Surface modifiers for paints or coatings, paints, and coatings

Abstract

The present invention provides a surface modifier for paints or coatings that maintains solubility even when the silicone content of a silicone-containing polymer is increased, and that can further reduce the surface tension of paints and coatings and improve the slipperiness and stain resistance of the resulting coating film. [Solution] The surface modifier comprises a silicone-containing unit (B) consisting of repeating units derived from a silicone compound monomer represented by formula (1), polymerized with polymerizable mercapto-derived or azo-derived groups of the silicone compound monomer, and a unit (A) consisting of repeating units derived from a compound monomer having polymerizable double bond groups that are polymerized to mercapto-derived or azo-derived groups, and comprises a block polymer having a block copolymer repeating structure in at least a portion of it. TIFF2026143188000026.tif33170 (In the formula, z is 1, Y is a mercapto group, R and R 1 x is an alkylene group, x is a mercapto group or alkyl group, or z is 1 to 20, Y is a hydroxyl group, and R is -CO-R 11 -N=NR 12 -, x is a hydrogen atom)

Description

Technical Field

[0001] The present invention relates to a surface conditioner for paints or coating agents, paints, and coating agents. Background Art

[0002] Leveling agent-containing paints and coating agents are applied to various base materials such as metal vehicle bodies of automobiles, metal materials for pre-coating, plastic housings of home electric appliances such as mobile phones and personal computers, and building materials, so as to protect the surface while improving the aesthetic appearance of these base materials. As a leveling agent for paints and coating agents that is blended in such paints and coating agents, for example, Patent Document 1 below proposes a polymer obtained by block-polymerizing a hydrophobic silicone graft portion and a hydrophilic polyethylene glycol graft portion. According to this polymer, since the density of silicone graft chains is increased, the cratering resistance effect is improved; and since the polyether graft chain portion is independent, the contact angle of water decreases immediately when water is dropped, thereby improving the wettability of the overcoated paint or coating agent when paints or coating agents are applied in multiple layers. Prior Art Literature Patent Literature

[0003] Patent Document 1 Japanese Unexamined Patent Application Publication No. 2018-199765 Summary of the Invention Problems to be Solved by the Invention

[0004] However, in recent years, in order to further improve the aesthetic appearance of metal bodies and the like of automobiles, there has been a demand for further reduction in the surface tension of paints and coating agents and further improvement in slip properties. In order to meet such demands, increasing the silicone content of a silicone-containing polymer used as a surface conditioner blended in a leveling agent for paints and coating agents poses problems such as decreased solubility of the leveling agent in paints and coating agents and easy occurrence of defects such as cissing.

[0005] The present invention solves the above problems, and provides a surface conditioner for paints and coating agents, a paint, and a coating agent, which can maintain the solubility of the silicone-containing polymer even when the silicone blending amount of the silicone-containing polymer used as a surface conditioner for paints and coating agents is increased, and can achieve further reduction in the surface tension of the paint or coating agent containing the silicone-containing polymer and improvement in the slip property and antifouling property of the produced coating film. The object of the present invention is to provide the aforementioned surface conditioner for paints and coating agents, paint, and coating agent. [Means for Solving the Problems]

[0006] A surface conditioner for paints or coating agents that can achieve the above object is the following chemical formula (1) [Chemical Formula] (wherein z is the number 1, Y is a mercapto group, R and R 1 is an alkylene group having 1 to 12 carbon atoms, and X represents a mercapto group or an alkyl group having 1 to 6 carbon atoms; or z is a number from 1 to 20, Y is a hydroxyl group, R is -CO-R 11 -N=N-R 12 -, R 1 is -(CH2) u -NH-, X represents a hydrogen atom. R 11 is [Chemical Formula] , where R a1 and R a2each independently represents hydrogen, alkyl having 1 to 6 carbon atoms or nitrile, and Ph represents a phenylene group. R 12 is

Chemical Formula

[0007] It is preferable that the weight average molecular weight of the block polymer is 1,000 to 100,000.

[0008] The compound monomer having the polymerizable double bond group is represented by the following chemical formula (2), the following chemical formula (3), and the following chemical formula (4)

Chemical Formula

[0009] Among the repeating units derived from the compound monomer having the polymerizable double bond group, the following chemical formula (5) or chemical formula (6) [ka] (In the above chemical formula (5), R 2 R is a hydrogen atom or a methyl group. 3 represents an alkylene group with 1 to 18 carbon atoms. In the above chemical formula (6), a and b are numbers from 0 to 30, R 5 represents a hydrogen atom or a methyl group.) The unit comprises repeating units derived from ), wherein the unit preferably contains repeating units in which an isocyanate group of an isocyanate monomer having a (meth)acrylic group or an epoxy group of an epoxy monomer having a (meth)acrylic group reacts with and bonds to a hydroxyl group derived from the chemical formula (5) or chemical formula (6).

[0010] Preferably, the copolymer contains a diblock (AB type), triblock (ABA type), or multiblock (ABABA type) block polymer comprising the silicone-containing unit (B) and a unit (A) consisting of repeating units derived from a compound monomer having a polymerizable double bond group.

[0011] In the unit (A) consisting of repeating units of the polymerizable double bond group compound monomer, the above-mentioned polymerizable double bond group compound monomer and other polymerizable double bond group compound monomers other than the aforementioned compound monomer are copolymerized, and it is preferable that the proportion of the other polymerizable double bond group compound monomers to the block polymer does not exceed 40% by mass.

[0012] A paint that can achieve the objectives of the present invention includes the aforementioned surface modifier for paints or coatings.

[0013] A coating agent that can achieve the objectives of the present invention includes the aforementioned surface modifier for paints or coating agents. [Effects of the Invention]

[0014] In the surface modifier for paints or coatings according to the present invention, even when the ratio of silicone chains to the contained block polymer is increased to 60% by mass, the solubility of the contained block polymer in paints and coatings is well maintained, while further reducing the surface tension of the paint or coating and improving the slipperiness and antifouling properties of the resulting coating film can be achieved. [Modes for carrying out the invention]

[0015] The surface modifier for paints or coatings of the present invention comprises a block polymer containing a copolymer having a block copolymer structure, at least a portion of which is a repeating structure of block copolymers, comprising: a silicone-containing unit (B) which is made up of repeating units derived from a silicone compound monomer and polymerized with polymerizable mercapto-derived groups or azo-derived groups of the silicone compound monomer; and a unit (A) which is made up of repeating units derived from a compound monomer having polymerizable double bond groups that are polymerized to the mercapto-derived groups or azo-derived groups.

[0016] The block polymer contained in the surface modifier for paints or coatings of the present invention is the following chemical formula (7) [ka] (In the formula, z is the number 1, Y is a mercapto group, R and R 1The formula consists of repeating units derived from a silicone compound monomer (where n is 0-500), and includes a silicone-containing unit (B) which is polymerized with a polymerizable mercapto-derived group of this silicone compound monomer. This "mercapto-derived group" means a group that can react with other compounds after being radicalized, etc. Here, a silicone compound monomer in which n is 50 to 300 is preferred, and R 1 Examples of one-terminated mercapto-modified silicone monomers in which X is an alkyl group having 1 to 12 carbon atoms include α-methyl-ω-(methylmercapto)polydimethylsiloxane, α-ethyl-ω-(methylmercapto)polydimethylsiloxane, α-propyl-ω-(methylmercapto)polydimethylsiloxane, α-butyl-ω-(methylmercapto)polydimethylsiloxane, α-butyl-ω-(ethylmercapto)polydimethylsiloxane, and α-butyl-ω-(propylmercapto)polydimethylsiloxane. Examples of two-terminated mercapto-modified silicone monomers in which X is a mercapto group include X-22-167B and X-22-167C (both product names of Shin-Etsu Chemical Co., Ltd.).

[0017] The following are examples of compound monomers having polymerizable double bond groups that polymerize to polymerizable mercapto-derived groups of the silicone compound monomer of chemical formula (7) above: chemical formula (8), chemical formula (9), and chemical formula (10) below. [ka] (R in the above chemical formula (8)) 2 R is a hydrogen atom or a methyl group. 3 R is an alkylene group with 1 to 18 carbon atoms. 4 represents a hydrogen atom or a hydroxyl group. In the above chemical formula (9), a and b are numbers from 0 to 30, R 5 R is a hydrogen atom or a methyl group. 6 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. In the above chemical formula (10), c is a number from 0 to 500, R7 R is an alkylene group with 1 to 8 carbon atoms. 8 R is an alkyl group having 1 to 12 carbon atoms. 9 (where represents a hydrogen atom or a methyl group.) Preferably, it is at least one selected from the group consisting of compound monomers having polymerizable double bond groups represented by (), (meth)acrylamide derivative monomers, and unsaturated group-containing morpholine monomers.

[0018] Examples of compound monomers represented by the above chemical formula (8) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0019] Examples of compound monomers represented by the above chemical formula (9) include polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, n-butoxyethyl (meth)acrylate, butoxydiethylene glycol (meth)acrylate, and polyethylene glycol-propylene glycol (meth)acrylate.

[0020] Examples of compound monomers represented by the above chemical formula (10) include, as single-end reaction types, Cyraplane® FM-0711, Cyraplane® FM-0721, Cyraplane® FM-0725 (all product names of JNC Corporation), X-22-174BX, KF-2012, and X-22-2426 (all product names of Shin-Etsu Chemical Co., Ltd.).

[0021] Examples of (meth)acrylamide derivative monomers include (meth)acrylamide monomers other than N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, hydroxyethyl(meth)acrylamide, and (meth)acryloylmorpholin, which may be (meth)acrylamide, unsubstituted, or substituted with ketone groups, amino groups, sulfonic acid groups, or salts thereof. Examples include N-alkyl(meth)acrylamide and N,N-dialkyl(meth)acrylamide with alkyl groups having 1 to 12 carbon atoms, cyclic (meth)acrylamide, dimethylaminopropyl(meth)acrylamide, or its quaternary salts, isopropyl(meth)acrylamide, N-[3-(dimethylamino)propyl](meth)acrylamide), diacetone(meth)acrylamide, (meth)acrylamide-tert-butylsulfonic acid, (meth)acrylamide-tert-butylsulfonic acid organic salts, and (meth)acrylamide-tert-butylsulfonic acid inorganic salts. Specifically, one example is DMAA (a product name of KJ Chemicals Co., Ltd.), which is N,N-dimethylacrylamide.

[0022] An example of an unsaturated group-containing morpholine monomer is acryloylmorpholine, specifically ACMO (a product name from KJ Chemicals Co., Ltd.).

[0023] A block polymer containing a copolymer having a block copolymer repeat structure, comprising a silicone-containing unit (B) polymerized with polymerizable mercapto-derived groups of the aforementioned silicone compound monomer, and a unit (A) consisting of repeating units derived from a compound monomer having polymerizable double bond groups polymerized to mercapto-derived groups, wherein at least a portion of the copolymer has a block copolymer repeat structure, has a silicone chain ratio of 10 to 60% by mass, preferably 15 to 45% by mass, relative to the block polymer. Block polymers with a silicone chain ratio of less than 10% by mass cannot sufficiently reduce surface tension or sufficiently improve slip properties when incorporated into paints or coatings. On the other hand, block polymers with a silicone chain ratio exceeding 60% by mass tend to experience a decrease in solubility in paints and coatings.

[0024] The weight-average molecular weight of the block polymer contained in the surface modifier for paints or coatings according to the present invention is preferably 1,000 to 100,000, and more preferably 5,000 to 50,000.

[0025] As described later, the mercapto group of the silicone compound monomer represented by the above chemical formula (7) is radicalized and copolymerized by successive radical reactions with the polymerizable double bond group of the compound monomer. Therefore, when a silicone compound monomer having mercapto groups on both ends of the silicone chain is used, the copolymer contained in the block polymer according to the present invention contains many triblock type (ABA type) units, which consist of a silicone-containing unit (B) polymerized with the polymerizable mercapto-derived group of the silicone compound monomer and a unit (A) consisting of repeating units derived from the compound monomer having a polymerizable double bond group that is polymerized to the mercapto-derived group. With a block polymer containing many of these triblock type (ABA type) units, the silicone-containing unit (B) and the unit (A) consisting of repeating units derived from the compound monomer having a polymerizable double bond group are separated. Therefore, while maintaining high solubility in paints and coatings, the silicone-containing unit (B) is efficiently oriented on the surface, which is expected to further reduce surface tension and improve the slipperiness and antifouling properties of the resulting coating film. Furthermore, when a silicone compound monomer having a mercapto group on only one end of the silicone chain is used, the copolymer contained in the block polymer according to the present invention contains many diblock type (AB type) block polymers, which consist of a silicone-containing unit (B) and a unit (A) consisting of repeating units derived from a compound monomer having a polymerizable double bond group. Block polymers containing many diblock type (AB type) units in this way can be expected to have similar effects to triblock type (ABA type) units. Furthermore, radical copolymerization can be terminated by, for example, the bonding of radicals or the deactivation of radicals, but during the bonding of radicals, a multi-block type (ABABA type) may be formed.

[0026] Among the repeating units derived from compound monomers having polymerizable double bond groups of block polymers contained in the surface modifier for paints or coatings according to the present invention, the following chemical formula (11) or chemical formula (12) [ka] (In the above chemical formula (11), R 2 R is a hydrogen atom or a methyl group. 3 represents an alkylene group with 1 to 18 carbon atoms. In the above chemical formula (12), a and b are numbers from 0 to 30, R 5 ) represents a hydrogen atom or a methyl group. The unit comprises repeating units derived from ), and it is preferable that this unit contains repeating units in which an isocyanate group of an isocyanate monomer having a (meth)acrylic group or an epoxy group of an epoxy monomer having a (meth)acrylic group reacts with and bonds to a hydroxyl group derived from the above chemical formula (11) or chemical formula (12). When this block polymer is used, for example, as an additive to paints or coatings, the (meth)acrylic groups derived from the isocyanate monomer having a (meth)acrylic group or the epoxy monomer having a (meth)acrylic group react with the double bond-containing components of the paint or coating, or react with each other as block polymers, thereby enabling immobilization on the coating and contributing to improved durability of the surface modifier.

[0027] In order to add other properties to the block polymer according to the present invention, the unit (A), which consists of repeating units derived from a compound monomer having a polymerizable double bond group, may be copolymerized with the compound monomer having a polymerizable double bond group described above and other compound monomers having polymerizable double bond groups other than this compound monomer. However, it is preferable that the proportion of other compound monomers having polymerizable double bond groups to the block polymer does not exceed 40% by mass. Examples of other compound monomers having polymerizable double bond groups include phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, ethylene glycol di(meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[0-(1'-methylpropyleneneamino)carboxyamino]ethyl (meth)acrylate, (meth)acrylic acid, 2-(meth)acryloxyethyl succinic acid, and 2-(meth)acryloyloxyethyl Examples include (meth)acrylate monomers such as hexahydrophthalic acid, 2-(meth)acryloyloxyethylphthalic acid, and isobornyl (meth)acrylate; aromatic vinyl monomers such as styrene and vinyltoluene; linear or cyclic alkyl vinyl AL monomers having 1 to 12 carbon atoms such as n-butyl vinyl ether, isobutyl vinyl ether, dodecyl vinyl ether, and cyclohexyl vinyl ether; and vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl laurate. Furthermore, the number and type of monomers used are not limited to those listed above, as long as they can polymerize with the silicone oil of chemical formula (11).

[0028] The method for producing the block polymer contained in the surface modifier for paints or coatings according to the present invention described above is: The following chemical formula (13) [ka] (In the formula, z is the number 1, Y is a mercapto group, R and R 1The process involves copolymerizing a silicone oil having mercapto groups at one or both ends of a silicone chain (where n is 0-500), with a compound having polymerizable double bond groups, by adding a radical initiator that radicalizes the mercapto groups.

[0029] Examples of compounds having this polymerizable double bond group are shown in the following chemical formulas (14), (15), and (16). [ka] (R in the above chemical formula (14) 2 R is a hydrogen atom or a methyl group. 3 R is an alkylene group with 1 to 18 carbon atoms. 4 represents a hydrogen atom or a hydroxyl group. In the above chemical formula (15), a and b are numbers from 0 to 30, R 5 R is a hydrogen atom or a methyl group. 6 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. In the above chemical formula (16), c is a number from 0 to 500, R 7 R is an alkylene group with 1 to 8 carbon atoms. 8 R is an alkyl group having 1 to 12 carbon atoms. 9 (where represents a hydrogen atom or a methyl group.) Preferably, it is at least one selected from the group consisting of compound monomers having polymerizable double bond groups represented by (), (meth)acrylamide derivative monomers, and unsaturated group-containing morpholine monomers. The compound having such polymerizable double bond groups is preferably used in an amount of 65 to 900 parts by mass, and more preferably 100 to 600 parts by mass, per 100 parts by mass of silicone oil.

[0030] Furthermore, examples of radical initiators that radicalize the mercapto groups of silicone oil include organic peroxide radical initiators such as Perocta-O, Perhexyl-O, Perbutyl-O, Perbutyl-L, and Perloyl-L (all product names of NOF Corporation), and azo polymerization initiators such as azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitride), and V-65 (product name of Fujifilm Wako Pure Chemical Industries, Ltd.). These radical initiators may be used individually or in combination. It is necessary to add the radical initiator so that the number of radical moles generated is 100 to 400 for every 100 moles of mercapto groups at the end of the silicone oil. If the amount of radical initiator added is less than 100 for every 100 moles of mercapto groups at the end of the silicone oil, the mercapto groups of the silicone oil cannot be sufficiently radicalized, and the desired block polymer cannot be obtained. On the other hand, if the amount of radical initiator added exceeds 400 moles of radicals per 100 moles of silicone oil-terminated mercapto groups, the reaction will stop due to the formation of a polymer without silicone oil, or due to the bonding of radicals or deactivation of radicals. The amount of radical initiator added is preferably such that the number of radicals generated per 100 moles of silicone oil-terminated mercapto groups is 100 to 400, and more preferably 100 to 200. The number of radical moles (Ra) is calculated using the following formula based on the amount of radical initiator W (g), the amount of silicone oil S (g), its molecular weight (Mn), and the molecular weight of the radical initiator (Mr). Ra = (W × Mn / S / Mr) × 100

[0031] The silicone oil and the compound having polymerizable double bond groups described above are dissolved in an inert solvent. Preferably, this inert solvent is capable of dissolving or suspending the copolymer and is miscible with the coating agent. Specifically, examples include hydrocarbon solvents such as xylene, toluene, and cyclohexane; ketone solvents such as cyclohexanone and methyl isobutyl ketone; ether solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, and propylene glycol monomethyl ether; ester solvents such as n-butyl acetate, isobutyl acetate, n-amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; and alcohol solvents such as isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, and 3-methyl-3-methoxybutanol. These solvents may be used individually or in combination. In this manner, a desired block polymer can be obtained by adding a predetermined amount of radical initiator to a solution obtained by dissolving silicone oil and a compound having polymerizable double bond groups in a solvent, and then maintaining the temperature at 80-130°C for 2-8 hours while stirring in a nitrogen atmosphere.

[0032] The block polymer contained in the surface modifier for paints or coatings according to the present invention, as described above, has a silicone-containing unit (B) which is polymerized with polymerizable mercapto groups of a silicone compound monomer having mercapto groups at one or both ends. The following chemical formula (17) [ka] (In the formula, z is a number from 1 to 20, Y is a hydroxyl group, and R is -CO-R) 11 -N=NR 12 -, R 1 ha-(CH2) u -NH-, where X represents a hydrogen atom. 11teeth [ka] And R a1 and R a2 Each of the following independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a nitrile, and Ph represents a phenylene group. 12 teeth [ka] And R b1 and R b2 Each of the following independently represents hydrogen, an alkyl or nitrile having 1 to 6 carbon atoms, and Ph represents a phenylene group. n is a number from 0 to 500, m1, m2, p, q1, q2, and u are numbers from 0 to 6.) A block polymer having a silicone-containing unit (B') which is polymerized with polymerizable azo-derived groups of this silicone compound monomer, exhibits the same effects and properties as a block polymer having a silicone-containing unit (B) which is polymerized with polymerizable mercapto-derived groups of a silicone compound monomer having mercapto groups at one or both ends. This "azo-derived group" refers to a group in which the azo group can be radicalized or otherwise react with other compounds.

[0033] As an azo group-containing silicone compound monomer of the above chemical formula (17), R 11 but [ka] And R 12 but [ka] It is preferable that it be such. A specific example of the azo group-containing silicone compound monomer of the above chemical formula (17) is VPS-1001 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Furthermore, since the compound monomer having a polymerizable double bond group that polymerizes to the polymerizable azo group of the silicone compound monomer of chemical formula (17) above can be the one described above, a detailed explanation is omitted.

[0034] A method for producing a block polymer having a silicone-containing unit (B') is: The following chemical formula (18) [ka] (In the formula, z is a number from 1 to 20, Y is a hydroxyl group, and R is -CO-R) 11 -N=NR 12 -, R 1 ha-(CH2) u -NH-, where X represents a hydrogen atom. 11 teeth [ka] And R a1 and R a2 Each of the following independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a nitrile, and Ph represents a phenylene group. 12 teeth [ka] And R b1 and R b2 Each of the following independently represents hydrogen, an alkyl or nitrile having 1 to 6 carbon atoms, and Ph represents a phenylene group. n is 0 to 500, and m1, m2, p, q1, q2, and u are numbers from 0 to 6.) A silicone compound monomer represented by ( ) is copolymerized with a compound monomer having a polymerizable double bond group in an amount of 65 to 900 parts by mass per 100 parts by mass of the silicone compound monomer. The compound monomer having a polymerizable double bond group can be any of the above-mentioned ones, so a detailed explanation is omitted.

[0035] By dissolving this silicone compound monomer and a compound monomer having a polymerizable double bond group in the above-mentioned inert solvent and maintaining the temperature at 80-130°C for 2-8 hours while stirring in a nitrogen atmosphere, the desired block polymer can be obtained.

[0036] The block polymer obtained in this way can be suitably used as a surface modifier for paints and coatings, which can improve surface properties such as leveling and slipperiness of paints and coatings. Paints containing such surface modifiers for paints and coatings improve leveling and slip resistance, and can protect surfaces while enhancing the aesthetic appearance of metal car bodies and other materials. The amount of surface modifier for paints and coatings to be blended into the paint or coating is preferably 0.05 to 0.5 parts by mass in terms of solid content per 100 parts by mass of the paint or coating. [Examples]

[0037] The following describes in detail some embodiments of the present invention, but the scope of the present invention is not limited to these embodiments.

[0038] Examples of block polymers to which the present invention is applied are shown in Preparation Examples 1 to 7 below, and examples of polymers to which the present invention is not applied are shown in Comparative Preparation Examples 1 and 2.

[0039] Example 1 (Preparation Example 1) 60 parts by mass of n-butyl acetate, an inert solvent, was added to a 500 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen gas inlet, and the temperature was raised to 110°C under a nitrogen gas atmosphere. While maintaining the temperature of n-butyl acetate at 110°C, the mercapto group-containing silicone X-22-167B (R, R in the above chemical formula (11)) of the dropping solution (a-1) shown in Table 1 below was added. 1The silicone oil is C3H6, and X and Y are mercapto groups, making it a double-terminated mercapto-modified silicone with a functional group equivalent of 1700 g / mol. 30 parts by mass of (manufactured by Shin-Etsu Chemical Co., Ltd.), 25 parts by mass of methyl methacrylate, a polymerizable double bond-containing monomer, 45 parts by mass of DMAA (N,N-dimethylacrylamide (manufactured by KJ Chemicals Co., Ltd.)), and 5 parts by mass of perocta-O (1,1,3,3,-Tetramethyl butyl peroxy-2-ethl hexannoate (manufactured by NOF Corporation)), a radical initiator, were added dropwise at a constant rate over 2 hours using a dropping funnel. After the addition was complete, the reaction solution was reacted at 110°C for 2 hours to obtain a copolymer, which is a block polymer. The amount of radical initiator added was such that 190 moles of radicals were generated for every 100 moles of terminal mercapto groups in the added silicone oil. Furthermore, the molecular weight of Mn (X-22-167B) and Mr (per octa-O) in the above-mentioned equation 1 are 3140 and 272.4, respectively.

[0040] The obtained block polymer was eluted by molecular weight using gel permeation chromatography, which can separate molecules of different molecular weights, and its molecular weight distribution was determined. A calibration curve was obtained from a polystyrene standard substance with a known molecular weight beforehand, and the weight-average molecular weight of this block polymer was determined by comparing the molecular weight distribution of the obtained block polymer with the calibration curve. As a result, the weight-average molecular weight of the obtained block polymer was 16,000 in polystyrene equivalent. The proportion of silicone chains in this block polymer was 30% by mass. Furthermore, this block polymer was predominantly of the ABA type, consisting of units (B) made of mercapto group-containing silicone and units (A) made of repeating units of polymerizable double bond-containing monomers.

[0041] (Preparation Example 2) In Preparation Example 1, the n-butyl acetate was changed to 75 parts by mass, and the dropper solution was changed to dropper solution (a-2) shown in Table 1 below, with the polymerizable double bond group-containing monomers being changed to 25 parts by mass of n-butyl acrylate, 15 parts by mass of 4-hydroxybutyl acrylate, and 30 parts by mass of DMAA (N,N-dimethylacrylamide (manufactured by KJ Chemicals Co., Ltd.)). Otherwise, a copolymer, which is a block polymer, was obtained in the same manner as in Preparation Example 1. The weight-average molecular weight of the obtained block polymer was determined in the same manner as in Preparation Example 1. The weight-average molecular weight of the obtained block polymer, as determined by gel permeation chromatography, was 14,000 in polystyrene equivalent. The proportion of silicone chains in this block polymer was 30% by mass.

[0042] (Preparation Example 3) In Preparation Example 1, the n-butyl acetate was changed to 90 parts by mass, and the dropper solution was changed to dropper solution (a-3) as shown in Table 1 below, with the mercapto group-containing silicone being X-22-167C (R, R in the above chemical formula (11)). 1 The silicone is C3H6, and X and Y are mercapto groups, making it a double-terminated mercapto-modified silicone with a functional group equivalent of 2300 g / mol and a molecular weight (Mn) of 4390. 30 parts by mass of (manufactured by Shin-Etsu Chemical Co., Ltd.) were used, along with 25 parts by mass of n-butyl acrylate and 15 parts by mass of 4-hydroxybutyl acrylate as polymerizable double-bond group-containing monomers, 30 parts by mass of DMAA (N,N-dimethylacrylamide (manufactured by KJ Chemicals Co., Ltd.)), and 3 parts by mass of the radical initiator Perocta O (manufactured by NOF Corporation), except that a copolymer block polymer was obtained in the same manner as in Preparation Example 1. The amount of radical initiator added was such that 160 moles of radicals were generated for every 100 moles of terminal mercapto groups in the added silicone oil. The weight-average molecular weight of the obtained block polymer was determined in the same manner as in Preparation Example 1. The weight-average molecular weight of the obtained block polymer, as determined by gel permeation chromatography, was 26,000 in polystyrene equivalent. The proportion of silicone chains in this block polymer was 30% by mass. Furthermore, this block polymer was predominantly of the ABA type, consisting of units (B) made of mercapto group-containing silicone and units (A) made of repeating units of polymerizable double bond-containing monomers.

[0043] (Preparation Example 4) In Preparation Example 1, the n-butyl acetate was changed to 90 parts by mass, and the dropper solution was changed to the dropper solution (a-4) shown in Table 1 below, with 10 parts by mass of X-22-167B (manufactured by Shin-Etsu Chemical Co., Ltd.), 40 parts by mass of methyl methacrylate, 50 parts by mass of DMAA (N,N-dimethylacrylamide (manufactured by KJ Chemicals Co., Ltd.)), and 2 parts by mass of the radical initiator Perocta O (manufactured by NOF Corporation). Otherwise, a copolymer, which is a block polymer, was obtained in the same manner as in Preparation Example 1. The amount of radical initiator added is such that the number of radical moles generated is 220 for every 100 moles of the added silicone oil terminal mercapto groups. The weight-average molecular weight of the obtained block polymer was determined in the same manner as in Preparation Example 1. The weight-average molecular weight of the obtained block polymer, as determined by gel permeation chromatography, was 60,000 in polystyrene equivalent. The proportion of silicone chains in this block polymer was 10% by mass.

[0044] (Preparation Example 5) In Preparation Example 1, the n-butyl acetate was changed to 90 parts by mass, and the dropper solution was changed to dropper solution (a-5) shown in Table 1 below, consisting of 60 parts by mass of X-22-167B (manufactured by Shin-Etsu Chemical Co., Ltd.), 20 parts by mass of methyl methacrylate, 20 parts by mass of DMAA (N,N-dimethylacrylamide (manufactured by KJ Chemicals Co., Ltd.)), and 8 parts by mass of the radical initiator Perocta-O (manufactured by NOF Corporation). Otherwise, a copolymer, which is a block polymer, was obtained in the same manner as in Preparation Example 1. The amount of radical initiator added is such that the number of radical moles generated is 150 for every 100 moles of the added silicone oil terminal mercapto groups. The weight-average molecular weight of the obtained block polymer was determined in the same manner as in Preparation Example 1. The weight-average molecular weight of the obtained block polymer, as determined by gel permeation chromatography, was 10,000 in polystyrene equivalent. The proportion of silicone chains in this block polymer was 60% by mass.

[0045] (Preparation Example 6) In Preparation Example 1, the n-butyl acetate was changed to 75 parts by mass, and the dropper solution was changed to dropper solution (a-6) shown in Table 1 below, with the polymerizable double bond group-containing monomer changed to 25 parts by mass of isovonyl methacrylate, 15 parts by mass of 4-hydroxybutyl acrylate, and 30 parts by mass of DMAA (N,N-dimethylacrylamide (manufactured by KJ Chemicals Co., Ltd.)). Otherwise, a copolymer, which is a block polymer, was obtained in the same manner as in Preparation Example 1. The weight-average molecular weight of the obtained block polymer was determined in the same manner as in Preparation Example 1. The weight-average molecular weight of the obtained block polymer, as determined by gel permeation chromatography, was 14,000 in polystyrene equivalent.

[0046] (Preparation Example 7) A copolymerized block polymer was obtained using the same method as in Preparation Example 6. Then, the block polymer and n-butyl acetate solution were adjusted to 60°C, 10 parts by weight of Karenz AOI (manufactured by Showa Denko K.K.), a 2-acryloyloxyethyl isocyanate, were added, and the solution temperature was raised and maintained at 80°C for 5 hours to obtain a block polymer containing acrylic groups. The reaction endpoint was 2250 cm⁻¹ by infrared absorption spectroscopy. -1 This was confirmed by the disappearance of the isocyanate group peak. The weight-average molecular weight of the obtained block polymer was determined in the same manner as in Preparation Example 1, and the weight-average molecular weight of the obtained block polymer determined by gel permeation chromatography was 14,500 in polystyrene equivalent.

[0047] (Preparation Example 8) In Preparation Example 1, the n-butyl acetate was changed to 90 parts by mass, and the dropper solution was changed to dropper solution (a-8) shown in Table 1 below, with 30 parts by mass of VPS-1001 (manufactured by Fujifilm Corporation), an azo group-containing silicone compound monomer, replacing the mercapto group-containing silicone, and the polymerizable double bond-containing monomers being 25 parts by mass of n-butyl acrylate, 15 parts by mass of 4-hydroxybutyl acrylate, and 30 parts by mass of DMAA (N,N-dimethylacrylamide (manufactured by KJ Chemicals Co., Ltd.)). Otherwise, a copolymerized block polymer was obtained in the same manner as in Preparation Example 1. Note that the azo group-containing silicone compound monomer also served as an initiator, and no radical initiator was added. The weight-average molecular weight of the obtained block polymer was determined in the same manner as in Preparation Example 1. The weight-average molecular weight of the obtained block polymer, as determined by gel permeation chromatography, was 36,000 in polystyrene equivalent. The proportion of silicone chains in this block polymer was 30% by mass. Furthermore, this block polymer was predominantly of the ABA type, consisting of units (B) made of azo group-containing silicone and units (A) made of repeating units of polymerizable double bond-containing monomers.

[0048] Comparative Example 1 (Comparative preparation example 1) A copolymer, or block polymer, was obtained in the same manner as in Preparation Example 1, except that the dropwise solution of Preparation Example 1 was changed to dropwise solution (b-1) shown in Table 1 below, which consisted of 90 parts by mass of X-22-167B (manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts by mass of methyl methacrylate, a monomer containing polymerizable double bonds, 7 parts by mass of DMAA (N,N-dimethylacrylamide, manufactured by KJ Chemicals Co., Ltd.), and 12 parts by mass of the radical initiator Perocta-O (manufactured by NOF Corporation). The amount of radical initiator added was such that 150 moles of radicals were generated for every 100 moles of silicone oil-terminated mercapto groups added. The weight-average molecular weight of the obtained block polymer was determined in the same manner as in Preparation Example 1. The weight-average molecular weight of the obtained block polymer, as determined by gel permeation chromatography, was 10,000 in polystyrene equivalent. The proportion of silicone chains in this block polymer was 90% by mass. Furthermore, this block polymer was predominantly of the ABA type, consisting of units (B) made of mercapto group-containing silicone and units (A) made of repeating units of polymerizable double bond-containing monomers.

[0049] (Comparative preparation example 2) The dropper solution of Preparation Example 1 is replaced with a mercapto-group-free silicone, Cylaprene® FM-0711 (Chemical Formula (14)R), as shown in Table 1 below (b-2). 8 A copolymerized graft polymer was obtained by the same method as in Preparation Example 1, except that 30 parts by mass of (n-Bu:H-C4H8) (manufactured by JNC Corporation) and 3 parts by mass of perocta-O (manufactured by NOF Corporation) as a radical initiator were used. The weight-average molecular weight of the obtained block polymer was determined in the same manner as in Preparation Example 1. The weight-average molecular weight of the obtained block polymer, as determined by gel permeation chromatography, was 22,000 in polystyrene equivalent. The proportion of silicone chains in this random polymer was 30% by mass.

[0050] [Table 1]

[0051] Example 2 (static surface tension) Solutions were prepared using the block polymers obtained in Preparation Examples 1-8 and Comparative Preparation Example 1, and the random polymer obtained in Comparative Preparation Example 2 as solid components, and the static surface tension of these solutions was measured. The measurement method involved preparing a propylene glycol monomethyl ether acetate solution with a solid content of 0.1% by mass, consisting of the block polymer and the random polymer, and measuring the static surface tension (mN / m) at 25°C using a surface tensile meter (KRUSS K100) based on the Wilhelmy method (plate method). The measured static surface tension was evaluated as follows: solutions with a static surface tension of 24.0 mN / m or less were considered pass (○), and solutions with a static surface tension exceeding 24.0 mN / m were considered fail (×). The results are shown in Table 2 below.

[0052] (Coating film evaluation) 1. Fabrication of the coating film Coating films were prepared for each of the block polymers (Preparation Examples 1-8 and Comparative Preparation Example 1) and random polymers (Comparative Preparation Example 2) obtained in Example 1 and Comparative Example 1. The preparation method involved kneading 25 parts by weight of urethane acrylate UA-306I (product name of Kyoeisha Chemical Co., Ltd., SP value: 10.9), 75 parts by weight of methyl ethyl ketone, 1.5 parts by weight of the photopolymerization initiator Omnirad184 (product name of IGM-Resins BV), and 0.2 parts by weight of solids consisting of the block polymer and random polymer obtained in Example 1 at 1000 rpm for 2 minutes using a labodies spar to prepare an ultraviolet-curable coating agent. Next, the prepared coating agent was applied to the easy-adhesion PET film CosmoShine A-4160 (product name of Toyobo Co., Ltd.) using a wet 20 μm bar coater, dried at 80°C for 1 minute, and then subjected to a 300 mJ / cm² treatment using an electrodeless lamp (H-bulb manufactured by Fusion Co., Ltd.). 2 The active energy was irradiated at a distance of 17 cm from the substrate to obtain a coating film.

[0053] 2. Evaluation The obtained coating film was evaluated by performing various tests, including compatibility tests, slip resistance tests, and antifouling tests. (Compatibility test) The compatibility test involved visually observing the transparency of coating films prepared using the block polymers (Preparation Examples 1-8 and Comparative Preparation Example 1) and random polymer (Comparative Preparation Example 2) obtained in Example 1 and Comparative Example 1. The compatibility of the copolymers in the coating agent was evaluated based on their transparency. Transparent films were judged as pass (○), and cloudy films were judged as fail (×). The results are shown in Table 2 below. (Slip resistance test) For the slip resistance test, coating films prepared using block polymers (Preparation Examples 1-8 and Comparative Preparation Example 1) and random polymer (Comparative Preparation Example 2) obtained in Example 1 and Comparative Example 1 were tested at 25°C using a Type 38 surface resistance tester (manufactured by Shinto Kagaku Co., Ltd.). A ball indenter was pressed with a load of 200g and moved at a speed of 600mm / min to measure the coefficient of dynamic friction. Films with a coefficient of dynamic friction of less than 0.1 were judged as pass (○), and those with a coefficient of dynamic friction of 0.1 or greater were judged as fail (×). The results are shown in Table 2 below. (Stain resistance test) The stain resistance test involved writing with Magic Ink® on a coating film prepared using block polymers (Preparation Examples 1-8 and Comparative Preparation Example 1) and a random polymer (Comparative Preparation Example 2) obtained in Example 1 and Comparative Example 1, and then wiping the film with gauze. The number of times the ink could be wiped off was used to evaluate the performance. The results were evaluated on a three-point scale: ○ if the ink could be wiped off within 10 times, △ if it could be wiped off within 20 times, and × if it could not be wiped off within 20 times.

[0054] [Table 2]

[0055] As is clear from Table 2, Preparation Examples 1 to 8 to which the present invention is applied exhibit superior static surface tension, compatibility, slipperiness, and antifouling properties compared to Comparative Preparation Examples 1 and 2, which are outside the scope of application of the present invention. [Industrial applicability]

[0056] The block polymer according to the present invention is incorporated into paints and coatings applied to various substrates such as metal car bodies of automobiles, metal materials for pre-coating, plastic housings of home appliances such as mobile phones and personal computers, and building materials, in order to protect the surface while improving its aesthetic appearance.

Claims

1. The following chemical formula (1) 【Chemistry 1】 (In the formula, z is the number 1, Y is a mercapto group, R and R １ is an alkylene group having 1 to 12 carbon atoms, X is a mercapto group or an alkyl group having 1 to 6 carbon atoms, or z is a number from 1 to 20, Y is a hydroxyl group, and R is -CO-R １１ -N = N - R １２ -, R １ ha- (CH ２ ) u -NH-, where X represents a hydrogen atom. R １１ teeth 【Chemistry 2】 wherein R ａ１ and R ａ２ are each independently hydrogen, alkyl having 1 to 6 carbon atoms or nitrile, and Ph represents a phenylene group. R １２ is 【Transformation 3】 And R ｂ１ and R ｂ２ A surface modifier for paints or coating agents, comprising a block polymer containing a copolymer having a block copolymer repeat structure, wherein each of the following independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or a nitrile, and Ph represents a phenylene group. n is 0 to 500, m1, m2, p, q1, q2, and u are numbers from 0 to 6. A silicone-containing unit (B) is made up of repeating units derived from a silicone compound monomer represented by ( ), polymerized with a polymerizable mercapto-derived group or azo-derived group of the silicone compound monomer, and a unit (A) is made up of repeating units derived from a compound monomer having a polymerizable double bond group that is polymerized to the mercapto-derived group or the azo-derived group, wherein at least a portion of the block polymer contains a block polymer having a block copolymer repeat structure, and the ratio of the silicone chain to the block polymer is 10 to 60% by mass.

2. The surface modifier for paints or coatings according to claim 1, characterized in that the weight-average molecular weight of the block polymer is 1,000 to 1,000,000.

3. The polymerizable double bond group compound monomer is represented by the following chemical formulas (2), (3), and (4) 【Chemistry 4】 (R in the above chemical formula (2)) ２ R is a hydrogen atom or a methyl group. ３ R is an alkylene group having 1 to 18 carbon atoms. ４ represents a hydrogen atom or a hydroxyl group. In the above chemical formula (3), a and b are numbers from 0 to 30, R ５ R is a hydrogen atom or a methyl group. ６ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. In the above chemical formula (4), c is a number from 0 to 500, R ７ R is an alkylene group having 1 to 8 carbon atoms. ８ R is an alkyl group having 1 to 12 carbon atoms. ９ It is preferable that the compound monomer having a polymerizable double bond group represented by ) (meth)acrylamide derivative monomer and unsaturated group-containing morpholine monomer is selected from the group consisting of ).

4. Among the repeating units derived from the compound monomer having the polymerizable double bond group, the following chemical formula (5) or chemical formula (6) 【Transformation 5】 (In the above chemical formula (5), R ２ R is a hydrogen atom or a methyl group. ３ represents an alkylene group having 1 to 18 carbon atoms. In the above chemical formula (6), a and b are numbers from 0 to 30, R ５ A surface modifier for paints or coatings according to claim 1, comprising a unit containing repeating units derived from (5) or (6), wherein the unit contains repeating units in which an isocyanate group of an isocyanate monomer having a (meth)acrylic group or an epoxy group of an epoxy monomer having a (meth)acrylic group reacts with and bonds to a hydroxyl group derived from the chemical formula (5) or (6).

5. The surface modifier for paints or coatings according to claim 1, characterized in that the copolymer contains a diblock (AB type), triblock (ABA type), or multiblock (ABABA type) block polymer comprising the silicone-containing unit (B) and a unit (A) consisting of repeating units derived from a compound monomer having a polymerizable double bond group.

6. The surface modifier for paints or coatings according to claim 1, wherein the unit consisting of repeating units of the polymerizable double bond group compound monomer is copolymerized with the polymerizable double bond group compound monomer described in claim 3 and other polymerizable double bond group compound monomers other than the said compound monomer, and the proportion of the other polymerizable double bond group compound monomer to the block polymer does not exceed 40% by mass.

7. A paint characterized by containing the surface modifier for paints or coatings described in claim 1.

8. A coating agent characterized by comprising the surface modifier for paints or coating agents described in claim 1.

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