JP6979791B2 - Leveling agent for paints using amphipathic block copolymers - Google Patents

Description

INDUSTRIAL APPLICABILITY According to the present invention, by adding a small amount to a paint, smoothness during painting can be imparted, and even if foreign matter that causes repelling is present in the painting process, it is possible to prevent the occurrence of painting defects. It is about the agent.

High-grade paints such as paints for automobiles, paints for pre-coated metal (hereinafter abbreviated as PCM), paints for home appliances, etc., which are painted by industrial line painting, require not only corrosion resistance but also high-quality finished appearance. Will be done. Therefore, it is indispensable that the finished coated surface is free from cissing, craters, fish eyes, cloudiness, etc., and has a smooth appearance. As an additive for a paint for satisfying this function, a surface conditioner such as a leveling agent, an antifoaming agent, an armpit inhibitor, a gloss-imparting agent, and an anti-repellent agent is used.

Conventionally, in line coating, atomization coating such as air spray and high-speed continuous coating such as roll coater have been performed. With these painting methods, the mist of lubricating oil used in compressors, roll coater machines, etc. and the mist of the paint itself may adhere to the surface of the object to be coated, and repellent is generated due to these mists. It was a problem to do. In addition, in a painting line that is painted and polished several times, such as automobile paint, sandpaper polishing debris and repellent caused by contamination by human hands during work may become a problem. There is (these repellent factors are hereinafter referred to as heterogeneous dust).

Conventionally, modified silicone oils and vinyl polymers having a low surface tension have been used as means for solving these problems of repelling during painting. For example, in Patent Document 1, a vinyl ether polymer having an alkyl group having 2 to 4 carbon atoms is useful. Additives that impart properties and anti-repellency properties, further impart excellent leveling properties to the coating film coated with the properties, and do not impair topcoat adhesion are described.

Special fair 1-2344478 Patent No. 5111665

However, in recent years, because the paint is environmentally friendly, the paint has become highly solid or water-based, and as a result, the resin used in the paint has become highly polar, and the effect of the solvent on the coated surface has diminished. , The problem of repellent is hard to solve. Further, when a modified silicone oil or a vinyl polymer having a low surface tension is blended, the interlayer adhesion may be impaired when the paint is repeatedly applied, or the color tone of the top coat surface may be changed, which may deteriorate the so-called recoating property. ..

Therefore, an object of the present invention is to provide a leveling agent (smoothing agent) that gives a smooth coated surface by preventing repelling against different kinds of dust without impairing the so-called recoating property.

As a result of various studies, the present inventors have conducted the general formula [I].

［式中、Ｒ１は水素原子又はメチル基、Ｒ２は炭素数１から１０のアルキレン基、Ｒ３は炭素数１から４のアルキル基、ｎは５〜５０の整数をそれぞれ表す。］
で示される、（メタ）アクリロイルオキシ基持つシリコーンオイルが、一般式［ＩＩ］

[In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 1 to 10 carbon atoms, R3 represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 5 to 50. ]
The silicone oil having a (meth) acryloyloxy group represented by the general formula [II]

［式中、Ｒ４は水素原子又はメチル基、Ｒ５は炭素原子数１〜１２のアルキル基を表す。］
で示される（メタ）アクリルエステルからなる主鎖ポリマーにリビングラジカル重合でグラフト重合することによって形成された疎水性シリコーングラフトポリマー部、および、一般式［ＩＩＩ］

[In the formula, R4 represents a hydrogen atom or a methyl group, and R5 represents an alkyl group having 1 to 12 carbon atoms. ]
A hydrophobic silicone graft polymer portion formed by graft-polymerizing a main chain polymer composed of a (meth) acrylic ester represented by (meth) by living radical polymerization, and a general formula [III].

［式中、Ｒ６は水素原子又はメチル基、Ｒ７は水素原子又は炭素原子数１〜１８のアルキル基、ｍは１〜５０の整数をそれぞれ表す。］
で示されるオキシエチレン基を持つ（メタ）アクリル酸エステルが、上記一般式［ＩＩ］で示される（メタ）アクリル酸エステルからなる主鎖ポリマーにリビングラジカル重合することによって形成された親水性グラフトポリマー部、を含んでなる両親媒性ブロック共重合体を主成分とする塗料用レベリング剤であって、上記両親媒性ブロック共重合体を構成するモノマーの全重量に基づいて、上記式［Ｉ］のモノマー、上記式［ＩＩ］のモノマー、及び上記式［ＩＩＩ］のモノマーの重合割合が、各々２〜５０重量％、２０〜８０重量％、及び、２０〜８０重量％、好ましくは各々５〜３５重量％、２０〜５０重量％及び３０〜６０重量％であり、上記疎水性グラフトポリマー部のポリスチレン換算の数平均分子量が、１０００〜３００００、好ましくは２０００〜２００００であり、上記親水性グラフトポリマー部のポリスチレン換算の数平均分子量が、１０００〜３００００、好ましくは２０００〜２００００であり、上記両親媒性ブロック共重合体のポリスチレン換算の
数平均分子量が、２０００〜６００００、好ましくは５０００〜３００００であることを特徴とする塗料用レベリング剤を塗料に配合することにより、塗装時にレベリング性（平滑性）を付与しつつ、異種ダストによるハジキを防止する効果が得られ、且つ、リコート性にも影響を与えないことを発見した。

[In the formula, R6 represents a hydrogen atom or a methyl group, R7 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and m represents an integer of 1 to 50. ]
A hydrophilic graft polymer formed by living radical polymerization of a (meth) acrylic acid ester having an oxyethylene group represented by (2) on a main chain polymer composed of a (meth) acrylic acid ester represented by the above general formula [II]. A leveling agent for paints containing an amphoteric block copolymer as a main component, the above formula [I] based on the total weight of the monomers constituting the amphoteric block copolymer. The polymerization ratios of the monomer of the above formula [II], the monomer of the above formula [III], and the monomer of the above formula [III] are 2 to 50% by weight, 20 to 80% by weight, and 20 to 80% by weight, preferably 5 to 80% by weight, respectively. It is 35% by weight, 20 to 50% by weight and 30 to 60% by weight, and the number average molecular weight of the hydrophobic graft polymer portion in terms of polystyrene is 1000 to 30,000, preferably 2000 to 20000, and the hydrophilic graft polymer is described above. The polystyrene-equivalent number average molecular weight of the part is 1000 to 30,000, preferably 2000 to 20000, and the polystyrene-equivalent number average molecular weight of the homomeric block copolymer is 2000 to 60,000, preferably 5000 to 30000. By blending a leveling agent for a paint, which is characterized by this, in the paint, it is possible to obtain the effect of preventing repelling due to different types of dust while imparting leveling property (smoothness) at the time of painting, and also affecting the recoat property. I found that I wouldn't give it.

The amphipathic block copolymer exhibits the same effect as a leveling agent for paints regardless of whether it is a diblock type, a triblock type, or a multi-block type graft copolymer.

Further, a monomer having another polymerizable double-bonding group copolymerizable with the monomer component of the formula [I], the formula [II] and / or the formula [III] is the total weight of the monomer constituting the block copolymer. A similar effect is also applied to a homomeric block copolymer having a number average molecular weight of 2000 to 60,000, preferably 5000 to 30000, which constitutes the main chain of the block copolymer in a range not exceeding 40% by weight based on the above. Was found to be obtained.

When the weight% of the monomer of the formula [I] is less than 2%, the effect of the leveling agent itself for exhibiting sufficient heterogeneous dust prevention property is not recognized. Further, if it exceeds 50% by weight, the recoatability is adversely affected.

The reason for copolymerizing 20 to 80% by weight of the acrylic acid ester or methacrylic acid ester of the formula [II] is to obtain an effect of obtaining good smoothness, and an alkyl group R5 having a carbon atom number longer than 12 is used. It is not possible to give sufficient smoothness with the monomer having. Further, when the number of polymerizations (m) of the polyalkylene glycol of the formula [III] exceeds 50, the water resistance of the coating film is adversely affected.

Hydrophilic graft polymer part composed of the monomer of the component formula [I] and the monomer of the formula [II] composed of the ratio shown above, and the hydrophilicity of the monomer of the formula [III] and the monomer of the formula [II]. The same effect can be obtained with either the diblock type or the triblock type as the homogenous block copolymer composed of the graft polymer portion. Further, as long as it is within the above number average molecular weight, the same effect can be obtained even if multi-blocking is performed.

In the amphoteric block copolymer composed of the ratios shown above, a copolymerizable double bond is formed in a range not exceeding 40% by weight based on the total weight of the monomers constituting the block copolymer. The copolymer in which the other monomers have the main chain of the block copolymer also has the same good leveling property and the effect of preventing repelling due to different kinds of dust. When copolymerization is carried out in a range exceeding 40% by weight, good leveling property and the effect of preventing repelling due to different kinds of dust cannot be obtained.

If the number average molecular weight of the amphipathic block copolymer is less than 2000 or greater than 60,000, the amphipathic block copolymer blended in the paint has sufficient ability to orient on the paint surface during painting. Since it does not have, sufficient leveling property and repelling prevention property cannot be obtained.

Examples of silicone oils having an acryloyloxy group or a methacryloyloxy group represented by the general formula [I] include Syrahplane FM-0711, Syrahplane FM-0721 and Shinetsu Silicone Co., Ltd., which are commercially available from JNC Corporation. Examples thereof include X-22-174ASX, X-22-174BX, KF-2012, etc., which are commercially available from Japan.

Examples of the (meth) acrylic acid ester represented by the general formula [II] having 1 to 12 carbon atoms include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, and (meth) acrylic acid normal propyl ester. (Meta) Acrylic acid isopropyl ester, (Meta) Acrylic acid normal butyl ester, (Meta) Acrylic acid isobutyl ester, (Meta) Acrylic acid tertiary butyl ester, (Meta) Acrylic acid normal octyl ester, (Meta) Acrylic acid 2 -Ethylhexyl ester, (meth) acrylic acid isononyl ester, (meth) acrylic acid normal dodecyl ester, (meth) acrylic acid isododecyl ester and the like can be mentioned.

Examples of the (meth) acrylic acid ester represented by the general formula [III] include (meth) acrylic acid 2-methoxyethyl ester, (meth) acrylic acid 2-ethoxyethyl ester, and (meth) acrylic acid 2-butoxyethyl ester. (Meta) Acrylic Acid 2-Octosiethyl Ester, (Meta) Acrylic Acid 2-Lauroxyethyl Ester, (Meta) Acrylic Acid 3-methoxybutyl Ester, (Meta) Acrylic Acid 4-methoxybutyl Ester, (Meta) Acrylic Examples thereof include acid ethyl carbitol ester, (meth) acrylate methoxypolyethylene glycol (the number of polymerization of ethylene glycol is 2 to 50) ester, and the like.

In the amphipathic block copolymer in the present invention, a segment made of a monomer other than the above may be contained in the main chain within a range not exceeding 40% by weight based on the total weight. The monomers constituting this segment are not limited, and are outside the above range, for example, (meth) acrylic acid stearyl ester, (meth) acrylic acid cyclohexyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid phenoxyethyl ester, and the like. (Meta) acrylic acid ester; acrylamides such as acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, diacetoneacrylamide, acloylmorpholin; styrene, α-methylstyrene, chlorostyrene , Aromatic hydrocarbon compounds such as vinyltoluene; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate, diallyl phthalate; ethyl vinyl ethers, normal propyl vinyl ethers, isopropyl vinyl ethers, normal butyl vinyl ethers, isobutyl vinyl ethers, tertiarys. Vinyl ethers such as butyl vinyl ether, normal octyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; other vinyl compounds such as vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide and the like can be mentioned.

As a method for synthesizing the amphoteric block type copolymer used in the present invention, atom transfer radical polymerization (ATRP) method and reversible addition-fragmentation chain transfer polymerization (ATRP) method are used. There are a RAFT polymerization method, a polymerization method using an organic tellurium compound, a Radical Polymerization method, and the like. The following is a review of each polymerization method.
ATRP Review:
M. Ouchi, T.M. Terrashima, M. et al. Sawamoto, Chem. Rev. , 109, 4963 (2009).
RAFT Review:
Graeme Moad, Ezio Rizzardo, San H Thang, Polymer, 49, 1079 (2008)
TERP Review:
Shigeru Yamago, Chem. Rev. , 109,5051 (2009).
Since the present invention relates to the function of block copolymers, the present invention is not limited by the synthesis method.

The paint suitable for using the leveling agent for paint of the present invention is a paint that requires a higher appearance such that repelling due to different kinds of dust becomes a problem. For example, paints for automobile top coats using baking paints such as acrylic melamine type high solid paints using acid catalysts, acid epoxy curable acrylic paints, and polyester melamine paints, or high appearance paints mainly for PCM for home appliances. The leveling agent of the present invention is used for different types of dust during painting, as opposed to paints for automobiles, paints for automobile repair, paints for plastics, etc. that use room temperature dry paints such as fluororesin paints, acrylic urethane paints and polyester urethane paints. It is possible to give both anti-repellency and leveling properties at the same time.

The timing at which the paint leveling agent according to the present invention is added to the paint is arbitrary, and can be added in the process of kneading the pigment or after the paint is manufactured.

The amount of the leveling agent for paint added according to the present invention varies depending on the type of resin of the paint, the composition of the pigment, etc., but is usually 0.01 to 5% by weight, preferably 0. 1 to 1% by weight.

If the addition amount is less than 0.01% by weight, it is not possible to impart anti-repellency to different kinds of dust, and it is not possible to sufficiently impart leveling property. Further, if it is added in an amount of more than 5% by weight, the defoaming property of the paint may be adversely affected or the recoating property may be impaired, which is not preferable.

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
In the following, "parts" and "%" indicate "parts by weight" and "% by weight", respectively.

Manufacturing Example 1 (ATRP method)
Toluene (300 g), ethyl methacrylate (60 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the following formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (150 g), ethyl 2-bromoisobutyrate (EtBrIB; 2.0 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g), and glucose (0.28 g). Copper (II) bromide (46 mg) and N, N, N', N'-tetrakis (20 g) previously dissolved in N, N-dimethylformamide (DMF) (20 g) after sufficient degassing with nitrogen gas. 2-Pyridylmethyl) ethylenediamine (TPEN) (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 10100 (Mw / Mn = 1.23) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 18100 (Mw / Mn = 1.19) in terms of polystyrene, and the monomer conversion rate was 90.1%. The molecular weight of the hydrophobic graft portion was calculated as 18100-10100 = 8000. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample A-1).

Manufacturing Example 2 (ATRP method)
Toluene (300 g), ethyl methacrylate (60 g), and methoxypolyethylene glycol # 600 (n = 13 mol) of the following formula b were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. ) Monoacrylate (150 g), ethyl 2-bromoisobutyrate (EtBrIB; 2.0 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g), and glucose (0.28 g). Copper bromide (II) (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) previously dissolved in DMF (20 g) after sufficient degassing with nitrogen gas. ) (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 9500 (Mw / Mn = 1.35) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the synthesized acrylic copolymer was 15900 (Mw / Mn = 1.32) in terms of polystyrene, and the monomer conversion rate was 94.4%. The molecular weight of the hydrophobic graft portion was calculated as 15900-9500 = 6400. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample A-2).

Manufacturing Example 3 (ATRP method)
Toluene (300 g), ethyl methacrylate (60 g), formula c below and methoxypolyethylene glycol # 400 (n = 9) in a 1000 ml reaction vessel equipped with a stirrer, reflux cooler, thermometer, and nitrogen gas inlet. Methyl) monoacrylate (150 g), ethyl 2-bromoisobutyrate (EtBrIB; 2.0 g) as initiator, tin 2-ethylhexanoate (II) (1.6 g), and glucose (0.28 g). Copper (II) bromide (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine previously dissolved in DMF (20 g) after being added and sufficiently degassed with nitrogen gas. TPN) (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 10600 (Mw / Mn = 1.46) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the synthesized acrylic copolymer was 18,000 (Mw / Mn = 1.42) in terms of polystyrene, and the monomer conversion rate was 98.5%. The molecular weight of the hydrophobic graft portion was calculated as 18000-10600 = 7400. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample A-3).

Manufacturing Example 4 (ATRP method)
Toluene (300 g), ethyl methacrylate (EMA) (60 g), and methoxypolyethylene glycol # 1000 (n) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. = 23 mol) Monomethacrylate (150 g), ethyl 2-bromoisobutyrate as initiator (EtBrIB; 2.0 g), tin 2-ethylhexanoate (II) (1.6 g), and glucose (0.28 g). ), And after sufficient degassing with nitrogen gas, copper (II) bromide (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) previously dissolved in DMF (20 g). Ethylenediamine (TPEN) (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 9400 (Mw / Mn = 1.41) in terms of polystyrene. Then, after 5 hours, X-22-174BX (60 g) and ethyl methacrylate (30 g) having the following structures were added and further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 17600 (Mw / Mn = 1.46) in terms of polystyrene, and the monomer conversion rate was 97.3%. The molecular weight of the hydrophobic graft portion was calculated as 17600-9400 = 8200. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample A-4).

Manufacturing Example 5 (ATRP method)
Toluene (300 g), ethyl methacrylate (60 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (150 g), ethyl 2-bromoisobutyrate (EtBrIB; 2.0 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g) and glucose (0.28 g) are added. Copper (II) bromide (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) previously dissolved in DMF (20 g) after sufficient degassing with nitrogen gas. (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 7100 (Mw / Mn = 1.20) in terms of polystyrene. Then, after 5 hours, KF-2012 (60 g) having the following structure and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 12000 (Mw / Mn = 1.30) in terms of polystyrene, and the monomer conversion rate was 89.5%. The molecular weight of the hydrophobic graft portion was calculated as 12000-7100 = 4900. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample A-5).

Manufacturing Example 6 (ATRP method)
Toluene (300 g), isobutyl acrylate (60 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (150 g), ethyl 2-bromoisobutyrate (EtBrIB; 2.0 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g), and glucose (0.28 g). Copper (II) bromide (46 mg) previously dissolved in DMF (20 g) after sufficient degassing with nitrogen gas.
) And N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) (88 mg) were added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 10000 (Mw / Mn = 1.17) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and isobutyl acrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 14600 (Mw / Mn = 1.19) in terms of polystyrene, and the monomer conversion rate was 95.3%. The molecular weight of the hydrophobic graft portion was calculated as 14600-10000 = 4600. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample A-6).

Manufacturing Example 7 (ATRP method)
Toluene (300 g), ethyl methacrylate (120 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (90 g), ethyl 2-bromoisobutyrate (EtBrIB; 3.2 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g), and glucose (0.28 g). Copper bromide (II) (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) previously dissolved in DMF (20 g) after sufficient degassing with nitrogen gas. ) (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 7500 (Mw / Mn = 1.28) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 16300 (Mw / Mn = 1.40) in terms of polystyrene, and the monomer conversion rate was 97.4%. The molecular weight of the hydrophobic graft portion was calculated as 16300-7500 = 8800. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample A-7).

Manufacturing Example 8 (ATRP method)
Toluene (300 g), ethyl methacrylate (45 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (120 g), ethyl 2-bromoisobutyrate (EtBrIB; 2.0 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g), and glucose (0.28 g). Copper bromide (II) (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) previously dissolved in DMF (20 g) after sufficient degassing with nitrogen gas. ) (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 4600 (Mw / Mn = 1.36) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (105 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 11900 (Mw / Mn = 1.40) in terms of polystyrene, and the monomer conversion rate was 98.8%. The molecular weight of the hydrophobic graft portion was calculated as 11900-4600 = 7300. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample A-8).

Manufacturing Example 9 (ATRP method)
Toluene (300 g), ethyl methacrylate (60 g), and methoxypolyethylene glycol # 1000 (n = 23) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. Mol) monomethacrylate (150 g), ethyl 2-bromoisobutyrate (EtBrIB; 0.4 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g), and glucose (0.28 g). Copper (II) bromide (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine previously dissolved in DMF (20 g) after being added and sufficiently degassed with nitrogen gas. TPN) (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 29300 (Mw / Mn = 1.32) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 52,500 (Mw / Mn = 1.36) in terms of polystyrene, and the monomer conversion rate was 88.3%. The molecular weight of the hydrophobic graft portion was calculated as 52500-29300 = 232000. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample A-9).

Manufacturing Example 10 (ATRP method)
Toluene (300 g), ethyl methacrylate (60 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (150 g), ethyl 2-bromoisobutyrate (EtBrIB; 8.2 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g), and glucose (0.28 g). Copper bromide (II) (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) previously dissolved in DMF (20 g) after sufficient degassing with nitrogen gas. ) (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 3100 (Mw / Mn = 1.25) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 5600 (Mw / Mn = 1.26) in terms of polystyrene, and the monomer conversion rate was 96.9%. The molecular weight of the hydrophobic graft portion was calculated as 5600-3100 = 2500. 20% after removing toluene using a rotary evaporator
A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to the concentration of propylene glycol monomethyl ether acetate (PEGMEA) was used for the subsequent coating test (test sample A-10).

Manufacturing Example 11 (RAFT method)
In a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), normal butyl acrylate (60 g), and methoxypolyethylene of the following formula d. Glycol # 200 (n = 4 mol) monoacrylate (150 g) and S, S-dibenzyltrithiocarbonate (2.5 g) as an initiator were added, and after sufficient degassing with nitrogen gas, 1,1 '-Azobis (cyclohexane-1-carbonitrile) (0.1 g) was added. Polymerization was carried out at 90 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 7000 (Mw / Mn = 1.19) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and normal butyl acrylate (30 g) were added, and the mixture was further polymerized at 90 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The polymer produced from S, S-dibenzyltrithiocarbonate proceeds with the reaction by the mechanism in which the monomer extends from both ends of S, S-dibenzyltrithiocarbonate, so that it is different from the ABA type triblock polymer. Become. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 13700 (Mw / Mn = 1.17) in terms of polystyrene, and the monomer conversion rate was 94.8%. The molecular weight of the hydrophobic graft portion was calculated as 13700-7000 = 6700. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample A-11).

Manufacturing Example 12 (RAFT method)
In a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), normal butyl acrylate (30 g), 2- of the following formula e After adding methoxyethyl acrylate (n = 1 mol) (180 g) and S, S-dibenzyltrithiocarbonate (2.0 g) as an initiator and sufficiently degassing with nitrogen gas, 1,1'-azobis (Cyclohexane-1-carbonitrile) (0.1 g) was added. Polymerization was carried out at 90 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 10600 (Mw / Mn = 1.16) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and normal butyl acrylate (30 g) were added, and the mixture was further polymerized at 90 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 13900 (Mw / Mn = 1.17) in terms of polystyrene, and the monomer conversion rate was 99.2%. The molecular weight of the hydrophobic graft portion was calculated as 13700-7000 = 6700. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample A-12).

Manufacturing Example 13 (RAFT method)
In a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), normal butyl acrylate (60 g), and methoxypolyethylene of the above formula a. Glycol # 1000 (n = 23 mol) monomethacrylate (150 g) and S, S-dibenzyltrithiocarbonate (2.0 g) as an initiator were added, and after sufficient degassing with nitrogen gas, 1,1'. -Azobis (cyclohexane-1-carbonitrile) (0.1 g) was added. Polymerization was carried out at 90 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 12700 (Mw / Mn = 1.19) in terms of polystyrene. Then, after 5 hours, X22-174BX (60 g) and normal butyl acrylate (30 g) were added, and the mixture was further polymerized at 90 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 23400 (Mw / Mn = 1.17) in terms of polystyrene, and the monomer conversion rate was 98.7%. The molecular weight of the hydrophobic graft portion was calculated as 23400-12700 = 10700. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample A-13).

Manufacturing Example 14 (RAFT method)
In a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), normal butyl acrylate (105 g), and methoxypolyethylene of the above formula a. Glycol # 1000 (n = 23 mol) monomethacrylate (150 g) and S, S-dibenzyltrithiocarbonate (2.0 g) as an initiator were added, and after sufficient degassing with nitrogen gas, 1,1'. -Azobis (cyclohexane-1-carbonitrile) (0.1 g) was added. Polymerization was carried out at 90 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 12200 (Mw / Mn = 1.20) in terms of polystyrene. Then, after 5 hours, X22-174BX (15 g) and normal butyl acrylate (30 g) were added, and the mixture was further polymerized at 90 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 15700 (Mw / Mn = 1.23) in terms of polystyrene, and the monomer conversion rate was 97.9%. The molecular weight of the hydrophobic graft portion was calculated as 15700-12200 = 3500. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample A-14).

Manufacturing Example 15 (RAFT method)
In a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), normal dodecyl acrylate (60 g), and methoxypolyethylene of the above formula a. Glycol # 1000 (n = 23 mol) monomethacrylate (150 g) and S, S-dibenzyltrithiocarbonate (4.8 g) as an initiator were added, and after sufficient degassing with nitrogen gas, 1,1'. -Azobis (cyclohexane-1-carbonitrile) (0.2 g) was added. Polymerization was carried out at 90 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 3600 (Mw / Mn = 1.29) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and normal dodecyl acrylate (30 g) were added, and the mixture was further polymerized at 90 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 8900 (Mw / Mn = 1.28) in terms of polystyrene, and the monomer conversion rate was 91.7%. The molecular weight of the hydrophobic graft portion was calculated as 8900-3600 = 5300. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample A-15).

Manufacturing Example 16 (RAFT method)
In a 1000 ml reaction vessel equipped with a stirrer, reflux cooler, thermometer, and nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), normal butyl acrylate (30 g) and benzyl acrylate (30 g). , Methoxypolyethylene glycol # 1000 (n = 23 mol) monomethacrylate (150 g) of the above formula a and S, S-dibenzyltrithiocarbonate (2.0 g) as an initiator are added, and nitrogen gas is sufficiently degassed. After that, 1,1'-azobis (cyclohexane-1-carbonitrile) (0.1 g) was added. Polymerization was carried out at 90 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 10600 (Mw / Mn = 1.18) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (60 g) and normal butyl acrylate (30 g) were added, and the mixture was further polymerized at 90 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 15100 (Mw / Mn = 1.20) in terms of polystyrene, and the monomer conversion rate was 91.7%. The molecular weight of the hydrophobic graft portion was calculated as 15100-10600 = 4500. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample A-16).

Manufacturing Example 17 (RAFT method)
In a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), normal butyl acrylate (30 g), and methoxypolyethylene of the above formula a. Glycol # 1000 (n = 23 mol) monomethacrylate (100 g) and S, S-dibenzyltrithiocarbonate (5.5 g) as an initiator were added, and after sufficient degassing with nitrogen gas, 1,1 '-Azobis (cyclohexane-1-carbonitrile) (0.2 g) was added. Polymerization was carried out at 90 ° C. for 5 hours while continuously injecting nitrogen gas. After 5 hours, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 6700 (Mw / Mn = 1.16) in terms of polystyrene. Then, after 5 hours, silaplane FM-0711 (40 g) and normal butyl acrylate (30 g) were added, and the mixture was further polymerized at 90 ° C. for 5 hours. At 10 hours from the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the amphipathic graft copolymer obtained by the above polymerization was 10800 (Mw / Mn = 1.25) in terms of polystyrene. The molecular weight of the hydrophobic graft portion was calculated as 10800-6700 = 4100. Then, at 10 hours from the start of the reaction, normal butyl acrylate (30 g) and methoxypolyethylene glycol # 1000 (n = 23 mol) monomethacrylate (100 g) of the above formula a were added, and the mixture was further polymerized at 90 ° C. for 5 hours. .. At 15 hours from the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the amphipathic graft copolymer obtained by the above polymerization was 16700 (Mw / Mn = 1.20) in terms of polystyrene. The total molecular weight of the two portions of the hydrophilic graft portion was calculated as 16700-10800 + 6700 = 9700. Further, at 15 hours from the start of the reaction, silaplane FM-0711 (40 g) and normal butyl acrylate (30 g) were added and polymerized at 90 ° C. for 5 hours. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The number average molecular weight of the amphipathic multiblock polymer obtained by the above polymerization was 22200 (Mw / Mn = 1.23) in terms of polystyrene, and the monomer conversion rate was 97.9%. The total molecular weight of the two portions of the hydrophobic graft section was calculated as 22200-9700 = 12500. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample A-17).

Manufacturing Example 18 (TERP method)
Tellurium compounds used in the TERP method are usually easily decomposed in air and are not easy to handle, but commercially available diphenylditelluride is not decomposed by oxygen, so it is polymerized with reference to the following documents. Was done.
・ S. Matsumoto. et al. , Macromolecules, 46, 8111 (2013)
・ S. Yamago, Chem. rev. , 109,5051, (2009)
In a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet, isobutylvinyl ether (500 g) as a monomer and solvent, and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a. Monomethacrylate (100 g), normal butyl acrylate (80 g), diphenylditerlide as initiator (8.2 g), 2,2'-azobis (isobutyronitrile) (AIBN: 3.1 g), and 2 , 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70: 8.2 g) was charged, and the temperature was raised to 60 ° C. while blowing nitrogen gas to initiate polymerization. At 8 hours after the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from diphenylditelluride by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 5500 (Mw / Mn = 1.26) in terms of polystyrene. Then, after 8 hours, silaplane FM-0711 (60 g) and normal butyl acrylate (60 g) were added, and the mixture was further polymerized at 60 ° C. for 8 hours. Conjugated / non-conjugated (acrylic / vinyl ether) diblock polymers were synthesized. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from diphenyl ditelluride were determined by GPC. Furthermore, the copolymerization ratio of isobutyl vinyl ether and normal butyl acrylate ^{was measured using 1} H-NMR. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 11000 (Mw / Mn = 1.33) in terms of polystyrene, and the monomer conversion rate was 49.5% including isobutyl vinyl ether. The molecular weight of the hydrophobic graft portion was calculated as 11000-5500 = 5500. The copolymerization ratio of isobutyl vinyl ether and normal butyl acrylate was ¹ H-NMR in which the ratio of isobutyl vinyl ether to 140 g of normal butyl acrylate was 100 g. After removing the unreacted isobutyl vinyl ether using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample A-18). ..

Production Comparative Example 1 (Random Copolymer: ATRP Method)
Using the living polymerization method (ATRP method), a polymer in which hydrophobic graft chains and hydrophilic graft chains were randomly present was synthesized. Toluene (300 g), ethyl methacrylate (90 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (150 g), silaplane FM-0711 (60 g), ethyl 2-bromoisobutyrate (EtBrIB; 2.0 g) as an initiator, tin 2-ethylhexanoate (II) (1.6 g), Copper (II) bromide (46 mg) and N, N, N', N'-tetrakis, which were previously dissolved in DMF (20 g) after adding glucose (0.28 g) and sufficiently degassing with nitrogen gas. (2-Pyridylmethyl) ethylenediamine (TPEN) (88 mg) was added. Polymerization was carried out at 80 ° C. for 12 hours while continuously injecting nitrogen gas. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the random copolymer obtained by the above polymerization was 14400 (Mw / Mn = 1.46) in terms of polystyrene, and the monomer conversion rate was 93.9%. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample N-1).

Production Comparative Example 2 (Random Copolymer: RAFT Method)
A living polymerization method (RAFT method) was used to synthesize a polymer in which hydrophobic graft chains and hydrophilic graft chains were randomly present. In a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), normal butyl acrylate (90 g), and methoxypolyethylene of the above formula b. Add glycol # 600 (n = 13 mol) monoacrylate (150 g), silaplane FM-0711 60 g, and S, S-dibenzyltrithiocarbonate (3.0 g) as an initiator, and sufficiently remove with nitrogen gas. After vaporization, 1,1'-azobis (cyclohexane-1-carbonitrile) (0.1 g) was added. Polymerization was carried out at 90 ° C. for 12 hours while continuously injecting nitrogen gas. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The number average molecular weight of the random copolymer obtained by the above polymerization was 9510 (Mw / Mn = 1.39) in terms of polystyrene, and the monomer conversion rate was 96.9%. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample N-2).

Production Comparative Example 3 (Random Copolymer)
A polymer in which hydrophobic graft chains and hydrophilic graft chains are randomly present was synthesized by a conventional radical polymerization method using a peroxide as an initiator. 150 parts of propylene glycol monomethyl ether acetate (PEGMEA) was placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, and the temperature was raised to 135 ° C. while introducing nitrogen gas. After warming, the dropping solution (a-1) shown below was dropped at a constant rate in 2 hours using a dropping funnel.
Drop solution (n-1)
Methoxypolyethylene glycol # 1000 (n = 23 mol) monomethacrylate of the above formula a 150 parts Acrylic acid normal butyl ester 90 parts Cyraplane FM-0711 60 parts PEGMEA 150 parts t-butylperoxy-2-ethylhexanoate 7. 5 parts 2,2-di- (t-amylperoxy) butane 4.1 parts

One hour after the completion of the dropping of the dropping solution (n-1), 1.5 parts of 2,2-di- (t-amylperoxy) butane was added, and the mixture was further reacted at 135 ° C. for 3 hours. The polystyrene-equivalent number average molecular weight of the synthesized acrylic copolymer by gel permeation chromatograph was 4900 (Mw / Mn = 2.03). A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample N-3).

Manufacturing Comparative Example 4 (ATRP method)
Using the living polymerization method (ATRP method), a high molecular weight amphipathic copolymer having a number average molecular weight outside the claimed range was polymerized. Toluene (300 g), ethyl methacrylate (60 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (150 g), ethyl 2-bromoisobutyrate (EtBrIB; 0.2 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g), and glucose (0.28 g). Copper bromide (II) (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) previously dissolved in DMF (20 g) after sufficient degassing with nitrogen gas. ) (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. At 5 hours after the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 31000 (Mw / Mn = 1.41) in terms of polystyrene. Then, 5 hours after the start of the reaction, silaplane FM-0711 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 66300 (Mw / Mn = 1.46) in terms of polystyrene, and the monomer conversion rate was 91.4%. The molecular weight of the hydrophobic graft portion was calculated as 66300-31000 = 35300. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample N-4).

Manufacturing Comparative Example 5 (ATRP method)
A living polymerization method (ATRP method) was used to polymerize a low molecular weight amphipathic copolymer having a number average molecular weight outside the claimed range. Toluene (300 g), ethyl methacrylate (60 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (150 g), ethyl 2-bromoisobutyrate as initiator (EtBrIB; 3)
0.8 g), tin 2-ethylhexanoate (II) (1.6 g) and glucose (0.28 g) were added, and after sufficient degassing with nitrogen gas, the bromide was previously dissolved in DMF (20 g). Copper (II) (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) (88 mg) were added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. At 5 hours after the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 810 (Mw / Mn = 1.46) in terms of polystyrene. Then, 5 hours after the start of the reaction, silaplane FM-0711 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 1860 (Mw / Mn = 1.45) in terms of polystyrene, and the monomer conversion rate was 96.2%. The molecular weight of the hydrophobic graft portion was calculated as 1860-810 = 1050. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample N-5).

Manufacturing Comparative Example 6 (RAFT method)
Using the living polymerization method (RAFT method), an amphipathic copolymer in which the amount of silicone macromer in the hydrophobic graft chain portion was less than the claimed range was polymerized. In a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), normal butyl acrylate (60 g), and methoxypolyethylene of the above formula a. Glycol # 1000 (n = 23 mol) monomethacrylate (150 g) and S, S-dibenzyltrithiocarbonate (2.5 g) as an initiator were added, and after sufficient degassing with nitrogen gas, 1,1 '-Azobis (cyclohexane-1-carbonitrile) (0.1 g) was added. Polymerization was carried out at 90 ° C. for 5 hours while continuously injecting nitrogen gas. At 5 hours after the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 8700 (Mw / Mn = 1.25) in terms of polystyrene. Then, 5 hours after the start of the reaction, silaplane FM-0711 (5 g) and normal butyl acrylate (85 g) were added, and the mixture was further polymerized at 90 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 15700 (Mw / Mn = 1.23) in terms of polystyrene, and the monomer conversion rate was 97.9%. The molecular weight of the hydrophobic graft portion was calculated as 15700-8700 = 7000. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample N-6).

Manufacturing Comparative Example 7 (RAFT method)
The living polymerization method (RAFT method) was used to polymerize an amphipathic copolymer in which the amount of silicone macromer in the hydrophobic graft chain portion was larger than the claimed range. In a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), normal butyl acrylate (30 g), and methoxypolyethylene of the above formula a. Glycol # 1000 (n = 23 mol) monomethacrylate (80 g) and S, S-dibenzyltrithiocarbonate (2.7 g) as an initiator were added, and after sufficient degassing with nitrogen gas, 1,1 '-Azobis (cyclohexane-1-carbonitrile) (0.1 g) was added. While continuing to blow nitrogen gas, 9
Polymerization was carried out at 0 ° C. for 5 hours. At 5 hours after the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 5200 (Mw / Mn = 1.30) in terms of polystyrene. Then, 5 hours after the start of the reaction, X22-174BX (160 g) and normal butyl acrylate (30 g) were added, and the mixture was further polymerized at 90 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 23,800 (Mw / Mn = 1.32) in terms of polystyrene, and the monomer conversion rate was 95.6%. The molecular weight of the hydrophobic graft portion was calculated as 23800-5200 = 18600. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample N-7).

Manufacturing Comparative Example 8 (ATRP method)
Using the living polymerization method (ATRP method), an amphipathic copolymer having a molecular weight of silicone macromer in the hydrophobic graft chain portion larger than the claimed range was polymerized. Toluene (300 g), ethyl methacrylate (60 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (150 g), ethyl 2-bromoisobutyrate (EtBrIB; 1.0 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g) and glucose (0.28 g) are added. Copper (II) bromide (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) previously dissolved in DMF (20 g) after sufficient degassing with nitrogen gas. (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. At 5 hours after the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 11700 (Mw / Mn = 1.30) in terms of polystyrene. Then, 5 hours after the start of the reaction, the following silaplane FM-0725 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 28900 (Mw / Mn = 1.45) in terms of polystyrene, and the monomer conversion rate was 89.2%. The molecular weight of the hydrophobic graft portion was calculated as 28900-11700 = 17200. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample N-8).

Manufacturing Comparative Example 9 (ATRP method)
The living polymerization method (ATRP method) was used to polymerize an amphipathic copolymer in which the amount of polyoxyethimacromar in the hydrophilic graft chain portion was less than the claimed range. Toluene (300 g), ethyl methacrylate (160 g), and methoxypolyethylene glycol # 1000 (n = 23 mol) of the above formula a were placed in a 1000 ml reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen gas inlet. ) Monomethacrylate (50 g), ethyl 2-bromoisobutyrate (EtBrIB; 4.0 g) as an initiator, tin (II) 2-ethylhexanoate (1.6 g) and glucose (0.28 g) are added. Copper (II) bromide (46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) previously dissolved in DMF (20 g) after sufficient degassing with nitrogen gas. (88 mg) was added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. At 5 hours after the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from ethyl EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 5800 (Mw / Mn = 1.30) in terms of polystyrene. Then, 5 hours after the start of the reaction, silaplane FM-0711 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 9600 (Mw / Mn = 1.16) in terms of polystyrene, and the monomer conversion rate was 96.4%. The molecular weight of the hydrophobic graft portion was calculated as 9600-4800 = 4800. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample N-9).

Manufacturing Comparative Example 10 (RAFT method)
The living polymerization method (RAFT method) was used to polymerize an amphipathic copolymer in which the amount of polyoxyethylene macromer in the hydrophilic graft chain portion was larger than the claimed range. In a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet, propylene glycol monomethyl ether acetate (PEGMEA) (300 g), methoxypolyethylene glycol # 200 (n = 4 mol) of the above formula d. ) Monoacrylate (210 g) and S, S-dibenzyltrithiocarbonate (2.0 g) as an initiator are added, and after sufficient degassing with nitrogen gas, 1,1'-azobis (cyclohexane-1-) is added. Carbonitrile) (0.1 g) was added. Polymerization was carried out at 90 ° C. for 5 hours while continuously injecting nitrogen gas. At 5 hours after the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 10900 (Mw / Mn = 1.36) in terms of polystyrene. Then, 5 hours after the start of the reaction, silaplane FM-0711 (60 g) and methoxypolyethylene glycol # 200 (n = 4 mol) monoacrylate (30 g) were added, and the mixture was further polymerized at 90 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography using n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from S, S-dibenzyltrithiocarbonate were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 17800 (Mw / Mn = 1.35) in terms of polystyrene, and the monomer conversion rate was 92.3%. The molecular weight of the graft copolymer grafted with both silicone macromer and polyethylene glycol macromer was calculated as 17800-10900 = 6900. A solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used in subsequent paint tests (Test Sample N-10).

Manufacturing Comparative Example 11 (ATRP method)
Using the living polymerization method (ATRP method), an amphipathic copolymer having a molecular weight of polyoxyethylene macromer in the hydrophilic graft chain portion larger than the claimed range was polymerized. Toluene (3) in a 1000 ml reaction vessel equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet.
00 g), ethyl methacrylate (60 g), methoxypolyethylene glycol # 4000 (n = 90 mol) monomethacrylate (150 g) of the following formula f, ethyl 2-bromoisobutyrate (EtBrIB; 1.8 g) as an initiator, Copper (II) bromide (II), which was previously dissolved in DMF (20 g) after adding tin (II) 2-ethylhexanate (1.6 g) and glucose (0.28 g) and sufficiently degassing with nitrogen gas. 46 mg) and N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) (88 mg) were added. Polymerization was carried out at 80 ° C. for 5 hours while continuously injecting nitrogen gas. At 5 hours after the start of the reaction, the molecular weight and molecular weight distribution of the polymer produced from EtBrIB by sampling were determined by GPC. The number average molecular weight of the hydrophilic graft copolymer obtained by the above polymerization was 8500 (Mw / Mn = 1.35) in terms of polystyrene. Then, 5 hours after the start of the reaction, silaplane FM-0711 (60 g) and ethyl methacrylate (30 g) were added, and the mixture was further polymerized at 80 ° C. for 7 hours. The monomer conversion rate was determined by gas chromatography with n-octane as an internal standard, and the molecular weight and molecular weight distribution of the polymer produced from EtBrIB were determined by GPC. The number average molecular weight of the amphipathic polymer obtained by the above polymerization was 13000 (Mw / Mn = 1.20) in terms of polystyrene, and the monomer conversion rate was 86.4%. The molecular weight of the hydrophobic graft portion was calculated as 13000-8500 = 4500. After removing toluene using a rotary evaporator, a solution diluted with propylene glycol monomethyl ether acetate (PEGMEA) to a concentration of 20% was used for the subsequent paint test (test sample N-11).

Production Comparative Example 12 (Commercially available acrylic polymer)
As a leveling agent for a commercially available acrylic polymer, a solution obtained by diluting an ethyl acrylate / 2 ethyl hexyl acrylate copolymer (number average molecular weight 8000) with PEGMEA so as to have a solid content of 20% was used for the subsequent coating test (. Test sample N-12).

Production Comparative Example 13 (Commercially available Polyether-Modified Silicone Oil)
As a commercially available polyether-modified silicone-based leveling agent, a solution obtained by diluting the two-ended type / polyether-modified (non-reactive silicone oil) of the following formula g with PEGMEA so that the solid content becomes 20% is used in the subsequent paint test. (Test sample N-13).

＊）ａ：主鎖のポリジメチルシロキサン部の分子量
＊）ｂ：両末端部のＰＥＧの付加モル数
ＥＭＡ：メタクリル酸エチルエステル
ＮＢＡ：アクリル酸ノルマルブチルエステル
ＩＢＡ：アクリル酸イソブチルエステル
ＮＬＡ：アクリル酸ノルマルドデシルエステル
ＢＺＡ：アクリル酸ベンジルエステル
ＩＢＶＥ：イソブチルビニルエーテル

*) A: Molecular weight of the polydimethylsiloxane portion of the main chain *) b: Number of moles of PEG added at both ends EMA: Ethyl methacrylate ester NBA: Normal butyl ester of acrylate IBA: Isobutyl ester of acrylic acid NLA: Normal of acrylic acid Dodecyl ester BZA: Acrylic acid benzyl ester IBVE: Isobutyl vinyl ether

Paint Test Examples The test results of various leveling agents shown in Production Examples and Comparative Production Examples are shown below.
The two-component acrylic polyol / isocyanate-curable coating composition having the formulation shown in Table 4 was subjected to a performance test of leveling property and repellency prevention property.
First, the paints having the formulations shown in Tables 3, 4, and 5 were prepared. The test samples A-1 to A-18 in Table 1 and the test samples N-1 to N-13 in Table 2 were added to the clear paint (main agent) for the top coat in Table 4, respectively, and the test samples were added to the lab disperser. Dispersed at 2000 rpm for 1 minute.

Evaluation Example 1 (Leveling test)
After adjusting the viscosity of the intermediate coating paint shown in Table 5 to 18 seconds with Ford Cup # 4, air spray coating is applied to a tin plate (200 mm x 300 mm) at 140 ° C. for 20 minutes. It was baked in an oven to create an intermediate coating plate. Next, the metallic base paint shown in Table 3 was diluted with a diluting solvent so that the viscosity of the paint was 13 seconds with Ford Cup # 4, and then air spray was used to make the dried coating film 15 μm. Was coated on the above intermediate coating plate, and the coating film was dried at room temperature for 5 minutes. Separately, Part A (main agent) of the above top coat clear paint to which each test sample is added and an isocyanate curing agent are stirred and mixed, and then diluted with a diluting solvent so that the viscosity of the paint becomes 25 seconds with Ford Cup # 4. did. This diluted top clear paint was applied on the metallic base coating film using an air spray so as to have a film thickness of 30 μm. After allowing to stand at room temperature for 5 minutes, it was baked in an oven at 140 ° C. for 30 minutes. In the evaluation of the leveling property of the coating film, the leveling property of the coating film surface was visually evaluated in comparison with the standard plate having five stages from the best to the worst. The results are shown in Table 7.

Evaluation Example 2 (Test for repelling prevention)
After adjusting the viscosity of the intermediate coating paint shown in Table 5 to 18 seconds with Ford Cup # 4, air spray coating is applied to a tin plate (200 mm x 300 mm) at 140 ° C. for 20 minutes. It was baked in an oven to create an intermediate coating plate. After cooling to room temperature, various different kinds of dust substances shown in Table 6 were adhered on the intermediate coating plate.
Separately, after stirring and mixing Part A (main agent) of the top coat clear paint in Table 4 to which various test samples were added and the isocyanate curing agent, the viscosity of the paint was adjusted to 25 seconds with Ford Cup # 4 using a diluting solvent. Diluted to be. Next, this diluted top clear paint is applied on the above intermediate coating film using an air spray so as to have a film thickness of 30 μm, allowed to stand at room temperature for 5 minutes, and then baked in an oven at 80 ° C. for 30 minutes. After that, the generation of repellent due to different kinds of dust (pollutant) was observed and evaluated on a five-point scale from "best" (5) to "worst" (1). The results are shown in Table 7.

Evaluation Example 3 (Evaluation of Ricoh Okasare property)
After diluting the metallic base paint in Table 3 with a diluting solvent so that the viscosity of the paint becomes 13 seconds with Ford Cup # 4, use an air spray to make the dried coating film medium to 15 μm. A coating was applied on a coated plate, and the coating film was allowed to stand at room temperature for 5 minutes. Separately, after stirring and mixing Part A (main agent) of the top coat clear paint in Table 4 to which the test sample was added and the isocyanate curing agent, the viscosity of the paint becomes 25 seconds in Ford Cup # 4 using a diluting solvent. Diluted as such. 30μ of this top coat clear paint using air spray
It was coated on the above-mentioned intermediate coating film so as to have a film thickness of m, allowed to stand at room temperature for 5 minutes, and then baked in an oven at 140 ° C. for 30 minutes. After cooling this to room temperature, the clear painted surface was wiped in stripes with petroleum benzine. After the petroleum benzine had dried, the metallic base coat paint and the top coat clear paint were repainted on the wiped painted surface by the same procedure as above, and baked in an oven at 140 ° C. for 30 minutes. After cooling to room temperature, the change in the color of the base coat between the wiped part and the non-wipe part was observed. The evaluation of the coating film test was performed as follows. The change in color due to petroleum benzine (denoted as stone benzine) and the appearance were visually evaluated and evaluated on a five-point scale from "best" (5) to "worst" (1). The test results are shown in Table 8.

Evaluation Example 4 (Evaluation of water resistance)
After stirring and mixing Part A (main agent) of the clear paint in Table 4 to which each test sample was added and the isocyanate curing agent, apply it to a glass plate (120 mm × 160 mm) with a 200 μ applicator, and in an oven at 80 ° C. for 30 minutes. The baked coating film was subjected to a water resistance test (whitening resistance test). In the water resistance test, the coated plate is immersed in warm water at 80 ° C. for 1 hour, allowed to cool until the water temperature reaches 25 ° C., the coated plate is taken out from the water tank, the surface is gently wiped off with gauze, and then the coating film is coated. Transparency was visually evaluated on a scale of 5 from "best" (5) to "worst" (1). The test results are shown in Table 8.

Evaluation Example 5 (Measurement of surface tension)
After stirring and mixing Part A (main agent) of the clear paint in Table 4 to which each test sample is added and the isocyanate curing agent, apply it to a glass plate (120 mm × 160 mm) with a 200 μ applicator, and in an oven at 80 ° C. for 30 minutes. After baking and cooling to room temperature, the contact angle of water and the contact angle of hexadecane were measured with an automatic contact angle meter (manufactured by Kyowa Surface Chemistry Co., Ltd .: DM-501). Then, the coated plate was immersed in a water tank at 25 ° C. for 1 hour and then taken out, and the contact angle of water immediately after the surface was gently wiped with gauze was measured. The measurement results are shown in Table 8.

疎水性のシリコーングラフト部と親水性のポリエチレングリコールグラフト部をブロックポリマー化した製造実施例のポリマーは、シリコーングラフト鎖の密度が高くなっているので、はじき防止効果が向上した。更に、ポリエーテルグラフト鎖部分が独立しているために、水を滴下した時にすぐに水の接触角が低下した。この理由により、塗料を塗り重ねた際の上塗りした塗料の濡れ性が向上した。これに対し、ランダムコポリマーでは、同じシリコーン量でははじき防止性が劣り、また、塗膜を完全に水中に浸漬しないと、水との接触角が低下しなかった。

In the polymer of the production example in which the hydrophobic silicone graft portion and the hydrophilic polyethylene glycol graft portion were block polymerized, the density of the silicone graft chain was high, so that the repelling prevention effect was improved. Furthermore, because the polyether graft chain portion is independent, the contact angle of water immediately decreases when water is dropped. For this reason, the wettability of the overcoated paint when the paint is repeatedly applied is improved. On the other hand, in the random copolymer, the repelling property was inferior at the same amount of silicone, and the contact angle with water did not decrease unless the coating film was completely immersed in water.

Claims (4)

General formula [I]

[In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 1 to 10 carbon atoms, R3 represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 5 to 50. ]
Silicone oil with (meth) acryloyloxy group, represented by the general formula [II].

[In the formula, R4 represents a hydrogen atom or a methyl group, and R5 represents an alkyl group having 1 to 12 carbon atoms. ]
In the illustrated as (meth) Rukoto the acrylic ester living radical polymerization match, the step of forming a polymer having a hydrophobic silicone grafts and,
General formula [III]

[In the formula, R6 represents a hydrogen atom or a methyl group, R7 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and m represents an integer of 1 to 50. ]
By performing living radical polymerization of the (meth) acrylic acid ester having an oxyethylene group represented by the above and the (meth) acrylic acid ester represented by the above general formula [II], a polymer having a hydrophilic oxyethylene graft portion can be obtained. characterized in that it comprises a step of forming a manufacturing method of the amphiphilic block copolymer, based on the total weight of the monomers constituting the amphiphilic block copolymer, the formula [ The polymerization ratios of the monomer of I], the monomer of the above formula [II], and the monomer of the above formula [III] are 2 to 50% by weight, 20 to 80% by weight, and 20 to 80% by weight, respectively. the number average molecular weight in terms of polystyrene of the polymer who has a hydrophobic silicone-grafted portion is 1,000 to 30,000, the number average molecular weight in terms of polystyrene of the polymer over with the hydrophilic oxyethylene grafts is a 1,000 to 30,000, A method for producing an amphoteric block copolymer, wherein the polystyrene-equivalent number average molecular weight of the amphoteric block copolymer is 2000 to 60,000. A method for producing a leveling agent for paints, which comprises an amphipathic block copolymer as an active ingredient, wherein the amphipathic block copolymer is produced by the method according to claim 1. Method. The production method according to claim 1 or 2 , wherein the amphipathic block copolymer is a diblock type, triblock type, or multi-block type block copolymer. Monomers having other polymerizable double-bonding groups copolymerizable with the monomers of the above formulas [I], [II] and [III] are 40 weights based on the total weight of the monomers constituting the block copolymer. The production method according to any one of claims 1 to 3, wherein the main chain of the block copolymer is formed in a range not exceeding%.