JP2014034634A - Resin and its application - Google Patents

Abstract

[PROBLEMS] To have excellent chemical resistance and excellent compatibility with paints using urethane resins, acrylic resins, etc., and excellent recoating properties when used in coating agents and paints. Provided are a resin capable of imparting excellent adhesion to a coating agent or paint, and its use.
The resin includes (a) a silicone macromonomer having a radical polymerizable group at one end, (b) a vinyl monomer having a hydroxyl group at the end and an alkylene oxide structure, and (c) a dioxolane structure. And (d) a radical polymerizable monomer other than the above (a) to (c) is copolymerized.
[Selection figure] None

Description

  The present invention relates to a resin adapted to a field requiring chemical resistance, and its use, specifically, a dispersion using the resin, a coating agent using the resin, and a paint using the resin. The present invention relates to a modifier and a coating composition using the resin.

  Plastic molded products made of resins such as acrylic resin, polycarbonate, polyethylene terephthalate (PET), ABS resin (acrylonitrile / butadiene / styrene copolymer) have various properties such as hardness, solvent resistance, contamination resistance, and weather resistance. Since it lacks, it is often used by coating the surface with a coating film using a coating agent or paint.

  More specifically, home appliances such as mobile phones, touch panels, compact discs, audio devices, and televisions; interior products such as automobile dashboards; and building materials are becoming more durable. Therefore, the coating film is required to have resistance such as scratch resistance that is not scratched by some external stimulus, resistance to contamination such as graffiti using oil-based ink, and resistance to oil stains. Yes.

  Conventionally, as a method of imparting chemical resistance such as stain resistance and oil resistance to a coating film, it is known to use a polymer containing a silicone component or a fluorine-based component as a coating component or paint. .

  As a polymer having a silicone component, it is known to use a silicone-based graft copolymer having an alkyl acrylate as a main chain and silicone as a graft chain (Patent Documents 1 to 4). Further, the polymer having a silicone component includes a (meth) acrylate monomer and a hydroxyalkyl (meth) acrylate monomer that include a hydroxyl group at the terminal and a hydrophilic chain such as a poly (oxypentamethylenecarbonyl) chain. A macromonomer having a radically polymerizable monomer as a main chain and having a radically polymerizable group at one end with (a) a content ratio of (meth) alkyl acrylate monomer units being 50% by weight or more; and (b) a piece It is known to use a silicone-based graft copolymer having a silicone-based macromonomer having a radical polymerizable group at the terminal as a graft chain (Patent Document 2).

  As a polymer having a fluorine-based component as a constituent component, a polymer obtained by curing a curable resin composition containing an ethylenically unsaturated group-containing fluoropolymer and a compound having a (meth) acryloyl group is known. (Patent Document 5).

JP 61-151272 A JP-A-10-330684 Japanese Patent Laid-Open No. 10-88066 JP 2001-11376 A JP 2007-254706 A

  However, coating agents and paints using a conventional copolymer containing a silicone component or a copolymer containing a fluorine-based component are effective for improving the chemical resistance. Adhesiveness is not good, and when the coating agent or paint is reapplied to the article coated with the coating film, the coating film or paint is not sufficiently prevented from repelling (repellency). It had the subject that recoat property (overcoat compatibility) was not good.

  Further, these conventional copolymers are not necessarily good in compatibility with resins such as urethane resins, acrylic resins, alkyd resins and the like that are usually used in paints. It did not have good properties as a paint modifier added to the paint.

  The present invention has been made in view of the above-described conventional problems, and its purpose is to use excellent chemical resistance (sunscreen resistance, stain resistance, oil resistance, etc.), urethane resin, acrylic resin, and the like. Resins and dispersions that have excellent compatibility with existing paints and that can impart excellent recoating properties and excellent adhesion to substrates when used in coating agents and paints. A paint modifier that has excellent chemical resistance and excellent compatibility with paints, and that can impart excellent recoatability and excellent adhesion to substrates to paint compositions when added to paints, and excellent Another object of the present invention is to provide a coating agent and a coating composition which have excellent chemical resistance and compatibility with paints, and have excellent recoatability and excellent adhesion to substrates.

  In order to solve the above-mentioned problems, the resin of the present invention includes (a) a silicone macromonomer having a radical polymerizable group at one end, and (b) a vinyl group having a hydroxyl group at the end and having an alkylene oxide structure. It is characterized by copolymerizing a monomer, (c) a vinyl monomer having a dioxolane structure, and (d) a radical polymerizable monomer other than the above (a) to (c).

  According to the above configuration, the chemical resistance of the resin can be improved by copolymerizing the radical polymerizable monomer (d) with the silicone macromonomer (a) having a radical polymerizable group at one end. it can.

  Further, according to the above configuration, the monomer (d) (a) is copolymerized with the vinyl monomer having a hydroxyl group at the terminal (b) and having an alkylene oxide structure, whereby the hydroxyl group is added to the resin. Can be introduced. Thus, when the resin is mixed with a crosslinking agent having a plurality of functional groups capable of reacting with a hydroxyl group (for example, polyfunctional isocyanate having two or more isocyanate groups, amino resin, etc.) and used as a coating agent, the resin is crosslinked. A crosslinked structure is formed by reaction with the agent, and the chemical resistance of the coating film (film formed by applying a coating agent or the like) is improved. Furthermore, according to the said structure, a urethane type resin or (a) can be obtained by copolymerizing the monomer (d) (a) with a vinyl monomer having a hydroxyl group at the terminal (b) and having an alkylene oxide structure. An alkylene oxide structure having high affinity for a paint using an acrylic resin or the like can be introduced into the resin. Thereby, the compatibility of the resin with respect to the coating material using a urethane resin, an acrylic resin, or the like can be improved. Therefore, when the resin is mixed with a paint and used as a paint composition, it is possible to suppress the occurrence of uneven application of the paint composition.

  Furthermore, according to the said structure, when resin is used for a coating agent or a coating material by copolymerizing the monomer of said (d) (a) (b) with the said (c) vinyl-type monomer which has a dioxolane structure. In addition, recoatability and adhesion to the substrate can be improved.

  From the above, according to the above configuration, it has excellent chemical resistance (sunscreen resistance, stain resistance, oil resistance, etc.) and excellent compatibility with paints, and is used for coating agents and paints. Sometimes, it is possible to provide a resin capable of imparting excellent recoating properties and excellent adhesion to a substrate to a coating agent or a coating composition.

  In order to solve the above problems, the dispersion of the present invention includes the resin of the present invention and an organic solvent, and the resin is dissolved or finely dispersed in the organic solvent.

  According to the above configuration, since the resin of the present invention is used, the coating agent has excellent chemical resistance (sunscreen resistance, contamination resistance, oil resistance, etc.) and excellent compatibility with paints. When used in coatings and paints, it can impart excellent recoatability and excellent adhesion to substrates to coating agents and coating compositions. Furthermore, according to the said structure, since resin is melt | dissolved or finely dispersed in the organic solvent, resin can be made into the state (dispersion) of the viscosity suitable as a coating agent or a coating material, and the coating agent containing resin When a coating film is formed using a paint composition, a coating can be formed uniformly.

  In order to solve the above-mentioned problems, the coating agent of the present invention is characterized by containing the resin of the present invention or the dispersion of the present invention.

  According to the above configuration, since the resin of the present invention or the dispersion of the present invention is used, it has excellent chemical resistance (sunscreen resistance, stain resistance, oil resistance, etc.) and excellent compatibility with paints. And has excellent recoatability and excellent adhesion to a substrate.

  The paint modifier of the present invention is a paint modifier that is added to a paint to modify the paint in order to solve the above-described problems, and includes the resin of the present invention or the dispersion of the present invention. It is characterized by including.

  According to the above configuration, since the resin of the present invention or the dispersion of the present invention is used, it has excellent chemical resistance (sunscreen resistance, stain resistance, oil resistance, etc.) and excellent compatibility with paints. When it is added to the paint, it can improve the recoatability of the paint and the adhesion to the substrate, and the coating composition (added with a paint modifier) has excellent recoatability and excellent adhesion to the substrate. Applied paint).

  In order to solve the above-mentioned problems, the paint modifier of the present invention comprises a paint and the resin of the present invention, the resin of the dispersion of the present invention, or the paint modifier of the present invention. .

  According to the above configuration, since the resin of the present invention, the dispersion of the present invention, or the paint modifier of the present invention is used, excellent chemical resistance (sunscreen resistance, stain resistance, oil resistance, etc.) In addition, it has excellent compatibility with paints, and has excellent recoatability and excellent adhesion to substrates.

  According to the present invention, it has excellent chemical resistance (sunscreen resistance, stain resistance, oil resistance, etc.) and excellent compatibility with paints, and is excellent when used in coating agents and paints. Resin and dispersion capable of imparting recoatability and excellent adhesion to substrates to coating agents and paints, excellent chemical resistance and excellent compatibility with paints, and excellent when added to paints A coating modifier capable of imparting a coating composition with excellent recoatability and adhesion to the substrate, and excellent chemical resistance and compatibility with the coating, and excellent recoatability and substrate A coating agent and a coating composition having adhesiveness can be provided.

〔resin〕
The resin of the present invention will be described below.
The resin of the present invention comprises (a) a silicone macromonomer having a radical polymerizable group at one end, (b) a vinyl monomer having a hydroxyl group at the end and an alkylene oxide structure, and (c) a dioxolane structure. And a vinyl monomer having (d) a radical polymerizable monomer other than the above (a) to (c). The resin of the present invention can be a silicone-based graft copolymer having (d) as the main skeleton.

  As the silicone macromonomer having a radically polymerizable group at one end of the above (a) (hereinafter referred to as “(a) silicone macromonomer”), a polymerizable unsaturated group (for example, an ethylenically unsaturated group) at one end is used. And various compounds having silicone units (organosiloxane units such as dimethylpolysiloxane units).

  Examples of the (a) silicone macromonomer include the following formula (1):

(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 4 carbon atoms, R ³ is the same as or different from each other, and represents an alkyl group or phenyl group having 1 to 4 carbon atoms. And a silicone macromonomer having a structure represented by the formula (n represents a positive integer).

Examples of the alkylene group having 2 to 4 carbon atoms represented by R ² in the formula (1) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, and an ethylethylene group. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ³ in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Groups and the like.

  Specific examples of the silicone macromonomer having the structure represented by the formula (1) include α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane (for example, “Silaplane manufactured by JNC Corporation). (Registered trademark) FM-0721 "(trade name)). Other examples of the silicone macromonomer having the structure represented by the formula (1) include “Silaplane (registered trademark) FM-0711 (trade name)” and “Silaplane (registered trademark) FM- manufactured by JNC Corporation. 0725 (trade name) "," X-22-174ASX (trade name) "," X-22-174DX (trade name) "," X-22-2426 (trade name) "manufactured by Shin-Etsu Chemical Co., Ltd., And “X-22-2475 (trade name)”, “AK-5 (grade)” and “AK-32 (grade)” manufactured by Toagosei Co., Ltd., and the like.

  The number average molecular weight of the (a) silicone macromonomer is preferably in the range of 500 to 40000, and more preferably in the range of 1000 to 20000. When the number average molecular weight of the (a) silicone macromonomer is less than 500, the coating film may be inferior in chemical resistance when the coating film is formed using a coating agent or paint containing resin. (A) When the number average molecular weight of the silicone macromonomer exceeds 40000, when the coating film is formed on the substrate using a coating agent or paint containing resin, the adhesion of the coating film to the substrate is sufficient It may be difficult to obtain. N in the formula (1) is preferably a number that can give this number average molecular weight. Each of the various (a) silicone macromonomers may be used alone or in combination of two or more.

  The content of the structural unit derived from the (a) silicone macromonomer in the resin of the present invention is not particularly limited, but is preferably in the range of 2 to 15% by weight with respect to 100% by weight of the resin. When the content of the structural unit derived from the (a) silicone macromonomer is less than 2% by weight, the lubricity and chemical resistance of the resin are apt to be insufficient, and therefore the coating agent or paint containing the resin is used. When a film is formed, the lubricity and chemical resistance of the coating film tend to be insufficient. On the other hand, when the content of the structural unit derived from the (a) silicone macromonomer exceeds 15% by weight, sufficient adhesion of the resin to the substrate is difficult to obtain, and a coating agent or paint containing the resin Resin tends to repel. Therefore, in this case, when the coating film is formed on the base material using a coating agent or paint containing resin, it is difficult to obtain sufficient adhesion of the coating film to the base material. Moreover, in this case, when a plurality of coating films are formed by using a coating agent or paint containing resin (for example, when an article coated with a paint containing resin is repainted with a paint containing resin) ), The coating film tends to repel the coating agent and the paint, and the recoatability of the coating film tends to be insufficient. In addition, content of the structural unit derived from each monomer of (a)-(d) in resin of this invention is the total amount of monomers ((a)-(d) total amount of monomers used for manufacture of resin). It corresponds to the ratio of each monomer in

  The vinyl monomer (b) having a hydroxyl group at the terminal and having an alkylene oxide structure (hereinafter referred to as “(b) a hydroxyl group-containing vinyl monomer”) has a hydroxyl group at the terminal and one ethylenic group. Any compound having an unsaturated group (broadly-defined vinyl group) and having at least one alkylene oxide structure (oxyalkylene group) may be used.

  More specific examples of such a (b) hydroxyl group-containing vinyl monomer include a vinyl monomer represented by a structural formula such as the following formula (2).

(In the formula, R ₁ is H or CH ₃ , R ₂ and R ₃ are different and have ₂ to 5 carbon atoms selected from C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , and C ₅ H _10. And m is 0 to 50 and n is 2 to 50)
The vinyl monomer represented by the formula (2) includes (meth) acrylic acid and at least one alkylene oxide having 2 to 5 carbon atoms (ethylene oxide, propylene oxide, 1,2-butylene oxide, tetrahydrofuran, etc.) It can be synthesized by the addition reaction of In this specification, “(meth) acryl” refers to acryl or methacryl.

  Examples of the vinyl monomer represented by the formula (2) include polypropylene glycol monomethacrylate, poly (ethylene glycol / propylene glycol) monomethacrylate, poly (ethylene glycol / tetramethylene glycol) monomethacrylate, poly (propylene glycol Tetramethylene glycol) monomethacrylate, polypropylene glycol / polybutylene glycol monomethacrylate, and the like can be used.

As a vinyl monomer represented by the formula (2), a product having a trade name “Blemmer (registered trademark) PP-1000” (manufactured by NOF Corporation, R ₁ is CH ₃ , R ₃ is C ₃ H ₆ , M is 0, n is a mixture of 4 to 6 on average) and the like (Blenmer (registered trademark) PP series) products (manufactured by NOF Corporation, polypropylene glycol monomethacrylate), “Blemmer (registered trademark) 50PEP-300” (manufactured by NOF Corporation, poly (ethylene glycol / propylene glycol) monomethacrylate, R ₁ is CH ₃ , R ₂ is C ₂ H ₄ , R ₃ is C ₃ H _6, m and n is a mixture of m = 3.5 and n = 2.5 on average), trade name "Blemmer (trademark) 70PEP-350B" product (NOF Corporation, polyethylene glycol Polypropylene glycol - monomethacrylate, R ₁ is CH _3, R ₂ is C ₂ H _4, R ₃ is a mixture of C ₃ H _6, m and n are average m = 5 and n = 2) , Bremer (registered trademark) 55PET-800 product (manufactured by NOF Corporation, poly (ethylene glycol-tetramethylene glycol) monomethacrylate, R ₁ is CH ₃ , R ₂ is C ₂ H ₄ , R ₃ is C ₄ H ₈ , m and n are on average a mixture of m = 10 and n = 5), a product of the product series name “Blemmer (registered trademark) PPT series” (manufactured by NOF Corporation, poly (propylene glycol Tetramethylene glycol) monomethacrylate), a product of the trade name “Blemmer (registered trademark) 10-PPB-500B” (manufactured by NOF Corporation, propylene glycol polybutylene glycol monome Acrylate, R ₁ is CH _3, R ₂ is C ₃ H _6, R ₃ is a mixture of C ₄ H _8, m and n are average m = 1 and n = 6), trade name "EPM Commercially available products such as hydroxy-polyalkylene glycol monomethacrylate (-109) manufactured by Toho Chemical Industry Co., Ltd. and hydroxy polypropylene glycol monoacrylate (trade name: PA-500) manufactured by Toho Chemical Industry Co., Ltd. can be used. These (b) hydroxyl group-containing vinyl monomers may be used alone or in combination of two or more.

  In the vinyl monomer represented by the formula (2), m + n (number of oxyalkylene groups) is preferably in the range of 2-100. When m + n is less than 2, the resin has poor compatibility with a paint using urethane resin or acrylic resin, or when the resin of the present invention is mixed with a crosslinking agent and used as a coating agent or paint. There is a risk that the chemical resistance of the coating film may be reduced by reducing the number of reaction points between the resin and the crosslinking agent. When m + n exceeds 100, the hardness of the coating film decreases, and the scratch resistance of the coating film may not be obtained. Moreover, the hydrophobicity of the structural unit derived from the (b) hydroxyl group-containing vinyl monomer in the resin becomes too high, and the compatibility of the resin with a paint using a urethane resin or an acrylic resin becomes low. Therefore, when the resin is mixed with a paint and used as a paint composition, uneven coating of the paint composition may easily occur.

  The (b) hydroxyl group-containing vinyl monomer preferably contains two or more alkylene oxide structures having 3 or more carbon atoms as essential. Thereby, since the affinity of the alkylene oxide structure with respect to the paint using a urethane resin, an acrylic resin, or the like becomes higher, the compatibility of the resin with the paint becomes higher. Therefore, when the resin is mixed with a paint and used as a paint composition, it is possible to further suppress the occurrence of uneven coating of the paint composition.

  The (c) vinyl monomer having a dioxolane structure (hereinafter referred to as “(c) dioxolane-containing vinyl monomer”) contains at least one dioxolane structure and has one ethylenically unsaturated group. If it is. Examples of the (c) dioxolane-containing vinyl monomer include 4- (meth) acryloyloxymethyl-2,2-dialkyl-1,3-dioxolane or 4- (meth) acryloyloxymethyl-2-cycloalkyl-1 , 3-dioxolane. As such (c) dioxolane-containing vinyl monomer, more specifically, for example, 4-methacryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2 -Methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-cyclohexyl-1 , 3-dioxolane and the like. In the present specification, “(meth) acryloyl” refers to acryloyl or methacryloyl. Examples of commercially available products of these compounds include a product with a trade name “MEDOL10” (4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane) and a product with a trade name “MIBDOL10” (4-acryloyl). Oxymethyl-2-methyl-2-isobutyl-1,3-dioxolane), product name “CHDOL10” (4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane), product name “MMDOL30” (4-methacryloyloxymethyl-2,2-dimethyl-1,3-dioxolane), product with trade name “MEDOL30” (4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane), product Product with name “MIBDOL30” (4-methacryloyloxymethyl-2-methyl- -Isobutyl-1,3-dioxolane), a product with a trade name “CHDOL30” (4-methacryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane) (all manufactured by Osaka Organic Chemical Industries, Ltd.) Etc. These (c) dioxolane-containing vinyl monomers may be used alone or in admixture of two or more.

  The content of the structural unit derived from the (c) dioxolane-containing vinyl monomer in the resin of the present invention is not particularly limited, but may be in the range of 2 to 20% by weight with respect to 100% by weight of the resin. preferable. When the content of the structural unit derived from the (c) dioxolane-containing vinyl monomer is less than 2% by weight, the resin easily repels a coating agent such as a paint containing the resin. Accordingly, in this case, when a plurality of coatings are formed by using a coating agent containing a resin (for example, when an article painted with a resin-containing paint is repainted with a resin-containing paint), The coating tends to repel the coating agent, and the recoatability of the coating may be insufficient. On the other hand, when the content of the structural unit derived from the (c) dioxolane-containing vinyl monomer exceeds 20% by weight, the resin may soften and the chemical resistance of the resin may decrease. Therefore, in this case, when a coating such as a coating film is formed using a coating agent such as a paint containing a resin, the coating film may be softened and the chemical resistance of the coating film may be lowered.

  The above (d) radical polymerizable monomers other than the above (a) to (c) (hereinafter referred to as “(d) other radical polymerizable monomers”) are the above-mentioned (a) silicone macromonomer, (b) Any compound that is not a hydroxyl group-containing vinyl monomer or the (c) dioxolane-containing vinyl monomer and has a polymerizable unsaturated group (for example, an ethylenically unsaturated group) may be used. Examples of (d) other radical polymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-propyl (meth) acrylate, (meth) Alkyl (meth) acrylates such as isobutyl acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate Styrenes such as styrene, α-methylstyrene and p-methylstrene (styrene or styrene derivatives); N-methoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meta ) N-alkoxymethyl (meth) acrylamids such as acrylamide ; It can be mentioned maleic acid, and the like; (meth) acrylic acid; (meth) acrylonitrile; vinyl acetate; (meth) acrylamide; itaconic acid. These (d) other radical polymerizable monomers may be used alone or in admixture of two or more. “(Meth) acrylonitrile” refers to acrylonitrile or methacrylonitrile.

  The (d) other radical polymerizable monomer is preferably an alkyl (meth) acrylate and / or styrene whose alcohol residue is an alkyl group having 4 or less carbon atoms. Thereby, permeation of oily contaminants into the inside of the coating film can be prevented, and film forming properties and adhesion to the substrate can be imparted to the coating film.

  The content of the structural unit derived from (d) another radical polymerizable monomer in the resin of the present invention is not particularly limited, but is within a range of 30 to 75% by weight with respect to 100% by weight of the resin. Is preferred. When the content of the structural unit derived from (d) another radical polymerizable monomer is less than 30% by weight, the resin may be softened and the chemical resistance of the resin may be inferior. When a coating film is formed using a paint, the coating film softens and the chemical resistance of the coating film may be inferior. On the other hand, if the content of the structural unit derived from (d) another radical polymerizable monomer exceeds 75% by weight, the resin may be cured and the impact resistance of the resin may be inferior. When a coating film is formed using an agent or paint, the coating film is cured and the impact resistance of the coating film tends to be insufficient.

  The hydroxyl value of the resin of the present invention is preferably in the range of 20 to 80 mgKOH / g. When the hydroxyl value of the resin is less than 20 mgKOH / g, when the resin of the present invention is mixed with a crosslinking agent having a plurality of functional groups capable of reacting with hydroxyl groups (described later) and used as a coating agent or paint, the resin is crosslinked. The degree of crosslinking due to reaction with the agent is insufficient, and the chemical resistance of the coating film is difficult to improve. On the other hand, when the hydroxyl value of the resin exceeds 80 mgKOH / g, when the resin of the present invention is mixed with a crosslinking agent having a plurality of functional groups capable of reacting with hydroxyl groups (described later) and used as a coating agent or paint, Crosslinking due to the reaction with the crosslinking agent becomes excessive, and the impact resistance of the coating film may be insufficient.

  The weight average molecular weight of the resin of the present invention is preferably in the range of 4,000 to 100,000. When the resin has a weight average molecular weight of less than 4000, when the resin is dissolved or finely dispersed in an organic solvent or the like and used as a coating agent or paint, the viscosity of the coating agent or paint becomes low. In some cases, liquid sagging may occur during coating of the paint, making it impossible to coat uniformly. On the other hand, if the weight average molecular weight of the resin exceeds 100,000, the viscosity of the coating agent or paint increases when the resin is dissolved or finely dispersed in an organic solvent or the like and used as a coating agent or paint. It may be difficult to apply the agent or paint.

  The resin of the present invention may be used alone as a coating agent, may be used as a coating agent by mixing with other components (for example, a crosslinking agent), or may be used as a coating improver in a paint. Good.

[Example of resin production method]
The resin of the present invention is not particularly limited. For example, the (a) silicone macromonomer, the (b) hydroxyl group-containing vinyl monomer, the (c) dioxolane-containing vinyl monomer, and the (d) other radicals. A mixture of polymerizable monomers can be obtained by a production method in which polymerization is carried out by a solution polymerization method which will be outlined below. That is, in the solution polymerization method, a ketone solvent, an acetate ester solvent, or an aromatic hydrocarbon solvent is used as a polymerization solvent, a radical generating compound is used as a polymerization initiator, and the mixture is combined with the polymerization initiator. The mixture is polymerized by heating in a polymerization solvent at a reaction temperature of 50 ° C. to 150 ° C. for 30 minutes to 10 hours.

  As the polymerization initiator (radical initiator) that can be used when the resin of the present invention is produced, a thermal polymerization initiator can be used. The thermal polymerization initiator is a compound that generates a radical as an active species by heat. Examples of the thermal polymerization initiator include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, o-chloroperoxybenzoic acid, o-methoxyperoxybenzoic acid, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide. Peroxide initiators such as cyclohexanone peroxide, tert-butyl hydroxide and diisopropylbenzene hydroperoxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero) Nitrile), 2,2′-azobis (2,3-dimethylbutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,3,3-trimethylbutyrate) Ronitrile), 2,2′-azobis (2 Isopropylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrolyl), 2- (carbamoylazo) And azo compounds such as isobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobisisobutyrate, and the like. Each of these thermal polymerization initiators may be used alone or in combination of two or more.

[Dispersion]
The dispersion of the present invention contains the resin of the present invention and an organic solvent, and the resin is dissolved or finely dispersed in the organic solvent. When the resin is dissolved or finely dispersed in an organic solvent, it can be made into a viscosity state (dispersion) suitable as a coating agent or paint, and when a coating film is formed using a coating agent or paint containing resin Moreover, a coating film can be formed uniformly.

  Specific examples of preferable organic solvents include ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, amyl methyl ketone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate; propylene glycol monomethyl ether, methanol, Alcohols such as ethanol, sec-butanol, tert-butanol, 2-propanol and isopropanol; aromatic hydrocarbons such as benzene, toluene and chlorobenzene; aliphatic hydrocarbons such as hexane; and alicyclic compounds such as cyclohexane A hydrocarbon etc. are mentioned. Each of these organic solvents may be used alone or in combination of two or more. More preferably, the organic solvent is at least one selected from a ketone solvent, an acetate ester solvent, and an aromatic hydrocarbon solvent.

  The content of the organic solvent in the dispersion of the present invention is not particularly limited, but is preferably in the range of 100 to 1000 parts by weight with respect to 100 parts by weight of the solid content. When the content of the organic solvent is less than 100 parts by weight with respect to 100 parts by weight of the solid content, it may be difficult to adjust the viscosity of the dispersion to a viscosity suitable as a coating agent or a paint. On the other hand, when the content of the organic solvent exceeds 1000 parts by weight with respect to 100 parts by weight of the solid content, the viscosity of the dispersion is too low, and the coating is formed using the dispersion as a coating agent or paint. In addition, it may be difficult to handle the dispersion.

  When the organic solvent is used as the polymerization solvent in the resin production method using the solution polymerization method described above, the resin contains the resin and the organic solvent, and the resin is dissolved or finely dispersed in the organic solvent. The resulting dispersion is obtained as a reaction product. Therefore, the reaction product can be used as a dispersion as it is. However, after isolating the resin from the reaction product, the isolated resin may be dissolved or finely dispersed in an organic solvent to obtain a dispersion, or the organic solvent may be added to the reaction product for viscosity adjustment. Alternatively, a dispersion may be obtained by removing a part of the organic solvent from the reaction product.

  The dispersion of the present invention may be used alone as a coating agent, or may be used as a coating agent by mixing with other components (for example, a cross-linking agent), or may be used in a paint as a paint improver. Also good.

[Coating agent and coating film forming method]
The coating agent of the present invention contains the resin of the present invention or the dispersion of the present invention.

  A coating film can be formed by adding a crosslinking agent having a plurality of functional groups capable of reacting with a hydroxyl group to the coating agent and reacting the resin with the crosslinking agent to cause crosslinking. Therefore, the coating agent may further contain the crosslinking agent.

  Specific examples of the crosslinking agent include polyfunctional isocyanates having two or more isocyanate groups, amino resins, and the like. Examples of the polyfunctional isocyanate having two or more isocyanate groups include a bifunctional isocyanate having two isocyanate groups, a trimer of the bifunctional isocyanate (biuret, allophanate, or isocyanurate).

  Examples of the bifunctional isocyanate having two isocyanate groups include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4 , 4′-diphenylpropane diisocyanate, 4,4′-diphenylhexafluoropropane diisocyanate, 1,4-naphthalene diisocyanate, 3,3′-dimethoxybiphenyl diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate, p-xylylene diisocyanate, hydrogenated p-xylylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate Aromatic difunctional isocyanates such as nates, 4-chloroxylylene-1,3-diisocyanate, 2-methylxylylene diisocyanate; 1,3-trimethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2- Aliphatic bifunctional isocyanates such as diisocyanate and 1,6-hexamethylene diisocyanate; cyclohexylene-1,2-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, isophorone diisocyanate, norbornane diisocyanate, etc. And alicyclic bifunctional isocyanate.

  It is preferable that the usage-amount of the polyfunctional isocyanate which has 2 or more of the said isocyanate groups is a ratio of 0.5-1.5 equivalent of isisoanate groups with respect to 1 equivalent of hydroxyl values in the said resin.

  Examples of the amino resin include alkyl etherified melamine, alkyl etherified urea resin, alkyl etherified benzoguanamine and the like. As the amino resin, alkyl etherified melamine is preferable. Examples of the alkyl etherified melamine include fully alkyl etherified melamines such as hexamethoxymethylol melamine and hexabutoxymethylol melamine; partially alkyl etherified melamines having an alkyl etherification degree of 5 or less. In addition, multimers such as dimers and trimers of alkyl etherified melamine can also be used as the amino resin. The amount of the amino resin used is preferably in the range of 15 to 50 parts by weight per 100 parts by weight of the resin.

  Examples of the method of forming a coating film by reacting the resin and the crosslinking agent include, for example, the coating agent and the crosslinking agent, a metal oxide, an organometallic compound (for example, tetrabutyl titanate, Add a condensation catalyst such as dibutyltin dilaurate, etc.), amine catalyst, etc., put it in a reaction vessel equipped with a stirrer, mix and stir, and adopt the method of coating the resulting mixture on the substrate Can do. Therefore, the coating agent may further contain the condensation catalyst.

  Further, the coating agent of the present invention is an inorganic particle, a photosensitizer, a thermal polymerization initiator, a polymerization inhibitor, a leveling agent, a wettability improver, a surfactant, within a range that does not impair the purpose and effect of the present invention. You may further contain additives, such as a plasticizer, a ultraviolet absorber, antioxidant, an antistatic agent, a silane coupling agent, a pigment, dye, and a slip agent.

[Coating composition]
The coating composition of the present invention comprises a coating and the resin of the present invention or the dispersion of the present invention. In the coating composition of the present invention, the resin of the present invention or the dispersion of the present invention can function as a coating modifier added to the coating to modify the coating.

  Examples of the paint include polyurethane resin paint (paint using urethane resin), acrylic resin paint (paint using acrylic resin), alkyd resin paint, silicone resin paint, fluororesin paint, epoxy resin paint, melamine Resin paints, vinyl ester resin paints, vinyl chloride resin paints and the like can be mentioned.

  The polyurethane resin paint contains a polyol and a polyfunctional isocyanate.

  Although the said polyol should just be a compound which has a 2 or more hydroxyl group, it is preferable that it is at least 1 sort (s) chosen from the group which consists of polyester polyol, polyether polyol, and acrylic polyol. Thereby, thermal responsiveness can be provided to the polyurethane obtained by the reaction of the polyfunctional isocyanate and the polyol.

  As the polyester polyol, polycaprolactone polyol is preferable. Examples of the polycaprolactone polyol include “Placcel (registered trademark) L212AL”, “Placcel (registered trademark) L205AL”, “Placcel (registered trademark) L220AL”, and “Placcel (registered trademark)” commercially available from Daicel Corporation. A product having a trade name such as “320AL” can be used.

  Further, as the polyether polyol, “Coronate (registered trademark)” (trade name) series manufactured by Nippon Polyurethane Industry Co., Ltd. can be used. As the acrylic polyol, “Acrynal (registered trademark)” (trade name) series manufactured by Toei Kasei Co., Ltd. can be used.

  The polyfunctional isocyanate may be a compound having two or more functional groups, may be a bifunctional isocyanate (a compound having two functional groups), or may be a trifunctional or more (three or more functional groups). May be a polyfunctional isocyanate, but it is preferably a trifunctional or higher polyfunctional isocyanate. When a trifunctional or higher polyfunctional isocyanate is used, the presence of three or more functional groups in the polyfunctional isocyanate makes it easy to impart a three-dimensional structure to the polyurethane obtained by the reaction of the polyfunctional isocyanate and the polyol. It is easy to improve the degree of crosslinking of polyurethane.

  Examples of the trifunctional or higher polyfunctional isocyanate include those having a main starting material of a bifunctional isocyanate having two general isocyanate groups, and more specifically, a trimer of the bifunctional isocyanate. (Biuret, allophanate or isocyanurate), adducts of the bifunctional isocyanate and trifunctional alcohols such as trimethylolpropane, adducts of the bifunctional isocyanate and trifunctional phenols such as phloroglysin, formalin of benzene isocyanate Examples thereof include a polymer of an isocyanate compound having a polymerizable group such as a condensate (polymethylene polyphenylene polyisocyanate) and methacryloyloxyethyl isocyanate, and lysine triisocyanate. As the trifunctional or higher polyfunctional isocyanate, an isocyanurate type polyfunctional isocyanate which is a trimer of the bifunctional isocyanate is particularly preferable.

  Examples of the bifunctional isocyanate having two isocyanate groups include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4 , 4′-diphenylpropane diisocyanate, 4,4′-diphenylhexafluoropropane diisocyanate, 1,4-naphthalene diisocyanate, 3,3′-dimethoxybiphenyl diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate, p-xylylene diisocyanate, hydrogenated p-xylylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate Aromatic difunctional isocyanates such as nates, 4-chloroxylylene-1,3-diisocyanate, 2-methylxylylene diisocyanate; 1,3-trimethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2- Aliphatic bifunctional isocyanates such as diisocyanate and 1,6-hexamethylene diisocyanate; cyclohexylene-1,2-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, isophorone diisocyanate, norbornane diisocyanate, etc. And alicyclic bifunctional isocyanate.

  The coating composition is an inorganic particle, a photosensitizer, a thermal polymerization initiator, a polymerization inhibitor, a leveling agent, a wettability improver, a surfactant, a plasticizer, as long as the objects and effects of the present invention are not impaired. You may further contain additives, such as a ultraviolet absorber, antioxidant, an antistatic agent, a silane coupling agent, a pigment, dye, and a slip agent.

[An example of a method for producing a coating composition and a method for forming a coating film]
The coating composition of this invention can be manufactured by the method of mixing the resin of this invention or the dispersion of this invention with the said coating material. When the paint is a paint containing a plurality of paint components such as a polyurethane resin paint containing a polyol and a polyfunctional isocyanate, the paint composition of the present invention includes a first paint component such as a polyol, You may manufacture by the method of mixing 2nd coating material components, such as functional isocyanate, and the resin of this invention, or the dispersion of this invention.

  The coating film is a method of adding a crosslinking agent having a plurality of functional groups capable of reacting with a hydroxyl group to the coating composition of the present invention, and reacting the resin with the crosslinking agent to cure the coating composition. Can be formed. Therefore, the coating composition may further contain the crosslinking agent. The crosslinking agent is as described in the section of the coating agent. When the paint is a paint containing the crosslinking agent and polyol, such as a polyurethane resin paint containing a polyfunctional isocyanate and polyol that functions as the crosslinking agent, the coating composition of the present invention is used as it is. The coating composition may be cured by reacting the crosslinking agent with the polyol and the resin.

  In addition, as a method for forming a coating film by reacting the crosslinking agent such as the polyfunctional isocyanate with the polyol and the resin, the same method as that for preparing a coating film made of a general polyurethane resin is employed. be able to. Examples of a method for forming a coating film by reacting the crosslinking agent such as the polyfunctional isocyanate with the polyol and the resin include, for example, the crosslinking agent such as the polyfunctional isocyanate, the polyol, the resin, and the dispersion. Add a condensation catalyst (for example, tetrabutyl titanate, dibutyltin dilaurate, etc.) such as a metal oxide, an organometallic compound, or an amine catalyst as necessary, and then mix and stir in a reaction vessel equipped with a stirrer. And the method of coating the obtained liquid mixture on a base material is employable.

  The thickness of the coating film formed by the coating composition of the present invention is preferably in the range of 1 to 100 μm.

  The resin of the present invention is an electric / electronic device such as a mobile phone, a wristwatch, a compact disc, an audio device, an OA (Office Automation) device; an electronic material component such as a touch panel, an anti-reflection plate of a cathode ray tube; a refrigerator, a vacuum cleaner, a microwave oven, etc. Automotive products such as automobile meter panels, dashboards, etc .; pre-coated metal steel plates; automobile bodies, bumpers, spoilers, door knobs, handles, headlamps, aluminum wheels (plated, evaporated or sputtered), Automotive parts such as door mirrors (plated, vapor-deposited and sputtered); motorcycle gasoline tanks; carport roofs, roofs such as daylight roofs; plastics such as polyvinyl chloride, acrylic resin, polyethylene terephthalate, polycarbonate, ABS resin Plastic Coated surfaces of articles in various fields such as stucco, film, or sheet; wood products such as stairs, floors, desks, chairs, chests, and other furniture; sheet base materials such as cloth and paper It is suitably used as a coating agent.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples.

  First, the resin measurement methods in the following examples and comparative examples, and the coating film evaluation methods in the following coating film formation examples are listed below.

[Measurement method of resin and evaluation method of coating film]
[Method for measuring weight average molecular weight of resin]
In this specification, “weight average molecular weight (Mw)” means a polystyrene (PS) equivalent weight average molecular weight measured using gel permeation chromatography (GPC).

  Specifically, in the following examples and comparative examples, 40 mg of a sample (resin) was dissolved in 12 mL of tetrahydrofuran (THF) (permeation time: approximately 24 hours (complete dissolution)), and a nonaqueous chromatographic disk having a pore size of 0.45 μm. And GPC measurement was performed. The weight average molecular weight of the sample (resin) was determined from the elution curve obtained by the GPC measurement and a standard polystyrene calibration curve prepared by GPC measurement of standard polystyrene in advance. The apparatus and measurement conditions for the GPC measurement are as follows.

GPC apparatus used: “HLC-8320GPC EcoSEC (registered trademark)” manufactured by Tosoh Corporation (with built-in RI detector (differential refractive index detector) and UV detector (ultraviolet absorption detector))
Guard column: “TSKgel (registered trademark) guardcolumn SuperMP (HZ) -H” (inside diameter 4.6 mm × 2 cm) × 1 manufactured by Tosoh Corporation Reference side column: “TSKgel (registered trademark) SuperHZ 1000” manufactured by Tosoh Corporation (Inner diameter 4.6 mm × length 15 cm) × 1 Sample side column: “TSKgel (registered trademark) SuperMultipore HZ-H” (inner diameter 4.6 mm × length 15 cm) × 2 manufactured by Tosoh Corporation Column temperature: 40 ° C.
Mobile phase: THF
Sample-side mobile phase flow rate (S.PUMP): 0.2 mL / min
Mobile flow rate on the reference side (R.PUMP): 0.2 mL / min
Detector: RI detector Sample concentration: 0.33% by weight
Sample injection volume: 20 μL
Measurement period: 0 to 25 min
Runtime (measurement duration): 25 min
Sampling pitch: 200 msec
As standard polystyrene samples for calibration curves, the trade name “Shodex (registered trademark)” manufactured by Showa Denko KK has a weight average molecular weight of 5,620,000, 3,120,000, 1,250,000, 442,000. 131,000, 54,000, 20,000, 7,590, 3,450, and 1,320.

  The calibration curve was prepared by using the standard polystyrene for calibration curve A (weight average molecular weights of 5,620,000, 1,250,000, 131,000, 20,000, and 3,450), B ( Weight average molecular weights of 3,120,000, 442,000, 54,000, 7,590, and 1,320) and A (weight average molecular weights of 5,620,000, 1,250,000) , 131,000, 20,000, and 3,450) were weighed 2 mg, 3 mg, 4 mg, 10 mg, and 10 mg, respectively, and then dissolved in 30 ml of THF. Was injected into the column. After weighing 3 mg, 4 mg, 8 mg, 10 mg, and 10 mg of each standard polystyrene of B (having a weight average molecular weight of 3,120,000, 442,000, 54,000, 7,590, and 1,320), respectively Then, it was dissolved in 30 ml of THF, and 20 μL of the obtained solution was injected into the column on the sample side. A calibration curve (third-order equation) was prepared as a calibration curve from the retention times of these standard polystyrenes, and used for weight average molecular weight measurement.

[Method for measuring hydroxyl value of resin]
The hydroxyl value is the number of mg of potassium hydroxide required to acetylate the OH group contained in 1 g of the sample. The hydroxyl value of the resin was calculated by an operation and calculation based on A method (acetylation method) of JIS K1557-1.

[Evaluation method of sunscreen resistance]
A sunscreen (trade name “Mentholatum (registered trademark) UV Protect”, SPF (ultraviolet ray protection index) 50+, manufactured by Rohto Pharmaceutical Co., Ltd.) was applied to the coating film, and allowed to stand overnight. After standing, the sunscreen on the coating film was removed with a paper wiping cloth (trade name “Kimwipe (registered trademark)”, manufactured by Nippon Paper Crecia Co., Ltd.), and the state of the coating film was observed. When the coating film is neither swollen nor peeled off, the sunscreen resistance was evaluated as “Good” (good), and when the coating film was swollen or peeled off, the sunscreen resistance was “x” (bad). ).

[Method for evaluating recoatability of coating film]
After creating the coating film, the coating film is further coated on the coating film in the same manner as the previous coating film, and after drying the coating film, the same as the cross-cut method described in JIS K5600-5-6 A crosscut test was conducted. However, the cut interval was not 5 mm as described in JIS K5600-5-6, but 5 mm. Then, in the same manner as the cross-cut method described in JIS K5600-5-6, the tape was attached to the coating film and peeled off, and the state of peeling of the coating film was observed. When the tape is peeled off, when the peeling of the coating film is not observed at all, the recoatability is evaluated as “◯”, and when the tape is peeled off, when a part or all of the peeling of the coating film is observed The recoatability was evaluated as “x”.

[Method for evaluating adhesion of coating film]
The adhesion of the coating film was evaluated by a cross-cut adhesion test using a cross-cut tape method in accordance with 8.5 of the former JIS K5400 _{: 1990} (4.15 of the current JIS D0202). When the cross-cut adhesion test score is 6 or more, the adherence is evaluated as “◯”, and when the cross-cut adhesion test score is less than 6, the adherence is “x”. It was evaluated.

[Example 1]
59.2 parts by weight of butyl acetate as an organic solvent was charged into a reaction container having an internal volume of 300 mL, and the temperature in the reaction container was raised to 80 ° C. while stirring at a stirring rotational speed of 250 rpm. Thereafter, 10 parts by weight of a silicone macromonomer (trade name “Silaplane (registered trademark) FM-0721”, manufactured by JNC Corporation) as component (a), (b) polypropylene glycol monomethacrylate (hydroxyl group-containing vinyl monomer) Trade name “Blemmer (registered trademark) PP-1000” (manufactured by NOF Corporation) 40 parts by weight, (c) 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane as a dioxolane-containing vinyl monomer (product) Name “CHDOL10” (manufactured by Osaka Organic Chemical Co., Ltd.) 10 parts by weight, (d) 38 parts by weight of methyl methacrylate (MMA) as another radical polymerizable monomer, and 2,2′-azobis as a polymerization initiator (2-methylbutyronitrile) (trade name “AVN-E”, Nippon Phi Co., Ltd.) A mixed solution (100 parts by weight) consisting of 2 parts by weight of Nchem was dropped into the reaction vessel every 30 minutes and polymerized at 80 ° C. for 8 hours. As a result, a dispersion composed of a resin and butyl acetate and having the resin dissolved in butyl acetate was obtained.

  The obtained resin had a hydroxyl value of 59 mgKOH / g, and the obtained resin had a weight average molecular weight of 24,000.

[Example 2]
(C) 4-acryloyloxymethyl-2-methyl-2-ethyl-1 instead of 10 parts by weight of 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane (“CHDOL10”) as a vinyl monomer containing dioxolane , 3-Dioxolane (trade name “MEDOL10”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used in the same manner as in Example 1 to obtain a dispersion in which the resin was dissolved in butyl acetate.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 28,000.

Example 3
(C) 4-acryloyloxymethyl-2-methyl-2-isobutyl-1 instead of 10 parts by weight of 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane (“CHDOL10”) as a dioxolane-containing vinyl monomer , 3-Dioxolane (trade name “MIBDOL10”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used in the same manner as in Example 1 to obtain a dispersion in which the resin was dissolved in butyl acetate.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 30000.

Example 4
Except for changing the amount of silicone macromonomer ("Silaplane (registered trademark) FM-0721") to 5 parts by weight and changing the amount of methyl methacrylate to 43 parts by weight, A dispersion was obtained in which the resin was dissolved in butyl acetate.
The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 35,000.

Example 5
Example 1 except that the amount of 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane (“CHDOL10”) used was changed to 2 parts by weight and the amount of methyl methacrylate used was changed to 46 parts by weight. Similarly, a dispersion in which the resin was dissolved in butyl acetate was obtained.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 26000.

Example 6
The amount of silicone macromonomer ("Silaplane (registered trademark) FM-0721") used was changed to 5 parts by weight, and the amount of 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane ("CHDOL10") used Was changed to 5 parts by weight, and a dispersion in which the resin was dissolved in butyl acetate was obtained in the same manner as in Example 1 except that the amount of methyl methacrylate used was changed to 48 parts by weight.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 32,000.

Example 7
The amount of silicone macromonomer ("Silaplane (registered trademark) FM-0721") used was changed to 2 parts by weight, and the amount of polypropylene glycol monomethacrylate ("Blemmer (registered trademark) PP-1000") used was 49 parts by weight. The dispersion in which the resin was dissolved in butyl acetate was obtained in the same manner as in Example 1 except that the amount of methyl methacrylate used was changed to 37 parts by weight.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 34,000.

Example 8
Except for changing the amount of silicone macromonomer ("Silaplane (registered trademark) FM-0721") to 3 parts by weight and changing the amount of methyl methacrylate to 45 parts by weight, A dispersion was obtained in which the resin was dissolved in butyl acetate.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 40,000.

Example 9
(D) In the same manner as in Example 1 except that 19 parts by weight of methyl methacrylate and 19 parts by weight of butyl methacrylate (BMA) are used in place of 38 parts by weight of methyl methacrylate as another radical polymerizable monomer, the resin is acetic acid. A dispersion dissolved in butyl was obtained.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 36000.

Example 10
(B) Poly (ethylene glycol / propylene glycol) monomethacrylate (trade name “Blemmer (registered trademark) 50 PEP-300” instead of polypropylene glycol monomethacrylate (“Blenmer (registered trademark) PP-1000”) as a hydroxyl group-containing vinyl monomer “NOF Corporation” was used in the same manner as in Example 2 to obtain a dispersion in which the resin was dissolved in butyl acetate.

  The obtained resin had a hydroxyl value of 57 mgKOH / g, and the obtained resin had a weight average molecular weight of 37,000.

Example 11
The amount of polypropylene glycol monomethacrylate ("Blemmer (registered trademark) PP-1000") used was changed to 35 parts by weight, and the amount of 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane ("CHDOL10") used A dispersion in which the resin was dissolved in butyl acetate was obtained in the same manner as in Example 1 except that the amount was changed to 15 parts by weight.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 30000.

Example 12
The amount of polypropylene glycol monomethacrylate ("Blemmer (registered trademark) PP-1000") used was changed to 35 parts by weight, and the amount of 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane ("CHDOL10") used Was changed to 20 parts by weight, and a dispersion in which the resin was dissolved in butyl acetate was obtained in the same manner as in Example 1 except that the amount of methyl methacrylate used was changed to 33 parts by weight.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 36000.

Example 13
Example 1 except that the amount of polypropylene glycol monomethacrylate ("Blemmer (registered trademark) PP-1000") used was changed to 20 parts by weight and the amount of methyl methacrylate used was changed to 58 parts by weight. A dispersion was obtained in which the resin was dissolved in butyl acetate.

  The obtained resin had a hydroxyl value of 28 mgKOH / g, and the obtained resin had a weight average molecular weight of 32,000.

[Comparative Example 1]
The resin was prepared in the same manner as in Example 1 except that 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane (“CHDOL10”) was not used and the amount of methyl methacrylate used was changed to 48 parts by weight. A dispersion dissolved in butyl acetate was obtained.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 35,000.

[Comparative Example 2]
Without using 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane (“CHDOL10”), the amount of methyl methacrylate used was changed to 24 parts by weight, and the amount of butyl methacrylate used was changed to 24 parts by weight. A dispersion in which the resin was dissolved in butyl acetate was obtained in the same manner as in Example 9 except for changing.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 47,000.

[Comparative Example 3]
The resin was dissolved in butyl acetate in the same manner as in Example 1 except that the silicone macromonomer ("Silaplane (registered trademark) FM-0721") was not used and the amount of methyl methacrylate used was changed to 48 parts by weight. A dissolved dispersion was obtained.

  The obtained resin had a hydroxyl value of 60 mgKOH / g, and the obtained resin had a weight average molecular weight of 42,000.

[Comparative Example 4]
The resin was dissolved in butyl acetate in the same manner as in Example 1 except that polypropylene glycol monomethacrylate ("Blemmer (registered trademark) PP-1000") was not used and the amount of methyl methacrylate used was changed to 78 parts by weight. A dissolved dispersion was obtained.

  The obtained resin had a hydroxyl value of 0 mgKOH / g, and the obtained resin had a weight average molecular weight of 38000.

  The types and amounts of the raw materials used in Examples 1 to 13 and Comparative Examples 1 to 4, and the weight average molecular weights and hydroxyl values of the resins obtained in Examples 1 to 13 and Comparative Examples 1 to 4 are shown in Table 1. Table 2 summarizes the results. In Tables 1 and 2, “FM-0721” represents “Silaplane (registered trademark) FM-0721”, “PP-1000” represents “Blemmer (registered trademark) PP-1000”, “ “50 PEP-300” represents “Blemmer (registered trademark) 50 PEP-300”.

[Coating film formation example 1 (using resin itself as coating agent)]
5 g of the dispersion (solid content 40% by weight) obtained in any one of the above Examples and Comparative Examples, polyfunctional isocyanate as a crosslinking agent (isocyanurate type polyfunctional isocyanate which is a trimer of hexamethylene diisocyanate) , Trade name “Duranate (registered trademark) TPA-100”, manufactured by Asahi Kasei Chemicals Corporation, NCO content: 23% by weight, 0.4 g, and isopropyl triisostearoyl titanate (manufactured by Ajinomoto Co., Inc., trade name) 0.2 g of “Plenact (registered trademark) KR TTS”) was mixed to obtain a coating agent. Thereafter, the coating agent was coated on an ABS resin plate (TP Giken Co., Ltd., standard: JIS K 6873, thickness 2 mm) with a 40 μm applicator and then dried. Thereafter, the dried coating agent was cured in an oven heated to 60 ° C. to obtain a coating film.

  The sunscreen resistance (a type of chemical resistance), recoatability, and adhesion of the coatings obtained using the dispersions obtained in each of the examples and comparative examples were evaluated by the methods described above. . The obtained evaluation results are shown in Tables 1 and 2 as “Evaluation of coating film (1) (using resin itself as coating agent)”.

[Coating film formation example 2 (resin used as paint modifier)]
90 g of polycaprolactone polyol (manufactured by Daicel Corporation, trade name “Placcel (registered trademark) L220AL”, hydroxyl value: 56 mgKOH / g) as a polyol constituting the polyurethane resin coating is placed in a 300 mL reaction vessel. The mixture was purged with nitrogen and stirred at 60 ° C.

  Next, polyfunctional isocyanate constituting the polyurethane resin paint (isocyanurate type polyfunctional isocyanate which is a trimer of hexamethylene diisocyanate, trade name “Duranate (registered trademark) TPA-100”, manufactured by Asahi Kasei Chemicals Corporation, containing NCO Amount: 23 wt%) 18.7 g, 30 g dispersion (solid content 40 wt%) obtained in any one of the above Examples and Comparative Examples as a coating modifier, and tetra n as a condensation catalyst -Butyl titanate 1.0g (Ajinomoto Co., Inc. make, a brand name "Plenact (trademark) KR TTS") was put, and these were fully mixed and stirred and the mixed solution was obtained. Then, this mixed solution was degassed under reduced pressure to obtain a coating composition.

  The obtained coating composition was coated on the same ABS resin plate as used in the coating film formation example 1 with a 40 μm applicator and then dried. Thereafter, the dried coating composition was cured in an oven heated to 60 ° C. to obtain a coating film.

  The sunscreen resistance (a type of chemical resistance), recoatability, and adhesion of the coatings obtained using the dispersions obtained in each of the examples and comparative examples were evaluated by the methods described above. . The obtained evaluation results are shown in Tables 1 and 2 as "Evaluation of coating film (2) (using resin as paint modifier)".

[Coating film formation example 3 (using resin as a paint modifier)]
Instead of the ABS resin plate, a PET film (manufactured by Toray Industries, Inc., trade name “Lumirror (registered trademark)”, type: S10, product number: # 125, thickness: 125 μm) was used in the same manner as in coating film formation example 2. A coating film was obtained.

  The sunscreen resistance (a type of chemical resistance), recoatability, and adhesion of the coatings obtained using the dispersions obtained in each of the examples and comparative examples were evaluated by the methods described above. . The obtained evaluation results are shown in Tables 1 and 2 as "Evaluation of coating film (3) (using resin as paint modifier)".

[Coating film formation example 4]
As an acrylic polyol constituting a polyurethane resin paint using acrylic polyol, 225 g of a product name “Acrynal (registered trademark) XB # 6000” (hydroxyl value 43 mg KOH / g, pure content 41 wt%) manufactured by Toei Kasei Co., Ltd. It put into reaction container, the inside of this reaction container was substituted with nitrogen, and it heated at 60 degreeC.

  Next, polyfunctional isocyanate (isocyanurate type polyfunctional isocyanate which is a trimer of hexamethylene diisocyanate, trade name “Duranate (registered trademark) TPA-100”), a component of Asahi Kasei Chemicals Co., Ltd. 12.5 g made by company, NCO content, 23 wt%), 30 g dispersion (solid content 40 wt%) obtained in any one of the examples and comparative examples as paint modifiers, and condensation 1.0 g of isopropyl triisostearoyl titanate as a catalyst (manufactured by Ajinomoto Co., Inc., trade name “Preneact (registered trademark) KR TTS”) was added, and these were sufficiently mixed and stirred to obtain a mixed solution. Then, this mixed solution was degassed under reduced pressure to obtain a coating composition.

  The obtained coating composition was coated on the same ABS resin plate as used in the coating film formation example 1 with a 40 μm applicator and then dried. Thereafter, the dried coating composition was cured in an oven heated to 60 ° C. to obtain a coating film.

  The sunscreen resistance (a type of chemical resistance), recoatability, and adhesion of the coatings obtained using the dispersions obtained in each of the examples and comparative examples were evaluated by the methods described above. . The obtained evaluation results are shown in Tables 1 and 2 as "Evaluation of coating film (4) (using resin as paint modifier)".

  By comparing Examples 1 to 13 with Comparative Examples 1 and 2, (a) the silicone macromonomer, (b) the hydroxyl group-containing vinyl monomer, (c) the dioxolane-containing vinyl monomer, and (d) the other Regardless of the amount of (a) to (d) or the type of (b) to (d), the resin of the present invention obtained by copolymerizing with a radically polymerizable monomer is the (c) dioxolane-containing vinyl-based resin. Compared to the resin obtained by copolymerization without using a monomer, it was found that the coating film formed by using a coating agent or a coating composition containing the resin is excellent in recoatability and adhesion. .

  Moreover, by comparing Examples 1 to 13 with Comparative Example 3, the (a) silicone macromonomer, the (b) hydroxyl group-containing vinyl monomer, the (c) dioxolane-containing vinyl monomer, and the (d) other Regardless of the amount of (a) to (d) or the type of (b) to (d), the resin of the present invention obtained by copolymerizing with a radical polymerizable monomer contains the (a) silicone macromonomer. It was found that compared with the resin obtained by copolymerization without using the above, the sunscreen resistance and recoatability of the coating film formed using the coating agent or coating composition containing the resin are superior. .

  Further, by comparing Examples 1 to 13 with Comparative Example 4, the (a) silicone macromonomer, the (b) hydroxyl group-containing vinyl monomer, the (c) dioxolane-containing vinyl monomer, the (d) other Regardless of the amount of (a) to (d) and the type of (b) to (d), the resin of the present invention obtained by copolymerizing with a radical polymerizable monomer is the above (b) hydroxyl group-containing vinyl type. Compared to a resin obtained by performing the above copolymerization without using a monomer, the coating film formed using a resin-containing coating agent or paint composition has excellent sunscreen resistance and recoatability. I understood.

  The resin and dispersion of the present invention have excellent chemical resistance and excellent compatibility with paints using urethane resins and acrylic resins, and are excellent when used in coating agents and paints. Since recoatability and excellent adhesion to a substrate can be imparted to a coating agent or paint, it is useful as a paint modifier, a material for a film damage prevention film, a component constituting a coating agent or paint composition, and the like.

Claims (10)

(A) a silicone macromonomer having a radical polymerizable group at one end;
(B) a vinyl monomer having a hydroxyl group at the terminal and having an alkylene oxide structure;
(C) a vinyl monomer having a dioxolane structure;
(D) A resin obtained by copolymerizing a radical polymerizable monomer other than the above (a) to (c). The resin according to claim 1,
A resin comprising the structural unit derived from (a) in a range of 2 to 15% by weight with respect to 100% by weight of the resin. The resin according to claim 1 or 2,
A resin comprising the structural unit derived from (c) in a range of 2 to 20% by weight with respect to 100% by weight of the resin. The resin according to any one of claims 1 to 3,
The resin (d) is characterized in that the alcohol residue is an alkyl (meth) acrylate and / or styrene whose alkyl group has 4 or less carbon atoms. It is resin of any one of Claims 1-4, Comprising:
The resin (b) contains two or more alkylene oxide structures having 3 or more carbon atoms. It is resin of any one of Claims 1-5, Comprising:
A resin having a hydroxyl value in the range of 20 to 80 mgKOH / g. The resin according to any one of claims 1 to 6 and an organic solvent,
A dispersion in which the resin is dissolved or finely dispersed in the organic solvent.   A coating agent comprising the resin according to any one of claims 1 to 6 or the dispersion according to claim 7. A paint modifier added to the paint to modify the paint,
A paint modifier comprising the resin according to any one of claims 1 to 6 or the dispersion according to claim 7. Paint,
A coating composition comprising the resin according to any one of claims 1 to 6, the dispersion according to claim 7, or the coating modifier according to claim 9.