) was dropped onto the coating of each glass plate on which each type of coating was formed, and the contact angle was measured.
A glass plate was immersed in each of the surface treatment agents 1 to 9 and the comparative surface treatment agents 1 and 2 having the polymer concentration adjusted to 0.1% by mass and 0.01% by mass at room temperature. And it took out after 1 minute and was made to dry at room temperature, and each glass plate which has a film of each processing agent was obtained. Next, IPA was dropped on the coating of each glass plate on which each type of coating was formed, and the contact angle was measured.
For the measurement of each contact angle, an automatic contact angle meter OCA-20 (manufactured by dataphysics) was used.
[接触角の測定]
重合体濃度を1質量%に調整した表面処理剤1~9および比較表面処理剤1、2の各々に、室温下で、ガラス板を浸漬した。そして1分後に取り出し室温で乾燥させ、各処理剤の被膜を有する各ガラス板を得た。
次に各々の種類の被膜を形成した各ガラス板の被膜上に、水またはn-ヘキサデカン(HD)を滴下し、接触角を測定した。
重合体濃度を0.1質量%および0.01質量%に調整した表面処理剤1~9および比較表面処理剤1、2の各々に、室温下で、ガラス板を浸漬した。そして1分後に取り出し室温で乾燥させ、各処理剤の被膜を有する各ガラス板を得た。次に各々の種類の被膜を形成した各ガラス板の被膜上に、IPAを滴下し、接触角を測定した。
各接触角の測定には、自動接触角計OCA-20[dataphysics社製]を用いた。 The following performance was evaluated for the surface treatment agents 1 to 9 and comparative surface treatment agents 1 and 2 obtained above. The evaluation results are shown in Table 6.
[Measurement of contact angle]
A glass plate was immersed in each of surface treatment agents 1 to 9 and comparative surface treatment agents 1 and 2 having a polymer concentration adjusted to 1% by mass at room temperature. And it took out after 1 minute and was made to dry at room temperature, and each glass plate which has a film of each processing agent was obtained.
Next, water or n-hexadecane (HD) was dropped onto the coating of each glass plate on which each type of coating was formed, and the contact angle was measured.
A glass plate was immersed in each of the surface treatment agents 1 to 9 and the comparative surface treatment agents 1 and 2 having the polymer concentration adjusted to 0.1% by mass and 0.01% by mass at room temperature. And it took out after 1 minute and was made to dry at room temperature, and each glass plate which has a film of each processing agent was obtained. Next, IPA was dropped on the coating of each glass plate on which each type of coating was formed, and the contact angle was measured.
For the measurement of each contact angle, an automatic contact angle meter OCA-20 (manufactured by dataphysics) was used.
[被膜の粘着性の評価]
表面処理剤1~9および比較表面処理剤1、2の高濃度溶液(15質量%)を、それぞれ、アルミカップ(φ45mm)に約2gずつ採取し、室温で乾燥させた。乾燥後、薬包紙を被膜の上に置き、その上に100gの分銅(φ24mm)を置いた。1分後、分銅を取り除き薬包紙の張り付き具合を確認した。
薬包紙をはがすとき、薬包紙に被膜に張り付き、被膜が剥がれてしまうものを×、やや張り付くものの、薬包紙だけが簡単に剥がれるものを△、薬包紙がまったく張り付かないものを○とした。 [Evaluation of film adhesion]
About 2 g each of high-concentration solutions (15% by mass) of surface treatment agents 1 to 9 and comparative surface treatment agents 1 and 2 were collected in aluminum cups (φ45 mm) and dried at room temperature. After drying, the medicine-wrapping paper was placed on the film, and 100 g of weight (φ24 mm) was placed thereon. After 1 minute, the weight was removed and the sticking of the medicine wrapping paper was confirmed.
When the medicine wrapper was peeled off, the film attached to the film and peeled off was evaluated as x. The film slightly stuck, but only the medicine paper was easily peeled out was marked as Δ, and the drug paper was not adhered at all.
表面処理剤1~9および比較表面処理剤1、2の高濃度溶液(15質量%)を、それぞれ、アルミカップ(φ45mm)に約2gずつ採取し、室温で乾燥させた。乾燥後、薬包紙を被膜の上に置き、その上に100gの分銅(φ24mm)を置いた。1分後、分銅を取り除き薬包紙の張り付き具合を確認した。
薬包紙をはがすとき、薬包紙に被膜に張り付き、被膜が剥がれてしまうものを×、やや張り付くものの、薬包紙だけが簡単に剥がれるものを△、薬包紙がまったく張り付かないものを○とした。 [Evaluation of film adhesion]
About 2 g each of high-concentration solutions (15% by mass) of surface treatment agents 1 to 9 and comparative surface treatment agents 1 and 2 were collected in aluminum cups (φ45 mm) and dried at room temperature. After drying, the medicine-wrapping paper was placed on the film, and 100 g of weight (φ24 mm) was placed thereon. After 1 minute, the weight was removed and the sticking of the medicine wrapping paper was confirmed.
When the medicine wrapper was peeled off, the film attached to the film and peeled off was evaluated as x. The film slightly stuck, but only the medicine paper was easily peeled out was marked as Δ, and the drug paper was not adhered at all.
表面処理剤1~9および比較処理剤1、2について、被膜の粘着性およびガラス板に処理した際の接触角について性能を評価した。評価結果を表6に示す。
For the surface treatment agents 1 to 9 and the comparative treatment agents 1 and 2, the performance was evaluated with respect to the adhesiveness of the coating and the contact angle when treated on a glass plate. The evaluation results are shown in Table 6.
以上の結果から、本発明の表面処理剤は、アクリル重合体(1)またはメタクリル重合体(2)の一方のみを含む比較表面処理剤と比べて、同等またはそれ以上の高い撥水性、撥油性および撥IPA性を有し、特に低濃度での高い撥IPA性を有することが分った。さらに、アクリル重合体(1)およびメタクリル重合体(2)の混合比である質量比を調整することで、撥水性、撥油性および撥IPA性を落とさずに被膜の粘着性を低減し、被膜特性について改善された優れた性能を有する表面処理剤になることが分った。
From the above results, the surface treatment agent of the present invention is equivalent to or higher in water repellency and oil repellency than the comparative surface treatment agent containing only one of the acrylic polymer (1) and the methacrylic polymer (2). And IPA repellency, especially high IPA repellency at low concentrations. Furthermore, by adjusting the mass ratio which is the mixing ratio of the acrylic polymer (1) and the methacrylic polymer (2), the adhesiveness of the coating is reduced without reducing the water repellency, oil repellency and IPA repellency. It has been found that the surface treatment agent has excellent performance with improved properties.
(実施例2)
次に、他のアクリル重合体(1)およびメタクリル重合体(2)として他の重合体を調製し、これを用いた表面処理剤および比較表面処理剤を調製した。
〔重合体3~5〕
前記重合体1および2と同様にして、重合体3~5を得た。得られた重合体のMwを重合体1および2と同様に測定した結果を表7に示す。
(Example 2)
Next, other polymers were prepared as other acrylic polymer (1) and methacrylic polymer (2), and a surface treatment agent and a comparative surface treatment agent were prepared using the other polymers.
[Polymers 3-5]
In the same manner as the polymers 1 and 2, polymers 3 to 5 were obtained. Table 7 shows the results obtained by measuring the Mw of the obtained polymer in the same manner as in polymers 1 and 2.
次に、他のアクリル重合体(1)およびメタクリル重合体(2)として他の重合体を調製し、これを用いた表面処理剤および比較表面処理剤を調製した。
〔重合体3~5〕
前記重合体1および2と同様にして、重合体3~5を得た。得られた重合体のMwを重合体1および2と同様に測定した結果を表7に示す。
Next, other polymers were prepared as other acrylic polymer (1) and methacrylic polymer (2), and a surface treatment agent and a comparative surface treatment agent were prepared using the other polymers.
[Polymers 3-5]
In the same manner as the polymers 1 and 2, polymers 3 to 5 were obtained. Table 7 shows the results obtained by measuring the Mw of the obtained polymer in the same manner as in polymers 1 and 2.
〔表面処理剤10~12および比較表面処理剤3~5〕
前記表面処理剤1~9および比較表面処理剤1、2と同様にして、表面処理剤10~12および比較表面処理剤3~5を得た。これらについて、実施例1と同様に測定した接触角および被膜の粘着性を評価した結果を表8に示す。前記比較表面処理剤1の評価結果も表8に示す。
[Surface treatment agents 10 to 12 and comparative surface treatment agents 3 to 5]
Surface treating agents 10 to 12 and comparative surface treating agents 3 to 5 were obtained in the same manner as the surface treating agents 1 to 9 and comparative surface treating agents 1 and 2. Table 8 shows the results of evaluating the contact angle and the adhesiveness of the film measured in the same manner as in Example 1. The evaluation results of the comparative surface treatment agent 1 are also shown in Table 8.
前記表面処理剤1~9および比較表面処理剤1、2と同様にして、表面処理剤10~12および比較表面処理剤3~5を得た。これらについて、実施例1と同様に測定した接触角および被膜の粘着性を評価した結果を表8に示す。前記比較表面処理剤1の評価結果も表8に示す。
Surface treating agents 10 to 12 and comparative surface treating agents 3 to 5 were obtained in the same manner as the surface treating agents 1 to 9 and comparative surface treating agents 1 and 2. Table 8 shows the results of evaluating the contact angle and the adhesiveness of the film measured in the same manner as in Example 1. The evaluation results of the comparative surface treatment agent 1 are also shown in Table 8.
重合単位(C)の構造を変更した場合においても、本発明の表面処理剤は、アクリル重合体(1)またはメタクリル重合体(2)の一方のみを含む比較表面処理剤と比べて、優れた性能を有する表面処理剤になることが分った。
Even when the structure of the polymerization unit (C) is changed, the surface treatment agent of the present invention is superior to the comparative surface treatment agent containing only one of the acrylic polymer (1) or the methacrylic polymer (2). It turned out that it becomes the surface treating agent which has performance.
Claims (10)
- 下記式(a)で表される化合物から導かれる重合単位(A)を80質量%以上の含有量で含有するアクリル重合体(1)と、下記式(b)で表される化合物から導かれる重合単位(B)を80質量%以上の含有量で含有するメタクリル重合体(2)とを、溶媒中に含んでなる表面処理剤。
CH2=CH-COO-(CH2)n1-(CF2)6F 式(a)
式(a)中、n1は0~4の整数である。
CH2=C(CH3)-COO-(CH2)n2-(CF2)6F 式(b)
式(b)中、n2は0~4の整数である。 Derived from an acrylic polymer (1) containing a polymer unit (A) derived from a compound represented by the following formula (a) at a content of 80% by mass or more and a compound represented by the following formula (b). A surface treatment agent comprising a methacrylic polymer (2) containing a polymerization unit (B) at a content of 80% by mass or more in a solvent.
CH 2 = CH-COO- (CH 2 ) n1- (CF 2 ) 6 F Formula (a)
In the formula (a), n 1 is an integer of 0-4.
CH 2 ═C (CH 3 ) —COO— (CH 2 ) n2 — (CF 2 ) 6 F Formula (b)
In the formula (b), n 2 is an integer of 0-4. - 前記アクリル重合体(1)およびメタクリル重合体(2)の少なくとも一方が、さらに下記式(c)で表される化合物から導かれる重合単位(C)を含有する請求項1に記載の表面処理剤。
CH2=C(R1)-COO-Q1-Y (c)
式(c)中の記号は以下の意味を示す。
R1:水素原子またはメチル基。
Q1:2価の連結基。
Y:1価の官能基。 The surface treating agent according to claim 1, wherein at least one of the acrylic polymer (1) and the methacrylic polymer (2) further contains a polymer unit (C) derived from a compound represented by the following formula (c). .
CH 2 = C (R 1 ) -COO-Q 1 -Y (c)
Symbols in the formula (c) have the following meanings.
R 1 : a hydrogen atom or a methyl group.
Q 1 : a divalent linking group.
Y: a monovalent functional group. - 前記アクリル重合体(1)およびメタクリル重合体(2)の質量比(1)/(2)が、50/50~5/95である、請求項1または2に記載の表面処理剤。 The surface treating agent according to claim 1 or 2, wherein a mass ratio (1) / (2) of the acrylic polymer (1) and the methacrylic polymer (2) is 50/50 to 5/95.
- 前記式(c)におけるYが、水酸基、カルボキシ基またはアルコキシシリル基である、請求項2または3に記載の表面処理剤。 The surface treating agent according to claim 2 or 3, wherein Y in the formula (c) is a hydroxyl group, a carboxy group or an alkoxysilyl group.
- 前記アクリル重合体(1)およびメタクリル重合体(2)の重量平均分子量(ポリメチルメタクリレート換算)が10万以上である請求項1~4のいずれかに記載の表面処理剤。 The surface treating agent according to any one of claims 1 to 4, wherein the acrylic polymer (1) and the methacrylic polymer (2) have a weight average molecular weight (in terms of polymethyl methacrylate) of 100,000 or more.
- 請求項1~5のいずれかに記載の表面処理剤を使用したはんだ用フラックス這い上がり防止剤。 A solder flux creeping-up preventive agent using the surface treating agent according to any one of claims 1 to 5.
- 請求項1~5のいずれかに記載の表面処理剤を使用した潤滑オイルの染み出し防止剤。 An anti-leaking agent for lubricating oil using the surface treating agent according to any one of claims 1 to 5.
- 請求項1~5のいずれかに記載の表面処理剤を使用した防水・防湿コーティング剤。 A waterproof / moisture-proof coating agent using the surface treatment agent according to any one of claims 1 to 5.
- 請求項1~5のいずれかに記載の表面処理剤を使用した電子部品用樹脂付着防止剤。 Resin adhesion preventive agent for electronic parts using the surface treating agent according to any one of claims 1 to 5.
- 請求項1~5のいずれかに記載の表面処理剤で被覆された基材。 A substrate coated with the surface treatment agent according to any one of claims 1 to 5.
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