Coating composition

Abstract

To provide a coating material composition that has high transparency, can be easily applied because of low viscosity, has high water resistance of coating material after drying, and can impart excellent wettability.SOLUTION: A coating material composition consists of component (A) by 10 to 50 mass%, component (B) by 10 to 60 mass%, and component (C) by 20 to 80 mass%. (A) polyoxyalkylene-modified silicone made of a reactant of alkenyl group-containing polyoxyalkylene derivative and hydrogen organopolysiloxane; (B) resin selected from the group consisting of urethane resin, acryl resin, amide resin, phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, polyimide resin, polyalkylene resin, polyvinylchloride resin, polystyrene resin, polyvinyl acetate resin and alloy of the resins; and (C) solvent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a paint composition that has high transparency, is easy to apply due to its low viscosity, has high water resistance of the paint after drying, and can impart excellent wettability.

Background Art

[0002] As a coating with a paint applied to the surface of an exterior material or the like, when rainwater or the like adheres during rainfall or the like, it spreads on the surface of the film so that the attached dirt or the like flows down, and the surface is made hydrophilic to impart an anti-pollution effect against environmental pollution (Patent Document 1).

[0003] On the other hand, in recent years, coatings with paints have been made for various applications for the purpose of preventing dirt, ranging from electrical appliances such as mobile phones, personal computers, televisions, plasma displays, transportation equipment such as automobiles and trains, to various daily goods. As paints with excellent dirt-preventing properties, generally, compositions using additives containing fluorine in the molecule (Patent Document 2) and additives containing polyether-modified silicone that impart even more excellent dirt-preventing performance such as surface leveling properties and defoaming properties are known (Patent Document 3), but in any of the additives, the paint composition has high water resistance.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in all prior art applications, while high water resistance was achieved, excellent wettability was sometimes not sufficiently attained. Conversely, improving the wettability of the paint composition may compromise its water resistance, thus requiring a balance between excellent water resistance and sufficient wettability.

[0006] The object of the present invention is to provide a coating composition that has high transparency, is easy to apply due to its low viscosity, has high water resistance after drying, and can also provide excellent wettability. [Means for solving the problem]

[0007] Therefore, after diligent research, the inventors have found that by the following combination, the present invention can provide a paint composition that has high transparency, is easy to apply due to its low viscosity, has high water resistance after drying, and has excellent wettability.

[0008] In other words, the inventors, after diligently studying the matter in view of the above, have found that the above problems can be solved by a composition in which (A) polyether-modified silicone, (B) resin, and (C) solvent are combined in a specific ratio.

[0009] In other words, the present invention is as follows: The following component (A) 15 ~50% by mass, component (B) 10~60% by mass, and component (C) 20~ 75 A paint composition characterized by comprising mass%. (A) M expressed by equation (1) and calculated from the chromatogram obtained by gel permeation chromatography measurement. H and M L Alkenyl group-containing polyoxyalkylene derivatives that satisfy the relationship in formula (2) The alkenyl group-containing polyoxyalkylene derivative is obtained by ring-opening addition polymerization of a carbon-2 to carbon-3 alkylene oxide with a moisture content of 0.01 wt% or less to a starting material with a moisture content of 0.5 wt% or less, in the presence of a complex metal cyanide catalyst, at 50°C to 120°C. When the rate during which 5 wt% to 20 wt% of the total supply of alkylene oxide is supplied is V1, the rate during which 20 wt% to 50 wt% of the total supply of alkylene oxide is supplied is V2, and the rate during which 50 wt% to 100 wt% of the total supply of alkylene oxide is supplied is V3, then the polyoxyalkylene derivative has V1 / V2 = 1.1 to 2.0 and V2 / V3 = 1.1 to 1.5. Polyoxyalkylene-modified silicone, which consists of a reaction product with a hydrogen organopolysiloxane represented by formula (3). R 1 O-(AO 1 )a -[(AO 2 ) b / (EO) c -R 2 ···(1) (In formula (1), R 1 represents an alkenyl group having 3 carbon atoms, [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ [ka] (In formula (3), d is between 1 and 1000. e is between 0 and 100. e / d is between 0 and 1. R 3 It is a hydrocarbon group having 1 carbon atom, R 4 and R 5 Each of these is independently a hydrogen atom or a hydrocarbon group with 1 carbon atom, and in the case of e=0, R 4 and R 5 At least one of them is a hydrogen atom. (B) Acrylic resin (C) Selected from acetone or ethyl acetate solvent [Effects of the Invention]

[0010] According to the present invention, a paint composition can be obtained that has high transparency, is easy to apply due to its low viscosity, has high water resistance after drying, and has good wettability. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 is a model chromatogram diagram illustrating the ML / MH ratio as defined in this invention. [Modes for carrying out the invention]

[0012] The paint composition of the present invention is composed of the following specific components (A), (B), and (C).

[0013] <Component (A): Polyoxyalkylene-modified silicone> One of the features of this invention is the use of a specific polyoxyalkylene-modified silicone as component (A). The polyoxyalkylene-modified silicone according to the present invention consists of a reaction product of a polyoxyalkylene derivative represented by formula (1) and a hydrogen organopolysiloxane represented by formula (3).

[0014] In equation (1), a (>0) is an oxyalkylene group AO having 3 to 4 carbon atoms. 1 This shows the average number of moles added, where b(≧0) is an oxyalkylene group AO with 3-4 carbon atoms. 2 The average number of moles added is shown, and c (>0) is shown, where c represents the average number of moles added of oxyethylene groups EO. The sum of a, b, and c should be 10 or more from the viewpoint of wettability, more preferably 15 or more, and particularly preferably 20 or more. Furthermore, if the sum of a, b, and c exceeds 100, the viscosity will increase, which may adversely affect the production of polyoxyalkylene-modified silicone, so it should be 100 or less, more preferably 80 or less, more preferably 60 or less, and particularly preferably 50 or less.

[0015] Furthermore, while a is not particularly limited as long as a+b+c=10 to 100, it is preferably 1 or greater, and more preferably 3 or greater. Also, a is preferably 80 or less, and more preferably 20 or less. Furthermore, while b is not particularly limited as long as a+b+c=10 to 100, it is preferably 1 or greater, and more preferably 3 or greater. Also, b is preferably 80 or less, and more preferably 20 or less. Furthermore, while c is not particularly limited as long as a+b+c=10 to 100, it is preferably 3 or greater, and more preferably 5 or greater. Also, c is preferably 80 or less, and more preferably 40 or less.

[0016] Furthermore, while b+c is not particularly limited as long as a+b+c=10 to 100, it is preferably 5 or greater, and more preferably 10 or greater. b+c is preferably 80 or less, and more preferably 60 or less.

[0017] The ratio of b to c is not particularly limited, but b / c = 0.1 to 5 is preferred, 0.15 to 3 is more preferred, 0.2 to 2 is even more preferred, and 0.2 to 1 is particularly preferred.

[0018] In equation (1), R 1 R is an alkenyl group with 2 to 8 carbon atoms. 1 The number of carbon atoms is more preferably 3 or more, and more preferably 5 or less. From the viewpoint of the productivity of the silicone modifier, allyl groups and methallyl groups are even more preferred.

[0019] In equation (1), R 2 R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of the productivity of silicone modifiers, 2 Hydrogen atoms and methyl groups are preferred, and hydrogen atoms are more preferred.

[0020] The polyoxyalkylene derivatives of the present invention are defined by a chromatogram obtained using a differential refractometer in gel permeation chromatography (GPC). This chromatogram is a graph that shows the relationship between refractive index intensity and elution time. In the polyoxyalkylene derivatives of the present invention, the chromatogram is asymmetrical and satisfies the relationship given by equation (2). L / M H The closer the value is to 1, the more symmetrical the chromatogram becomes. 0.20 ≤ M L / M H ≤0.60 ····(2)

[0021] Here, Figure 1 is a model diagram of a chromatogram obtained by gel permeation chromatography of a polyoxyalkylene derivative, where the horizontal axis represents the elution time and the vertical axis represents the refractive index intensity obtained using a differential refractometer.

[0022] When a sample solution is injected into a gel permeation chromatograph and developed, elution begins with the molecules with the highest molecular weight, and the elution curve rises as the refractive index strength increases. After passing the maximum point K where the refractive index strength is highest, the elution curve begins to decline.

[0023] Furthermore, in gel permeation chromatography of the polyoxyalkylene derivative of the present invention, if there are multiple maximum points of refractive index intensity in the chromatogram, the point with the highest refractive index intensity among them is designated as maximum point K. If there are multiple maximum points with the same refractive index intensity, the point with the later elution time is designated as maximum point K. In this case, peaks caused by the developing solvent used in gel permeation chromatography, and false peaks caused by baseline fluctuations due to the column or equipment used are excluded.

[0024] M L / M H These are calculated from the chromatogram as follows: (1) Draw a perpendicular line from the point of maximum refractive index intensity K on the chromatogram to the baseline B, and let the length of the perpendicular line be L. (2) Of the two points on the chromatogram where the refractive index intensity is L / 20, the point with the earlier elution time is designated as point O, and the point with the later elution time is designated as point Q. (3) Let P be the intersection of the line G connecting point O and point Q and the perpendicular line drawn from the point K, where the refractive index intensity is maximum, to the baseline B. (4) The distance between point O and intersection point P is M. H The distance between intersection point P and point Q is M. L Let's assume that.

[0025] The polyoxyalkylene derivative of the present invention is M L / M H 0.20 ≤ M L / M H It satisfies ≤0.60. M L / M H When M exceeds 0.60, the distribution of the polyoxyalkylene chain structure in the polyoxyalkylene-modified silicone becomes smaller, reducing the transparency of the appearance, increasing viscosity, and worsening wettability. From this perspective, L / M H It should be 0.60 or less, but it is even more preferable to make it 0.50 or less.

[0026] Also, M L / M HAs the value decreases, the bias towards higher molecular weights in the molecular weight distribution increases, leading to a rise in viscosity and other related issues. L / M H If the ratio becomes less than 0.20, the viscosity becomes too high, which is undesirable as it negatively impacts the production of polyoxyalkylene-modified silicone. From this perspective, M L / M H The value should be 0.20 or higher, but it is even more preferable to set it to 0.25 or higher.

[0027] In the present invention, M L and M H To determine the reaction, gel permeation chromatography (GPC) is performed using a SHODEX® GPC101 GPC-dedicated system, a SHODEX RI-71s differential refractometer, a SHODEX KF-G guard column, and three SHODEX KF804L columns mounted in sequence. The column temperature is 40°C, and tetrahydrofuran is flowed at a rate of 1 ml / min as the developing solvent. 0.1 ml of a 0.1 wt% tetrahydrofuran solution of the resulting reaction is injected, and a chromatogram representing refractive index intensity and elution time is obtained using the BORWIN GPC calculation program.

[0028] The polyoxyalkylene derivatives of the present invention are produced by ring-opening addition of a C3-C4 alkylene oxide in the presence of a composite metal cyanide catalyst (hereinafter abbreviated as DMC catalyst), or by further ring-opening addition of a C3-C4 alkylene oxide and ethylene oxide thereafter.

[0029] In the production of polyoxyalkylene derivatives, preferably, an initiator having an alkenyl group with 2 to 8 carbon atoms and one hydroxyl group in its molecule, and a DMC catalyst are added to a reaction vessel, and an alkylene oxide with 3 to 4 carbon atoms is added continuously or intermittently under stirring in an inert gas atmosphere to carry out addition polymerization. The alkylene oxide with 3 to 4 carbon atoms may be added under pressure or under atmospheric pressure.

[0030] Furthermore, the reaction temperature is preferably 50°C to 150°C, and more preferably 80°C to 120°C. If the reaction temperature is higher than 150°C, the catalyst may become inactive. If the reaction temperature is lower than 50°C, the reaction rate will be slow and productivity will be low. There are no particular restrictions on the trace amounts of water contained in the initiator and alkylene oxide, but it is desirable that the amount of water in the initiator be 0.5 wt% or less, and that the amount of water in the alkylene oxide be 0.01 wt% or less.

[0031] The amount of DMC catalyst used is not particularly limited, but preferably 0.0001 to 0.1 wt%, and more preferably 0.001 to 0.05 wt%, relative to the polyoxyalkylene derivative produced. The DMC catalyst may be introduced into the reaction system all at once at the beginning, or it may be introduced sequentially in portions. After the polymerization reaction is complete, the composite metal complex catalyst is removed. Catalyst removal can be carried out by known methods such as filtration, centrifugation, or treatment with synthetic adsorbents.

[0032] A known DMC catalyst can be used, but it can be represented, for example, by formula (4). M f [M' x (CN) y ] g (H2O) h ·(R 6 ) i ...(4) In equation (4), M and M' are metals, R 6 is an organic ligand, f, g, x, and y are positive integers that vary depending on the valence and coordination number of the metal, and h and i are positive integers that vary depending on the coordination number of the metal.

[0033] Examples of metal M include Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV), and W(VI), with Zn(II) being the most preferred choice.

[0034] Examples of metal M' include Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ni(II), V(IV), and V(V), with Fe(II), Fe(III), Co(II), and Co(III) being particularly preferred.

[0035] organic ligand R 6 Suitable ligands include alcohols, ethers, ketones, and esters, with alcohols being more preferred. Preferred organic ligands are water-soluble, and specific examples include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, N,N-dimethylacetamide, ethylene glycol dimethyl ether (glyme), and diethylene glycol dimethyl ether (diglyme). Particularly preferred is Zn3[Co(CN)6]2 coordinated with tert-butyl alcohol.

[0036] Polyoxyalkylene derivatives produced using a DMC catalyst can be used to produce silicone modifiers having an alkyl group with 1 to 4 carbon atoms at the end, represented by formula (1), by a Williamson etherification reaction with an organic halide in the presence of a base. Specific examples of bases used in the etherification reaction include sodium hydroxide, potassium hydroxide, sodium hydride, and potassium carbonate. Organic halides are compounds in which an alkyl group with 1 to 4 carbon atoms is bonded to a halogen atom. Specific examples include methyl chloride and butyl chloride.

[0037] Furthermore, in the production of polyoxyalkylene derivatives, the addition polymerization of alkylene oxide may be carried out first using an initiator having an alkyl group with 1 to 4 carbon atoms and one hydroxyl group in the molecule, and a DMC catalyst. In this case, after the addition polymerization of alkylene oxide, a Williamson etherification reaction can be carried out in the presence of a base with a compound in which an alkenyl group with 3 to 5 carbon atoms and a halogen atom is bonded, to produce a silicone modifier having an alkyl group with 1 to 4 carbon atoms at the terminal end, represented by formula (1). Specific examples of organic halides include allyl chloride, allyl iodide, methallyl chloride, and allyl bromide. There is no limit to the average supply rate of alkylene oxide, but it is desirable to vary it depending on the amount of alkylene oxide being charged. Specifically, when V1 is the rate (amount supplied per unit time) when supplying 5 wt% to 20 wt% of the total supply of alkylene oxide, V2 is the rate when supplying 20 wt% to 50 wt% of the total supply of alkylene oxide, and V3 is the rate when supplying 50 wt% to 100 wt% of the total supply of alkylene oxide, it is preferable to control the average supply rate of alkylene oxide so that V1 / V2 = 1.1 to 2.0 and V2 / V3 = 1.1 to 1.5.

[0038] (Hydrogen organopolysiloxane) In formula (3), d is between 1 and 1000, and e is between 0 and 100. From the viewpoint of wettability, d should be 1000 or less, preferably 900 or less, and more preferably 800 or less. From the viewpoint of water resistance, d should be 1 or more, preferably 10 or more, and more preferably 50 or more. Also, from the viewpoint of transparency of appearance, e should be 100 or less, preferably 80 or less, and more preferably 60 or less. From the viewpoint of viscosity, e should be 0 or more, preferably 1 or more, and more preferably 3 or more. From the viewpoint of wettability and water resistance of the paint after drying, e / d should be 1 or less, preferably 0.4 or less, and more preferably 0.2 or less.

[0039] R 3This represents a hydrocarbon group having 1 to 8 carbon atoms. Examples of such hydrocarbon groups include alkyl groups, cycloalkyl groups, and alkenyl groups, but alkyl groups are preferred. Specific compound names include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, and octyl group, with methyl group being particularly preferred.

[0040] R 4 and R 5 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms. Examples of such hydrocarbon groups include alkyl groups, cycloalkyl groups, and alkenyl groups, but alkyl groups are preferred. Specific compound names include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, etc., with methyl group being preferred. When c=0, R 4 or R 5 At least one of them is a hydrogen atom.

[0041] When the total amount of components (A), (B), and (C) is 100% by mass, from the viewpoint of the present invention, the mass of component (A) is set to 10 to 50% by mass. From the viewpoint of wettability and water resistance, it is preferable that the mass of component (A) be 12% by mass or more, and more preferably 15% by mass or more. Furthermore, it is preferable that the mass of component (A) be 45% by mass or less, and more preferably 40% by mass or less.

[0042] <Ingredient (B)> One of the features of this invention is that it uses the following resin as component (B). The component is selected from the group consisting of urethane resin, acrylic resin, amide resin, phenolic resin, epoxy resin, melamine resin, urea resin, alkyd resin, polyimide resin, polyalkylene resin, polyvinyl chloride, polystyrene, polyvinyl acetate, and alloys of these resins. From the viewpoint of compatibility with polyether-modified silicone, which is component (A), acrylic resin or urethane resin is preferred.

[0043] When the total amount of components (A), (B), and (C) is 100% by mass, from the viewpoint of the present invention, the mass of component (B) is 10 to 60% by mass, but from the viewpoint of transparency of appearance and viscosity, 12 to 50% by mass is preferred, and 15 to 45% by mass is more preferred.

[0044] <Ingredient (C)> One of the features of this invention is the use of a solvent as component (C). The solvent is not particularly limited, but examples include water, alcohol, ester, aliphatic hydrocarbon, aromatic hydrocarbon, and ketone. Water, acetone, ethyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, propylene glycol monomethyl ether acetate, butyl acetate methyl ethyl ketone, and methyl isobutyl ketone are preferred, and water, acetone, ethyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, and dipropylene glycol ethyl ether are particularly preferred.

[0045] When the total amount of components (A), (B), and (C) is 100% by mass, the ratio of component (C) is 20 to 80% by mass, but from the viewpoint of transparency of appearance and viscosity, it is preferably 25 to 75% by mass, and more preferably 30 to 70% by mass.

[0046] (Other additives) Furthermore, the paint composition of the present invention may optionally contain other components well known in the industry, such as curing agents, diluents, ultraviolet absorbers, polymerization initiators, polymerization inhibitors, neutralizing agents, stabilizers (light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers), antioxidants, leveling agents, defoamers, viscosity modifiers, anti-settling agents, pigments, dyes, dispersants, antistatic agents, anti-fogging agents, and rubbers. [Examples]

[0047] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The amounts in the examples are in "mass%".

[0048] (Synthesis Example 1: Synthesis of Complex Metal Cyanide (DMC) Catalysts) To a 2.0 ml aqueous solution containing 2.1 g of zinc chloride, a 15 ml aqueous solution containing 0.84 g of potassium hexacyanocobaltate K3Co(CN)6 was added dropwise over 15 minutes at 40°C while stirring. After the addition was complete, 16 ml of water and 16 g of tert-butyl alcohol were added, and the temperature was raised to 70°C and stirred for 1 hour. After cooling to room temperature, filtration (first filtration) was performed to obtain a solid. To this solid, 14 ml of water and 8.0 g of tert-butyl alcohol were added, and after stirring for 30 minutes, filtration (second filtration) was performed to obtain a solid.

[0049] Furthermore, 18.6 g of tert-butyl alcohol and 1.2 g of methanol were added to this solid again, and after stirring for 30 minutes, a filtration procedure (third filtration) was performed. The resulting solid was dried at 40°C under reduced pressure for 3 hours to obtain 0.7 g of DMC catalyst.

[0050] (Synthesis Example 2: Synthesis of Polyoxyalkylene Derivative 1) 700g of allyl alcohol (Showa Denko) and 7g of sodium methylate (Nippon Soda) were charged into a 5-liter autoclave equipped with a stirrer, nitrogen inlet tube, and thermocouple. After purging with nitrogen, the temperature was raised to 100°C, and 2150g of propylene oxide was charged over 20 hours under conditions of 0.5 MPa or less. The remaining propylene oxide was removed by reducing the pressure at 75-85°C and -0.097 MPa (gauge pressure) for 1 hour. After neutralization with hydrochloric acid, water was removed at 80°C under nitrogen bubbling. Then, 14 g each of Kyoward #300 and #700 (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and adsorption treatment was carried out at 80°C at -0.097 MPa (gauge pressure) or less under nitrogen bubbling for 1 hour. By filtration, 2360 g of tripropylene glycol allyl ether (degree of unsaturation: 4.11 meq / g, Mn: 240) was obtained.

[0051] 200 g of tripropylene glycol allyl ether and 0.15 g of the complex metal cyanide catalyst obtained in Synthesis Example 1 were charged into a 5-liter autoclave equipped with a stirrer, nitrogen inlet tube, and thermocouple. After nitrogen purging, the temperature was raised to 120°C, and 50 g of propylene oxide was added over 1 hour under conditions of 0.3 MPa or less. During this time, the changes in pressure and temperature inside the reaction vessel were measured over time. After 5 hours, the pressure inside the reaction vessel decreased rapidly. Thereafter, while maintaining the temperature inside the reaction vessel at 120°C, 780 g of propylene oxide and 750 g of ethylene oxide were gradually added under conditions of 0.6 MPa or less, and the addition was carried out under continuous pressurization over 13 hours with stirring. After vacuum treatment at 75-85°C and -0.097 MPa (gauge pressure) for 1 hour, filtration was performed to obtain 1700 g of polyoxyalkylene compound 1 (degree of unsaturation: 0.50 meq / g, Mn: 2,080). Furthermore, M can be obtained from the chromatogram obtained by gel permeation chromatography. L / M H The result was 0.28.

[0052] (Synthesis Example 3: Synthesis of Polyoxyalkylene Derivative 2) 200 g of tripropylene glycol allyl ether obtained in Synthesis Example 2 and 0.13 g of the complex metal cyanide catalyst obtained in Synthesis Example 1 were charged into a 5-liter autoclave equipped with a stirrer, nitrogen inlet tube, and thermocouple. After nitrogen purging, the temperature was raised to 120°C, and 50 g of propylene oxide was added over 1 hour under conditions of 0.3 MPa or less. During this time, the changes in pressure and temperature inside the reaction vessel were measured over time. After 3 hours, the pressure inside the reaction vessel decreased rapidly. Thereafter, while maintaining the temperature inside the reaction vessel at 120°C, 520 g of propylene oxide and 550 g of ethylene oxide were gradually added under conditions of 0.6 MPa or less, and the addition was continuously pressurized over 13 hours under stirring. After being subjected to reduced pressure treatment at 75-85°C and -0.097 MPa (gauge pressure) for 1 hour, filtration was performed to obtain 1710 g of polyoxyalkylene derivative 2 (degree of unsaturation: 0.67 meq / g, Mn: 1,490). Furthermore, M can be obtained from the chromatogram obtained by gel permeation chromatography. L / MH The result was 0.30.

[0053] (Synthesis Example 4: Synthesis of Polyoxyalkylene Derivative 3) 200 g of tripropylene glycol allyl ether obtained in Synthesis Example 2 and 0.16 g of the complex metal cyanide catalyst obtained in Synthesis Example 1 were charged into a 5-liter autoclave equipped with a stirrer, nitrogen inlet tube, and thermocouple. After nitrogen purging, the temperature was raised to 120°C, and 50 g of propylene oxide was added over 1 hour under conditions of 0.3 MPa or less. During this time, the changes in pressure and temperature inside the reaction vessel were measured over time. After 5 hours, the pressure inside the reaction vessel decreased rapidly. Thereafter, while maintaining the temperature inside the reaction vessel at 120°C, 570 g of propylene oxide and 790 g of ethylene oxide were gradually added under conditions of 0.6 MPa or less, and the addition was continuously pressurized over 13 hours under stirring. After being subjected to reduced pressure treatment at 75-85°C and -0.097 MPa (gauge pressure) for 1 hour, the mixture was filtered to obtain 1730 g of polyoxyalkylene derivative 3 (degree of unsaturation: 0.55 meq / g, Mn: 1,820). Furthermore, M can be obtained from the chromatogram obtained by gel permeation chromatography. L / M H The result was 0.42.

[0054] (Synthesis Example 5: Synthesis of Polyoxyalkylene Derivative 4) 80g of allyl alcohol and 4g of sodium methylate were charged into a 5-liter autoclave equipped with a stirrer, nitrogen inlet tube, and thermocouple. After nitrogen purging, the temperature was raised to 100°C, and 320g of propylene oxide was charged over 5 hours under conditions of 0.3 MPa or less. Subsequently, while maintaining the reaction vessel temperature at 100°C, 1400g of propylene oxide and 1340g of ethylene oxide were gradually charged over 45 hours under conditions of 0.5 MPa or less. The remaining propylene oxide and ethylene oxide were removed by reducing the pressure at 75-85°C and -0.097 MPa (gauge pressure) for 1 hour. After neutralization with hydrochloric acid, water was removed at 80°C under nitrogen bubbling. 3.2 g each of Kyoward #300 and #700 were added, and adsorption treatment was carried out at 80°C at -0.097 MPa (gauge pressure) or less under nitrogen bubbling for 2 hours. By filtration, 3130 g of polyoxyalkylene derivative 4 (degree of unsaturation: 0.42 meq / g, Mn: 2,050) was obtained. Furthermore, M can be obtained from the chromatogram obtained by gel permeation chromatography. L / M H The result was 1.06.

[0055] (Synthesis Example 6: Synthesis of polyoxyalkylene-modified silicone (A-1)) A 300 ml four-necked flask equipped with a stirrer, nitrogen inlet tube, thermocouple, and condenser was charged with polyoxyalkylene derivative 1 (100 parts by mass, unsaturated equivalent: 0.50 meq / g) synthesized in Synthesis Example 2 and hydrogen dimethylpolysiloxane (20 parts by mass, HMS-013 (Gelest), SiH equivalent per g: 0.10 eq / g, d=702, e=5). An isopropyl alcohol solution of hexahydrate chloroplatinic acid (1 × 10⁻³ mol / liter) was added as a catalyst to a concentration of 50 ppm in terms of platinum, and the reaction was carried out at 90°C with stirring under a nitrogen atmosphere. After sampling, an isopropyl alcohol solution of N / 10 potassium hydroxide was added and the reaction was continued until no more hydrogen gas was generated. FT-IR measurement revealed a concentration of 2100-2300 cm⁻¹ derived from the SiH group. -1After confirming that the absorption had disappeared, polyoxyalkylene-modified silicone (A-1) was obtained.

[0056] (Synthesis Example 7: Synthesis of polyoxyalkylene-modified silicone (A-2)) Polyoxyalkylene derivative 2 (20 parts by mass, unsaturated equivalent: 0.68 meq / g) synthesized in Synthesis Example 3 and hydrogen dimethylpolysiloxane (135 parts by mass, HMS-013 (manufactured by Gelest), SiH equivalent per gram: 0.10 meq / g, d=702, e=5) were charged, and the procedure was carried out in the same manner as in Synthesis Example 7 to obtain polyoxyalkylene-modified silicone (A-2).

[0057] (Synthesis Example 8: Synthesis of polyoxyalkylene-modified silicone (A-3)) Polyoxyalkylene derivative 3 (20 parts by mass, unsaturated equivalent: 0.55 meq / g) synthesized in Synthesis Example 4 and hydrogen dimethylpolysiloxane (109 parts by mass, HMS-013 (manufactured by Gelest), SiH equivalent per gram: 0.10 meq / g, d=702, e=5) were charged, and the procedure was carried out in the same manner as in Synthesis Example 7 to obtain polyoxyalkylene-modified silicone (A-3).

[0058] (Synthesis Example 9: Synthesis of polyoxyalkylene-modified silicone (A-4)) Polyoxyalkylene derivative 1 (20 parts by mass, unsaturated equivalent: 0.50 meq / g) synthesized in Synthesis Example 2 and hydrogen dimethylpolysiloxane (100 parts by mass, HMS-082 (manufactured by Gelest), SiH equivalent per gram: 1.06 meq / g, d=73, e=6) were charged, and the procedure was carried out in the same manner as in Synthesis Example 7 to obtain polyoxyalkylene-modified silicone (A-4).

[0059] (Synthesis Example 10: Synthesis of polyoxyalkylene-modified silicone (A'-1)) Polyoxyalkylene derivative 4 (20 parts by mass, unsaturated equivalent: 0.42 meq / g) synthesized in Synthesis Example 5 and hydrogen dimethylpolysiloxane (83 parts by mass, HMS-013 (manufactured by Gelest), SiH equivalent per gram: 0.10 meq / g, d=702, e=5) were charged, and the procedure was carried out in the same manner as in Synthesis Example 7 to obtain polyoxyalkylene-modified silicone (A'-1).

[0060] Table 1 shows the polyoxyalkylene derivatives produced in Synthesis Examples 2-5.

[0061] [Table 1]

[0062] (Synthesis Example 11: Synthesis of Acrylic Resin (B)) A 300 ml four-necked flask equipped with a stirrer, nitrogen inlet tube, thermocouple, and condenser was charged with butyl acrylate (57 parts by mass), 2-hydroxyethyl acrylate (3 parts by mass), ethyl acetate (110 parts by mass) as a solvent, and 2,2'-azobisisobutylnitrile (0.12 parts by mass) as a polymerization initiator. The contents were then heated to 70°C while introducing nitrogen gas. The polymerization reaction was then carried out at 70°C for 8 hours to produce acrylic resin (B) (solids content 35%).

[0063] <Examples 1-6> Paint compositions were prepared using the manufacturing methods described below, based on the compositions listed in Table 2. Compatibility and viscosity were then evaluated. Subsequently, the compositions were coated onto a glass substrate using an applicator to a thickness of 30 μm, and a coating layer was formed by heating at 80°C for 120 minutes. The resulting coating layers were evaluated for water resistance and wettability, and the results are shown in Table 2.

[0064] <Comparative Example 1-3> Paint compositions were prepared using the composition shown in Table 3 and the manufacturing method described below. Compatibility and viscosity were then evaluated. Subsequently, the compositions were coated onto a glass substrate using an applicator to a thickness of 30 μm, and a coating layer was formed by heating at 80°C for 120 minutes. The water resistance and wettability of the resulting coating layer were evaluated, and the results are shown in Table 3.

[0065] <Manufacturing method> Components (A), (B), and (C) were measured out into 50 ml glass screw-top tubes and mixed using a rotary-rotating agitator (2000 rpm, 2 minutes) to obtain a paint composition.

[0066] <Exterior> The paint composition was prepared and observed after being left to stand at room temperature (20°C) for 10 minutes. ◎: Transparent 〇: Slightly cloudy △: Cloudiness or separation

[0067] <Viscosity> The viscosity (Pa·s) of the paint composition was measured in flow mode using a dynamic viscoelasticity analyzer (Paar Physica MCR-300, manufactured by Anton Paar) at a temperature of 20°C and a shear rate of 1 (1 / s).

[0068] <Water resistance> The coating layer obtained on the glass substrate was rinsed with running water for 10 seconds, and the condition of the coating layer was visually inspected. ◎: No change ○: Partial peeling △: Completely detached

[0069] <Wettability> Using a contact angle meter (DropMaster500, manufactured by Kyowa Interface Science Co., Ltd.), 0.3 μL of water was dropped onto the coating layer, and the contact angle (°) was measured at room temperature of 20°C.

[0070] [Table 2]

[0071] [Table 3]

[0072] The paint compositions of Examples 1 to 6, which conform to the composition of the present invention, exhibited high transparency in appearance, low viscosity, high water resistance of the coating layer, and high wettability.

[0073] In Comparative Example 1, the paint composition did not contain component (A) and contained component (A') outside the present invention, resulting in high viscosity and inferior appearance, water resistance, and wettability. In Comparative Example 2, the low content of component (A) resulted in high viscosity and poor water resistance and wettability. In Comparative Example 3, the appearance was inferior due to the high content of component (A).

Claims

[Claim 1] A paint composition characterized by comprising 15 to 50% by mass of component (A), 10 to 60% by mass of component (B), and 20 to 75% by mass of component (C). (A) M, which is expressed by equation (1) and calculated from the chromatogram obtained by gel permeation chromatography. Ｈ and M Ｌ A polyoxyalkylene derivative containing an alkenyl group that satisfies the relationship of formula (2), wherein the alkenyl group-containing polyoxyalkylene derivative is obtained by ring-opening addition polymerization of a C2-C3 alkylene oxide with a moisture content of 0.01 wt% or less to a starting material with a moisture content of 0.5 wt% or less in the presence of a composite metal cyanide catalyst at 50°C to 120°C, where V1 is the rate during which 5 wt% to 20 wt% of the total supply of alkylene oxide is supplied, V2 is the rate during which 20 wt% to 50 wt% of the total supply of alkylene oxide is supplied, and V3 is the rate during which 50 wt% to 100 wt% of the total supply of alkylene oxide is supplied, and the polyoxyalkylene derivative having V1 / V2 = 1.1 to 2.0 and V2 / V3 = 1.1 to 1.5 is reacted with a hydrogen organopolysiloxane represented by formula (3), resulting in a polyoxyalkylene-modified silicone. R １ O-(AO １ ) ａ - {AO} ２ ) ｂ / (EO) ｃ ]-R ２ ・・・(1) (In formula (1), R １ This represents an alkenyl group with 3 carbon atoms. AO １ and AO ２ This represents an oxyalkylene group with 3 carbon atoms, EO indicates an oxyethylene group. a is the oxyalkylene group AO １ The average number of moles added, satisfying a > 0. b is the oxyalkylene group AO ２ The average number of moles added, satisfying b≧0. c is the average number of moles of the oxyethylene group EO added, and c > 0 is satisfied. The sum of a, b, and c is between 10 and 100. If b is greater than 0, (AO ２ ) ｂ / (EO) ｃ is the oxyalkylene group AO ２ This indicates that the oxyethylene group EO is randomly added. R ２ (This is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 0.20≦ M Ｌ / M Ｈ ≦0.60 ・・・(2) (In equation (2), let L be the length of the perpendicular from the maximum point K on the chromatogram where the refractive index intensity is maximum to the baseline B. Of the two points on the chromatogram where the refractive index intensity is L / 20, let O be the point with the earlier elution time and Q be the point with the later elution time. Let P be the intersection of the line G connecting points O and Q and the perpendicular drawn from the maximum point K to the baseline B. Then, let M be the distance between point O and the intersection point P.) Ｈ Let M be the distance between point Q and intersection point P. Ｌ (Let's assume that.) 【Chemistry 1】 (In formula (3), d is between 1 and 1000. e is between 0 and 100. e / d is between 0 and 1. R ３ It is a hydrocarbon group having 1 carbon atom, R ４ and R ５ Each of these is independently a hydrogen atom or a hydrocarbon group having 1 carbon atom, and when e=0, R ４ and R ５ At least one of them is a hydrogen atom. (B) Acrylic resin (C) Solvent selected from acetone or ethyl acetate

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