KR102084794B1 - Surface modifiers - Google Patents

Abstract

식 중, R¹은 수소 원자 또는 메틸기, R²는 탄소수 1 내지 10의 알킬렌기, R³은 탄소수 1 내지 12의 알킬기, m은 2 내지 150의 수를 나타낸다.An object of this invention is to provide the surface modifier which can mix | blend a small amount with coating agents, such as the paint which forms a film, and can provide a hydrophilic property and antifouling property to the smoothly formed film surface by preventing a crater phenomenon.
In order to solve the above problems, according to one aspect of the present invention, the surface modifier is at least one acrylamide monomer 80.00 to 99.99 selected from dimethyl (meth) acrylamides and diethyl (meth) acrylamides 0.01 to 20.00 parts by weight of the single-terminal (meth) acryl-modified siloxy group-containing mono (meth) acrylate monomer represented by the weight part, and hydroxyl group-containing (meth) acrylates and hydroxyl group-containing (meth) acryl At least one functional group-containing monomer selected from amides and block isocyanate group-containing (meth) acrylates is at least 10 parts by weight of at least an acrylamide monomer and a siloxy group-containing mono (meth) acrylate monomer. It is copolymerized to contain a copolymer having a weight average molecular weight of 1500 to 50000. To W:
[Formula 1]

In formula, R <^1> is a hydrogen atom or a methyl group, R <^2> is a C1-C10 alkylene group, R <^3> is a C1-C12 alkyl group, m shows a number of 2-150.

Description

Surface modifier {SURFACE MODIFIERS}

TECHNICAL FIELD This invention relates to the surface modifier which provides hydrophilicity and antifouling property to the coating surface formed with this coating agent by mix | blending a small amount with the coating agent which forms a film.

In recent years, there has been a desire to hydrophilize a coating surface formed of various coating agents such as aqueous and oil paints, baking paints, and inks with high added value using such silica films, and to improve its antifouling properties.

In general, as a method of imparting hydrophilicity to a film, the surface of the formed film is often made hydrophilic by making the resin itself contained in the coating agent for forming the film or the crosslinkable component itself for forming the film hydrophilic (for example, See Patent Documents 1 to 5). However, in this case, since the whole resin becomes hydrophilic by selecting a hydrophilic resin or functionalizing the resin or the crosslinkable component, the resin or crosslinkable component that can be used depending on the use of the coating is limited. Further, as a result of imparting hydrophilicity to the coating agent, since the entire coating becomes hydrophilic, invasion of moisture into the coating easily occurs, causing concern about the durability of the coating itself. As described above, when the existing coating agent is improved and the hydrophilicity is imparted thereto, improvement from the resin forming the film or the crosslinkable component is required, and extensive reexamination of the resin or the like is required for each coating agent.

As another method of imparting hydrophilicity to a film, hydrophilicity may be imparted by forming a film by coating the above-described hydrophilic coating agent on a coating film formed of an existing coating agent. In this case, however, since the coating is a hydrophilic coating in a state of being separated from the coating film formed by the existing coating agent (laminated state), weather resistance is hardly obtained by peeling off due to the interlayer peeling. In addition, since the film peels gradually, the film surface shape changes, and appearance defects, such as glossiness fall, are shown. In recent years, there are many demands for making the baking paint hydrophilic, and examples thereof include outdoor warehouses and roofing precoat metals. Long-term weather resistance is required for these films.

On the other hand, as a method of providing hydrophilicity to a film without changing resin or a crosslinkable component, a hydrophilic surface modifier may be added to an existing coating agent. In this case, by adding a small amount of hydrophilic surface modifier, the surface of the film can be made hydrophilic without changing the physical properties required for the film such as durability and hardness of the formed film. As hydrophilic surface modifiers, in most cases, silicates typified by ethyl silicate, which exhibits hydrophilicity by hydrolysis, are often used. Since the silicates require about 2 to 3 months to hydrolyze on the surface of the film, the film becomes hydrophobic by the non-hydrolyzed silicate immediately after the film is formed, so that lipophilic dirt tends to adhere. Is under. Long-term hydrophilic expression is possible after hydrophilic expression by hydrolysis of silicates, but long-term hydrophilicity may invade moisture into the film gradually, thereby lowering the durability of the film itself. In addition, as a problem of a coating agent containing a hydrophilic surface conditioner such as silicates, it is also easy to cause defects from the viewpoint of aging stability such as gelation of the hydrophilic surface conditioner itself and increase in viscosity of the coating by crosslinking with the resin. . The hydrophilic surface conditioner itself may cause hydrolysis due to moisture in the air, resulting in high polarization, loss of surface orientation due to hydrophobicity of silicates, and deterioration of hydrophilization performance.

As a hydrophilic surface modifier which expresses hydrophilicity from the beginning of film formation, there exist some containing polyalkylene oxide which is a hydrophilic segment. A coating agent containing such a hydrophilic surface modifier is relatively suitable for forming a film at room temperature, but when forming a film by high temperature baking such as baking paint, hydrophilicity considered to be pyrolysis or hydrolysis from the low heat resistance of polyalkylene oxide. A tendency to lower expression performance is recognized. Moreover, since this hydrophilic surface modifier is easy to stabilize the foam in a coating agent, the fine foam curled at the time of coating of a coating agent may generate a bubble trace (crater phenomenon) at baking.

In addition, Patent Document 6 below describes a hydrophilic surface modifier having a hydrophilic organic functional silicone polymer in which a silicone macromonomer such as siloxy group-containing acrylates, an unsaturated polyether component, and acrylamide are radically polymerized. . This hydrophilic surface conditioner needs to contain 30% or more of polyether components in a polymer. The coating agent containing this hydrophilic surface conditioner tends to generate thermal decomposition of a polyether component in a high temperature baking process, and scattered decomposition products contaminate equipment, such as a baking furnace. Moreover, the coating film formed from this coating agent becomes a high polar amphiphilic skeleton by having a hydrophobic silicone part and a hydrophilic polyether part, and it is easy to stabilize the bubble in a coating agent, and it is easy to produce a crater phenomenon.

Even when these surface modifiers and an antifoamer are added to a coating agent, the problem of a crater phenomenon may arise in the film formed with the coating agent. The occurrence of the crater phenomenon not only greatly impairs the appearance of the film, but also damages the film from defect sites and the protective effect of the substrate. Thus, according to the coating agent containing the conventional hydrophilic surface modifier, even if the formed film can express hydrophilicity from the beginning, complete prevention of the crater phenomenon becomes very difficult.

JPH5-179145 A JPH7-196977 A JPH9-31401 A JP 2002-80789 A JPH4-370176 A JP 2008-542462 A

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and by blending a small amount into a coating agent such as a coating material to form a film, it is possible to prevent the crater phenomenon and impart hydrophilicity to the smoothly formed film surface, thereby providing antifouling properties. A surface modifier, a coating agent, and a coating formed by applying the same, and curing the same, are provided.

80.00-99.99 weight of at least 1 acrylamide monomer chosen from the dimethyl (meth) acrylamides and the diethyl (meth) acrylamides, the surface modifier of Claim 1 made | formed in order to achieve the said objective. 0.01 to 20.00 parts by weight of a single-terminal (meth) acryl-modified siloxy group-containing mono (meth) acrylate monomer represented by the following and General Formula 1, and hydroxyl-containing (meth) acrylates and hydroxyl-containing (meth) acrylamide Of the acrylamide monomer and the siloxy group-containing mono (meth) acrylate monomer in a maximum of 10 parts by weight of at least one functional group-containing monomer selected from the group and the block isocyanate group-containing (meth) acrylates. Is copolymerized to contain a copolymer having a weight average molecular weight of 1500 to 50000. Characterized in that for imparting hydrophilicity to the film surface:

[Formula 1]

In formula, R <^1> is a hydrogen atom or a methyl group, R <^2> is a C1-C10 alkylene group, R <^3> is a C1-C12 alkyl group, m shows a number of 2-150.

The coating agent of Claim 2 contains the surface modifier and film forming component of Claim 1, It is characterized by the above-mentioned.

The film of Claim 3 is a coating agent of Claim 2, and it apply | coated and hardened | cured and formed on the base material, It is characterized by the above-mentioned.

The film of Claim 4 is described in Claim 3, and has antifouling property on the said film surface by the said hydrophilicity. It is characterized by the above-mentioned.

According to the surface conditioner of the present invention, even by adding a small amount to the coating agent, it is possible to impart hydrophilicity to the surface of the film immediately after the film is formed without requiring a reaction such as hydrolysis. The washability by water can be improved and antifouling property can be expressed.

Moreover, the coating agent of this invention containing this surface modifier is excellent in storage stability, without the performance change of the surface modifier at the time of storage, and / or the viscosity change of the coating agent resulting from a surface modifier. In addition, defoaming / breaking by the antifoaming agent blended in the coating agent is promoted, and the prevention of crater development can be achieved to form a smooth film.

The film formed from this coating agent is imparted with hydrophilicity to the surface, which is smooth and has excellent coating properties, and does not generate haze or foreign matter adhesion at the time of ignition treatment and is excellent in heat resistance.

EMBODIMENT OF THE INVENTION Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

The surface modifiers of the present invention include dimethyl (meth) acrylamides such as N, N-dimethylacrylamide and N, N-dimethylmethacrylamide, and N, N-diethylacrylamide and N, N-di Contains 80.00 to 99.99 parts by weight of at least one acrylamide monomer selected from diethyl (meth) acrylamides such as ethyl methacrylate, and 0.01 to 20.00 parts by weight of a siloxy group-containing mono (meth) acrylate monomer. It is. In order to harden | cure a surface adjustment agent and to form a film, it is used for adding it to the various coating agent which is a film formation composition, and to contain. When the acrylamide monomer is less than 80 parts by weight, the obtained surface modifier cannot express sufficient hydrophilicity to the film. In addition, the compatibility with the other ingredients blended in the coating agent containing the surface modifier is extremely poor, and when the coating is applied, not only a dent occurs, a recess is formed on the surface of the coating film, but also a coating on the formed film. The leveling property of the film is deteriorated, and sufficient coating adhesion cannot be obtained. It is preferable that an acrylamide monomer is 90-99 weight part and a siloxy group containing mono (meth) acrylate monomer is 1-10 weight part.

In the copolymer of the acrylamide monomer mentioned above and the siloxy group containing mono (meth) acrylate monomer, hydroxyl-containing (meth) acrylates, hydroxyl-containing (meth) acrylamides, and block isocyanate group-containing (meth) At least one functional group-containing monomer selected from acrylates may be copolymerized. It is preferable that this functional group containing monomer is 10 weight part or less with respect to the gross weight of a (meth) acrylamide monomer and a siloxy group containing mono (meth) acrylate monomer. Thereby, since it reacts with resin in the coating on the surface of a coating film, the elution of the surface regulator by rain water becomes difficult to generate | occur | produce further, and it can act advantageously to antifouling property. If it is 10 weight part or more, there exists a possibility that it may impair original performance. These functional group containing monomers may be used independently as long as gross weight is below the prescribed compounding quantity, and may be used together.

The weight average molecular weight of this copolymer is in the range of 1500-50000. When the weight average molecular weight is less than 1500, a bubble problem tends to occur during coating of the copolymer-containing coating agent. On the other hand, when the weight average molecular weight exceeds 50000, the orientation with respect to the film surface falls and sufficient hydrophilicity will not be obtained. It is preferable that the weight average molecular weights of a copolymer are 2500-20000.

As a siloxy group containing mono (meth) acrylate monomer, the siloxy group containing mono (meth) acrylate monomer of the single-end (meth) acryl modification represented by following General formula 1 can be used:

[Formula 1]

In formula, R <^1> is a hydrogen atom or a methyl group, R <^2> is a C1-C10 alkylene group, R <^3> is a C1-C12 alkyl group, m shows the integer of 2-150.

As for the siloxy group containing mono (meth) acrylate monomer represented by General formula 1, cyraprene FM-0711, cyraprene FM-0721, cyraprene FM-0725 (above, Chisso Corporation (CHISSO) CORPORATION; Cyrapren is a registered trademark of Chisso Corp., X-22-174DX, X-22-2426, X-22-2475 (above, Shin-Etsu Chemical Co., Ltd.) Product name).

Acrylamide monomers are dimethyl (meth) acrylamide and diethyl (meth) acrylamide, for example, DEAA (cozin) which is DMAA, N, N-diethylacrylamide which is N, N-dimethylacrylamide Film & Chemical Co., Ltd. (product name of KOHJIN Holdings Co., Ltd.) is mentioned.

Hydroxyl-containing (meth) acrylates are 2-hydroxyethyl (meth) acrylates, for example. 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, hydroxyl group The monomer which added (epsilon) -caprolactone to the (meth) acrylate which has is mentioned (for example, the Fraxel FM series), etc. are mentioned. As hydroxyl-containing (meth) acrylamide, N-hydroxyethyl acrylamide, N-hydroxymethyl acrylamide, etc. are mentioned, for example. Block isocyanate group-containing (meth) acrylates are (meth) acrylate monomers having an isocyanate group blocked with a blocking agent, for example, block in 2-isocyanatoethyl (meth) acrylate Examples of the agent include those obtained by reacting ethyl alcohol, isopropyl alcohol, caprolactam, MEK-oxime, dimethylpyrazole, diethyl malonate and the like.

At least one unsaturated monomer selected from alkyl (meth) acrylates, (meth) acrylamides and vinyl group-containing compounds in the copolymer of the acrylamide monomer and the siloxy group-containing mono (meth) acrylate monomer described above. May be copolymerized. However, the copolymerization amount of the unsaturated monomer should be such that the obtained copolymer does not impair hydrophilicity imparting performance, and is preferably 30% by weight or less based on the total weight of the acrylamide monomer and the siloxy group-containing mono (meth) acrylate monomer. .

Alkyl (meth) acrylates are alkyl acrylates or alkyl methacrylates, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, for example. , Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth ) Acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2 -Acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl-phthalic acid, tetrahydrofurfuryl (meth) acrylate, etc. are mentioned.

(Meth) acrylamides are things other than dimethyl (meth) acrylamide and diethyl (meth) acrylamide, For example, dimethylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, ( Meta) acryloyl morpholine, diacetone acrylamide, (meth) acrylamide-tert-butylsulfonic acid, (meth) acrylamide-tert-butylsulfonic acid organic salt, (meth) acrylamide-tert-butylsulfonic acid inorganic salt Etc. can be mentioned.

The vinyl group-containing compounds are, for example, straight chains having 1 to 12 carbon atoms such as n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, and lauryl vinyl ether. Branched or cyclic alkylvinyl ether monomers; And vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl laurate.

This copolymer can be obtained by a radical polymerization method. As the radical polymerization method, a predetermined amount of at least one acrylamide monomer selected from dimethyl (meth) acrylamide and diethyl (meth) acrylamide, a predetermined siloxy group-containing mono (meth) acrylate monomer, and At least one functional group-containing monomer selected from a predetermined amount of hydroxyl group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylamides, and block isocyanate group-containing (meth) acrylates, and As necessary, at least one unsaturated monomer selected from a predetermined amount of alkyl (meth) acrylates, (meth) acrylamides, and vinyl group-containing compounds can be suitably used in a solvent to Therefore, it can be obtained by random copolymerization in the presence of a chain transfer agent. As the radical polymerization initiator, tert-butylperoxy-2-ethylhexanoate can be used, for example, and dodecyl mercaptan can be used as the chain transfer agent. As the solvent, for example, an inert solvent such as cyclohexanone can be used. In addition, the copolymer may be obtained by radical polymerization or may be obtained by ionic polymerization such as anionic polymerization. The copolymer may be a random copolymer, a block copolymer, a graft copolymer, or an alternating copolymer.

The surface modifier containing the obtained copolymer may consist only of a copolymer, and may be used, melt | dissolving or suspending a copolymer with an inert solvent. Inert solvents are those which can dissolve or suspend this copolymer. Specifically, hydrocarbon solvents such as xylene, toluene and cyclohexane; Ketone solvents such as cyclohexanone and methylisobutyl ketone; Ether solvents such as methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether; Ester solvents such as n-butyl acetate, isobutyl acetate, n-amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; and alcohol solvents such as n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, and 3-methyl-3-methoxybutanol. These solvents may be used alone or in combination of two or more thereof.

A coating agent contains a surface modifier and a film forming component. When the coating agent is prepared by blending the surface modifier, a known coating agent that does not contain the surface modifier and contains the film-forming component is produced in advance, and then the desired coating agent is obtained by blending and kneading the surface modifier. You may mix them simultaneously or in arbitrary order. It is preferable that a coating agent is mix | blended so that it may become a copolymer of 0.1-10 weight%, Preferably it is 0.5-5.0 weight% in solid content conversion value with respect to coating agent whole quantity. 3rd components other than a film formation component and an inert solvent may be mix | blended with a coating agent. Although the 3rd component is not specifically limited, For example, coloring agents, such as a pigment and dye, resin, a diluent solvent, a catalyst, and surfactant are mentioned. Moreover, a sensitizer, an antistatic agent, an antifoamer, a dispersing agent, and a viscosity modifier may be mix | blended as needed.

As resin which is a film formation component mix | blended in a coating agent, an acrylic resin, a polyester resin, a urethane resin, an alkyd resin, an epoxy resin, and a polyamine resin are mentioned. This resin is cured with a chemical reaction in the presence of a catalyst or in the absence of a catalyst, for example, a heat curing type, an ultraviolet curing type, an electron beam curing type, an oxidation curing type, a photocation curing type, a peroxide curing type, and an acid / epoxy curing type. The resin may be a resin having a high glass transition point, and may not be accompanied by a chemical reaction, and may be a film only by volatilization of the solvent.

The dilution solvent is not particularly limited as long as it is generally water or an organic solvent that can be used. Examples of the organic solvent include hydrocarbon solvents such as xylene, toluene and cyclohexane; Ketone solvents such as cyclohexanone and methylisobutyl ketone; Ether solvents such as methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether; Ester solvents such as n-butyl acetate, isobutyl acetate, n-amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; and alcohol solvents such as n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, and 3-methyl-3-methoxybutanol. These solvents may be used alone or in combination.

The coating agent containing this surface modifier can be apply | coated to the surface of a base material, and the coating film obtained can be dried or hardened | cured, and the film which the surface became hydrophilic can be formed. This film has an antifouling property that the surface becomes hydrophilic, so that it is easily compatible with water, and even when dust is attached, the film is easily washed with water such as rain water.

Although the base material is not specifically limited, It is formed from the material of plastic, rubber, paper, wood, glass, metal, stone, cement material, mortar material, and ceramics, and can mention the exterior material of household appliances, the automobile, daily necessities, building materials. .

Moreover, the coating method of a coating agent is a spin coat, a slit coat, a spray coat, a dip coat, a bar coat, a doctor blade, a roll coat, and a flow coat, for example.

Thus, the film formed by apply | coating and hardening | curing the coating agent containing the surface modifier of this invention on the surface of a base material achieves crater development prevention, it is smooth, hydrophilicity is given to the surface immediately after film formation, and, thereby, rain water etc. The washability by water can improve and antifouling property can be expressed. That is, the surface modifier does not require a reaction such as hydrolysis for imparting hydrophilicity, and can provide the hydrophilic surface immediately after the film formation. Thus, according to the film formed by the coating agent containing the surface modifier, even when a film forming component such as a hydrophobic resin having a low surface tension is used, the surface of the formed film can be made hydrophilic and wet when the coating agent having a high surface tension is coated. The expandability can be improved and the smoothness of the overcoat can be improved from the effect. In addition, by making the surface of the coating hydrophilic, the hydrophilic surface has a low water contact angle with respect to the substrate, and can exhibit high antifouling properties by improving the washability by water such as rain water. This antifouling property is also expressed immediately after film formation.

This surface conditioner is a high polar amphiphilic skeleton similar to the hydrophilic organic functional silicone copolymer described in Patent Document 6 described above at room temperature, and thus has excellent compatibility with the film-forming component, but is in a state in which bubbles are difficult to stabilize. The detailed reason for this is not necessarily clear, but is assumed as follows. This surface modifier contains the copolymer which has acrylamide as a main component. The copolymer has a hydrophobic polysiloxane segment and a segment derived from hydrophilic / hydrophobic acrylamide. Since acrylamide has a hydrophobic part and a hydrophilic part in its structure, the copolymer having a segment derived from dimethyl and / or diethyl (meth) acrylamide becomes a thermosensitive polymer in an aqueous solution. This is similarly observed even when the monomer is copolymerized to a certain ratio. Before and after the temperature reduction, the polymer mainly containing acrylamide has a phase change in hydrophilicity / hydrophobicity. Due to this characteristic, during the baking process in which crater phenomenon occurs, the surface modifier is changed from hydrophilicity to hydrophobicity, the stabilized bubbles become unstable by the phase change of the surface modifier, and the defoaming and foaming by the antifoaming agent is promoted. , Crater phenomenon prevention is achieved. After baking, when returned to room temperature, hydrophobicity becomes hydrophilic again, and the formed film has hydrophilicity.

When the coating agent containing this surface modifier is applied onto a substrate to form a film, the surface modifier also has an orientation to a high interface, and the leveling property is expressed by the uniformity effect of surface tension, resulting in coating unevenness or an orange peel. The defect of the surface is slight. In addition, even when the coating is applied to the coating, coating unevenness does not occur, the adhesion between the coating and the coating layer is not lowered, and the film is closely adhered to each other, and both the coating and the coating layer do not come off and fall off, so that the aesthetic appearance is good. In addition, even when baking is performed at a high temperature, as in the case of coating a coating material for a precoat metal, the heat resistance is excellent. Therefore, the coating film is excellent in smoothness and cured and formed without causing dents or foreign substances on the surface of the coating film. There is no impairment of the coating adhesion to, and the durability is excellent.

(Example)

Hereinafter, the example which prepared the surface modifier of this invention is shown in Examples 1-9, and the example which prepared the surface modifier other than the application of this invention is shown in Comparative Examples 1-7.

<Example 1>

100 parts by weight of cyclohexanone was added to a 1000 ml reaction vessel equipped with a stirring device, a reflux cooling tube, a dropping funnel, a thermometer, and a nitrogen gas inlet, and the temperature was raised to 110 ° C. under a nitrogen gas atmosphere. The temperature of cyclohexanone was hold | maintained at 110 degreeC, and the dripping solution (a-1) shown in following Table 1 was dripped uniformly in 2 hours by the dropping funnel, and the monomer solution was prepared. After completion of the dropwise addition, the monomer solution was heated up to 115 ° C, reacted for 2 hours to synthesize a copolymer, thereby obtaining a surface conditioner. Gel permeation chromatography that can separate molecules of different molecular weight (column is manufactured by TOSOH CORPORATION, product name TSKGEL SUPERMULTIPORE HZ-M, and elution solvent is THF (tetrahydrofuran). Elution was performed to determine the molecular weight distribution A calibration curve was obtained from a polystyrene standard material having a known molecular weight in advance, and compared with the molecular weight distribution of the surface modifier, the weight average molecular weight of the surface modifier was determined. The weight average molecular weight was 3500 in polystyrene conversion.

<Example 2>

The copolymer was synthesize | combined by the method similar to Example 1 except having changed the dripping solution in Example 1 to (a-2) of Table 1 below, and changing dripping temperature to 90 degreeC, and obtained the surface regulator. The weight average molecular weight of the obtained surface conditioner was obtained by gel permeation chromatography in the same manner as in Example 1, and was 8000 in terms of polystyrene.

<Example 3>

The copolymer was synthesize | combined by the method similar to Example 1 except having changed the dripping solution in Example 1 to (a-3) of Table 1 below, and changing dripping temperature to 90 degreeC, and obtained the surface regulator. The weight average molecular weight of the obtained surface modifier was obtained by gel permeation chromatography in the same manner as in Example 1, and was 15000 in terms of polystyrene.

<Example 4>

Except having changed the dripping solution in Example 1 to (a-4) of following Table 1, the copolymer was synthesize | combined by the method similar to Example 1, and the surface conditioner was obtained. The weight average molecular weight of the obtained surface modifier was obtained in gel conversion chromatography in the same manner as in Example 1, and was 3500 in terms of polystyrene.

Example 5

The copolymer was synthesize | combined by the method similar to Example 1 except having changed the dripping solution in Example 1 to (a-5) of Table 1 below, and changing dripping temperature to 90 degreeC, and obtained the surface regulator. The weight average molecular weight of the obtained surface modifier was obtained by gel permeation chromatography in the same manner as in Example 1, and was 8000 in terms of polystyrene.

<Example 6>

Except having changed the dripping solution in Example 1 to (a-6) of following Table 1, the copolymer was synthesize | combined by the method similar to Example 1, and the surface conditioner was obtained. The weight average molecular weight of the obtained surface conditioner was determined in the same manner as in Example 1 by gel permeation chromatography, and was 4500 in terms of polystyrene.

<Example 7>

The copolymer was synthesize | combined by the method similar to Example 1 except having changed the dripping solution in Example 1 to (a-7) of Table 1 below, and changing dripping temperature to 90 degreeC, and obtained the surface regulator. The weight average molecular weight of the obtained surface modifier was obtained by gel permeation chromatography in the same manner as in Example 1, and was 8000 in terms of polystyrene.

<Example 8>

The copolymer was synthesize | combined by the method similar to Example 1 except having changed the dripping solution in Example 1 to (a-8) of Table 1 below, and changing dripping temperature to 90 degreeC, and obtained the surface regulator. The weight average molecular weight of the obtained surface conditioner was found in gel permeation chromatography in the same manner as in Example 1, and was 2000 in terms of polystyrene.

Example 9

A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (a-9) in Table 1 below, and the dropping temperature was changed to 90 ° C to obtain a surface conditioner. The weight average molecular weight of the obtained surface modifier was obtained in gel conversion chromatography in the same manner as in Example 1, and was 3500 in terms of polystyrene.

TABLE 1

Comparative Example 1

100 parts by weight of cyclohexanone was added to a 1000 ml reaction vessel equipped with a stirring device, a reflux cooling tube, a dropping funnel, a thermometer, and a nitrogen gas inlet, and the temperature was raised to 110 ° C. under a nitrogen gas atmosphere. The temperature of cyclohexanone was hold | maintained at 110 degreeC, and the dripping solution (b-1) shown in following Table 2 was dripped uniformly in 2 hours by the dropping funnel, and the monomer solution was prepared. After completion of the dropwise addition, the monomer solution was heated up to 115 ° C, reacted for 2 hours to synthesize a copolymer, thereby obtaining a surface conditioner. The molecular weight distribution was obtained by eluting the obtained surface conditioner for each molecular weight using gel permeation chromatography (column manufactured by Tosoh Corporation, product name: TSKGEL SUPERMULTIPORE HZ-M, and elution solvent THF). A calibration curve was obtained from a polystyrene standard material having a known molecular weight in advance, and compared with the molecular weight distribution of the surface modifier, the weight average molecular weight of the surface modifier was obtained. As a result, the weight average molecular weight of this surface conditioner was 3500 in polystyrene conversion. In Comparative Example 1, acrylamide monomer was not added to the monomer solution.

Comparative Example 2

The dropping solution in Comparative Example 1 was changed to (b-2) in Table 2 below, and a copolymer was synthesized in the same manner as in Comparative Example 1 to obtain a surface conditioner. The weight average molecular weight of the obtained surface conditioner was obtained by gel permeation chromatography in the same manner as in Comparative Example 1, and was 10000 in terms of polystyrene. In the comparative example 2, the acrylamide monomer in the monomer solution was less than 80 weight part, and the siloxy group containing mono (meth) acrylate monomer exceeded 20 weight part.

Comparative Example 3

A copolymer was synthesized in the same manner as in Comparative Example 1 except that the dropping solution in Comparative Example 1 was changed to (b-3) in Table 2 below, and the dropping temperature was changed to 90 ° C to obtain a surface conditioner. The weight average molecular weight of the obtained surface modifier was obtained by gel permeation chromatography in the same manner as in Comparative Example 1, and was 70000 in terms of polystyrene. In the comparative example 3, the weight average molecular weight of the obtained surface modifier exceeded 50000.

<Comparative Example 4>

The dripping solution in the comparative example 1 was changed to (b-4) of following table 2, the copolymer was synthesize | combined by the method similar to the comparative example 1, and the surface conditioner was obtained. The weight average molecular weight of the obtained surface modifier was obtained by gel permeation chromatography in the same manner as in Comparative Example 1, and was 4000 in terms of polystyrene. In Comparative Example 4, acrylamide monomer was not added to the monomer solution.

Comparative Example 5

The dropping solution in Comparative Example 1 was changed to (b-5) in Table 2 below, and a copolymer was synthesized in the same manner as in Comparative Example 1 to obtain a surface conditioner. The weight average molecular weight of the obtained surface modifier was obtained by gel permeation chromatography in the same manner as in Comparative Example 1, and was 4000 in terms of polystyrene. In Comparative Example 4, no siloxy group-containing mono (meth) acrylate monomer was added to the monomer solution.

Comparative Example 6

Ethyl silicate 48 (manufactured by COLCOAT CO., Ltd.) was used as the surface conditioner.

TABLE 2

<Example 10, Comparative Example 8>

Surface preparation agents obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were blended with the prepared paints prepared in advance, and test coatings were obtained as coating agents. Evaluation of the characteristics of the cured film obtained by applying the test paint to the substrate, the aging stability of the test paint, and the like.

(Preparation of Preparation Paint)

Becolite M-6154-40 (polyester polyol resin, non-volatile content: 50%, hydroxyl value 50; Dainippon Ink and Chemicals, Incorporated) 324 parts by weight and CR-93 (titanium oxide, The glass beads were added to the 270 weight part mill base of Ishihara Industrial Co., Ltd. (ISHIHARA SANGYO KAISHA, LTD.), And it stirred for 6 hours by the paint shaker. In addition, 135 parts by weight of Bekkolight M-6154-40 (product of Dainippon Ink and Chemicals, Inc.), super betamine L-117-60 (butylated melamine resin, NV60%, Dainippon ink) 22 parts by weight of Chemical Industries, Ltd., 45 parts by weight of SuperVetamine L-105-60 (Methylated Melamine Resin NV60%, Dainippon Ink and Chemicals, Inc.) and thinner (Sorbetso 150 / cyclohexanone = 50/50) 204 After mix | blending the red down which consists of a weight part, glass beads were filtered and obtained the preparative paint.

(Adjustment of paint and film preparation)

The surface preparation agent obtained in Examples 1-9 and Comparative Examples 1-6 as 0.5% of antifoamer (Florene AC-300, Kyoeisha Chemical Co., Ltd.) and solid content to the obtained preparation paint. 1.5% was added and it stirred at 2000 rpm x 2 minutes with the mixer, and the test paint which is a baking polyester paint was obtained. The obtained test paint was immediately coated on a substrate with a # 42 bar coater, immediately baked at 245 ° C. × 60 seconds (PMT: 225 ° C.), and cured to form a cured film.

In addition, for comparison, the cured film prepared by the test paint obtained using the surface modifier of Comparative Example 6 was immersed in 1% sulfuric acid solution for 24 hours, and the cured film obtained by promoting hydrolysis was used as Comparative Example 7. And the cured film for hydrophilic comparison.

Evaluation of Crater Phenomenon on Hardened Film

The number of crater developments generated per 10 cm 2 of the cured coating was visually counted, and the results evaluated by the following evaluation criteria are shown in Table 3 below.

Evaluation standard of crater phenomenon occurrence

No occurrence of crater phenomenon: ◎

About 3 places or less: ○

About 7 places or less: ○-△

10 or more places: △

Crater Phenomenon Occurs on Entire Surface: ×

(Evaluation of leveling property of hardened film surface)

The surface state of the coating surface after hardening was observed visually, and the result evaluated by the following evaluation criteria is shown in Table 3 below.

Evaluation criteria of leveling

Good: ○

A little bit of paint on the bar coater: ○ ~ △

Marker line of bar coater remains remarkably: △

Occurrence: ×

(Measurement of Water Contact Angle of Hardened Film)

0.02 microliter of water droplets were dripped at the surface of the cured coating immediately after hardening, and the initial water contact angle was measured using the contact angle measuring instrument (made by Kyowa Interface Science Co., Ltd.). The results are shown in Table 3 below. In addition, the water contact angle was measured for the hydrophilic comparison of the cured film of the comparative example 7.

(Evaluation of actual width of hardened film)

The coated plate having a cured coating formed on the surface was folded at 45 ° to be bent vertically, exposed for 2 months to the south side outdoors, and the degree of contamination was visually evaluated by the following evaluation criteria. The results are written together in Table 3 below.

Pollution Assessment Criteria

Almost no pollution and good: ○

Somewhat dirty: △

High pollution: ×

TABLE 3

As apparent from Table 3, the cured coatings of Examples 1 to 9 had a smaller amount of crater development and better leveling properties than the cured coatings of Comparative Examples 1 to 6, and the coating surface was smooth. Moreover, the contamination degree in the water contact angle and the explosion test of the cured films of Examples 1-9 is about the same as that of the cured film of the comparative example 7 for hydrophilicity comparison, and shows favorable hydrophilicity and antifouling property.

(Evaluation of test stability over time)

The viscosity (type B viscometer) after the initial storage of the prepared test paint, 40 ° C. × 1 month and 2 months was measured, and the results are shown in Table 4 below. In addition, the cured film was produced by the above-mentioned film | membrane preparation method about each of the initial stage and after storage for 40 degreeC * 1 month, the water contact angle evaluation was performed by the above-mentioned water contact angle measuring method, and the result was put together in Table 4 below. In addition, in the following Table 4, the water contact angle shown in Table 3 was written together as an initial water contact angle.

TABLE 4

As is apparent from Table 4, the cured coating using the test paints of Examples 1 to 9 has good aging stability and no increase in viscosity or gelation. Moreover, also in the cured film of the test paint stored at 40 degreeC x 1 month, the water contact angle is substantially the same as the initial water contact angle, and shows favorable hydrophilicity. On the other hand, the cured films of Comparative Examples 1 to 7 had high water contact angles or caused crater phenomenon, and had insufficient surface characteristics.

(Industrial availability)

The surface conditioner of the present invention is a paint applied to the surface of household appliances, automobile exterior materials, daily necessities, and building materials formed of plastic, rubber, paper, wood, glass, metal, stone, cement, mortar, ceramics, etc. It can mix | blend in the coating agent of.

Claims (4)

80.00 to 99.99 parts by weight of at least one acrylamide monomer selected from dimethyl (meth) acrylamide and diethyl (meth) acrylamide, and a single-terminal (meth) acryl-modified siloxy group represented by the following general formula (1): 0.01 to 20.00 parts by weight of a containing mono (meth) acrylate monomer and at least one selected from hydroxyl group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylamides and block isocyanate group-containing (meth) acrylates At least 10 parts by weight of any functional group-containing monomer, at least the acrylamide monomer and the siloxy group-containing mono (meth) acrylate monomer is copolymerized to contain a copolymer having a weight average molecular weight of 1500 to 50000, Surface modifiers that impart hydrophilicity to the coating surface:
[Formula 1]

In formula, R <^1> is a hydrogen atom or a methyl group, R <^2> is a C1-C10 alkylene group, R <^3> is a C1-C12 alkyl group, m shows the number of 2-150. A coating agent comprising the surface modifier of claim 1 and a film forming component. The coating agent of Claim 2 applied and hardened | cured and formed on the base material, The film characterized by the above-mentioned. The film according to claim 3, wherein the film has antifouling property on the surface of the film due to the hydrophilicity.