JP2010008035A - Heat exchanger - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat exchanger excellent in odor resistance while keeping its hydrophilicity high. <P>SOLUTION: A paint film formed from a paint composition containing an organic solvent, a resin, and one or two kinds or more of organic silicon compounds represented by the general formula (I) covers at least one of the heat transfer pipe and the fin of the heat exchanger. In the formula, (n) is an integer of 1-20; R<SP>1</SP>s are all different or at least two of R<SP>1</SP>s are the same and each represent a 1-1,000C monovalent organic group; the organic group may contain at least one kind of atom selected from oxygen atom, nitrogen atom and silicon atom; and some or all of the hydrogen atoms in the organic group may be substituted with fluorine atoms or both fluorine atoms and chlorine atoms. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a heat exchanger.

  In the past, a hydrophilic coating with antifouling and deodorizing agents was formed on the fin surface of the fin-and-tube heat exchanger to decompose organic substances adhering to the fin surface, preventing mold growth and adsorbing The proposal of “preventing generation of odor and mold odor and maintaining hydrophilicity” has been made (see, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2001-201288)).

  It is said that the hydrophilicity of the fin surface is caused by the suppression of the occurrence of water splashing into the room.

  The subject of this invention is providing the heat exchanger which is excellent in deodorizing property, maintaining hydrophilicity favorably.

  In the heat exchanger according to the present invention, a coating film formed from a coating composition containing an organic solvent, a resin, and one or more organic silicon compounds represented by the following general formula (I) includes a heat transfer tube and a fin. At least one of them. The resin may be soluble in the organic solvent or may be dispersed in the organic solvent.

（式中、ｎは１〜２０の整数である。Ｒ¹は、全て異なるか又は少なくとも二つが同じであり、いずれも炭素数が１〜１０００の１価の有機基である。また、この有機基には、酸素原子、窒素原子およびケイ素原子の少なくとも一種の原子が含まれていてもよい。また、この有機基は、一部又は全部の水素原子がフッ素原子またはフッ素原子と塩素原子とで置換されていてもよい。）

(In the formula, n is an integer of ¹ to 20. R ¹ is all different or at least two are the same, both are monovalent organic groups having 1 to 1000 carbon atoms. The group may contain at least one kind of oxygen atom, nitrogen atom, and silicon atom, and this organic group is a part or all of hydrogen atoms formed of a fluorine atom or a fluorine atom and a chlorine atom. May be substituted.)

In the present invention, at least one R ¹ is preferably an organic group in which some or all of the hydrogen atoms are substituted with fluorine atoms. In such a case, the organic group preferably has 3 to 9 fluorine atoms, and the organosilicon compound preferably has a fluorine atom content of at least 5% by weight.

  In the present invention, n is an integer of 2 to 20, and the organic group is preferably at least one of a methyl group and an ethyl group.

  Moreover, in this invention, it is preferable that 0.1-50 weight part of organosilicon compounds are added with respect to 100 weight part of resin.

  In the present invention, the resin is at least one selected from the group consisting of a functional group-containing fluororesin, a functional group-containing non-fluorinated acrylic resin, a functional group-containing polyester resin, a functional group-containing urethane resin, and a functional group-containing epoxy resin. A resin is preferable, but a functional group-containing fluororesin or a functional group-containing polyester resin is more preferable. In addition, it is preferable that the functional group here is a hydroxyl group. In such a case, it is preferable to further add a curing agent that reacts with the functional group to the coating composition. The curing agent is preferably at least one of an amino resin and an isocyanate compound.

  The resin is polyethylene resin, polypropylene resin, polyvinyl chloride resin, polystyrene resin, ethylene / vinyl acetate copolymer resin, ethylene / vinyl alcohol copolymer resin, AS resin, ABS resin, AAS resin, AES resin, ASA resin. SAS resin, polyacrylonitrile resin, polyethylene terephthalate resin, acrylic resin, polyester resin, polyamide resin, polyimide resin, polycarbonate resin, polyacetal resin, modified polyphenylene ether resin, polybutylene terephthalate resin, fluororesin, polyphenylene sulfide resin, Polyarylate resin, polysulfone resin, polyether ketone resin, polyether ether ketone resin, polyurethane resin, polyvinyl alcohol resin, polyvinyl acetate Fat, epoxy resin, phenol resin, urea resin, may be a melamine resin, diallyl phthalate resin, silicone resin, at least one resin selected from the group consisting of unsaturated polyester resins and elastomeric resins.

  Further, in the present invention, the coating composition is (1) one or two or more aliphatic hydrocarbon compounds having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and (2) a fluorine atom. It is preferable to further contain at least one compound of one or two or more alkoxy compounds having 2 to 10 carbon atoms which may be substituted with.

  In the present invention, the organosilicon compound preferably has a fluorine content of 5 to 50% by mass, more preferably 7 to 30% by mass.

  In the present invention, the organosilicon compound preferably contains 5 to 95% by mass of a non-fluorine organosilicon compound.

  In addition, the heat exchanger which concerns on this invention is mounted in a freezing apparatus or an air conditioning apparatus. Note that the “refrigeration apparatus and air conditioner” mentioned here includes a refrigeration apparatus and the like.

  When the coating composition is applied to the substrate surface and dried, a coating film in which the organosilicon compound represented by the general formula (I) is unevenly distributed on the air side surface of the resin coating film is obtained. This has been confirmed by ESCA analysis. In addition, when the organosilicon compound comes into contact with moisture in the atmosphere or condensed water generated on the fins of the heat exchanger functioning as an evaporator, the ester group in the compound is hydrolyzed to produce a hydroxyl group, The compound becomes hydrophilic. This has been confirmed by contact angle measurement (see Table 1).

  Therefore, by adjusting the content of the organosilicon compound in the coating composition appropriately, a very thin hydrophilic film of nanometer order can be formed on the resin film of micrometer order. In such a coating film, the surface shows sufficient hydrophilicity. For this reason, condensed water flows easily. Therefore, in the heat exchanger according to the present invention covered with such a coating film, the adhesion amount of microorganisms per unit area is sufficiently reduced as compared with the conventional case. This has also been confirmed by measuring the amount of microorganisms attached. In addition, even if microorganisms are attached, the hydrophilic coating is extremely thin and moisture necessary for the inhabiting of the microorganisms is difficult to remain, so that the growth of microorganisms and the increase of metabolites are suppressed.

  Therefore, the heat exchanger according to the present invention is excellent in deodorization properties while maintaining good hydrophilicity.

The external view of the air conditioning apparatus carrying the heat exchanger concerning one Embodiment of this invention. It is the schematic of the refrigerant circuit of an air conditioning apparatus. It is side surface sectional drawing of the indoor unit of an air conditioning apparatus. It is a bottom view of the main-body part of the indoor unit of an air conditioning apparatus. It is a figure showing a part of indoor heat exchanger. It is an expanded sectional view of an indoor heat exchanger.

  As shown in FIG. 1, an air conditioner 1 according to an embodiment of the present invention is a separate type air conditioner, and is mainly a ceiling-buried indoor unit 2 that is buried in the interior of a ceiling. And an outdoor unit 3 installed outdoors. An indoor heat exchanger is accommodated in the indoor unit 2, and an outdoor heat exchanger is accommodated in the outdoor unit 3, and these heat exchangers are connected by a refrigerant pipe 4 so that a refrigerant circuit is formed. It is configured. As shown in FIG. 2, the refrigerant circuit mainly includes an indoor heat exchanger 20, an accumulator 31, a compressor 32, a four-way switching valve 33, an outdoor heat exchanger 130, and an electric expansion valve 34. The

  Hereinafter, each of the indoor unit 2 and the outdoor unit 3 will be described in detail.

<Indoor unit>
As shown in FIG. 3, the indoor unit 2 mainly includes a main body 201 that is embedded in a ceiling at the time of installation, and a decorative panel 202 that is exposed to the living room side at the time of installation.

  3 and 4, the main body 201 includes a main body casing 211, a centrifugal blower 23, an indoor heat exchanger 20, a drain pan 214, a bell mouth 215, a suction temperature sensor (not shown), and the like.

  As shown in FIG. 3, the main casing 211 is a box having an open bottom surface, and includes a top plate 211 a and a side plate 211 b extending downward from the peripheral edge of the top plate 211 a. The main body casing 211 accommodates various components therein.

  The centrifugal blower 23 is a turbo fan in the present embodiment, and includes a fan motor 22 provided at the center of the top plate 211a of the main body casing 201, and an impeller 21 that is connected to the fan motor 22 and rotationally driven. Have. The centrifugal blower 23 can suck air in the living room (hereinafter referred to as room air) into the impeller 21 and blow it out to the outer peripheral side of the impeller 21.

  In the present embodiment, the indoor heat exchanger 20 is a cross fin tube type heat exchanger formed by being bent so as to surround the outer periphery of the centrifugal blower 23, as shown in FIG. The indoor heat exchanger 20 can function as an evaporator of refrigerant flowing inside during the cooling operation and as a condenser of refrigerant flowing inside during the heating operation. The indoor heat exchanger 20 cools the indoor air sucked into the main body casing 211 through the bell mouth 215 and blown to the outer peripheral side of the impeller 21 of the centrifugal blower 23 during the cooling operation and is heated during the heating operation. Can do. The details of the indoor heat exchanger 20 will be described later.

  The drain pan 214 is disposed below the indoor heat exchanger 20 and receives drain water generated by condensation of moisture in the indoor air when the indoor air is cooled in the indoor heat exchanger 20.

  The electrical component box 33 is built in the indoor unit 2 and installed at the edge of the bell mouth 215. The electrical component box 33 accommodates a control board (not shown) as an electrical component. The control board is connected to the centrifugal blower 23 and the temperature sensor arranged in the indoor unit 2, and controls the rotational speed of the centrifugal blower 23, the angle of the louver 221 and the like based on the control signal.

  The decorative panel 202 is a substantially quadrangular plate-like body. As shown in FIG. 3, the decorative panel 202 mainly has a suction port 224 for sucking indoor air into the main body casing 211 at the substantially center thereof, and the main body casing 211. There are a plurality (four in this embodiment) of air outlets 222 that blow out conditioned air from the inside toward the living room. The air outlet 222 is provided with a louver 221 for adjusting the wind direction. The suction port 224 is provided with a suction grill 223 and a prefilter 225 for removing relatively large dust in the indoor air sucked from the suction port 224.

  When the impeller 21 is rotated by the fan motor 22, the room air is sucked into the suction port 224 of the indoor unit 2 as indicated by an arrow F1 in FIG. The sucked room air reaches the impeller 21 through the bell mouth 215 of the main body 201 and then blows out to the outer peripheral side of the impeller 21 (see arrow F1a in FIG. 3). The room air blown to the outer peripheral side of the impeller 21 is subjected to heat exchange by the indoor heat exchanger 20 disposed on the outer peripheral side of the impeller 21 and then blown into the room from the blowout port 222 (arrow in FIG. 3). F2). The louver 221 is designed to be reciprocated in the vertical direction by a small motor (not shown) dedicated to driving the louver.

<Outdoor unit>
The outdoor unit 3 mainly includes a compressor 32, a four-way switching valve 33 connected to the discharge side of the compressor 32, an accumulator 31 connected to the suction side of the compressor 32, and a four-way switching valve 33. An outdoor heat exchanger 130 connected to the outdoor heat exchanger 130 and an electric expansion valve 34 connected to the outdoor heat exchanger 130 are accommodated. The electric expansion valve 34 is connected to the pipe 41 via the filter 35 and the liquid closing valve 36, and is connected to one end of the indoor heat exchanger 20 via the pipe 41. The four-way switching valve 33 is connected to the pipe 42 via the gas closing valve 37 and is connected to the other end of the indoor heat exchanger 20 via the pipe 42. The pipes 41 and 42 correspond to the refrigerant pipe 4 in FIG. Further, the outdoor unit 3 is provided with a propeller fan 38 for discharging the air after heat exchange in the outdoor heat exchanger 30 to the outside. In this propeller fan 38, the propeller fan rotor 40 is rotationally driven by a fan motor 39.

<Indoor heat exchanger>
As shown in FIG. 5 and FIG. 6, the indoor heat exchanger 20 is mainly configured by a heat transfer tube 24 that is bent back and forth at both ends, and a plurality of fins 25 through which the heat transfer tube 24 is inserted. ing. In the indoor heat exchanger 20, the heat transfer tubes 24 are formed so as to surround the outer periphery of the centrifugal blower 23, and are folded back by U-shaped heat transfer tubes 26 a at both ends of the indoor heat exchanger 20. As shown in FIG. 6, the fin 25 is formed of a strip-like thin metal plate (aluminum plate) 251 and a coating film 252 formed on the surface thereof. In the indoor heat exchanger 20, a plurality of fins 25 are arranged in parallel to each other with a minute predetermined interval, and heat transfer tubes 24 a are vertically inserted into the fins 25.

<Coating film>
The coating film 252 is formed from an organic solvent, a resin, a coating composition containing one or more organic silicon compounds represented by the following formula (I), and a curing agent. The coating composition includes (1) one or more aliphatic hydrocarbon compounds having 1 to 10 carbon atoms which may be substituted with a fluorine atom having a hydroxyl group, and (2) substitution with a fluorine atom. It may contain at least one of one or two or more alkoxy compounds having 2 to 10 carbon atoms.

以下、塗料組成物について詳述する。

Hereinafter, the coating composition will be described in detail.

(1) Composition of coating composition (1-1) Organosilicon compound The organosilicon compound (silicate or oligomer thereof) represented by the above formula (I) is a mixture of compounds having n in a certain range industrially. And n is expressed as an average value thereof.

  In addition to the chain structure, the organosilicon compound represented by the above formula (I) also includes a condensate (oligomer) such as a branched or cyclic structure.

  In the above formula (I), n is an integer of 1 to 20, preferably an integer of 2 to 15, and more preferably an integer of 4 to 10. When n is small, the boiling point of the compound tends to be low. For example, when it is made into a paint and spray-coated, it tends to evaporate and is difficult to be taken into the coating film. On the other hand, when n exceeds 20, for example, compatibility with a resin or a curing agent when forming a paint tends to be lowered and storage stability tends to be lowered, and the appearance of the coating tends to be poor, and the viscosity is high. Or even difficult to obtain industrially.

R ¹ is all different or at least two are the same, both of which are monovalent organic groups having 1 to 1000 carbon atoms. Further, this organic group may contain an oxygen atom, a nitrogen atom and / or a silicon atom. In this organic group, part or all of the hydrogen atoms may be substituted with fluorine atoms or fluorine atoms and chlorine atoms.

  The organic group preferably has hydrolyzability, and preferably exhibits detachability such as volatility, water solubility, and thermal decomposability after hydrolysis.

  The organic group preferably has 1 to 100 carbon atoms, more preferably 1 to 16 carbon atoms. When the carbon number is small, for example, the storage stability tends to be low during coating and storage of the coating composition, and when the carbon number exceeds 1000, compatibility with the resin and hydrolyzability tend to be low. Because there is.

  In addition, this organic group may be a linear substituent or a branched substituent, but when these substituents have a fluorine atom, a branched substituent is preferred from the viewpoint of solubility. .

  In addition, this organic group may contain an oxygen atom, a nitrogen atom and / or a silicon atom, from the viewpoint of surface concentration (a property that a substance is unevenly distributed on the air side surface when a coating film is formed). The organic group is preferably a fluorine atom or a group containing a non-hydrolyzable group-containing silicon atom. Specifically, the organic group is more preferably a trifluoromethyl group-containing group or a dimethylsiloxane chain-containing group.

  In addition, some of the hydrogen atoms of the organic group may be substituted with fluorine atoms, and such an organic group tends to exhibit high surface concentration. In addition, it is preferable that the number of fluorine atoms in such an organic group is 1-50, and it is more preferable that it is 3-9 from the point of hydrolyzability or detachability.

  In addition, the organosilicon compound represented by the above formula (I) preferably has a fluorine content of 5 to 50% by mass, and 7 to 30% by mass from the viewpoint of surface concentration and hydrolyzability. More preferred.

  Moreover, a part of hydrogen atoms of this organic group may be substituted with fluorine atoms and chlorine atoms, and such organic groups tend to exhibit high solubility.

  The organosilicon compound represented by the above formula (I) preferably contains 5 to 95% by mass of a non-fluorine organosilicon compound.

The organic group that does not contain a fluorine atom in R ¹ is preferably a hydrocarbon group having 1 to 8 carbon atoms, such as CH ₃ , C ₂ H ₅ , CH ₃ CH ₂ CH ₂ , (CH ₃ ) _2. CH, CH ₃ (CH ₂ ) ₂ CH ₂ , CH ₃ CH ₂ CH ₂ CH ₂ CH (C ₂ H ₅ ) CH ₂ , a dimethylsiloxane chain-containing group, and the like. Of these hydrocarbon groups, CH ₃ and C ₂ H ₅ are preferable, and CH ₃ is more preferable in terms of hydrolyzability, detachability, availability, and workability.

In addition, the organic group containing a fluorine atom in R ¹ is preferably a group having a surface concentrating property. For example, F (CF ₂ ) _n CHF (CF ₂ ) _m CH ₂ , F (CF ₂ ) _n CF (CHF ₂ ) CH ₂ , F (CF ₂ ) _n (CH ₂ ) _m , (CF ₃ ) ₂ CH, H (CF ₂ ) _n (CH ₂ ) _m , F (CF ₂ ) _n (CH ₂ ) _m C ═O, H (CF ₂ ) _n (CH ₂ ) _m C═O, (F (CF ₂ ) _n (CH ₂ ) _m ) ₂ N, ((CF ₃ ) ₂ CH) ₂ N, (H (CF ₂ ) _N (CH ₂ ) _m ) ₂ N, F (CF ₂ ) _n O (CF (CF ₃ ) CF ₂ O) _m CF (CF ₃ ) C═O, (F (CF ₂ ) _n (CH ₂ ) _m ) ₂ C = N, ((CF ₃ ) ₂ CH) ₂ C = N, (H (CF ₂ ) _n (CH ₂ ) _m ) ₂ C = N, F (CF ₂ ) _n (CH ₂ ) _m C = _{ONR 3, H (CF 2)} n (CH 2) m C = ONR 3, F _{CF 2) n (CH 2)} m C = CH 2, H (CF 2) n (CH 2) m C = CH 2, F (CF 2) n (CH 2) m C = CF 2, H (CF 2 ) _N (CH ₂ ) _m C═CF ₂ (wherein, m is 0 or an integer of 1 to 6, n is an integer of 1 to 10, and R ₃ is an alkyl group having 1 to 6 carbon atoms) And the organic group containing a fluorine atom may be a branched chain).

Specific examples of these organic groups include, for example, CF ₃ CHFCF ₂ CH ₂ , CF ₃ CF (CHF ₂ ) CH ₂ , CF ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , CF ₃ (CF ₂ ) _{2. CH 2, CF 3 (CF 2} ) 3 CH 2 CH 2, (CF 3) 2 CH, CF 3 (CF 2) 7 CH 2 CH 2, H (CF 2) 2 CH 2, H (CF 2) 3 CH ₂ , H (CF ₂ ) ₄ CH ₂ , CF ₃ C═O, CF ₃ CF ₂ C═O, CF ₃ (CF ₂ ) ₆ C═O, CF ₃ (CF ₂ ) ₇ C═O, etc. . Among these organic groups, CF ₃ CHFCF ₂ CH ₂ , CF ₃ CF (CHF ₂ ) CH ₂ , CF ₃ CH ₂ , CF ₃ CF ₂ CH ₂ are used in terms of surface concentration, hydrolyzability, and detachability. CF ₃ (CF ₂ ) ₂ CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , CF ₃ C═O, CF ₃ CF ₂ C═O are preferred CF ₃ CHFCF ₂ CH ₂ , CF ₃ CH ₂ , More preferred is CF ₃ CF ₂ CH ₂ .

  Specific examples of the organosilicon compound represented by the above formula (I) include, for example,

（式中、ｍおよびｎは上記と同じ）などが挙げられる。なお、これらの有機ケイ素化合物の中でも表面濃縮性、加水分解性、脱離性、入手の容易さの点から

(Wherein, m and n are the same as above). Among these organosilicon compounds, surface concentration, hydrolyzability, detachability, and availability

が好ましい。

Is preferred.

  A method for synthesizing the organosilicon compound represented by the above formula (I) will be described below. Here, the organosilicon compound will be described separately for fluorine-containing silicate and its oligomer.

  The fluorine-containing silicate is obtained by, for example, reacting an alkyl silicate such as tetrachlorosilane, tetramethoxysilane, or tetraethoxysilane with a fluorine-containing organic compound such as fluorine-containing alcohol, fluorine-containing carboxylic acid, or metal salt of fluorine-containing carboxylic acid. Can be synthesized.

  The fluorine-containing silicate oligomer includes, for example, chlorosiloxane compounds such as hexachlorodisiloxane, octachlorotrisiloxane, decachlorotetrasiloxane, oligomers of tetramethoxysilane (for example, methyl silicate 51 manufactured by Colcoat Co.), tetraethoxysilane, and the like. Can be synthesized by reacting the above-mentioned fluorine-containing organic compound with an alkoxysiloxane compound such as an oligomer (eg, ethyl silicate 40 manufactured by Colcoat Co., Ltd.).

  In addition, the fluorine-containing silicate oligomer can be synthesized, for example, by further condensing a fluorine-containing silicate (monomer) obtained in advance.

  In addition, as a synthesis method of alkyl silicate not containing fluorine, for example, the method described in JP-B-62-918 can be mentioned, and this can also be applied to the synthesis of fluorine-containing silicate.

  Hereinafter, a method for synthesizing the fluorine-containing silicate or its oligomer will be described in more detail.

  As a first synthesis method of the fluorine-containing silicate or its oligomer, for example, in the presence or absence of a catalyst, the formula (9):

（式中、Ｒ_fは炭素数１〜１０００の１価の有機基である。また、Ｒ_fは酸素原子、窒素原子および／またはケイ素原子を含んでいてもよい。また、Ｒ_fは有機基の水素原子の一部または全部がフッ素原子またはフッ素原子と塩素原子とで置換されている）で示される化合物と式（１０）:

(Wherein R _f is a monovalent organic group having 1 to 1000 carbon atoms. R _f may contain an oxygen atom, a nitrogen atom and / or a silicon atom. R _f is an organic group. And a compound represented by the formula (10): a part or all of the hydrogen atoms are substituted with fluorine atoms or fluorine atoms and chlorine atoms

（式中、ｎは１〜２０の整数である。Ｒ³は全て異なるか又は少なくとも二つが同じでありいずれも炭素数１〜１０００の１価の有機基である）で示される化合物とを反応させて式（１１）:

(Wherein n is an integer of 1 to 20. R ³ is all different or at least two are the same, both of which are monovalent organic groups having 1 to 1000 carbon atoms). Let formula (11):

（式中、n、Ｒ³およびＲ_fは上記と同じ）または式（１２）:

(Wherein n, R ³ and R _f are the same as above) or formula (12):

（式中、nおよびＲ_fは上記と同じ）で示される含フッ素シリケートまたはそのオリゴマーを製造する方法が挙げられる。

(Wherein n and R _f are the same as above), and a method for producing a fluorine-containing silicate or an oligomer thereof.

  It is preferable to use an acid, an alkali, an organometallic compound, or a metal salt as the catalyst.

In the above formula (9), the carbon number of R _f is preferably 1 to 100, and more preferably 1 to 16. When the carbon number is small, the difference in boiling point from R ³ OH substituted during synthesis is small, the substitution rate is lowered, and the storage stability tends to be low during storage of the coating composition after coating, This is because the solubility of R _f OH during synthesis tends to be low and the compatibility with the resin and hydrolyzability tend to be low when it is made into a paint.

The R _f may be a linear substituent or a branched substituent, but it must be a branched substituent from the viewpoint of solubility during synthesis and solubility during coating. Is preferred.

Further, this R _f may contain an oxygen atom, a nitrogen atom and / or a silicon atom, and contains a non-hydrolyzable group-containing silicon atom from the viewpoint of alcohol substitution and surface concentration after coating. When present, it is preferably a dimethylsiloxane chain-containing group.

Further, when a part of hydrogen atoms in R _f is substituted with fluorine atoms, the viscosity becomes low, and the coating composition after coating tends to exhibit high surface concentration.

In addition, since some of the hydrogen atoms in R _f are substituted with fluorine atoms and chlorine atoms, R _f OH has a high boiling point, and the paint composition after coating tends to exhibit high solubility. is there.

The R _f is preferably a group having surface concentrating properties. For example, F (CF ₂ ) _n CHF (CF ₂ ) _m CH ₂ , F (CF ₂ ) _n CF (CHF ₂ ) CH ₂ , F (CF ₂ ) _n (CH ₂ ) _m , (CF ₃ ) ₂ CH, H (CF ₂ ) _n (CH ₂ ) _m , F (CF ₂ ) _n (CH ₂ ) _m C═O, H (CF ₂ ) _n (CH ₂ ) _m C═O, (F (CF ₂ ) _n (CH ₂ ) _m ) ₂ N, ((CF ₃ ) ₂ CH) ₂ N, (H (CF ₂ ) _n (CH ₂ ) _{m) 2 n, F (CF} 2) n O (CF (CF 3) CF 2 O) m CF (CF 3) C = O, (F (CF 2) n (CH 2) m) 2 C = n, ((CF ₃ ) ₂ CH) ₂ C = N, (H (CF ₂ ) _n (CH ₂ ) _m ) ₂ C = N, F (CF ₂ ) _n (CH ₂ ) _m C = ONR ₃ , H (CF _{2) n (CH 2) m} C = ONR 3, F (CF 2) n (CH 2 _{m C = CH 2, H (} CF 2) n (CH 2) m C = CH 2, F (CF 2) n (CH 2) m C = CF 2, H (CF 2) n (CH 2) m C ═CF ₂ (wherein m is 0 or an integer of 1 to 6, n is an integer of 1 to 10, R ³ is an alkyl group having 1 to 6 carbon atoms, and may be a branched chain). It is done.

Specific examples of these R _f include, for example, CF ₃ CHFCF ₂ CH ₂ , CF ₃ CF (CHF ₂ ) CH ₂ , CF ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , and CF ₃ (CF ₂ ) _{2. CH 2, CF 3 (CF 2} ) 3 CH 2 CH 2, (CF 3) 2 CH, CF 3 (CF 2) 7 CH 2 CH 2, H (CF 2) 2 CH 2, H (CF 2) 3 CH ₂ , H (CF ₂ ) ₄ CH ₂ , CF ₃ C═O, CF ₃ CF ₂ C═O, CF ₃ (CF ₂ ) ₆ C═O, CF ₃ (CF ₂ ) ₇ C═O, etc. . Of these R _f , CF ₃ CHFCF ₂ CH ₂ , CF ₃ CF (CHF ₂ ) CH are available from the viewpoints of availability, operability, surface concentration after coating, hydrolyzability, and detachability. ₂ , CF ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , CF ₃ (CF ₂ ) ₂ CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , CF ₃ C═O, CF ₃ CF ₂ C═O CF ₃ CHFCF ₂ CH ₂ , CH ₃ CH ₂ , and CF ₃ CF ₂ CH ₂ are more preferable.

  In formula (10), n is an integer of 1 to 20, preferably an integer of 2 to 10, and more preferably an integer of 4 to 6. When n is small, the raw material silane compound has a low boiling point during synthesis and tends to be difficult to synthesize. Moreover, the boiling point of the compound to be produced is lowered, and for example, when it is made into a paint and spray-coated, it tends to evaporate, and it tends to be difficult to be taken into the coating film. On the other hand, if n exceeds 20, the reproducibility of the synthesis reaction is difficult, and the compatibility with the resin and the curing agent when forming a paint tends to be reduced, so that the storage stability tends to be reduced. Defects are likely to occur, the viscosity is increased, and it is difficult to obtain industrially.

R ³ is all different or at least two are the same, both of which are monovalent organic groups having 1 to 1000 carbon atoms.

R ³ preferably has 1 to 100 carbon atoms, more preferably 1 to 16 carbon atoms. When the carbon number is small, the hydrolysis resistance of the raw material is inferior, and the storage stability tends to be low when the coating composition is preserved after coating. When the carbon number exceeds 1000, the raw material is soluble. This is because there is a tendency that the compatibility with the resin and the hydrolyzability tend to be low.

R ³ may be a linear substituent or a branched substituent, but is preferably a branched substituent from the viewpoint of solubility when forming a paint.

As specific examples of R ³ , for example, CH ₃ , C ₂ H ₅ , CH ₃ CH ₂ CH ₂ , (CH ₃ ) ₂ CH, CH ₃ (CH ₂ ) ₂ CH ₂ , CH ₃ CH ₂ CH ₂ CH ₂ CH (C ₂ H ₅ ) CH ₂ , a dimethylsiloxane chain-containing group, and the like. Of these R ³ , CH ₃ and C ₂ H ₅ are preferable, and CH ₃ is more preferable in terms of alcohol substitution, detachability, availability, and workability.

  Specific examples of the compound represented by the above formula (10) include, for example,

などが挙げられるが、溶解性、脱離性、入手の容易さの点から、

From the point of solubility, detachability, and availability,

が好ましい。

Is preferred.

(1-2) Resin In the present embodiment, the resin is not particularly limited, and polyethylene resin, polypropylene resin, polyvinyl chloride resin, polystyrene resin, ethylene / vinyl acetate copolymer resin, ethylene / vinyl alcohol copolymer Combined resin, AS resin, ABS resin, AAS resin, AES resin, ASA resin, SAS resin, polyacrylonitrile resin, acrylic resin, polyester resin (including polyethylene terephthalate resin, polybutylene terephthalate resin, etc.), polyamide resin, polyimide Resin, polycarbonate resin, polyacetal resin, modified polyphenylene ether resin, polyphenylene sulfide resin, polyarylate resin, polysulfone resin, polyether ketone resin, polyether ether ketone resin, polyurethane Letane resins, polyvinyl alcohol resins, polyvinyl acetate resins, epoxy resins, phenol resins, urea resins, melamine resins, diallyl phthalate resins, silicone resins, unsaturated polyester resins, fluororesins and elastomer resins, and blends of these resins Such as things.

  Of these resins, there are fluorine resins containing functional groups, non-fluorinated acrylic resins containing functional groups, polyester resins containing functional groups, urethane resins containing functional groups, and epoxy resins containing functional groups. Preferably, a fluororesin having a functional group is particularly preferable because it is excellent in corrosion resistance and acceleration of surface concentration of the organosilicon compound, and in consideration of economics in addition to acceleration of corrosion resistance and surface concentration of the organosilicon compound. A polyester resin having a functional group is particularly preferred.

  More specifically, a polyester resin having a hydroxyl group, a fluoroolefin copolymer having a hydroxyl group, an acrylic polyol resin, an acrylic silicone resin, a fluorosilicone resin, a urethane resin having a hydroxyl group, and an epoxy resin having a hydroxyl group are exemplified.

  The resin may be soluble in the organic solvent or may be dispersed in the organic solvent.

  Examples of the fluororesin include vinylidene fluoride copolymers described in JP-A-4-189879, and can be blended with a resin having a functional group as described above. Examples of the fluoroolefin copolymer having a hydroxyl group include each of JP-B-60-21686, JP-A-3-121107, JP-A-4-279612, JP-A-4-28707, JP-A-2-232221, and the like. Those described in the publication are listed. In addition, the number average molecular weight (by GPC) of the copolymer is preferably 1000 to 100,000, and more preferably 1500 to 30000. This is because if the molecular weight is less than 1,000, curability and weather resistance tend to be insufficient, and if it exceeds 100,000, there is a tendency for problems in workability and paintability. In addition, it is preferable that the hydroxyl value of such a copolymer is 0-200 (mgKOH / g), and it is more preferable that it is 0-150 (mgKOH / g). This is because if the number of hydroxyl groups is reduced, the curing tends to be poor, and if the hydroxyl value exceeds 200 (mgKOH / g), there is a tendency to cause a problem in the flexibility of the coating film.

  Moreover, it is preferable that the acid value of such a copolymer is 0-200 (mgKOH / g), and it is further more preferable that it is 0-100 (mgKOH / g). This is because if the acid value decreases, the curing tends to be poor, and if it exceeds 200 (mgKOH / g), the flexibility of the coating film tends to cause a problem.

  In addition, as one of such copolymers, a tetrafluoroethylene copolymer can be used from the viewpoint of resistance to microorganisms.

  Examples of the copolymer include: Zaffle manufactured by Daikin Industries, Ltd., Lumiflon manufactured by Asahi Glass Co., Ltd., Cefral Coat manufactured by Central Glass Co., Ltd., Fluonate manufactured by Dainippon Ink & Chemicals, Inc. Commercial products.

  The acrylic polyol resin may be, for example, a polymer having a hydroxyl group-containing polymerizable unsaturated monomer (a) and, if necessary, another polymerizable unsaturated monomer (b) as monomer components. .

  Examples of the monomer (a) include compounds represented by the following formulas (2) to (5).

（式中、Ｒ⁴は水素原子またはヒドロキシアルキル基を示す。）

(In the formula, R ⁴ represents a hydrogen atom or a hydroxyalkyl group.)

（式中、Ｒ⁴は上記に同じ。）

(Wherein R ⁴ is the same as above)

（式中、Ｚは水素原子またはメチル基であり、ｍは２〜８の整数であり、ｐは２〜１８の整数であり、ｑは０〜７の整数である。）

(In the formula, Z is a hydrogen atom or a methyl group, m is an integer of 2 to 8, p is an integer of 2 to 18, and q is an integer of 0 to 7).

（式中、Ｚは上記に同じであり、Ｔ₁およびＴ₂は同一もしくは異なって炭素数１〜２０の２価の炭化水素基である。ｓおよびｖはそれぞれ０〜１０の整数である。ただし、ｓとｖの和は１〜１０である。）
式（２）および（３）におけるヒドロキシアルキル基は、アルキル部分の炭素数が１〜６のヒドロキシアルキル基である。具体的には、−Ｃ₂Ｈ₄ＯＨ、−Ｃ₃Ｈ₆ＯＨ、−Ｃ₄Ｈ₈ＯＨなどを挙げることができる。

(In the formula, Z is the same as above, and T ₁ and T ₂ are the same or different and are divalent hydrocarbon groups having 1 to 20 carbon atoms. S and v are each an integer of 0 to 10). However, the sum of s and v is 1-10.)
The hydroxyalkyl group in Formula (2) and (3) is a hydroxyalkyl group having 1 to 6 carbon atoms in the alkyl moiety. _{Specifically, -C 2 H 4 OH, -C} 3 H 6 OH, and the like -C ₄ H ₈ OH.

  As a C1-C20 bivalent hydrocarbon group in Formula (5), for example,

などを挙げることができる。

And so on.

As a monomer component of Formula (2), for example,
CH ₂ = CHOH
CH ₂ = CHO (CH ₂ ) ₄ OH
And so on.

  As a monomer component of Formula (3), for example,

などを挙げることができる。

And so on.

  As a monomer component of Formula (4), for example,

などを挙げることができる。

And so on.

  As a monomer component of Formula (5), for example,

などを挙げることができる。

And so on.

  In addition to the above, adducts of hydroxyl group-containing unsaturated monomers represented by the above formulas (2) to (5) with lactones such as ε-caprolactone and γ-valerolactone can be used.

Other polymerizable unsaturated monomer (b)
The following (b-1) to (b-9) can be mentioned.

  (B-1) Olefin compounds: For example, ethylene, propylene, butylene, isoprene, chloroprene and the like.

  (B-2) Vinyl ether and allyl ether: For example, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4-methyl-1- Chain alkyl vinyl ethers such as pentyl vinyl ether, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, o-, m-, and p-trivinyl ethers, benzyl vinyl ether, phenethyl vinyl ether, etc. Aralkyl vinyl ethers.

  (B-3) Vinyl esters and propenyl esters; for example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl pivalate, vinyl caprate, and isopropenyl acetate. And propenyl esters such as isopropenyl propionate.

  (B-4) Acrylic acid or methacrylic acid ester: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methacrylic acid Acrylic acid such as methyl, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, etc. or alkyl ester having 1 to 18 carbon atoms of methacrylic acid; methoxy acrylate C2-C1 of acrylic acid or methacrylic acid such as butyl, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate Such as alkoxyalkyl esters.

  (B-5) Vinyl aromatic compound: For example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene and the like.

  (B-6) Others: Acrylonitrile, methacrylonitrile and the like.

  (B-7) Carboxyl group-containing monomer:

（式中、Ｒ５、Ｒ６およびＲ７は同じか又は異なり、いずれも水素原子、アルキル基、フェニル基、カルボキシル基またはエステル基であり、ｎは０または１である）または式（７）：

(Wherein R5, R6 and R7 are the same or different, and each is a hydrogen atom, an alkyl group, a phenyl group, a carboxyl group or an ester group, and n is 0 or 1) or formula (7):

（式中、Ｒ１３およびＲ１４は同じか又は異なり、いずれも飽和または不飽和の直鎖また不飽和の直鎖または環状アルキル基、ｎは０または１であり、ｍは０または１である）で表わされるカルボキシル基含有ビニル単量体が挙げられる。具体例としては、例えば、アクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、桂皮酸、３−アリルオキシプロピオン酸、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、マレイン酸無水物、フマル酸、フマル酸モノエステル、フタル酸ビニル、ピロメリット酸ビニルなどが挙げられる。

Wherein R13 and R14 are the same or different, both are saturated or unsaturated linear or unsaturated linear or cyclic alkyl groups, n is 0 or 1, and m is 0 or 1. The carboxyl group-containing vinyl monomer represented is mentioned. Specific examples include, for example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, Examples include fumaric acid, fumaric acid monoester, vinyl phthalate, and vinyl pyromellitic acid.

  (B-8) Epoxy group-containing monomer:

（ｂ−９）アミノ含有単量体：

(B-9) Amino-containing monomer:

アクリルポリオール樹脂としては、水酸基、カルボキシル基、エポキシ基、アミノ基を有していてもよい。

As an acrylic polyol resin, you may have a hydroxyl group, a carboxyl group, an epoxy group, and an amino group.

  The hydroxyl value of the acrylic polyol resin is preferably 0 to 200 (mgKOH / g), and more preferably 0 to 100 (mgKOH / g). This is because if the hydroxyl value decreases, the curing tends to be poor, and if it exceeds 200 (mgKOH / g), the flexibility of the coating tends to be problematic.

  The acid value of the acrylic polyol resin is preferably 0 to 200 (mgKOH / g), and more preferably 0 to 100 (mgKOH / g). This is because if the acid value decreases, the curing tends to be poor, and if it exceeds 200 (mgKOH / g), the flexibility of the coating film tends to cause a problem.

  Examples of the acrylic polyol resin include DYNAL manufactured by Mitsubishi Rayon Co., Ltd., Acridic manufactured by Dainippon Ink & Chemicals, Ltd., Hitachi Chemical Co., Ltd., Hitaroid, and Olester manufactured by Mitsui Toatsu Chemicals Co., Ltd. Commercial products can be used.

  The acrylic silicone resin may have a hydrolyzable silyl group, a hydroxyl group, and an epoxy group.

  As the acrylic silicon resin, for example, commercially available products such as Kaneka Chemical Co., Ltd. Zemlac, Sanyo Kasei Kogyo Co., Ltd. clearer can be used.

  Examples of the fluorosilicone resin include those described in JP-A-4-279612.

  The polyester resin is a condensation polymerization reaction product of a polybasic acid component and a polyhydric alcohol component.

  As the polybasic acid component, for example, one or more selected from phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid, adipic acid, sebacic acid, maleic anhydride, etc. The dibasic acid of these, or the lower alkyl esterified product of these acids is mainly mentioned. Moreover, you may use together monobasic acids, such as benzoic acid, crotonic acid, and pt-butyl benzoic acid, as needed.

  Examples of the polyhydric alcohol component include divalent compounds such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, and 1,6-hexanediol. Alcohol is mainly cited. These polybasic acid components and polyhydric alcohols can be used alone or in admixture of two or more. The polycondensation reaction (esterification reaction or transesterification reaction) between the polybasic acid component and the polyhydric alcohol component can be performed by a known method.

  In addition, as a method for introducing a hydroxyl group into such a polyester resin, a method in which a trihydric or higher polyhydric alcohol such as trimethylolethane, trimethylolpropane, pentaerythritol or the like is used in combination as a part of the polyhydric alcohol component. .

  Further, the polyester-based resin may be a resin modified with fatty acid (so-called alkyd resin), a modified polyester resin such as a urethane-modified polyester resin or an epoxy-modified polyester resin, or a silicone-modified polyester polyol resin.

  The hydroxyl group-containing polyester resin has a hydroxyl value in the range of 40 to 200 mgKOH / g, particularly 50 to 120 mgKOH / g, from the viewpoint of the balance of processability, hardness, curability and resistance to cracking of the resulting coating film. The number average molecular weight is preferably in the range of 1000 to 30000, particularly 2000 to 10000, and the glass transition temperature (Tg) is preferably in the range of −40 ° C. to 100 ° C., in particular −20 to 80 ° C.

(1-3) Curing agent and curing catalyst Examples of the curing agent include isocyanate compounds, blocked isocyanate compounds, amino resins, dibasic acids, non-hydrolyzable group-containing silane compounds, epoxy resins, and acid anhydrides. However, an isocyanate compound, a blocked isocyanate compound, and an amino resin are preferable.

  Examples of isocyanate compounds and blocked isocyanate compounds include 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate. Hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts and burettes thereof, polymers having two or more isocyanate groups, and further blocked Although isocyanate etc. are mentioned, it is not limited to these.

  The mixing ratio of isocyanate and resin is preferably NCO / OH (molar ratio) of 0.5 to 5.0, more preferably 0.8 to 1.2. Moreover, 1.1-1.5 are preferable when isocyanate is a moisture hardening type.

  Examples of the melamine resin include, besides melamine resins, methylolated melamine resins obtained by methylolating melamine, alkyletherified melamine resins obtained by etherifying methylolated melamine with alcohols such as methanol, ethanol, and butanol. It is not limited to these.

  Examples of amino resins include urea resins, melamine resins, benzoguanamine resins, glycoluril resins, methylolated melamine resins obtained by methylolation of melamine, and alkyl etherifications obtained by etherifying methylolated melamine with alcohols such as methanol, ethanol, and butanol. A melamine resin etc. are mentioned.

  As an epoxy compound, for example,

などが挙げられるがこれらに限定されるものではない。

However, it is not limited to these.

  Examples of the acid anhydride include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,2-cyclohexyldicarboxylic anhydride, succinic anhydride, maleic anhydride, and the like. It is not a thing.

  In addition, dibasic acids such as fumaric acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and 1,2-cyclohexyldicarboxylic acid are also used as a curing agent.

  Examples of the curing catalyst include an organic tin compound, an organic acidic phosphate ester, an organic titanate compound, a reaction product of an acidic phosphate ester and an amine, a saturated or unsaturated polycarboxylic acid or acid anhydride thereof, and an organic sulfonic acid. , Amine compounds, aluminum chelate compounds, titanium chelate compounds, zirconium chelate compounds and the like.

  Specific examples of the organic tin compound include dibutyltin dilaurate, dibutyltin maleate, dioctyltin maleate, dibutyltin diacetate and the like.

  As a specific example of organic acid phosphate ester,

などが挙げられる。

Etc.

  Examples of the organic titanate compound include titanate esters such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate.

  Specific examples of the amine compound include, for example, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylene. Range amine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) Amine-based compounds such as salts of these carboxylic acids, low-volume polyamide resins obtained from excess polyamines and polybasic acids, reaction of excess polyamines and epoxy compounds Such as the formation thereof.

  Specific examples of the chelate compound include tris (acetylacetonato) aluminum, tetrakis (acetylacetonato) zirconium, diisopropoxy bis (ethylacetoacetate) titanate, and the like.

  One curing catalyst may be used, or two or more curing catalysts may be used in combination.

  In the present invention, the combination of the resin and the curing agent and / or the curing catalyst is not particularly limited, but preferred combinations include the following.

  In the case of a fluoroolefin copolymer or acrylic polyol resin having a hydroxyl group, an isocyanate compound, a blocked isocyanate compound or a melamine resin is preferred as the curing agent when these have a hydroxyl group. In these systems, a curing catalyst can be used together.

  In the case of acrylic silicon or fluorine silicone, a curing catalyst may be used.

(1-4) Organic solvent Examples of the organic solvent include hydrocarbon solvents such as xylene, toluene, Solvesso 100, Solvesso 150, mineral spirit, octane, hexane, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol, diethylene glycol acetate, diethyl adipate, diethyl succinate, Ester solvents such as diethyl fumarate, dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Ether solvents such as glyceryl dibutyl ether, tetrahydrofuran, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone, methyl amyl ketone, cyclohexanone, isophorone, N, N-dimethylacetamide, N-methylacetamide, acetamide, Amide solvents such as, N-dimethylformamide, N, N-diethylformamide, N-methylformamide, sulfonate solvents such as dimethyl sulfoxide, methanol, ethanol, isopropanol, butanol, ethylene glycol, diethylene glycol, polyethylene glycol (polymerization) _{3 to} 100), POVAL, CF ₃ CH ₂ OH, F (CF ₂ ) ₂ CH ₂ 0H, (CF ₃ ) ₂ CHOH, F (CF ₂ ) ₃ CH ₂ 0H, F (CF ₂ ) ₄ C ₂ H ₅ Alcohol solvents such as OH, H (CF ₂ ) ₂ CH ₂ 0H, H (CF ₂ ) ₃ CH ₂ OH, H (CF ₂ ) ₄ CH ₂ 0H, and the like. Among these organic solvents, alcohol solvents such as lower alcohols and lower fluorine alcohols are preferable from the viewpoints of compatibility, coating film appearance, and storage stability.

  The blending ratio of the resin and the alcohol solvent is 1 to 50 parts by weight of alcohol with respect to 100 parts by weight of the resin, and more preferably 1 to 25 parts by weight from the viewpoint of curability and coating film appearance.

  In addition, when the curing agent is highly reactive with an alcohol such as a room temperature curable isocyanate, the content is preferably 1 to 15 parts by weight, and the alcohol is preferably a secondary or tertiary alcohol.

(1-5) Other additives The coating composition of the present invention includes, for example, pigments, pigment dispersants, thickeners, leveling agents, antifoaming agents, film-forming aids, HALS, matting agents, fillers, colloidal Additives for paints such as silica, antifungal agents, silane coupling agents, anti-skinning agents, antioxidants, flame retardants, anti-sagging agents, antistatic agents, and rust inhibitors can also be blended.

  Examples of the pigment include titanium oxide, iron oxide, aluminum metallic pigment, carbon black, calcined pigment, phthalocyanine pigment, organic pigment, extender pigment and the like.

  Examples of the titanium oxide include Ipehara Sangyo Co., Ltd., Taipei CR-90, CR-93, CR-95, CR-97, and the like.

  Examples of the iron oxide include Toda Color 120ED, 140ED, 160ED, KN-R, KN-V, Toda Egyo Co., Ltd., TAROX LL-XLO, HY-100, HY-200, BL manufactured by Titanium Industry Co., Ltd. -100, BL-500 and the like.

  As an aluminum metallic pigment, Toyo Aluminum Co., Ltd. Alpaste 0100MA, 0700M, 0200M, 0215M, 1950M, 1900M, 1100M, 1109M, 1200M, 8820YF, 7080N, MG600, 1700N, etc. are mentioned, for example.

  Examples of carbon black include MA7, MA11, MA100, OIL7B, OIL30B, and OIL31B manufactured by Mitsubishi Chemical Corporation.

  Examples of the calcined pigment include Dipyroxide # 9510, # 9512, # 9410, # 9310 manufactured by Dainichi Seika Co., Ltd.

  Examples of the phthalocyanine pigment include # 5195N and # 5370 manufactured by Dainichi Seika Co., Ltd.

  Examples of extender pigments include asbestos, calcium carbonate, precipitated calcium carbonate, clay, kaolin, porcelain clay, aluminum silicate, diatomaceous earth, white carbon, silica white, hydrous finely divided silicic acid, bentonite, talc, magnesium silicate, magnesium carbonate, barite powder. , Barium sulfate, precipitated barium sulfate and the like.

  Examples of the silane coupling agent include methyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, vinyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, and N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropyl isocyanate, 3-triethoxysilylpropyl isocyanate, etc. The thing containing an amino group or an isocyanate group is preferable. In particular, when it contains an isocyanate group, it is excellent in recoatability and repair adhesion. Furthermore, what has alkyl isocyanate groups, such as 3-trimethoxysilylpropyl isocyanate, is more preferable.

(2) Form of coating composition The coating composition can take various forms such as clear, solid, and filler (filler) blending.

(3) Coating method of coating composition Moreover, as a coating method of a coating composition, it is possible to employ | adopt various methods, such as a spray, a brush, a roller, a curtain flow, a roll, and a dip.

<Example>
Next, although the coating composition which concerns on this Embodiment is demonstrated based on an Example and a comparative example, this invention is not limited to these examples. In the following examples, “parts” represents parts by weight, and “%” represents% by weight.

(Formulation example 1)
First, 0.45 g of Zeffle GH-700 (Fluoropolysiloxane manufactured by Daikin Industries) was added to 4.05 g of butyl acetate, and the mixture was stirred with a magnetic stirrer at 500 rpm for 5 minutes and then at 300 rpm for 5 minutes. -700 is uniformly dissolved in butyl acetate.

  Next, 34.2 g of a polyester resin (Desmophen T1665 manufactured by Sumika Bayer Urethane Co., Ltd.), 12.8 g of a blocked isocyanate curing agent (Desmodule BL3175 manufactured by Sumika Bayer Urethane Co., Ltd.), 0.1 g of dibutyltin dilaurate, 14.6 g of cyclohexanone, 29.2 g of Solvesso 100 (manufactured by ExxonMobil) and 4.5 g of ethyl orthoformate are stirred and mixed uniformly with a magnetic stirrer at 500 rpm for 5 minutes. The liquid mixture thus obtained is hereinafter referred to as “polyester solution”.

  Then, a desired coating composition can be obtained by mixing a solution such as Zeffle GH-700 butyl acetate solution and polyester with a magnetic stirrer at 500 rpm for 10 minutes. At this time, the amount of Zeffle GH-700 in the coating composition is 1.4% by weight based on the solid content (a combination of the polyester resin and the blocked isocyanate curing agent).

(Formulation example 2)
A coating composition was prepared in the same manner as in Preparation Example 1 except that the amount of Zeffle GH-700 was changed to 1.11 g and the amount of butyl acetate was changed to 9.99 g. At this time, the amount of Zeffle GH-700 in the coating composition is 3.5% by weight with respect to the solid content (a combination of the polyester resin and the blocked isocyanate curing agent).

(Formulation example 3)
A coating composition was prepared in the same manner as in Preparation Example 1 except that Zeffle GH-700 was replaced with Zeffle GH-701 (Daikin Industries' fluoropolysiloxane). At this time, the amount of Zeffle GH-701 in the coating composition is 1.4% by weight based on the solid content (a combination of the polyester resin and the blocked isocyanate curing agent).

(Formulation example 4)
A coating composition was prepared in the same manner as in Preparation Example 3 except that the amount of Zeffle GH-701 was changed to 1.11 g and the amount of butyl acetate was changed to 9.99 g. At this time, the amount of Zeffle GH-701 in the coating composition is 3.5% by weight based on the solid content (a combination of the polyester resin and the blocked isocyanate curing agent).

(Formulation example 5)
A coating composition was prepared in the same manner as in Preparation Example 3 except that the zaffle GH701 was replaced with methyl silicate (product number MS56 manufactured by Mitsubishi Chemical Corporation). At this time, the methyl silicate in the coating composition is 1.4% by weight based on the solid content (a combination of the polyester resin and the blocked isocyanate curing agent).

(Formulation Example 6)
First, 0.45 g of Zeffle GH-701 (a fluoropolysiloxane manufactured by Daikin Industries) is dissolved in 4.05 g of butyl acetate.

  Next, 26.9 g of an acrylic resin (Desmophen A870 manufactured by Sumika Bayer Urethane Co., Ltd.), 17.7 g of a blocked isocyanate-based curing agent (Desmodule BL3175 manufactured by Sumika Bayer Urethane Co., Ltd.), 0.1 g of dibutyltin dilaurate, A mixed liquid of 15.7 g of cyclohexanone, 31.4 g of Solvesso 100 (manufactured by ExxonMobil) and 4.6 g of ethyl orthoformate (hereinafter referred to as “acrylic solution”) is prepared.

  Then, a desired coating composition is obtained by mixing a solution of Zeffle GH-701 butyl acetate and a solution such as acrylic. At this time, the amount of Zeffle GH-701 in the coating composition is 1.4% by weight based on the solid content (a combination of the acrylic resin and the blocked isocyanate curing agent).

(Formulation example 7)
First, 0.45 g of Zeffle GH-701 (a fluoropolysiloxane manufactured by Daikin Industries) is dissolved in 4.05 g of butyl acetate.

  Next, 38.1 g of a fluororesin (Zeffle GK570 manufactured by Daikin Industries, Ltd.), 9.9 g of a block isocyanate curing agent (Desmodur BL3175 manufactured by Sumika Bayer Urethane Co., Ltd.), 0.1 g of dibutyltin dilaurate, 14. A mixed solution of 6 g of cyclohexanone, 29.3 g of Solvesso 100 (manufactured by ExxonMobil) and 4.6 g of ethyl orthoformate (hereinafter referred to as “fluorine resin solution”) is prepared.

  Then, a desired coating composition can be obtained by mixing a solution such as ZEFFLE GH-701 butyl acetate solution and fluororesin. At this time, the amount of Zeffle GH-701 in the coating composition is 1.4% by weight based on the solid content (a combination of the fluororesin resin and the blocked isocyanate curing agent).

  After applying the coating composition of Formulation Example 1 to an aluminum plate by the bar coater method, the aluminum plate was dried with a hot air dryer (ADVANTEC, FC-610) to reach a surface temperature of 220 ° C. to prepare a sample plate.

  Hereinafter, the evaluation of the sample plate will be described in detail.

(1) Hydrophilicity evaluation of sample plate surface The contact angle of water with the sample plate surface before water immersion and after 24 hours from water immersion was measured. In addition, this contact angle was measured using the contact angle meter (Kyowa Interface Science CA-VP). The results are shown in Table 1. As apparent from Table 1, the contact angle on the surface of the sample plate is lowered by immersing the sample plate in water. Therefore, it can be seen that the fluoropolysiloxane on the coating surface is hydrolyzed and the coating surface is sufficiently hydrophilic.

(2) Evaluation of microorganism adhesion A bacterial solution is dropped on a sample plate (50 mm square), and the droplet is stretched by a loop (platinum ear), and then the sample plate is immersed in sterilized water for a predetermined time. Then, the aluminum plate is gently pulled up to check the number of remaining bacteria. In addition, the number of bacteria was measured according to the following method for counting the number of bacteria. The results are shown in Table 2. In the same table, the number of viable bacteria immediately after dropping the staphylococcus aureus solution is also shown. As is clear from Table 2, the fin coated with the coating composition of Formulation Example 1 is an aluminum plate coated with a conventional product (fins of a heat exchanger mounted on an indoor unit FXYFP140MC manufactured by Daikin). More difficult to attach microorganisms.

(Bacteria count method)
Place the sample in a bag containing sterile physiological saline and rinse well to wash out the bacteria. Subsequently, the number of viable bacteria was counted after diluting the liquid from which the bacteria were washed out.

  After applying the coating composition of Formulation Example 2 to an aluminum plate by the bar coater method, the aluminum plate was dried to prepare a sample plate. In addition, the sample plate was evaluated in the same manner as in Example 1. The results are shown in Table 1. As apparent from Table 1, the contact angle on the surface of the sample plate is lowered by immersing the sample plate in water. Therefore, it can be seen that the fluoropolysiloxane on the coating surface is hydrolyzed and the coating surface is sufficiently hydrophilic. Further, as apparent from Table 2, the sample plate coated with the coating composition of Formulation Example 2 is an aluminum plate coated with a conventional product (a heat exchanger mounted on an indoor unit FXYFP140MC manufactured by Daikin). Microorganisms are less likely to adhere than

  After applying the coating composition of Formulation Example 3 to an aluminum plate by the bar coater method, the aluminum plate was dried to prepare a sample plate. Further, the hydrophilicity of the sample plate surface was evaluated in the same manner as in Example 1. The results are shown in Table 1. As apparent from Table 1, the contact angle on the surface of the sample plate is lowered by immersing the sample plate in water. Therefore, it can be seen that the fluoropolysiloxane on the coating surface is hydrolyzed and the coating surface is sufficiently hydrophilic. Further, as apparent from Table 2, the sample plate coated with the coating composition of Formulation Example 3 is an aluminum plate coated with a conventional product (a heat exchanger mounted on an indoor unit FXYFP140MC manufactured by Daikin). Microorganisms are less likely to adhere than

  After applying the coating composition of Formulation Example 4 to an aluminum plate by the bar coater method, the aluminum plate was dried to prepare a sample plate. Further, the hydrophilicity of the sample plate surface was evaluated in the same manner as in Example 1. The results are shown in Table 1. As apparent from Table 1, the contact angle on the surface of the sample plate is lowered by immersing the sample plate in water. Therefore, it can be seen that the fluoropolysiloxane on the coating surface is hydrolyzed and the coating surface is sufficiently hydrophilic. As is clear from Table 2, the sample plate coated with the coating composition of Formulation Example 4 is an aluminum plate coated with a conventional product (a heat exchanger mounted on an indoor unit FXYFP140MC manufactured by Daikin). Microorganisms are less likely to adhere than

  After applying the coating composition of Formulation Example 5 to an aluminum plate by the bar coater method, the aluminum plate was dried to prepare a sample plate. Further, the hydrophilicity of the sample plate surface was evaluated in the same manner as in Example 1. The results are shown in Table 1. As apparent from Table 1, the contact angle on the surface of the sample plate is lowered by immersing the sample plate in water. However, the degree of decrease is small compared to Formulation Examples 1 to 4. This is considered to be due to the fact that the organosilicon compound is a non-fluorine silicon compound. Further, as is apparent from Table 2, the sample plate coated with the coating composition of Formulation Example 5 is an aluminum plate coated with a conventional product (a heat exchanger mounted on an indoor unit FXYFP140MC manufactured by Daikin). Microorganisms are less likely to adhere than

  After applying the polyester solution obtained in Formulation Example 1 to an aluminum plate by the bar coater method, the aluminum plate was dried to prepare a sample plate. Further, the hydrophilicity of the sample plate surface was evaluated in the same manner as in Example 1. The results are shown in Table 1. As apparent from Table 1, the contact angle on the surface of the sample plate does not decrease even after the sample plate is immersed in water. This is considered to be due to the fact that no organic silicon compound is contained in the coating composition. Further, as is apparent from Table 2, this sample plate is less susceptible to microorganisms than the aluminum plate coated with the conventional product (the fins of the heat exchanger mounted on the indoor unit FXYFP140MC manufactured by Daikin). It has become. However, this is due to the effect that the surface is not hydrophilized, and the surface is not capable of maintaining the original hydrophilicity well.

  After applying the coating composition of Formulation Example 6 to an aluminum plate by the bar coater method, the aluminum plate was dried to prepare a sample plate. Further, the hydrophilicity of the sample plate surface was evaluated in the same manner as in Example 1. The results are shown in Table 1. As is clear from Table 1, the contact angle on the surface of the sample plate is lowered by immersing the sample plate in water. Further, as is apparent from Table 2, the sample plate coated with the coating composition of Formulation Example 7 is an aluminum plate coated with a conventional product (a heat exchanger mounted on an indoor unit FXYFP140MC manufactured by Daikin). Microorganisms are less likely to adhere than

  After applying the acrylic solution obtained in Formulation Example 6 to an aluminum plate by a bar coater method, the aluminum plate was dried to prepare a sample plate. Further, the hydrophilicity of the sample plate surface was evaluated in the same manner as in Example 1. The results are shown in Table 1. As is clear from Table 1, the contact angle on the surface of the sample plate does not decrease even when the sample plate is immersed in water. This is considered to be due to the fact that no organic silicon compound is contained in the coating composition. Further, as is apparent from Table 2, this sample plate is less susceptible to microorganisms than the aluminum plate coated with the conventional product (the fins of the heat exchanger mounted on the indoor unit FXYFP140MC manufactured by Daikin). It has become. However, this is due to the effect that the surface is not hydrophilized, and the surface is not capable of maintaining the original hydrophilicity well.

  After applying the coating composition of Formulation Example 7 to an aluminum plate by a bar coater method, the aluminum plate was dried to prepare a sample plate. Further, the hydrophilicity of the sample plate surface was evaluated in the same manner as in Example 1. The results are shown in Table 1. As is clear from Table 1, the contact angle on the surface of the sample plate is lowered by immersing the sample plate in water. Further, as is apparent from Table 2, the sample plate coated with the coating composition of Formulation Example 7 is an aluminum plate coated with a conventional product (a heat exchanger mounted on an indoor unit FXYFP140MC manufactured by Daikin). Microorganisms are less likely to adhere than In addition, the sample plate is less likely to adhere than the sample plates coated with the coating compositions of Formulation Example 3, Formulation Example 5 and Formulation Example 6 having the same organosilicon compound content.

  After applying the fluororesin solution obtained in Formulation Example 7 to an aluminum plate by the bar coater method, the aluminum plate was dried to prepare a sample plate. Further, the hydrophilicity of the sample plate surface was evaluated in the same manner as in Example 1. The results are shown in Table 1. As is clear from Table 1, the contact angle on the surface of the sample plate does not decrease even when the sample plate is immersed in water. This is considered to be due to the fact that no organic silicon compound is contained in the coating composition. Further, as is apparent from Table 2, this sample plate is less susceptible to microorganisms than the aluminum plate coated with the conventional product (the fins of the heat exchanger mounted on the indoor unit FXYFP140MC manufactured by Daikin). It has become. However, this is due to the effect that the surface is not hydrophilized, and the surface is not capable of maintaining the original hydrophilicity well.

  After applying the coating composition of Formulation Example 3 to an aluminum plate by the bar coater method, the aluminum plate was dried to prepare a sample plate. In this example, the contact angle of water to the sample plate surface before water immersion, 24 hours after water immersion, and 240 hours or more after immersion in running water was measured in the same manner as in Example 1 to measure the sample plate surface. The hydrophilicity evaluation of was performed. The results are shown in Table 1. As is clear from Table 1, the contact angle on the surface of the sample plate is lowered by immersing the sample plate in water for 24 hours. Therefore, it can be seen that the fluoropolysiloxane on the coating surface is hydrolyzed and the coating surface is sufficiently hydrophilic. Further, as is apparent from Table 1, the contact angle on the surface of the sample plate after 240 hours or more after being immersed in running water maintains the same contact angle as the contact angle on the surface of the sample plate before immersion in water. Therefore, even when the sample plate is immersed in water for a long time, the hydrophilicity of the sample plate surface can be maintained relatively well.

 Furthermore, in this example, the microbial adhesion evaluation on the surface of the sample plate before water immersion, after 24 hours after water immersion and after 240 hours or more after immersion in running water was performed in the same manner as in Example 1. The results are shown in Table 2. In Table 2, the term “240 (running water)” indicates that the bath was immersed in running water for 240 hours or more. As is clear from Table 2, the sample plate coated with the coating composition of Formulation Example 3 was an aluminum plate coated with a conventional product (fins of heat exchangers mounted on indoor unit FXYFP140MC manufactured by Daikin). ) Microorganisms are less likely to adhere.

<Reference example>
A commercially available water-based paint (aqueous Serratite (registered trademark) F manufactured by SK Kaken Co., Ltd.) was applied to an aluminum plate by the bar coater method, and then the aluminum plate was dried to prepare a sample plate. Then, in the same manner as in Example 11, the water contact angle with the sample plate surface was measured before immersion in water, after 24 hours after immersion in water, and after 240 hours or more after immersion in running water, to determine the hydrophilicity of the sample plate surface. Evaluation was performed. The results are shown in Table 1. Further, in the same manner as in Example 11, microbial adhesion evaluation on the surface of the sample plate was performed before soaking in water, after 24 hours after soaking in water, and after 240 hours or more after soaking in running water. The results are shown in Table 2.

<Characteristics of heat exchanger according to the present embodiment>
The heat exchanger according to the present embodiment has a sufficiently hydrophilic surface and a sufficiently low amount of microorganisms per unit area than before. Therefore, the heat exchanger is superior in deodorization than before and can maintain good hydrophilicity.

<Modification>
(A)
In the previous embodiment, the coating film 252 is formed on the fin 25 of the cross fin tube type indoor heat exchanger 20, but the coating film 252 according to the present embodiment is formed on a heat exchanger other than the cross fin tube type. May be. In such a case, the coating film 252 according to the present embodiment may be formed only on the heat transfer tubes, not on the fins.

(B)
In the previous embodiment, the coating film 252 is formed on the fin 25 of the cross fin tube type indoor heat exchanger 20, but the coating film 252 may be formed on the U-shaped heat transfer tube 26 in addition to the fin 25. .

  The heat exchanger according to the present invention has a feature of excellent deodorization while maintaining good hydrophilicity, and is particularly suitable for air conditioners for homes and offices and transportation equipment (car air conditioners, low temperature air conditioners, etc.) It is useful as a heat exchanger for air conditioning equipment, refrigeration equipment for food preservation and the like.

20 Indoor heat exchanger (heat exchanger)
24 heat transfer tube 25 fin 26 U-shaped heat transfer tube (heat transfer tube)
252 paint film

JP 2001-201288 A

Claims (12)

An organic solvent,
Resin,
One or more organosilicon compounds represented by the following general formula (I):

(In the formula, n is an integer of ¹ to 20. R ¹ is all different or at least two are the same, both are monovalent organic groups having 1 to 1000 carbon atoms. The group may contain at least one kind of oxygen atom, nitrogen atom and silicon atom, and this organic group may be a part or all of hydrogen atoms composed of fluorine atoms or fluorine atoms and chlorine atoms. May be substituted.)
A heat exchanger (20) in which a coating film (252) formed from a coating composition containing slag covers at least one of the heat transfer tubes (24, 26) and the fins (25). The heat exchanger according to claim 1, wherein at least one R ¹ is an organic group in which some or all of the hydrogen atoms are substituted with fluorine atoms. The organic group has 3 to 9 fluorine atoms,
The heat exchanger according to claim 2, wherein the organosilicon compound has a fluorine atom content of at least 5 wt%. N is an integer of 2 to 20,
The heat exchanger according to claim 1, wherein the organic group is at least one of a methyl group and an ethyl group. The heat exchanger according to any one of claims 1 to 4, wherein the organosilicon compound is added in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin. The resin is at least one resin selected from the group consisting of a functional group-containing fluororesin, a functional group-containing non-fluorinated acrylic resin, a functional group-containing polyester resin, a functional group-containing urethane resin, and a functional group-containing epoxy resin. Item 6. The heat exchanger according to any one of Items 1 to 5. The resin is a functional group-containing fluororesin,
The heat exchanger according to any one of claims 1 to 5, wherein the coating composition further contains a curing agent that reacts with a functional group of the functional group-containing fluororesin. The resin is a functional group-containing polyester resin,
The heat exchanger according to any one of claims 1 to 5, wherein the coating composition further contains a curing agent that reacts with a functional group of the functional group-containing polyester resin. The heat exchanger according to any one of claims 6 to 8, wherein the functional group is a hydroxyl group. The heat exchanger according to claim 9, wherein the curing agent is at least one of an amino resin and an isocyanate compound.   A refrigeration apparatus on which the heat exchanger according to claim 1 is mounted.   An air conditioner on which the heat exchanger according to claim 1 is mounted.

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