WO2012005166A1 - Nonflammable solvent and surface-treating agent - Google Patents
Nonflammable solvent and surface-treating agent Download PDFInfo
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- WO2012005166A1 WO2012005166A1 PCT/JP2011/065047 JP2011065047W WO2012005166A1 WO 2012005166 A1 WO2012005166 A1 WO 2012005166A1 JP 2011065047 W JP2011065047 W JP 2011065047W WO 2012005166 A1 WO2012005166 A1 WO 2012005166A1
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- C—CHEMISTRY; METALLURGY
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- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
Definitions
- the present invention relates to a non-flammable solvent and a fluorinated surface treatment agent containing the same.
- various base materials have fluorine-based polymers for imparting IPA repellency to a solvent (2-propanol: IPA) such as water repellency, oil repellency, and flux, and in many cases, have a perfluoroalkyl group in many cases.
- a surface treatment agent containing a fluoropolymer in a drying solvent is applied.
- the solvent used for this surface treating agent has good drying properties and can be a solvent for a fluoropolymer. Since the fluorine-based polymer has essentially poor solubility in a normal organic solvent, the solvent of the fluorine-based polymer is substantially a fluorine-based solvent.
- a typical example of a fluorine-based solvent that has been used so far is a so-called chlorofluorocarbon solvent such as hydrochlorofluorocarbon (HCFC) such as dichloropentafluoropropane and dichlorofluoroethane.
- HCFC hydrochlorofluorocarbon
- HCFC hydrochlorofluorocarbon
- PFC perfluorocarbons
- hydrofluoroether is one of the recently developed fluorine-based solvents that can be used instead of the above.
- (perfluorobutoxy) methane C 4 F 9 OCH 3
- (perfluorobutoxy) ethane C 4 F 9 OC 2 H 5
- 2-tetrafluoroethane CF 3 CH 2 OCF 2 CF 2 H
- HFE has advantages such as non-flammability, good drying properties, excellent chemical and thermal stability, zero ozone depletion coefficient and relatively little global warming effect.
- these HFEs are very expensive.
- fluorine polymer solvent that can be obtained at low cost
- a fluorine solvent having a benzene skeleton such as bis (trifluoromethyl) benzene.
- most of these fluorinated solvents having a benzene skeleton are flammable.
- a fluorine-based solvent having a flammable benzene skeleton is mixed with a non-flammable fluorine-based solvent to form a solvent for a fluorine-based polymer.
- 1,3-di (trifluoromethyl) benzene is contained as a mixed solvent with the above HFE, HFC or the like in an amount of 5 wt% or 49.75 wt% in the total solvent (see Patent Document 2). ).
- the present invention is an inexpensive non-flammable solvent that can be used as a solvent for a fluorine-based polymer and has a low environmental impact. Furthermore, the present invention repels various substrate surfaces that can be provided at low cost. It is an object of the present invention to provide a fluorine-based surface treatment agent that can sufficiently impart water repellency, oil repellency, and IPA repellency to an environment.
- the mass ratio (1) / (2) is particularly preferably 80/20 to 96.25 / 3.75.
- the non-flammable solvent may contain a solvent component other than the above (1) and (2) in an amount of 20% by mass or less in the total amount of the solvent.
- the amount of the flammable solvent component other than (1) in the non-flammable solvent is preferably 1% by mass or less in the total amount of the solvent.
- the non-flammable solvent component other than (2) is preferably hydrofluoroether.
- a surface treatment agent comprising a non-flammable solvent as described above and a fluorine-containing compound as a solute.
- the fluorine-containing compound is preferably a fluorine-containing polymer or a phosphoric acid ester compound containing a polyfluoroalkyl group.
- the solute concentration of the surface treatment agent is preferably 20% by mass or less.
- the kinematic viscosity of the surface treatment agent is preferably 1.0 ⁇ 10 ⁇ 5 m 2 / s or less.
- the surface treatment agent of the present invention can be used as a solder flux creep-up preventive agent, a lubricant ooze-out preventive agent, a waterproof / moisture-proof coating agent, a resin adhesion preventive agent for electronic parts, and a mold release agent.
- covered with the above surface treating agents can also be provided.
- the present invention can provide an inexpensive non-flammable solvent as a solvent for the fluoropolymer.
- water and oil repellency and IPA repellency can be sufficiently imparted to various substrate surfaces, and non-flammable, environmentally and economically superior fluorine-based surface treatment agents can be provided. It was.
- Bis (trifluoromethyl) benzene used in the present invention is also called as xylene hexafluoride and is available as a commercial product.
- XHF represents regioisomers o-XHF (1,2-di (trifluoromethyl) benzene), m-XHF (1,3-di (trifluoromethyl) benzene) and p-XHF (1, 4-di (trifluoromethyl) benzene) may be used, or a mixture of two or more of these may be used.
- m-XHF is preferable as XHF.
- HFE-347pc CF 3 CH 2 OCF 2 CF 2 H
- HFE-347pc CF 3 CH 2 OCF 2 CHF 2
- HFE-347 may be described as CF 3 CH 2 OCF 2 CHF 2 in a product catalog or the like.
- the mass ratio of (1) / (2) is 50/50 to 97/3, usually 60/40 to 97/3, preferably 70/30 to 97/3.
- the ratio is preferably 80/20 to 96.25 / 3.75, particularly preferably 85/15 to 96.25 / 3.75.
- the amount of expensive HFE-347 used can be significantly reduced by the mass ratio of (1) / (2).
- the total mass of (1) and (2) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in the total amount of the solvent. In these ranges, the solubility of the fluorine-containing compound as the solute of the non-flammable solvent is good, and the amount of other expensive solvent such as HFE used can be suppressed.
- the other solvent component is a solvent component having flammability other than (1)
- it is not particularly limited as long as it is 20% by mass or less in the total amount of the solvent and does not affect the flammability. As a range, it is 1 mass% or less in the total amount of the solvent.
- HFC and HFE which are non-flammable solvents other than (2), are preferably used because of the uniform solubility of the solute fluorine-containing compound.
- HFE is particularly preferable.
- HFE other than (2) include the following. C 6 F 13 OCH 3 C 6 F 13 OC 2 H 5 C 3 F 7 OCH 3 C 3 F 7 OC 2 H 5 CF 2 HCF 2 CH 2 OCF 2 CF 2 H 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 And mixtures of these.
- the subscripts m and n each represent an integer of 1 to 20, and the alkyl skeleton group includes a linear or branched embodiment.
- the non-flammable solvent other than (2) is not particularly limited as long as it is 20% by mass or less based on the total amount of the solvent.
- flammability is defined as having a flash point by performing flash point measurement according to the following procedure.
- Each flash point measurement method shall follow the method specified in JIS-K-2265.
- flash point measurement procedure> (A) Implementation of flash point measurement by tag sealing method. (B) When the flash point cannot be measured at a temperature of 80 ° C. or lower in (a), the flash point is measured by the Cleveland open method.
- the surface treating agent of the present invention is formed from the non-flammable solvent as described above and a solute.
- the solvent is defined as a liquid component having a kinematic viscosity of less than 1.0 ⁇ 10 ⁇ 5 m 2 / s at room temperature
- the solute is a solid or kinematic viscosity at room temperature of 1.0 ⁇ 10 ⁇ 5 m. It is defined as a liquid component of 2 / s or more.
- the surface treatment agent according to the present invention contains at least a fluorine-containing compound as a solute.
- This fluorine-containing compound is usually a compound containing a polyfluoroalkyl group, and specific examples thereof include a fluorine-containing polymer or a fluorine-containing phosphate ester containing the group.
- the fluoropolymer contains at least a structural unit derived from the polyfluoroalkyl group-containing compound (a).
- This compound (a) is typically a (meth) acrylic acid compound, specifically, (meth) acrylic acid ester or (meth) acrylamide.
- the following structure is mentioned as a compound (a).
- CH 2 CR 1 -COX-Q 1 -Rf 1
- R 1 is a hydrogen atom or a methyl group
- X is —O— or —NH—
- Q 1 is a single bond or a divalent linking group
- Rf 1 has 1 to 20 carbon atoms. It is a polyfluoroalkyl group.
- the divalent linking group is preferably an alkylene group having 1 to 5 carbon atoms.
- the term “(meth) acryl” means both or one of acrylic and methacrylic. If such a compound (a) is specifically exemplified by (meth) acrylic acid ester, CH 2 ⁇ CH—COO— (CH 2 ) n — (CF 2 ) m F, CH 2 ⁇ C (CH 3 ) —COO— (CH 2 ) n — (CF 2 ) m F (In the above example, the subscript n is an integer from 0 to 4, and the subscript m is an integer from 1 to 16.) The compound (a) is not limited to these. Of these, those in which m is 1 to 6 are preferred.
- (meth) acrylic acid ester can be suitably selected by the performance calculated
- methacrylic acid ester is preferable when water repellency is particularly important, and acrylic acid ester is preferable when oil repellency and IPA repellency are particularly important, or when heat resistance of the film is particularly important.
- the fluoropolymer usually contains 50 mass% or more, preferably 80 mass% or more, more preferably 90 mass% or more of the structural unit derived from the compound (a).
- the mass% of the structural unit in a polymer is the value considered that all the raw material compounds used for superposition
- the fluorinated polymer is a polymer composed solely of the compound (a), it may be a single homopolymer or two or more copolymers of the compound (a).
- the fluorinated polymer when it is a copolymer, it may contain one or more structural units derived from other compounds (b).
- the compound (b) is usually a compound that does not contain a polyfluoroalkyl group, such as (meth) acrylic acid, a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms, a reactive functional group.
- fluorine-containing phosphate ester examples include the following structures.
- Rf 2 is a polyfluoroalkyl group having 1 to 20 carbon atoms
- Q 2 is a single bond or a divalent linking group
- M is a hydrogen atom, an ammonium group, a substituted ammonium group or an alkali metal atom.
- r is an integer from 1 to 3
- s is an integer from 0 to 2
- r + s is 3.
- the divalent linking group is preferably an alkylene group having 1 to 5 carbon atoms which may be substituted with an OH group.
- fluorine-containing phosphate ester examples include the following compounds, but are not limited thereto.
- the subscript m is an integer of 1 to 16, preferably 1 to 6.
- the fluorine-containing phosphate ester is particularly suitable for treating a metal surface as a surface treatment agent. It is also particularly suitable when used as a release agent.
- the surface treatment agent of the present invention can be dissolved or dispersed in the above-mentioned solvent, and does not impair the object of the present invention and does not impair the stability, performance, appearance, etc.
- other solutes can be contained without particular limitation. Examples thereof include dimethylmethyl silicone and polyethylene glycol alkylamine.
- diluting pH adjusters, rust inhibitors, and surface treatment agents to prevent coating surface corrosion the purpose is to control the concentration of the polymer in the liquid and to distinguish it from untreated parts.
- Other components such as dyes, dye stabilizers, flame retardants, antifoaming agents and antistatic agents.
- the surface treatment agent of the present invention preferably has a solute concentration of 20% by mass or less.
- This solute means not only the whole solute in the surface treatment agent, that is, not only the fluorine-containing compound but also other solutes and other components.
- the concentration of the fluorine-containing compound of the surface treatment agent of the present invention is preferably set as appropriate depending on the application.
- the content is preferably 1 to 20% by mass.
- the content is preferably 1 to 5% by mass.
- the concentration is preferably 0.01 to 1% by mass.
- the content is preferably 0.1 to 10% by mass.
- the concentration of the fluorine-containing compound may be a final concentration for each application. For use in each application, even if it exceeds the high concentration, for example, 1% by mass in the case of the solder flux scooping-up inhibitor, there is no problem.
- the fluorine-containing compound is a fluorine-containing polymer
- a polymerization solution containing the polymer at a high concentration solid content concentration
- the amount of the fluorine-containing compound in the total amount of the solute may vary depending on the application.
- a lubricant preventing bleeding agent for example, in a waterproof / moisture-proof coating agent, a lubricant preventing bleeding agent, an electronic component resin adhesion preventing agent, and a solder flux creeping-up preventing agent, it is preferable that 90% by mass or more of the solute component is a fluorine-containing compound.
- the fluorine-containing compound may be 50% by mass or less of the solute component.
- the kinematic viscosity of the surface treatment agent of the present invention is preferably less than 1.0 ⁇ 10 ⁇ 5 m 2 / s, more preferably 5.0 ⁇ 10 ⁇ 6 m 2 / s or less. Within these kinematic viscosity ranges, the workability of the surface treatment agent is good.
- the surface treatment agent of the present invention can be used by forming a film by applying it to a portion to which performance such as water repellency, oil repellency and IPA repellency is desired.
- the film is formed by removing the solvent from the surface treatment agent of the present invention, and is mainly composed of the solute component of the present invention.
- 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, among which precision equipment parts, sliding parts (motors, watches, HDDs), electrical parts (electronic circuits, substrates, electronic parts, etc.) and various resins. It is preferable to use it for the processing of molds for production. Among them, it is preferable to use the surface treatment agent of the present invention as a solder flux creeping-up inhibitor, a lubricant oozing-out preventing agent, a waterproof coating agent, a moisture-proof coating agent, an electronic component resin adhesion preventing agent, and a release agent. .
- the fluoropolymer solution obtained in Synthesis Example 1 was diluted with each predetermined amount of solvent to a polymer concentration of 0.2%.
- Table 2 shows the solvent composition in each surface treatment agent obtained.
- the contact angle, kinematic viscosity and density were measured as follows. The results are shown in Table 3.
- Table 3 [Measurement of contact angle] A glass plate was immersed in each surface treating agent of Examples 1 to 4 at room temperature for 1 minute and then dried at room temperature to obtain each glass plate having a coating of each treating agent. Next, water, IPA or n-hexadecane (n-HD) was dropped onto the coating on each glass plate, and the contact angle was measured.
- an automatic contact angle meter OCA-20 manufactured by dataphysics
- kinematic viscosity in 25 degreeC was measured using the Ubbelohde viscometer.
- specific gravity measurement About each surface treating agent, the specific gravity at room temperature was measured using the standard specific gravity meter (floating).
- the fluoropolymer solution obtained in Synthesis Example 1 was diluted to a concentration shown in Table 4 with a mixed solvent in which the mass ratio of the solvent components (1) / (2) was 75/25.
- the contact angle, kinematic viscosity and density were measured in the same manner as in Examples 1 to 4. The results are shown in Table 4.
- the above-mentioned flash point measurement was performed for the surface treatment agent 8 and the presence or absence of flammability was tested, it was non-flammable.
- Table 6 shows the structures of the compounds (a1) to (b2) in Table 5.
- the polymer 2 solution was diluted to a polymer concentration of 0.2% with a mixed solvent having a solvent component (1) / (2) mass ratio of 90/10. This is designated surface treating agent 9.
- the polymer 3 diluted with the same conditions is used as the surface treatment agent 10.
- the surface treating agent 11 containing the compound (P1) which is a fluorine-containing phosphate ester, and the compound (Z1) which is an additive was prepared. Table 7 summarizes each surface treatment agent.
- Compound (P1) (F (CF 2 ) 6 —CH 2 CH (OH) CH 2 O) 2 P (O) (OH)
- Compound (Z1) C 18 H 37 N ((C 2 H 4 O) x H) (C 2 H 4 O) y H (x + y is 20 on average)
- the water repellency, oil repellency, and IPA repellency are sufficient for surface treatment on various substrates, have no flammability, and have a low adverse effect on the environment. Nevertheless, it has become possible to provide surface treatment agents with extremely high economic benefits.
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Abstract
Description
この引火性のベンゼン骨格を有するフッ素系溶媒を、非引火性フッ素系溶媒と混合してフッ素系重合体の溶剤とする開示がある。たとえば、1,3-ジ(トリフルオロメチル)ベンゼンを上記HFE、HFCなどとの混合溶媒として全溶媒中5重量%または49.75重量%の量で含ませた例がある(特許文献2参照)。 On the other hand, as a fluorine polymer solvent that can be obtained at low cost, there is a fluorine solvent having a benzene skeleton, such as bis (trifluoromethyl) benzene. However, most of these fluorinated solvents having a benzene skeleton are flammable.
There is a disclosure that a fluorine-based solvent having a flammable benzene skeleton is mixed with a non-flammable fluorine-based solvent to form a solvent for a fluorine-based polymer. For example, there is an example in which 1,3-di (trifluoromethyl) benzene is contained as a mixed solvent with the above HFE, HFC or the like in an amount of 5 wt% or 49.75 wt% in the total solvent (see Patent Document 2). ).
本発明は、フッ素系重合体の溶剤として使用することができる、安価で、環境への負荷が少ない非引火性溶媒、さらには該溶媒の使用により安価に提供され得る、各種基材表面に撥水性、撥油性および撥IPA性を充分に付与し得る環境への負荷が少ないフッ素系表面処理剤の提供を目的とする。 If the surface treatment agent is flammable and falls under the category of dangerous goods under the Fire Service Act, not only is the handling place, storage place, and storage quantity extremely limited, but the equipment used must be explosion-proof, A huge economic burden is required. For this reason, the solvent which occupies most surface treatment agents is desired to be inexpensive and non-flammable.
The present invention is an inexpensive non-flammable solvent that can be used as a solvent for a fluorine-based polymer and has a low environmental impact. Furthermore, the present invention repels various substrate surfaces that can be provided at low cost. It is an object of the present invention to provide a fluorine-based surface treatment agent that can sufficiently impart water repellency, oil repellency, and IPA repellency to an environment.
この場合、非引火性溶媒中の(1)以外の引火性溶媒成分の量は、溶媒全量中1質量%以下であることが好ましい。
(2)以外の非引火性溶媒成分としては、ハイドロフルオロエーテルが好ましい。 The non-flammable solvent may contain a solvent component other than the above (1) and (2) in an amount of 20% by mass or less in the total amount of the solvent.
In this case, the amount of the flammable solvent component other than (1) in the non-flammable solvent is preferably 1% by mass or less in the total amount of the solvent.
The non-flammable solvent component other than (2) is preferably hydrofluoroether.
上記含フッ素化合物は、含フッ素重合体またはポリフルオロアルキル基含有のリン酸エステル化合物であることが好ましい。 A surface treatment agent comprising a non-flammable solvent as described above and a fluorine-containing compound as a solute.
The fluorine-containing compound is preferably a fluorine-containing polymer or a phosphoric acid ester compound containing a polyfluoroalkyl group.
表面処理剤の動粘度は、1.0×10-5m2/s以下であることが好ましい。 The solute concentration of the surface treatment agent is preferably 20% by mass or less.
The kinematic viscosity of the surface treatment agent is preferably 1.0 × 10 −5 m 2 / s or less.
本発明では、上記のような表面処理剤で被覆された基材も提供することができる。 The surface treatment agent of the present invention can be used as a solder flux creep-up preventive agent, a lubricant ooze-out preventive agent, a waterproof / moisture-proof coating agent, a resin adhesion preventive agent for electronic parts, and a mold release agent.
In this invention, the base material coat | covered with the above surface treating agents can also be provided.
C6F13OCH3
C6F13OC2H5
C3F7OCH3
C3F7OC2H5
CF2HCF2CH2OCF2CF2H
CF3(OCF2CF2)n(OCF2)mOCF2H
C8F17OCH3
C7F15OCH3
C4F9OCH3
C4F9OC2H5
およびこれらの混合物。
上記例示中、添字mおよびnは各々1~20の整数を表し、アルキル骨格基は直鎖または分岐の態様を含む。 Specific examples of HFE other than (2) include the following.
C 6 F 13 OCH 3
C 6 F 13 OC 2 H 5
C 3 F 7 OCH 3
C 3 F 7 OC 2 H 5
CF 2 HCF 2 CH 2 OCF 2 CF 2 H
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
And mixtures of these.
In the above examples, the subscripts m and n each represent an integer of 1 to 20, and the alkyl skeleton group includes a linear or branched embodiment.
<引火点の測定手順>
(a)タグ密閉法による引火点測定の実施。
(b)(a)において、引火点が80℃以下の温度で引火点が測定できない場合にあっては、クリーブランド開放法による引火点測定の実施。 In the present invention, “flammability” is defined as having a flash point by performing flash point measurement according to the following procedure. Each flash point measurement method shall follow the method specified in JIS-K-2265.
<Flash point measurement procedure>
(A) Implementation of flash point measurement by tag sealing method.
(B) When the flash point cannot be measured at a temperature of 80 ° C. or lower in (a), the flash point is measured by the Cleveland open method.
化合物(a)としては、下記構造が挙げられる。
CH2=CR1-COX-Q1-Rf1
該式中のR1は水素原子またはメチル基であり、Xは-O-または-NH-であり、Q1は単結合または2価の連結基であり、Rf1は炭素数1~20のポリフルオロアルキル基である。2価の連結基としては炭素数1~5のアルキレン基が好ましい。
なお、本発明において、「(メタ)アクリル」の語は、アクリルおよびメタクリルの両方またはどちらか一方を意味する。このような化合物(a)を具体的に(メタ)アクリル酸エステルで例示すれば、
CH2=CH-COO-(CH2)n-(CF2)mF、
CH2=C(CH3)-COO-(CH2)n-(CF2)mF
(上記例示中、添字nは0~4、添字mは1~16の整数である。)
などが挙げられるが、化合物(a)は、これらに限定されるものではない。
これらのうちでも、mが1~6であるものが好ましい。
なお、(メタ)アクリル酸エステルは、表面処理剤に求める性能により適宜選択できる。例えば、撥水性を特に重視する場合はメタクリル酸エステルが好ましく、撥油性や撥IPA性を特に重視する場合や、被膜の耐熱性を特に重視する場合は、アクリル酸エステルである場合が好ましい。 The fluoropolymer contains at least a structural unit derived from the polyfluoroalkyl group-containing compound (a). This compound (a) is typically a (meth) acrylic acid compound, specifically, (meth) acrylic acid ester or (meth) acrylamide.
The following structure is mentioned as a compound (a).
CH 2 = CR 1 -COX-Q 1 -Rf 1
In the formula, R 1 is a hydrogen atom or a methyl group, X is —O— or —NH—, Q 1 is a single bond or a divalent linking group, and Rf 1 has 1 to 20 carbon atoms. It is a polyfluoroalkyl group. The divalent linking group is preferably an alkylene group having 1 to 5 carbon atoms.
In the present invention, the term “(meth) acryl” means both or one of acrylic and methacrylic. If such a compound (a) is specifically exemplified by (meth) acrylic acid ester,
CH 2 ═CH—COO— (CH 2 ) n — (CF 2 ) m F,
CH 2 ═C (CH 3 ) —COO— (CH 2 ) n — (CF 2 ) m F
(In the above example, the subscript n is an integer from 0 to 4, and the subscript m is an integer from 1 to 16.)
The compound (a) is not limited to these.
Of these, those in which m is 1 to 6 are preferred.
In addition, (meth) acrylic acid ester can be suitably selected by the performance calculated | required by a surface treating agent. For example, methacrylic acid ester is preferable when water repellency is particularly important, and acrylic acid ester is preferable when oil repellency and IPA repellency are particularly important, or when heat resistance of the film is particularly important.
含フッ素重合体が、化合物(a)のみの重合体である場合には、化合物(a)の1種の単独重合体でも2種以上の共重合体でもよい。 The fluoropolymer usually contains 50 mass% or more, preferably 80 mass% or more, more preferably 90 mass% or more of the structural unit derived from the compound (a). In addition, in this invention, the mass% of the structural unit in a polymer is the value considered that all the raw material compounds used for superposition | polymerization comprise a structural unit.
When the fluorinated polymer is a polymer composed solely of the compound (a), it may be a single homopolymer or two or more copolymers of the compound (a).
(Rf2-Q2-O-)r-P(O)(OM)s
該式中のRf2は炭素数1~20のポリフルオロアルキル基であり、Q2は単結合または2価の連結基であり、Mは水素原子、アンモニウム基、置換アンモニウム基またはアルカリ金属原子であり、rは1~3の整数であり、sは0~2の整数であり、r+sは3である。2価の連結基としてはOH基で置換されていてもよい炭素数1~5のアルキレン基が好ましい。
含フッ素リン酸エステルの具体例としては、以下の化合物が挙げられるが、これらに限定されるものではない。
F(CF2)m-CH2CH2-P(O)(OH)2
(F(CF2)m-CH2CH2)2P(O)(OH)
F(CF2)m-CH2CH(OH)CH2O-P(O)(OH)2
(F(CF2)m-CH2CH(OH)CH2O)2P(O)(OH)
F(CF2)m-CH2CH2O-P(O)(OH)2
(F(CF2)m-CH2CH2O)2-P(O)(OH)
上記例示中、添字mは1~16の整数であり、好ましくは1~6である。
含フッ素リン酸エステルは、表面処理剤として金属表面を処理する場合に特に好適である。また、離型剤として用いる場合にも特に好適である。 Examples of the fluorine-containing phosphate ester include the following structures.
(Rf 2 -Q 2 -O-) rP (O) (OM) s
In the formula, Rf 2 is a polyfluoroalkyl group having 1 to 20 carbon atoms, Q 2 is a single bond or a divalent linking group, M is a hydrogen atom, an ammonium group, a substituted ammonium group or an alkali metal atom. Yes, r is an integer from 1 to 3, s is an integer from 0 to 2, and r + s is 3. The divalent linking group is preferably an alkylene group having 1 to 5 carbon atoms which may be substituted with an OH group.
Specific examples of the fluorine-containing phosphate ester include the following compounds, but are not limited thereto.
F (CF 2 ) m —CH 2 CH 2 —P (O) (OH) 2
(F (CF 2 ) m —CH 2 CH 2 ) 2 P (O) (OH)
F (CF 2 ) m —CH 2 CH (OH) CH 2 O—P (O) (OH) 2
(F (CF 2 ) m —CH 2 CH (OH) CH 2 O) 2 P (O) (OH)
F (CF 2 ) m —CH 2 CH 2 O—P (O) (OH) 2
(F (CF 2 ) m —CH 2 CH 2 O) 2 —P (O) (OH)
In the above examples, the subscript m is an integer of 1 to 16, preferably 1 to 6.
The fluorine-containing phosphate ester is particularly suitable for treating a metal surface as a surface treatment agent. It is also particularly suitable when used as a release agent.
たとえば、ジメチルメチルシリコーンやポリエチレングリコールアルキルアミンなどが挙げられる。さらに、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の他の成分が挙げられる。 The surface treatment agent of the present invention can be dissolved or dispersed in the above-mentioned solvent, and does not impair the object of the present invention and does not impair the stability, performance, appearance, etc. In addition to the compound, other solutes can be contained without particular limitation.
Examples thereof include dimethylmethyl silicone and polyethylene glycol alkylamine. Furthermore, when diluting pH adjusters, rust inhibitors, and surface treatment agents to prevent coating surface corrosion, the purpose is to control the concentration of the polymer in the liquid and to distinguish it from untreated parts. Other components such as dyes, dye stabilizers, flame retardants, antifoaming agents and antistatic agents.
密閉容器に、CH2=C(CH3)-COO-CH2CH2(CF2)6F(C6FMA)を294質量部、CH2=C(CH3)-COO-CH2CH2OH(HEMA)を6質量部、m-XHFを299質量部および開始剤(ジメチル2,2'-アゾビス(2-メチルプロピオナート,和光純薬工業,V-601)を1質量部、それぞれ仕込み、70℃で18時間反応させた。
反応後の重合溶液に、m-XHFを加えて希釈し、含フッ素重合体濃度20%のm-XHF溶液を得た。 (Synthesis Example 1) Synthesis sealed container of the fluoropolymer 1 (C6FMA / HEMA copolymer), CH 2 = C (CH 3) -COO-CH 2 CH 2 (CF 2) 6 F a (C6FMA) 294 Parts by mass, 6 parts by mass of CH 2 ═C (CH 3 ) —COO—CH 2 CH 2 OH (HEMA), 299 parts by mass of m-XHF and an initiator (dimethyl 2,2′-azobis (2-methylpro) 1 part by weight of Pionate, Wako Pure Chemical Industries, V-601) was charged and reacted at 70 ° C. for 18 hours.
M-XHF was added to the polymerized solution after the reaction for dilution to obtain an m-XHF solution having a fluoropolymer concentration of 20%.
表面処理剤の調製に使用した溶媒成分を表1に示す。
[接触角の測定]
実施例1~4の各表面処理剤に室温でガラス板を1分間浸漬した後、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。
次に各ガラス板の被膜上に、水、IPAまたはn-ヘキサデカン(n-HD)を滴下し、接触角を測定した。
接触角の測定には、自動接触角計OCA-20[dataphysics社製]を用いた。
[動粘度の測定]
各表面処理剤について、ウベローデ粘度計を用いて、25℃での動粘度を測定した。
[比重測定]
各表面処理剤について、室温での比重を標準比重計(浮ひょう)を用いて測定した。 For the surface treating agents of Examples 1 to 4, the contact angle, kinematic viscosity and density were measured as follows. The results are shown in Table 3.
[Measurement of contact angle]
A glass plate was immersed in each surface treating agent of Examples 1 to 4 at room temperature for 1 minute and then dried at room temperature to obtain each glass plate having a coating of each treating agent.
Next, water, IPA or n-hexadecane (n-HD) was dropped onto the coating on each glass plate, and the contact angle was measured.
For the measurement of the contact angle, an automatic contact angle meter OCA-20 (manufactured by dataphysics) was used.
[Measurement of kinematic viscosity]
About each surface treating agent, kinematic viscosity in 25 degreeC was measured using the Ubbelohde viscometer.
[Specific gravity measurement]
About each surface treating agent, the specific gravity at room temperature was measured using the standard specific gravity meter (floating).
化合物(Z1):C18H37N((C2H4O)xH)(C2H4O)yH (x+yは平均20) The polymer 2 solution was diluted to a polymer concentration of 0.2% with a mixed solvent having a solvent component (1) / (2) mass ratio of 90/10. This is designated surface treating agent 9. The polymer 3 diluted with the same conditions is used as the surface treatment agent 10. Moreover, the surface treating agent 11 containing the compound (P1) which is a fluorine-containing phosphate ester, and the compound (Z1) which is an additive was prepared. Table 7 summarizes each surface treatment agent.
Compound (Z1): C 18 H 37 N ((C 2 H 4 O) x H) (C 2 H 4 O) y H (x + y is 20 on average)
Claims (14)
- (1)ビス(トリフルオロメチル)ベンゼンと(2)CF3CH2OCF2CF2Hとを、(1)/(2)=50/50~97/3の質量比で、かつ両者の合計で溶媒全量中80質量%以上の量で含む非引火性溶媒。 (1) Bis (trifluoromethyl) benzene and (2) CF 3 CH 2 OCF 2 CF 2 H at a mass ratio of (1) / (2) = 50/50 to 97/3 and the sum of both A non-flammable solvent containing 80% by mass or more of the total amount of the solvent.
- 前記(1)/(2)質量比が80/20~96.25/3.75である請求項1に記載の非引火性溶媒。 The non-flammable solvent according to claim 1, wherein the mass ratio (1) / (2) is 80/20 to 96.25 / 3.75.
- 前記(2)以外の非引火性溶媒成分としてハイドロフルオロエーテルを含む請求項1または2に記載の非引火性溶媒。 The non-flammable solvent according to claim 1 or 2, comprising a hydrofluoroether as a non-flammable solvent component other than (2).
- 前記(1)以外の引火性溶媒成分の溶媒全量中の量が1質量%以下である請求項1~3のいずれかに記載の非引火性溶媒。 The non-flammable solvent according to any one of claims 1 to 3, wherein the amount of the flammable solvent component other than (1) in the total amount of the solvent is 1% by mass or less.
- 請求項1~4のいずれかに記載の非引火性溶媒と、溶質としての含フッ素化合物とを含む表面処理剤。 A surface treating agent comprising the non-flammable solvent according to any one of claims 1 to 4 and a fluorine-containing compound as a solute.
- 前記含フッ素化合物が、含フッ素重合体またはポリフルオロアルキル基含有のリン酸エステル化合物である請求項5に記載の表面処理剤。 The surface treating agent according to claim 5, wherein the fluorine-containing compound is a fluorine-containing polymer or a phosphoric acid ester compound containing a polyfluoroalkyl group.
- 溶質濃度が20質量%以下である請求項5または6に記載の表面処理剤。 The surface treatment agent according to claim 5 or 6, wherein the solute concentration is 20% by mass or less.
- 動粘度が1.0×10-5m2/s以下である請求項5~7のいずれかに記載の表面処理剤。 The surface treating agent according to any one of claims 5 to 7, having a kinematic viscosity of 1.0 × 10 -5 m 2 / s or less.
- 請求項5~8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 5 to 8.
- 請求項5~8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 5 to 8.
- 請求項5~8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 5 to 8.
- 請求項5~8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。 A resin adhesion preventive agent for electronic parts using the surface treating agent according to any one of claims 5 to 8.
- 請求項5~8のいずれかに記載の表面処理剤を使用した離型剤。 A mold release agent using the surface treatment agent according to any one of claims 5 to 8.
- 請求項5~8のいずれかに記載の表面処理剤で被覆された基材。 A base material coated with the surface treatment agent according to any one of claims 5 to 8.
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WO2013168763A1 (en) * | 2012-05-11 | 2013-11-14 | ダイキン工業株式会社 | Coating composition for water-proofing and moisture-proofing |
CN104220541A (en) * | 2012-04-02 | 2014-12-17 | 大金工业株式会社 | Durable water- and moisture-proof coating composition |
JP2018177857A (en) * | 2017-04-04 | 2018-11-15 | Agcセイミケミカル株式会社 | Mixed solvent and surface treatment agent |
JP2020029533A (en) * | 2018-08-24 | 2020-02-27 | Agcセイミケミカル株式会社 | Inflammable mixture solvent and surface treatment agent containing the same |
JP7416612B2 (en) | 2019-12-16 | 2024-01-17 | Agcセイミケミカル株式会社 | surface treatment composition |
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CN106939064B (en) * | 2016-12-28 | 2019-05-14 | 衢州氟硅技术研究院 | A kind of composition comprising perfluoropolyether active constituent |
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CN104220541A (en) * | 2012-04-02 | 2014-12-17 | 大金工业株式会社 | Durable water- and moisture-proof coating composition |
WO2013168763A1 (en) * | 2012-05-11 | 2013-11-14 | ダイキン工業株式会社 | Coating composition for water-proofing and moisture-proofing |
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CN104271690A (en) * | 2012-05-11 | 2015-01-07 | 大金工业株式会社 | Coating composition for water-proofing and moisture-proofing |
JP2018177857A (en) * | 2017-04-04 | 2018-11-15 | Agcセイミケミカル株式会社 | Mixed solvent and surface treatment agent |
JP2020029533A (en) * | 2018-08-24 | 2020-02-27 | Agcセイミケミカル株式会社 | Inflammable mixture solvent and surface treatment agent containing the same |
JP7257119B2 (en) | 2018-08-24 | 2023-04-13 | Agcセイミケミカル株式会社 | Non-flammable mixed solvent and surface treatment agent containing the same |
JP7416612B2 (en) | 2019-12-16 | 2024-01-17 | Agcセイミケミカル株式会社 | surface treatment composition |
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