JPH09221630A - Coating composition and coating film therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition excellent in compatibility, easy to handle, capable of giving bleed-free, uniform coating film, and useful-as a water- resistant, water-repellent topcoating material for civil-engineering structures, etc., by incorporating a base coating material with a specific hydroxyl-contg. polysilsesquioxane. SOLUTION: This coating composition is obtained by incorporating a coating material containing (A) a reaction-curable organic resin as resin component with (B) such a hydroxyl-contg. polysilsesquioxane that the side chain organic groups consist of at least cane kind of substituent selected from alkyl, aralkyl and (substituted) phenyl groups and hydroxyl-contg. group of formula I (R<1> is an alkylene; R<2> and R<3> are each a single bond, alkylene, cycloalkylene, etc.; X<1> and X<2> are each a single bond, ester linkage, sulfide linkage, amido linkage, etc.), and the main chain end group(s) is trialkylsilylated (e.g. a compound of formula II). It is preferable that the component A is an organic resin bearing active hydrogen-contg. functional group and either polyisocyanate resin or blocked polyisocyanate resin is used as a crosslinking agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention contains a reaction-curable organic resin containing a polysilsesquioxane having a hydroxyl group, which imparts unique surface properties such as water repellency, low friction, stain resistance, and chemical resistance. The present invention relates to a solvent-based coating composition (hereinafter referred to as an organic coating composition) and a coating film having a unique surface property obtained from the coating composition.

[0002]

2. Description of the Related Art Since polyorganosiloxane has excellent properties such as water resistance, water repellency and stain resistance, polyorganosiloxane having a reactive group has been conventionally used for the purpose of imparting these properties to products. Paints and coating agents added as modifiers of various resins are widely used. For example, in JP-A-63-161013, an isocyanate group-containing modified polyorganosiloxane is compounded as a modifier of a resin containing active hydrogen that reacts with an isocyanate group in the polyorganosiloxane to reduce friction to the resin. Properties, water repellency, oil repellency and the like can be imparted, and a modified polyorganosiloxane having a hydroxyl group at the main chain terminal for this purpose is described. Further, JP-A-5-320578 proposes to obtain a coating film having improved stain resistance and chemical resistance by using a coating composition containing a polyorganosiloxane having an isocyanate group.

However, all of the polyorganosiloxanes described in these publications are polyorganosiloxane polymers having polydimethylsiloxane as a main skeleton, and are soluble only in a limited solvent such as hexane and chloroform, and thus are generally used. Since it has low solubility in the oily solvent used in the paint, the limitation in use was unavoidable.

Therefore, even if the above-mentioned polyorganosiloxane having an isocyanate group or the like is added to a general resin composition (paint) to be modified containing various solvents, it is often a solvent-based composition. It is difficult to disperse uniformly, and even if the above-mentioned polyorganosiloxane having an isocyanate group is added to the paint, the solution undergoes phase separation, and the resulting coating film has the additive bleeding to the coating surface. There is a problem that a uniform coating film is not formed such as a phenomenon such as so-called "bleeding", and it cannot be used as an additive for a wide variety of paints. In addition, since polyorganosiloxane having a polydimethylsiloxane skeleton has low solubility in a solvent, it can be added to various resin compositions (paints) only in a very small amount. There is a problem that it is difficult to obtain a resin (composition) to which sufficient characteristics are given.

Therefore, it is highly soluble in various oil-based solvent-based coating compositions, can be mixed in an arbitrary ratio, has no problem such as "bleeding" in the coating film, and has sufficient water resistance and water repellency. It has been desired to develop a coating composition containing a polyorganosiloxane that can impart unique properties such as stain resistance, chemical resistance, and abrasion resistance.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the prior art as described above, and provides a hydroxyl group-containing polysilsesquioxane having good compatibility with solvents and various resins as a reaction-curable organic resin. An object of the present invention is to provide an organic coating composition that forms a coating film having high water repellency by using it as a modifier, and a coating film having high water repellency formed from this coating composition.

[0007]

The present invention provides a coating material containing a reaction-curable organic resin as a resin component, comprising: a. The side chain organic group is at least one selected from an alkyl group, an aralkyl group, and a substituted or unsubstituted phenyl group.
One or more kinds of substituents and the following general formula (1) R ¹ —X ¹ —R ² —X ² —R ³ —OH (1) [wherein, R ¹ may have a substituent , An alkylene group which may contain O or S, R ² and R ³ are each independently a single bond, an alkylene group, a cycloalkylene group, a phenylene group or any two or more kinds of these groups excluding a single bond. Which may have a substituent or may contain O or S, and X ¹ and X ² each independently represent a single bond,
Indicates any one of an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond, an ether bond and a carbonyl bond. ] And a hydroxyl group-containing group, b. The main chain end group is trialkylsilylated, an organic coating composition containing a hydroxyl-containing polysilsesquioxane,

[0008] An organic resin containing a functional group having active hydrogen as a reaction-curable organic resin and a coating composition described using an amino resin cross-linking agent, an organic resin containing a functional group having an active hydrogen as a reaction-curable organic resin. The coating composition described above using either a polyisocyanate resin cross-linking agent or a blocked polyisocyanate resin cross-linking agent as a resin and a cross-linking agent, and a hydroxyl group-containing polysulfate such that the surface silicon content in the coating film is 6% or more. After coating the coating composition according to any one of 1 and which contains lusesquioxa and the organic coating composition according to any one of 1 to 3, it is heated and dried in air at a temperature of 50 ° C or higher and lower than 300 ° C. The above object was achieved by developing a coating film in which a hydroxyl-containing polysilsesquioxane is segregated on the surface of the coating film.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The organic coating composition of the present invention contains a reaction-curable organic resin as a resin component, and can itself be reaction-cured to form a crosslinked coating film structure. The organic resin composition is not particularly limited as long as the above-mentioned conditions are satisfied, and conventionally known resin compositions can be used. For example, general-purpose paint resins such as urethane resins and acrylic resins, and further modified resins such as fluorine-based resins, polyester-based resins, alkyd resins, silicone-based resins and polyester-modified acrylic-based resins, and silicone-based modified acrylic-based resins. , Selected appropriately from the required performance. At this time, two or more kinds may be used in combination. This organic resin composition contains a resin containing a functional group-containing organic resin having active hydrogen such as a hydroxyl group as a base resin. The organic resin composition contains the one dissolved or dispersed in an organic solvent.

A hydroxyl group-containing polysilsesquioxane is added to the organic coating composition of the present invention. The hydroxyl group-containing polysilsesquioxane used in the present invention is represented by the following general formula (A)

Embedded image [Wherein, R ^m and R ⁿ are side chain organic groups, and —OR
^g, -OR ^r, OR ^s, and OR ^t are trialkyl silylating a main chain terminal group, p is a repeating unit. In the trialkylsilylated main chain terminal group, OSiR ⁴ R ⁵ R ⁶ : R ⁴ , R ⁵ and R ⁶ are the same or different alkyl groups. ). ] Has a structure represented by. The side chain organic group (represented by R ^m and R ⁿ in the general formula (A)) of this hydroxyl group-containing polysilsesquioxane is at least one or two.
Those selected from one or more alkyl groups, aralkyl groups, substituted or unsubstituted phenyl groups (hydrocarbon group substituents, preferably methyl groups, ethyl groups or phenyl groups)
When, both of at least one or more of the general formula ^{(1) -R 1 -X 1 -R} 2 -X 2 -R 3 made of -OH · · · (1) (hydroxyl-containing group) are present.

Such a hydroxyl group-containing group (1) is generally 0.01 or more (may be 100%), preferably 1 in all side chain organic groups in the hydroxyl group-containing polysilsesquioxane. It is preferably present in an amount of -20%. In the general formula (1), R ¹ represents an alkylene group having about 1 to 10 carbon atoms, the alkylene group may have a substituent, and the heteroatoms O and S are each an ether bond, It may be contained as a thioether bond, and for example, a linear, branched, or cyclic alkylene group having about 1 to 10 carbon atoms, a thioether bond-containing alkylene group [eg: "-
_{C 3 H 6 -S-CH 2} CH (CH 3) - "two alkylene chain" -C ₃ via a thioether bond, such as
"H _6- " and "-CH ₂ CH (CH ₃ )-" are bound to each other], ether bond-containing alkylene group [Example: "-
_{C 3 H 6 -O-CH 2} CH (CH 3) - "things two alkylene chain via an ether bond is bonded], and the like, such as, preferably carbon atoms 2-8 Included to the extent are linear or branched alkylene groups.

R ² and R ³ are each independently a single bond, an alkylene group, a cycloalkylene group, a phenylene group, or a group consisting of any two or more of these groups (excluding a single bond) (eg: Aromatic hydrocarbon group-containing alkylene group,
For example _{-CH 2 - (p-C 6} H 4) -CH 2; cycloalkylene group containing chain alkylene group, for example -CH ₂ -
(1,4-C ₆ H ₁₀ )-), which may have a substituent, and may contain O or S as a hetero atom. Of such R ² and R ³ , it is preferable that both are groups other than a single bond, and further, they are each independently an alkylene group having about 1 to 10 carbon atoms or an alkylene group containing an aromatic hydrocarbon group. Preferably selected from

X ¹ and X ² are each independently a single bond,
Any one of an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond, an ether bond, and a carbonyl bond [-C (O)-], preferably both are groups other than a single bond, More preferably, each independently, a thioether bond (-S-, also called a sulfide bond), an ester bond (-COO- or -OC).
O-), urethane bond (-NH-COO- or -OC
O-NH-) is preferred.

In the hydroxyl group-containing group (1), R ¹ , R ² and R ³ each independently have 1 to 10 carbon atoms.
It is preferable that each of X ¹ and X ² is independently selected from a thioether bond and an ester bond, and specific examples thereof include the following.

Embedded image

Embedded image

Embedded image

The number average molecular weight of the hydroxyl group-containing polysilsesquioxane is not particularly limited, but is 500 to 10,000.
It is 0, preferably 1000 to 10000, has excellent solubility in a wide variety of solvents, can be easily mixed with paints containing various reaction-curable organic resins, and has water resistance and water repellency to coating films. It imparts excellent properties such as stain resistance. The compounding ratio of this hydroxyl group-containing polysilsesquioxane to the reaction-curable organic resin is 100
A range of 0.01 to 15 parts by weight, preferably a range of 0.05 to 10 parts by weight is blended with respect to parts by weight. If this amount is less than 0.01 part by weight, the water repellency effect cannot be obtained. On the other hand, even if it exceeds 15 parts by weight, no further increase in the water contact angle is recognized, and the performance of the base resin may be impaired, so it is preferable to avoid it.

The method for mixing the hydroxyl group-containing polysilsesquioxane into the organic coating composition is not particularly limited as long as it can be uniformly dissolved or dispersed in the organic coating composition, and the method is not particularly limited. Can be performed by a mixing method such as rotating mixing with a stirring blade and a motor. It is also possible to use a mixing method that applies a shearing force, such as a high-speed stirring / dispersing machine, a bead mill, or a ball mill.

In the organic coating composition thus obtained, when a functional group-containing organic resin having an active hydrogen such as a hydroxyl group and an amino group is used as a base resin, it reacts with the active hydrogen, for example, an amino resin, a poly Isocyanate compound,
1 reactive crosslinking agent such as blocked isocyanate compound
It can be used in combination of more than one species. Amino resin cross-linking agents include melamine, urea, benzoguanamine,
Examples thereof include a methylolated amino resin obtained by reacting an amino component such as acetoguanamine, steroganamin, spiroguanamine, dicyandiamide and the like with an aldehyde. Examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. Further, a product obtained by etherifying the methylolated amino resin with a suitable alcohol can also be used.
Examples of alcohols used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, 2-ethylbutanol, 2
-Ethylhexanol and the like. A conventional curing catalyst such as paratoluene sulfonic acid may be added during drying.

As the polyisocyanate resin crosslinking agent,
Hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, aliphatic such as lysine diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate and other cyclic aliphatic, tolylene diisocyanate, aromatic such as diphenylmethane diisocyanate Diisocyanate, and /
Alternatively, biuret-type, adduct-type, or isocyanurate-type polyisocyanates based on these diisocyanates can be used. As the blocked polyisocyanate resin crosslinking agent, a lactam-based blocking agent such as ε-caprolactam in the above polyisocyanate compound,
Examples thereof include those blocked with alcohol-based blocking agents such as butanol and cyclohexanol, phenol-based blocking agents such as phenol and cresol, and oxime-based blocking agents such as acetoxime. Further, an organic tin compound such as dibutyltin dilaurate may be added as a curing catalyst. The mixing ratio of the functional group-containing acrylic resin having active hydrogen such as a hydroxyl group and the cross-linking agent is such that the functional group of the cross-linking agent is 0.3 to 1.5 equivalents, preferably 0.8 with respect to the active hydrogen such as a hydroxyl group. A range of up to 1.2 equivalents is included. If the compounding amount is less than 0.3 equivalent, the solvent resistance and durability of the coating film are deteriorated, while if it is more than 1.5 equivalents, cracks and peeling are likely to occur in the coating film, and the durability tends to be deteriorated. Not preferable.

In the organic coating composition according to the present invention, if necessary, conventional coating materials such as known ultraviolet absorbers, light stabilizers, surface modifiers, leveling agents, defoamers, thickeners, pigment dispersants, etc. These additives can be used alone or in combination of two or more. Furthermore, known pigments and / or dyes may be appropriately added alone or in combination of two or more kinds to the organic coating composition as needed. These dispersions are not particularly limited as long as they are uniformly dissolved or dispersed in the organic coating composition, and can be carried out by a method used for dispersing a general coating pigment. For example, a kneader, a three-roll mill, a high speed stirring / dispersing machine, a bead mill, a ball mill and the like can be mentioned.

The organic solvent used in the organic coating composition of the present invention is substantially inert to the curable organic resin composition and capable of dissolving or dispersing these organic resin compositions, It can be appropriately selected and used from conventionally known materials. Specifically, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane and cyclohexane, esters such as ethyl acetate and n-butyl acetate,
Examples thereof include ethers such as cellosolve acetate, methyl cellosolve, dioxane, and ethylene glycol diethyl ether, and alcohols such as i-propanol and n-butanol. You may use these solvents in mixture of 2 or more types.

The method of coating the organic coating composition according to the present invention is arbitrary and can be appropriately selected from brush coating, bar coating, spray coating, roller coating, dip coating, electrostatic coating and the like. The coating thickness is not particularly limited, and an appropriate thickness may be selected depending on the application and the like. In the case of ordinary paint, it is about 5 to 500 μm. The drying method requires heating at 50 ° C. or higher in air for the purpose of segregating the hydroxyl group-containing polysilsesquioxane on the surface in order to impart sufficient water repellency to the coating film. Satisfying this condition, depending on the type of crosslinkable reactive group and curing agent,
Appropriate methods and conditions may be selected. Preferably, heat drying is performed at 70 to 230 ° C. for 1 minute to 3 hours. For example, in the case of melamine cross-linking with an amino resin cross-linking agent, or in the case of urethane cross-linking with a blocked polyisocyanate resin cross-linking agent, the treatment is performed at about 140 ° C. for about 30 minutes. In the case of urethane cross-linking with a polyisocyanate resin cross-linking agent, it is carried out at about 80 ° C for about 1 hour.

In the coating film thus obtained, the hydroxyl-containing polysilsesquioxane migrates to the surface of the coating film, and
Compounded so that the silicon content is 6% or more, preferably 10% or more when measured by a line photoelectron spectroscopy (hereinafter referred to as XPS) as a content of photoelectron escape angle of 15 °. It is necessary to perform heat drying. When the silicon content of the coating film surface is less than 6%, it is difficult to obtain a coating film having high water repellency.

The organic coating composition according to the present invention is used in civil engineering structures, buildings, vehicles, home appliances, electronic / electrical devices,
Can be painted on furniture etc. Such an organic coating composition,
Although it can be directly applied to the surface of a base material such as a civil engineering structure, it is generally applied to the surface of a base material that has been subjected to a base treatment with an intermediate coating material or an undercoat material. As the intermediate coating material and the undercoat material, fluororesin, urethane resin, acrylic resin, amino acrylic resin, epoxy resin, amino polyester resin, silicone alkyd resin, amino alkyd resin, silicone polyester resin, vinyl chloride resin, polyvinyl butyral resin, urea General-purpose paint resins such as melamine resin, polybutadiene resin, polyamide resin, and polyethylene resin can be used. Further, it can be applied to the surface of the base material which has been subjected to the surface treatment by the chemical conversion treatment. As the chemical conversion treatment, a general-purpose treatment such as a chromate treatment, a zinc phosphate treatment, an anodizing treatment on a metal base material or a silane coupling material treatment on another base material can be performed. For the metal base material, the above-mentioned intermediate coating material and undercoat material can be used in combination.

Examples of the material of the base material coated with the organic coating composition of the present invention include metals such as aluminum, copper and stainless steel, 6-nylon, ABS, polycarbonate, polyethylene, polypropylene, acrylic resin, polyurethane resin, Plastics such as melamine resin, PPO, PVC, polyester resin, phenol resin, wood materials such as various woods, particle boards, fiber boards, fibers such as paper and cloth, silica boards, slate boards, concrete, plaster, glass, etc. Various materials such as ceramics can be used.

[0025]

EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. (Measurement Method) Physical property values in Examples and Comparative Examples were measured according to the following methods. The molecular weight is measured by GPC (gel permeation chromatography) (in terms of polystyrene), and the number average molecular weight is Mn and the weight average molecular weight is Mw. For the viscosity, the viscosity at 20 ° C. is measured with a B type rotational viscometer. Regarding the contact angle, after the coating film is cured, about 0.03 cc of ion-exchanged water is dropped on the surface of the coating film, and the contact angle within 30 seconds immediately after that is measured. The surface silicon content is measured by XPS (photoelectron escape angle is 15 degrees). Fourier transform infrared spectroscopy (hereinafter referred to as FT-I) is used to determine the qualities of the mercapto group and the methacryl group.
Abbreviated as R) (mercapto group is 2560 cm ^-1
Absorption in the vicinity, and (meth) acrylic group is judged by the presence or absence of absorption of double bond near 1640 cm ^-1 ). The quantification of hydroxyl groups is measured by a nuclear magnetic resonance method (abbreviated as ¹ H-NMR).

[Synthesis of raw materials and the like] (Synthesis of polymer A) In a 2 liter flask equipped with a thermometer, a stirrer, and a reflux condenser, 322 g (3.2 mol) of methyl methacrylate and 102 g of 2-hydroxyethyl methacrylate were added. (0.78 mol), 86 g of a mixed solution (mixed monomer solution) of 6.1 g (0.03 mol) of 1-dodecanethiol and n-butyl acetate 400
g, 3.3 g of α-α'azobisisobutyronitrile
(0.02 mol) was charged, the temperature was raised to 80 ° C. under a nitrogen stream, and after 30 minutes, the rest of the mixed monomer solution shown above was added over 3 hours, and α-α′azobisisobutyronitrile was further added. 1.6 g (0.01 mol) of n-butyl acetate 3
The solution dissolved in 5 g was added over 15 minutes, the temperature was raised to 90 ° C., and the temperature was maintained for 3 hours to complete the polymerization. The obtained solution is referred to as a polymer A solution. Polymer A has Mn = 7500 and Mw = 13
000 and a viscosity of 20000 cps.

(Synthesis of polysilsesquioxane having mercapto group: polymer B) In a 300 cc flask equipped with a thermometer, a stirrer and a reflux condenser, 7.76 g (39.5) of 3-mercaptopropyltrimethoxysilane was placed.
mmol), 77.4 g of methyltriethoxysilane (4
34 mmol), phenyltrimethoxysilane 2.42
g (12.2 mmol) and pure water 26.3 g (1460)
(mmol) was added and the temperature of the solution was kept at 5 ° C while stirring under a nitrogen stream. 5 g of 10% hydrochloric acid aqueous solution was added dropwise with stirring over 30 minutes, and then the solution temperature was kept at 10 ° C. for 1 hour. Next, the temperature of the solution was raised to 70 ° C. and reacted for 3 hours, 19.1 g of hexamethyldisiloxane (77.5 mmol) was added, and stirring was continued at 70 ° C. for 3 hours. The solution temperature was lowered to 40 ° C., 5.5 g of a 5% potassium hydroxide methanol solution was added, and the mixture was allowed to stand at room temperature for 12 hours. After extracting the lower layer portion and adding 80 g of butyl acetate, the mixture was concentrated with stirring at 40 ° C. under a reduced pressure of 200 mmHg, 80 g of the liquid was distilled off, and 170 g of butyl acetate was further added at normal pressure to give 1 Stir for a period of time. The obtained solution was filtered and then concentrated under reduced pressure to obtain 38.9 g of a colorless transparent viscous liquid. The number average molecular weight of the obtained liquid (hereinafter referred to as polymer B) was 3300 as measured by GPC. IR spectrum and Raman spectrum were measured and found to be 2560
Absorption based on the mercapto group appeared near cm ^-1 .

(Synthesis of Polysilsesquioxane Having Hydroxyl Group: Polymer C) In a 200 cc flask equipped with a thermometer, a stirrer, and a reflux condenser, 40.0 g of polysilsesquioxane having a mercapto group (polymer) B) 5.48 g of 2-hydroxyethyl methacrylate, 80 g of toluene and 0.68 g of lauroyl peroxide were charged, and the solution temperature was kept at 50 ° C. with stirring under a nitrogen stream, and the reaction was carried out for 1 hour. The temperature was further raised, and stirring was continued at 60 ° C. for 1 hour and at 70 ° C. for 2 hours. After completion of the reaction, the mixture was cooled, the solvent was distilled off under reduced pressure, and further dried under reduced pressure for 8 hours to obtain 45.1 g of a viscous colorless transparent liquid (hereinafter referred to as polymer C). The number average molecular weight of this product was 3,500 when measured by GPC. IR
2 of the methacrylic group around 1640 cm ^-1 from the spectrum
It was confirmed that the absorption due to the heavy bond disappeared. The amount of hydroxyl group-containing side chains in this (polymer C) was determined by ¹ H-NMR.
When measured by, the content in all side chain groups was 8% on average.
Met.

(Synthesis of Polysilsesquioxane Having Hydroxyl Group: Polymer D) In a synthesis example of polymer C,
Instead of 2-hydroxyethyl methacrylate, 6.
45.8 g of a viscous liquid (hereinafter referred to as polymer D) was obtained by the same synthesis as in Polymer C except that 07 g of 4-hydroxybutyl acrylate was used. When the number average molecular weight of this polymer was measured by GPC,
3400. 1640 cm ^-1 from IR spectrum
It was confirmed that the absorption due to the double bond of the acrylic group in the vicinity disappeared. When the amount of hydroxyl group-containing side chains in this (Polymer D) was measured by ¹ H-NMR, the content in all side chain groups was 8% on average.

(Synthesis of Polysilsesquioxane Having Hydroxyl Group: Polymer E-2) 3-methacryloxypropyltrimethoxysilane 9 was added to a 300 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 2.8 g (39.5 mmol), methyltriethoxysilane 77.4 g (434 mmol), phenyltrimethoxysilane 2.42 g (12.2 mmol) and pure water 2
6.3 g (1460 mmol) was charged, and the temperature of the solution was kept at 5 ° C while stirring under a nitrogen stream. While stirring, 5 g of 10% hydrochloric acid aqueous solution was added dropwise over 30 minutes, and then the solution temperature was kept at 10 ° C. for 1 hour. Next, after raising the temperature of the solution to 70 ° C. and reacting for 3 hours, 19.1 g of hexamethyldisiloxane (77.5 mmol) was added,
Further, stirring was continued at 70 ° C. for 3 hours. The solution temperature was lowered to 40 ° C. and 5.5 g of a 5% methanol solution of potassium hydroxide was added.
After the addition, the mixture was left at room temperature for 12 hours. Remove the lower layer, add 80 g of butyl acetate and stir 40
After concentrating under a reduced pressure of 200 mmHg at 80 ° C and distilling off 80 g of liquid, 170 g of butyl acetate was further added at normal pressure.
It was added and stirred for 1 hour. The obtained solution was filtered and then concentrated under reduced pressure to obtain 38.0 g of a colorless transparent viscous liquid. This liquid (hereinafter referred to as polymer E-1)
It was 3200 when the number average molecular weight of was measured by GPC. From the result of IR spectrum measurement of the polymer, 16
Absorption due to the double bond of the methacryl group appeared near 40 cm ^-1 . Further, in a 200 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 38.0
g of the above “Polymer E-1”, 3.73 g of mercaptoethanol, 0.78 g of lauroyl peroxide and 41.7 g of toluene were charged, and the solution temperature was kept at 50 ° C. while stirring under a nitrogen stream, and 1 Reacted for hours.
The temperature was further raised, and stirring was continued at 60 ° C. for 1 hour and at 70 ° C. for 1 hour. After completion of the reaction, the mixture was cooled, the solvent was distilled off under reduced pressure, and further dried under reduced pressure for 8 hours to obtain 41.1 g of a viscous colorless transparent liquid (hereinafter referred to as polymer E-2). The number average molecular weight of this polymer was 3300 as measured by GPC. 1640 from IR spectrum
It was confirmed that the absorption due to the double bond of the methacrylic group near cm ⁻¹ disappeared, and the absorption due to the hydroxyl group around 3500 cm ⁻¹ appeared. When the amount of the hydroxyl group-containing side chain group of this “polymer E-2” was measured by ¹ H-NMR, it was 8% on average in all the side chain groups.

(Curing agent) Isocyanate (Sumijour N-3500: manufactured by Sumitomo Bayer Urethane Co., Ltd.) Blocked isocyanate (Desmodur BL-317)
5: Sumitomo Bayer Urethane Co., Ltd.) Isobutylated melamine (Uban 2061: Mitsui Toatsu Chemicals, Inc.) (Additive) UV absorber (Tinuvin 384: Ciba Geigy)
Light stabilizer (Tinuvin 123: Ciba Geigy Co., Ltd.) Titanium oxide (CR-50: Ishihara Sangyo Co., Ltd.)

Examples 1 to 3 44.4 g of Polymer A as a reaction-curable organic resin and propylene glycol monomethyl ether acetate (hereinafter referred to as PGM-) as a solvent.
It is called AC. ) 33.4 g, Polymer C as polysilsesquioxane, 0.0150 g as shown in Table 1.
(Example 1), 0.3000 g (Example 2) and 3.0
000 g (Example 3), N-3500 as a curing agent, 7.8 g, and dibutyltin dilaurate (hereinafter referred to as DBTDL) as a curing catalyst, 0.2 g of a 0.25 wt% n-butyl acetate solution was added to the coating composition. And spraying it onto a phosphoric acid-treated aluminum base material (A1050P) so that the dry coating film thickness becomes 30 μm.
It was heated and dried at 80 ° C. for 1 hour. The surface silicon content and water contact angle of the obtained coating film were measured. The results are shown in Table 1.

(Examples 4 to 5) The same as Example 2 except that Polymer D (Example 4) and Polymer E-2 (Example 5) were used in the same amount in place of Polymer C of polysilsesquioxane. Then, the surface silicon content and the water contact angle were measured. The results are shown in Table 1. Example 6 Polymer C as polysilsesquioxane
0.3629g, BL-3175 as a curing agent 1
4.1 g, heat dried at 70 ° C for 30 minutes, then 150 ° C
The coating film was measured in the same manner as in Example 2 except that the coating was performed for 30 minutes. The results are shown in Table 1.

(Example 7) Uban 206 as a curing agent
The coating film was measured in the same manner as in Example 6 except that 10.7 g of 1 and 0.2 g of paratoluenesulfonic acid were used as a curing catalyst. The results are shown in Table 1. (Example 8) T.
The coating film was measured in the same manner as in Example 2 except that 6 g and 0.3 g of tinuvin 123 as a light stabilizer were added to the coating composition of Example 2. The results are shown in Table 1.

Comparative Example 1 Example 1 except that 0.0015 g of polysilsesquioxane was used in Example 1.
The coating film was measured in the same manner as above, and the results are shown in Table 1. (Comparative Example 2) Instead of polymer C in Example 2, polydimethylsiloxane modified with carbinol at both ends (KF-
6002: The coating film was measured in the same manner as in Example 2 except that 0.3000 g of Shin-Etsu Chemical Co., Ltd. was used. The results are shown in Table 1. (Comparative Example 3) A coating film was measured in the same manner as in Example 2 except that the addition of polysilsesquioxane was omitted in Example 2. The results are shown in Table 1.

[0036]

[Table 1]

Example 9 A pigment (titanium oxide: CR-5) was used as a mill base in a 220 ml glass container.
0) 20.0 g, glass beads 48 mm in diameter 1 mmφ.
9 g, PGM-AC 150.0 g, polymer A 20.0 g as a reaction-curable organic resin, and polymer C 0.30 g as a polysilsesquioxane were charged, and dispersed for 1 hour with a paint shaker manufactured by Asada Iron Works Co., Ltd. .
Polymer A as a reaction-curable organic resin is added to this mill base.
24.4 g, PGM-AC 18.4 g, and a DBTDL 0.25 wt% solution 0.2 g as a curing catalyst agent were added, and the mixture was further dispersed for 1 hour with a paint shaker. 7.8 g of N-3500 was added and further mixed for 15 minutes with a paint shaker to obtain an organic coating composition. This coating composition was applied to a phosphoric acid-treated aluminum substrate in the same manner as in Example 1 to form a dry coating film.
The coating was sprayed so as to have a thickness of 0 μm, dried by heating at 80 ° C. for 1 hour, and the coating film was measured in the same manner as in Example 1. The obtained coating film did not change as a result even if a pigment or the like was added, the contact angle with water was 100 °, and the content of silicon on the surface was 15%.

[0038]

The organic coating composition containing the hydroxyl group-containing polysilsesquioxane according to the present invention has excellent compatibility between the coating and polysilsesquioxane, and is easy to handle as a coating. Not only does the coating give a uniform coating without bleeding, but the coating is simply heated and dried to cause polysilsesquioxane to segregate on its surface,
High water resistance, water repellency, chemical resistance, as seen from the contact angle with water,
It can be estimated that the coating film has unique properties such as abrasion resistance. Therefore, the organic coating composition of the present invention is a civil engineering structure, building, vehicle, home appliances, electronic and electrical equipment,
It is useful as a water-repellent and water-repellent top coat for furniture.

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Claims (5)

[Claims] 1. A coating material containing a reaction-curable organic resin as a resin component, comprising: a. The side chain organic group is at least one selected from an alkyl group, an aralkyl group, and a substituted or unsubstituted phenyl group.
One or more kinds of substituents and the following general formula (1) R ¹ —X ¹ —R ² —X ² —R ³ —OH (1) [wherein, R ¹ may have a substituent , An alkylene group which may contain O or S, R ² and R ³ are each independently a single bond, an alkylene group, a cycloalkylene group, a phenylene group or any two or more kinds of these groups excluding a single bond. Which may have a substituent or may contain O or S, and X ¹ and X ² each independently represent a single bond,
Indicates any one of an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond, an ether bond and a carbonyl bond. ] And a hydroxyl group-containing group, b. A coating composition comprising a polysilsesquioxane having a hydroxyl group, wherein the main chain terminal group is trialkylsilylated. 2. The coating composition according to claim 1, wherein an organic resin containing a functional group having active hydrogen and an amino resin crosslinking agent are used as the reaction-curable organic resin. 3. An organic resin containing a functional group having active hydrogen as the reaction-curable organic resin, and a polyisocyanate resin crosslinking agent or a blocked polyisocyanate resin crosslinking agent as the crosslinking agent. Coating composition. 4. The coating composition according to claim 1, wherein the hydroxyl group-containing polysilsesquioxane is blended so that the silicon content on the surface of the coating film is 6% or more. 5. The coating composition according to any one of claims 1 to 4 is applied and then dried by heating in air at a temperature of 50 ° C. or higher and lower than 300 ° C. to apply a hydroxyl group-containing polysilsesquioxa. A coating film characterized by being segregated on the film surface.