JP7091848B2 - A composition containing an acrylic-modified polysiloxane compound and a method for producing the same, a cured product, a substrate, a substrate with a cured product, a vehicle, and a vehicle with a cured product. - Google Patents

Description

The present invention relates to a composition containing an acrylic-modified polysiloxane composition that can be used as a paint, a method for producing the same, a substrate to which the composition is applied, and a vehicle.

Normally, structures used in outdoor environments such as automobiles, aircraft, railroad vehicles, houses, buildings, and bridges are exposed to wind and rain, earth and sand, metal powder, etc., and their aesthetic appearance is gradually spoiled. Maintenance such as cleaning work is required. Since the object cannot be used temporarily during maintenance, a great deal of cost is incurred in preparing alternative means in addition to the labor of the work itself. Therefore, there is a demand for a method of reducing the maintenance frequency as much as possible.

To solve these problems, a method of applying an antifouling paint to the surface of an object has been proposed. For example, a method is known in which a paint containing a resin such as urethane or acrylic, which has a water-repellent and oil-repellent functional group, is coated on the surface of an object to prevent stains from adhering. However, since these organic resins have poor weather resistance, deterioration of the resin itself due to ultraviolet rays has been a problem. On the other hand, there is an example in which an ultraviolet absorber or a hindered amine-based light stabilizer is added to the paint to prevent deterioration of the resin, but there is a problem that the appearance is deteriorated due to bleeding or outflow of the additive.

On the other hand, paints using silicon-based resins have also been proposed. For example, in Patent Document 1, weather resistance can be imparted to a paint by using colloidal silica, but bending resistance is by no means sufficient, and for example, when painted on a curved exterior portion, cracks occur during curing. Was likely to occur, and the intended use was limited.

Further, an antifouling paint using a hybrid resin of an organic component and an inorganic component has also been proposed. For example, Patent Document 2 proposes a paint resin composition in which an (meth) acrylate-based resin is modified with a siloxane skeleton to impart antifouling properties. However, since the curing method of the paint resin composition is ultraviolet rays, it is not suitable for application to buildings and vehicles due to the structure of the irradiation device. In addition, curing paints using urethane or alkoxysiloxane are also found, but both have restrictions on pod life due to the two-component curing method, and each time painting requires preparation by the installer, so workability is possible. Did not lead to a fundamental improvement in.

Japanese Unexamined Patent Publication No. 2013-81941 Japanese Patent Application Laid-Open No. 2003-165929

The present invention is intended to solve the above problems. That is, an object of the present invention is to apply a composition containing a polysiloxane acrylic modified compound, a method for producing the same, and the composition, which are excellent in stain resistance and weather resistance and can be easily painted and cured. It is to provide the board and the vehicle.

The means for solving the above problems are as follows.
[1] A composition containing an acrylic-modified polysiloxane compound (A) having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

［ｍは１以上の自然数、Ｒ^１はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基、Ｒ^２は水素原子又はメチル基、Ｒ^３は２価の結合基を示す。］

[M is a natural number of 1 or more, R ¹ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a divalent bonding group. ]

［ｎは３以上の自然数、Ｒ^４はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基を示す。］

[N represents a natural number of 3 or more, R ⁴ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ]

[2] A structural unit formed by polymerizing a compound having at least one ethylenically unsaturated bond with a structural unit represented by the following general formula (1), and a structural unit represented by the following general formula (2). A composition comprising the acrylic modified polysiloxane compound (B) having at least.

［ｍは１以上の自然数、Ｒ^１はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基、Ｒ^２は水素原子又はメチル基、Ｒ^３は２価の結合基を示す。］

[M is a natural number of 1 or more, R ¹ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a divalent bonding group. ]

［ｎは３以上の自然数、Ｒ^４はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基を示す。］

[N represents a natural number of 3 or more, R ⁴ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ]

［ｍは１以上の自然数、Ｒ^１はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基、Ｒ^２は水素原子又はメチル基、Ｒ^３は２価の結合基を示す。］

［ｎは３以上の自然数、Ｒ^４はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基を示す。］
アクリル変性ポリシロキサン化合物（Ａ）と、少なくとも１種のエチレン性不飽和結合を有する化合物とを重合する工程と、を含む組成物の製造方法。 [3] A step of preparing an acrylic-modified polysiloxane compound (A) having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

[M is a natural number of 1 or more, R ¹ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a divalent bonding group. ]

[N represents a natural number of 3 or more, R ⁴ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ]
A method for producing a composition, comprising a step of polymerizing an acrylic-modified polysiloxane compound (A) and a compound having at least one ethylenically unsaturated bond.

[4] A cured product obtained by curing the composition according to the above [1] or the above [2].

[5] A substrate coated with the composition according to the above [1] or the above [2].

[6] A substrate with a cured product, which is obtained by curing the composition according to the above [5].

[7] A vehicle coated with the composition according to the above [1] or the above [2].

[8] A vehicle with a cured product, which is obtained by curing the composition according to the above [7].

According to the present invention, a composition containing a polysiloxane acrylic modified compound, which is excellent in stain resistance, bending resistance, and weather resistance, and which can be easily painted and cured, and a method for producing the same, and the composition is applied. Acrylic substrates as well as vehicles can be provided.

<Composition>
The composition of the present embodiment has two embodiments, a first embodiment and a second embodiment, and any of the compositions can be suitably used as a coating material. First, the composition of the first embodiment will be described below.

(First Embodiment)
The composition of the first embodiment contains an acrylic-modified polysiloxane compound (A) having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

［ｍは１以上の自然数、Ｒ^１はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基、Ｒ^２は水素原子又はメチル基、Ｒ^３は２価の結合基を示す。］

[M is a natural number of 1 or more, R ¹ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a divalent bonding group. ]

［ｎは３以上の自然数、Ｒ^４はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基を示す。］

[N represents a natural number of 3 or more, R ⁴ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ]

The composition of the first embodiment is excellent in stain resistance and weather resistance because the acrylic-modified polysiloxane compound (A) has a siloxane skeleton. Further, since the acrylic-modified polysiloxane compound (A) has a silanol group of the general formula (2) and is dehydrated and condensed by heating, it can be cured by heating. Further, since the composition of the present embodiment is cured only with the composition, that is, with one liquid, it is easy to paint because it does not require preparation such as mixing with other liquids at the time of painting.

In the general formula (1), m represents a natural number of 1 or more, but 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 3 is further preferable.

R ¹ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group indicated by R ¹ include an alkyl group, an alkenyl group and an alkynyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group and a hexadecyl group. Octadecyl group, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1- Examples thereof include a linear, branched or cyclic alkyl group such as an adamantyl group and a 2-norbornyl group. Specific examples of the alkenyl group include linear and branched groups such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group and 1-cyclohexenyl group. , Or a cyclic alkenyl group. Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-octynyl group and the like.
Among the above, the hydrocarbon group indicated by ^R1 is preferably a methyl group or a phenyl group.
The hydrocarbon group indicated by R ¹ may have an arbitrary substituent, and examples of the substituent include an ether group, a fluoro group, an epoxy group and the like.

R ² represents a hydrogen atom or a methyl group, and the atomic group bonded to R ³ of the general formula (1) (the side of the two bonds of R ³ that is bonded to the O atom) has R ² as the hydrogen atom. In the case of, an acryloyl group is indicated, and in the case of R ² being a methyl group, a methacryloyl group is indicated.

R ³ represents a divalent linking group. Examples of the divalent bonding group represented by R ³ include a bonding group represented by the following general formula (3), a divalent hydrocarbon group having 1 to 20 carbon atoms, or an alkylene ether group. The alkylene ether group is a divalent group having one or more alkylene groups and one or more ether bonds. The hydrocarbon group and the alkylene group may each have an arbitrary substituent. Examples of the substituent include an ether group, a fluoro group, an epoxy group and the like.

［ｐ及びｑはそれぞれ独立に０～２の整数（ただし、ｐ＋ｑ≦２）、Ｒ^５はフェニル基又は炭素数１～２０の飽和又は不飽和の炭化水素基、Ｒ^６はメチル基又はエチル基であり、Ｒ^７は炭素数１～２０の飽和又は不飽和の２価の炭化水素基を示す。］

[P and q are independently integers of 0 to 2 (where p + q ≦ 2), R ⁵ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a methyl group or an ethyl group. R ⁷ represents a saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms. ]

In the general formula (3), R ⁵ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group indicated by R ⁵ is the same as the hydrocarbon group indicated by R ¹ .

In the general formula (3), unlike the O atom represented by O atom (OR ⁶ ), one bond is bonded to the Si atom and the other bond is not bonded to a specific atom in the formula. Of the bonds of O atom), the bond that is not bonded to a specific atom may be bonded to the Si atom in the general formula (1).

R ⁷ represents a saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms. The divalent hydrocarbon group indicated by R ⁷ corresponds to one in which any hydrogen atom in the above-mentioned hydrocarbon group indicated by R ¹ is replaced with a bond.

p and q each independently represent an integer of 0 to 2 (where p + q ≦ 2), and in p + q ≦ 1, the portions of R ⁵ and OR ⁶ corresponding to p = 0 and q = 0 are hydrogen atoms. Further, when p = 2 and q = 0, it is shown that two substituents represented by R ⁵ are independently present and no substituent represented by OR ⁶ is present. When p = 0 and q = 2, it means that there are two independent substituents represented by OR ⁶ and no substituent represented by R ⁵ . From the viewpoint of improving reactivity, the cases of p = 0 and q = 2 are preferable.

On the other hand, as the divalent hydrocarbon group having 1 to 20 carbon atoms indicated by R ³ , any hydrogen atom in the above-mentioned hydrocarbon group indicated by R ¹ is replaced with a bond.

In the general formula (2), n represents a natural number of 3 or more, preferably 10 to 90, preferably 30 to 80.

^R4 represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group represented by R ⁴ is the same as the hydrocarbon group represented by R ¹ of the general formula (1).

In the acrylic modified polysiloxane compound (A) in the present embodiment, the ratio of m to n is preferably 0.5: 100 to 10: 100, preferably 1: 100, from the viewpoint of bending resistance at the time of forming a coating film. It is more preferably ~ 5: 100.

［ｍは１以上の自然数、Ｒ^１はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基、Ｒ^２は水素原子又はメチル基、Ｒ^３は２価の結合基を示す。］

［ｎは３以上の自然数、Ｒ^４はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基を示す。］ (Second embodiment)
The composition of the second embodiment comprises a structural unit obtained by polymerizing a compound having at least one ethylenically unsaturated bond into a structural unit represented by the following general formula (1), and the following general formula (2). It contains an acrylic modified polysiloxane compound (B) having at least a structural unit represented by.

[M is a natural number of 1 or more, R ¹ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a divalent bonding group. ]

[N represents a natural number of 3 or more, R ⁴ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ]

In the acrylic-modified polysiloxane compound (B) in the composition of the second embodiment, at least one kind of ethylenically unsaturated is used in the structural unit represented by the general formula (1) of the acrylic-modified polysiloxane compound (B). It differs from the acrylic-modified polysiloxane compound (A) in the composition of the first embodiment in that it is formed by polymerizing a compound having a bond. The other structures are the same as those of the acrylic-modified polysiloxane compound (A) in the composition of the first embodiment, and the same substituents, the number of structural units, etc. are indicated by the same symbols (alphabet). Is omitted.

The composition of the second embodiment is excellent in stain resistance and weather resistance because the acrylic-modified polysiloxane compound (B) has a siloxane skeleton. Further, the acrylic-modified polysiloxane compound (B) is rich in flexibility and excellent in bending resistance because a compound having at least one ethylenically unsaturated bond is polymerized in the structural unit represented by the general formula (1). .. Further, since the acrylic-modified polysiloxane compound (B) has a silanol group of the general formula (2) and is dehydrated and condensed by heating, it can be cured by heating. Further, since the composition of the present embodiment is cured only with the composition, that is, with one liquid, it is easy to paint because it does not require preparation such as mixing with other liquids at the time of painting.

Examples of the compound having an ethylenically unsaturated bond polymerized into the structural unit represented by the general formula (1) include methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, and 2-ethylhexyl acrylate. Octyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid. Acrylate or alkyl ester of acrylate such as tertiary butylhexyl, lauryl methacrylate, behenyl methacrylate, glycidyl group-containing monomer such as glycidyl methacrylate, vinyl monomer having nitrile group such as acrylonitrile, 2-hydroxyacrylic acid. Ethyl, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol / polypropylene glycol monoacrylate, poly (ethylene glycol / tetramethylene glycol) monoacrylate, poly (propylene glycol / tetramethylene glycol) monoacrylate, 2-hydroxyethyl methacrylate , Polyethylene glycol monomethacrylate, hydroxypropylmethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol / polypropylene glycol monomethacrylate, poly (ethylene glycol / tetramethylene glycol), hydroxyl group-terminated polyalkylene glycol mono (meth) acrylate, methoxypolyethylene glycol, etc. Monoacrylate, Octoxypolyethylene glycol / polypropylene glycol monoacrylate, lauroxypolyethylene glycol monoacrylate, stearoxypolyethylene glycol monoacrylate, phenoxypolyethylene glycol monoacrylate, nonylphenoxypolyethylene glycol monoacrylate, nonylphenoxypolypolyglycol monoacrylate, methoxypolyethylene glycol Monomethacrylate, Octoxy Polyethylene Glycol / Polypropylene Glycol Monomethacrylate, Lauroxy Polyethylene Glycol Monomethacrylate, Stearoxy Polyethylene Glycol Mono Alkyl group such as methacrylate, phenoxypolyethylene glycol monomethacrylate, nonylphenoxypolyethylene glycol monomethacrylate, nonylphenoxypolypropylene glycol monomethacrylate, nonylphenoxypoly (ethylene glycol / propylene glycol) monomethacrylate or aryl group-terminated polyalkylene glycol mono (meth) acrylate. And so on. Among the compounds having an ethylenically unsaturated bond, a compound having a (meth) acryloyl group is preferable. These monomers may be used alone or in combination of two or more.

As a structure obtained by polymerizing a compound having an ethylenically unsaturated bond in a structural unit represented by the general formula (1) of the acrylic modified polysiloxane compound (B), for example, the structure represented by the following general formula (4) is used. Can be mentioned. The structure represented by the following general formula (4) is obtained by polymerizing one compound having a (meth) acryloyl group on the structural unit represented by the general formula (1). The following structure is an example, and the second embodiment is not limited to the following structure.

［ｍは１以上の自然数、ｏは５以上の自然数、Ｒ^１はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基、Ｒ^２及びＲ^８はそれぞれ独立に水素原子又はメチル基、Ｒ^３は２価の結合基、Ｒ^９は、置換基を有してもよい炭素数１～２０の飽和若しくは不飽和の炭化水素基を示す。ｏは１０以上であってもよい。］

[M is a natural number of 1 or more, o is a natural number of 5 or more, R ¹ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and R ² and R ⁸ are independent hydrogen atoms or methyl groups, respectively. , R ³ is a divalent bonding group, and R ⁹ is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. o may be 10 or more. ]

In the general formula (4), R ¹ , R ² , and R ³ are the same as those in the general formula (1), R ¹ , R ² , and R ³ . R ⁸ is similar to the hydrogen atom or methyl group represented by R ² .
R ⁹ represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the hydrocarbon group is represented by R ¹ of the above-mentioned general formula (1). Similar to the hydrocarbon group. Further, as the substituent having the hydrocarbon group, a compound having a (meth) acryloyl group to be polymerized into the structural unit represented by the above-mentioned general formula (1) such as a hydroxyl group, an ether group, an epoxy group and a nitrile group ( Examples thereof include a group attached to a (meth) acryloyl group of a compound having an ethylenically unsaturated bond.
^In the present embodiment, as R9, a methyl group, an ethyl group, a butyl group, and a 2-ethylhexyl group are preferable from the viewpoint of imparting flexibility to the acrylic-modified polysiloxane compound (B) and improving bending resistance.

[Other additives]
In any of the embodiments, the composition of the present embodiment contains commonly used surface modifiers, defoaming materials, curing agents, rheology control agents, dyes, pigments, and difficulties as long as the effects are not impaired. Additives such as a flame retardant and an ultraviolet absorber may be used.

When the composition of the present embodiment is used as a paint, a coating film can be formed by applying the paint to a base material. The composition formed as a coating film can be cured by the method described later. The base material contains at least one of an inorganic material such as glass, ceramic, stainless steel, aluminum, and copper, and an organic resin material such as epoxy, bakelite, polyacrylate, polyethylene terephthalate, and polystyrene. The material made of the material to be used is mentioned. The base material is not limited to a single composition, and may be an electronic-related member such as a silicon wafer or one in which the above-mentioned components are laminated on the surface of the base material. Further, the shape of the base material can be applied to curved portions and stepped portions.

The coating method of the composition of the present embodiment is not particularly limited, but spray coating, bar coater coating, spin coating coating and the like are preferable. The film thickness at the time of coating is not particularly limited, but is preferably 100 μm or less, and more preferably 50 μm or less in order to prevent foaming and curing failure. Thick film coating can also be performed by recoating after film formation. The film thickness when the coating film is cured is not particularly limited, but may be 100 μm or less, 60 μm or less, or 40 μm or less.

As described above, the composition of the present embodiment can be cured by heating. A cured product can be obtained by curing the composition by heating. The heating temperature is preferably 40 ° C. or higher for the convenience of work, and more preferably 120 ° C. or higher at which the silanol groups react efficiently. The reaction time varies depending on the curing method and temperature, but is generally preferably about 1 to 48 hours, and an acid catalyst or an alkali catalyst may be added to increase the curing rate.
As described above, the composition of the present embodiment can be cured by heating, but it can also be cured by ultraviolet rays or two-component curing by appropriately introducing a functional group into the resin structure depending on the intended use.

The composition of the present embodiment can be easily applied and cured to a wide range of structures including curved surfaces, and can further impart sufficient antifouling property and bending resistance. In addition, it has excellent weather resistance and can reduce maintenance costs.

<Board and vehicle>
The substrate of the present embodiment is coated with the composition of the present embodiment. Further, the vehicle of the present embodiment is coated with the composition of the present embodiment. Since both the substrate and the vehicle of the present embodiment are coated with the composition of the present embodiment, they can be easily painted and easily cured. By curing the composition on the substrate coated with the composition of the present embodiment, a substrate with a cured product can be obtained. By curing the composition in a vehicle coated with the composition of the present embodiment, a vehicle with a cured product can be obtained. Further, since the composition of the present embodiment is applied, it is excellent in stain resistance, bending resistance, and weather resistance.
The composition of the present embodiment can be applied to various coatings such as aircraft, ships, buildings, etc., in addition to substrates and vehicles. Here, the substrate is not particularly limited, and the above-mentioned base material may be used as the substrate. Further, the vehicle is not particularly limited, and examples thereof include automobiles and railroad vehicles.

［ｍは１以上の自然数、Ｒ^１はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基、Ｒ^２は水素原子又はメチル基、Ｒ^３は２価の結合基を示す。］

［ｎは３以上の自然数、Ｒ^４はフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基を示す。］
アクリル変性ポリシロキサン化合物（Ａ）と、少なくとも１種のエチレン性不飽和結合を有する化合物とを重合する工程（以下、「工程Ｂ」とも呼ぶ。）と、
を含む。 <Manufacturing method of composition>
In the method for producing the composition of the present embodiment, an acrylic-modified polysiloxane compound (A) having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) is prepared. The process to be performed (hereinafter, also referred to as "process A") and

[M is a natural number of 1 or more, R ¹ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a divalent bonding group. ]

[N represents a natural number of 3 or more, R ⁴ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ]
A step of polymerizing the acrylic-modified polysiloxane compound (A) and a compound having at least one ethylenically unsaturated bond (hereinafter, also referred to as “step B”).
including.

By the method for producing a composition of the present embodiment, the composition of the second embodiment described above can be produced. In addition, the composition of the first embodiment described above can be produced by the step A of the method for producing the composition of the present embodiment.

[Step A]
Step A is a step of preparing an acrylic-modified polysiloxane compound (A) having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). The acrylic-modified polysiloxane compound (A) can be produced, for example, as follows.
First, a siloxane compound having a silicon-hydrogen bond is used as a starting material, and the siloxane compound and a compound having a hydroxy group are reacted in the presence of a metal complex of a catalyst in a solvent. By this reaction, a hydroxysiloxane compound in which hydrogen at the silicon-hydrogen bond site is replaced with a hydroxyl group is obtained.

As the siloxane compound having a silicon-hydrogen bond as a starting material used in the step A, for example, a compound having a structural unit represented by the following general formula (5) can be used.

［ｌは３以上の自然数、Ｒはフェニル基又は炭素数１～２０の飽和若しくは不飽和の炭化水素基を示す。］

[L indicates a natural number of 3 or more, R indicates a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ]

The compound having the structural unit represented by the general formula (5) may be cyclic, and if necessary, as a functional group, a carbinol group, an amino group, a diamino group, a carboxy group, an acid anhydride group, a vinyl group, etc. It may have a mercapto group, an epoxy group, a glycidyl group and the like. The functional group may be at the end. Considering the film-forming property, the average value of the numerical values indicated by l is preferably 10 to 90, and more preferably 30 to 80 in consideration of the coating workability.

The hydrocarbon group represented by R in the general formula (5) is the same as the hydrocarbon group represented by R ¹ in the above-mentioned general formula (1).

Water is preferably used as the compound having a hydroxy group used in the step A. In addition, other compounds having a hydroxy group may be used in combination with water. Here, examples of the compound having a hydroxy group other than water include methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl. Ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, phenol, cresol and the like are preferable, and these are used alone or in combination. be able to. Further, a compound having a functional group at the opposite end of the hydroxy group may be used, and for example, 2-hydroxyethyl (meth) acrylate, 2,2,2-trifluoroethanol and the like can be used.

As the solvent used in the step A, an alcohol-based solvent, an ester-based solvent, a lactone-based solvent, an ether-based solvent, a ketone-based solvent, an amide-based solvent, a hydrocarbon-based solvent, or the like can be used depending on the intended use. Of these, alcohol-based, ester-based, ether-based, and ketone-based compounds that are compatible with both siloxane compounds and compounds having a hydroxy group are preferable because they do not require a desolubilization step, and are more preferably alcohols. It is a system, a lactone system, a cyclic ether system, and a ketone system.

As the catalyst used in the step A, a tin, iron, nickel, ruthenium complex or the like containing a carbonyl ligand can be used. Of these, the use of a ruthenium complex is more preferable because there are fewer side reactions.

In reacting the siloxane compound having a silicon-hydrogen bond with the compound having a hydroxy group, the temperature is not particularly limited as long as it is below the boiling point of the solvent under reflux conditions. For example, the temperature can be 5 to 120 ° C. and the reaction time can be 1 to 120 hours. From the viewpoint of preventing gelation due to side reactions, the temperature is preferably 50 to 90 ° C. and the reaction time is preferably 4 to 24 hours.

Then, by introducing a (meth) acrylic group into the obtained hydroxysiloxane compound, a hydroxysiloxane compound having a (meth) acrylic group, that is, an acrylic-modified polysiloxane compound (A) can be obtained.

Examples of the method for introducing a (meth) acrylic group into a hydroxysiloxane compound include the following methods. For example, a method of reacting a (meth) acrylic-modified alkoxysilane with a silanol group of a hydroxysiloxane compound can be mentioned. As (meth) acrylic-modified alkoxysilanes, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldiethoxymethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-acryloxy. Propyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyldiethoxymethylsilane, 3-acryloxypropyldimethoxymethylsilane and the like can be used. The alkoxysilane moiety of the (meth) acrylic-modified alkoxysilane is R3 in the structural unit represented by the above-mentioned general formula (1), that is, the structural unit represented by the general formula ( ³ ).

In the reaction for introducing a (meth) acrylic group into a hydroxysiloxane compound, the temperature may be 20 to 120 ° C. and the reaction time may be 1 to 6 hours. From the viewpoint of preventing gelation due to side reactions, the temperature is preferably 60 to 80 ° C. and the reaction time is preferably 1 to 4 hours.

In the above, a siloxane compound having a silicon-hydrogen bond was used as a starting material, and a (meth) acrylic group was introduced via a hydroxysiloxane compound in which hydrogen at the silicon-hydrogen bond site of the siloxane compound was replaced with a hydroxyl group. A (meth) acrylic group may be introduced directly into the siloxane compound having a bond. For example, a dehydration condensation reaction is carried out with respect to the silicon-hydrogen bond of the siloxane compound by using -2-hydroxyethyl (meth) acrylate as the hydroxyl group-containing (meth) acrylic acid ester compound. In this case, R ³ in the structural unit represented by the general formula (1) is a hydrocarbon group.

[Step B]
Step B is a step of polymerizing the acrylic-modified polysiloxane compound (A) and the compound having at least one ethylenically unsaturated bond. The polymerization reaction in step B is carried out by using an acrylic-modified polysiloxane compound (A) and a compound having at least one ethylenically unsaturated bond with an appropriate polymerization initiator.

The compound having an ethylenically unsaturated bond used in the step B is the same as the compound having an ethylenically unsaturated bond polymerized into the structural unit represented by the above-mentioned general formula (1).

Examples of the polymerization initiator used in the polymerization reaction in step B include compounds that generate radicals by heating at 30 ° C. or higher (thermal polymerization initiator). Specifically, ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy)-. 2-Methylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexyl) Peroxy) -3,3,5-Peroxyketal such as trimethylcyclohexane; Hydroperoxide such as p-menthanhydroperoxide; α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumylperoxide , T-butylcumyl peroxide, dialkyl peroxide such as di-t-butyl peroxide; diacyl peroxide such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide; bis (4-t-butyl). Cyclohexyl) Peroxycarbonate such as peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutylperoxycarbonate; t-butylperoxypivalate , T-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) Hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropylmonocarbonate, t-butylper Oxy-3,5,5-trimethylhexanoate, t-butylperoxylaurylate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, t-butylperoxybenzoate, t -Peroxy esters such as hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate; 2,2'-azobisisobutyronitrile, 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2'-dimethylvaleronitrile), etc. Can be mentioned.

Further, as the polymerization initiator, a photopolymerization initiator may be used. Specifically, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone- 1,2,2-Dimethoxy-1,2-diphenylethan-1-one (Irgacure 651 (manufactured by Nippon Ciba Geigy Co., Ltd.)), 2,4-diethylthioxanthone (KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.)) Aromatic ketones such as; quinone compounds such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoins; benzyl derivatives such as benzyldimethyl ketal; 2- (2-chlorophenyl) -4,5 -2,4,5-Triarylimidazole dimer such as diphenylimidazole dimer, 2- (2-fluorophenyl) -4,5-diphenylimidazole dimer; 9-phenylacridin, 1,7- ( Examples thereof include an acridin derivative such as 9,9'-acrydinyl) heptane. From the viewpoint of workability and control of polymerization reaction, it is preferable to use a thermal polymerization initiator.

These polymerization initiators can be used alone or in combination of two or more. Further, the amount of the polymerization initiator used can be, for example, 0.01 to 3.0 parts by mass with respect to 100 parts by mass of the compound having a (meth) acrylic group used when synthesizing the acrylic resin.

The temperature when the thermal polymerization initiator is used in the polymerization reaction in step B can be set according to the half-life temperature of the polymerization initiator. For example, the temperature can be 30 to 90 ° C. and the reaction time can be 1 to 12 hours. From the viewpoint of preventing gelation due to side reactions, the temperature is preferably 30 to 70 ° C. and the reaction time is preferably 1 to 12 hours.

In the method for producing the composition of the present embodiment, in addition to steps A and B, a step of introducing other functional groups into the structure of the acrylic-modified polysiloxane compound (A) or (B), depressurization, heating, etc. A desolubilization step for distilling off the solvent or a step for mixing an additive, a diluent and the like may be provided.

Hereinafter, the present embodiment will be described in more detail by way of examples, but the present embodiment is not limited thereto.

[Example 1]
First, the inside of a 2000 ml scale three-necked flask was sufficiently filled with nitrogen. Next, in a three-necked flask, 500 g of polymethyl hydrogensiloxane (KF-99, manufactured by Shin-Etsu Chemical Industries, Ltd.), 500 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), 335 g of ion-exchanged water, ruthenium dodecacarbonyl (Co., Ltd.) ) Furuya Metal) 0.2g was added. Then, heating and stirring were performed while performing a reflux operation. Sampling was performed 6 hours later, and it was confirmed by FT-IR spectrum measurement that the peak derived from Si—H of 2200 cm ^-1 had disappeared. That is, it was confirmed that the polyhydroxysiloxane compound was produced. 1000 g of the obtained polyhydroxysiloxane compound was separated, 10 g of metharoxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was heated and stirred while refluxing at 60 ° C. After 1 hour, the mixture was heated to 75 ° C., mixed with 43.0 g of butyl acrylate, 43.0 g of methyl methacrylate, and 2.1 g of azobisisobutyronitrile, and then added dropwise over 30 minutes using a dropping funnel. .. As described above, a composition containing an acrylic-modified polysiloxane compound as a monoyellow varnish was obtained.

(Preparation and evaluation of coating film)
The obtained varnish was applied to a commercially available aluminum substrate using an applicator having a clearance of 50 μm, and cured at 135 ° C. for 1 hour to obtain a coating film (thickness: 5 μm). The following evaluation was performed on the obtained coating film. The evaluation results are shown in Table 1.

(1) Antifouling property One drop of a 10% by mass carbon dispersion aqueous solution was dropped on the obtained coating film, dried at 80 ° C. for 30 minutes, washed with water, and the state of carbon residue was visually confirmed. The case where no abnormality was observed in the appearance was evaluated as "○", and the case where an abnormality such as coloring, swelling or cracking was observed was evaluated as "x".
(2) Weather resistance For the obtained coating film, use a sunshine weather meter (Sunshine Super Long Life Weather Meter, manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ± 2 ° C, and ionize for 12 minutes in 60 minutes. The test was carried out for 360 hours under the condition of spraying with exchange water, and the appearance of the coating film was visually confirmed. The case where no abnormality was observed in the appearance was evaluated as "○", and the case where an abnormality such as discoloration, swelling or cracking was observed was evaluated as "x".
(3) Bending resistance A mandrel of 10 mmφ was installed with the coating film facing outward, bent 5 degrees with the mandrel as a fulcrum, and the degree of cracking on the end face of the coating film was visually confirmed. The case where cracks did not occur when bent was evaluated as "○", and the case where cracks occurred was evaluated as "x".
(4) Adhesion The obtained coating film was evaluated by a cross-cut method according to JIS K 5600-5-6. The interval between the cuts was 1 mm, and the cuts were made so as to be 100 squares of 10 × 10. As a result of the test, the ones that did not peel off were set to "0", and the ones that did not peel off were all set to "5".
(5) Pencil hardness The evaluation was made according to JIS K 5600-5-4. Specifically, after the tip of the pencil was placed on the coating film, a load of 750 g was applied and the pencil was pushed at a distance of 10 mm so as to separate at a speed of 1 mm / s. The hardness of the hardest pencil that did not cause scratches was defined as the pencil hardness.

[Examples 2 to 5]
A composition containing an acrylic-modified polysiloxane compound was obtained in the same manner as in Example 1 except that the raw material components were changed to the blending amounts shown in Table 1. Using the obtained composition, it was applied to an aluminum substrate in the same manner as in Example 1 and cured to obtain a coating film. Then, the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 1.

[Comparative Example 1]
In Example 1, a composition containing a polyhydroxysiloxane compound not acrylic-modified with methacryloxypropyltrimethoxysilane was applied to an aluminum substrate in the same manner as in Example 1 and cured to obtain a coating film. .. Then, the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 1.

[Comparative Example 2]
A commercially available acrylic urethane (Fine Urethane U-100, manufactured by Nippon Paint Co., Ltd.) was used, applied to an aluminum substrate in the same manner as in Example 1, and cured at 25 ° C. for 24 hours to obtain a coating film. Then, the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 1.

[Comparative Example 3]
Using a commercially available orthotetramethylsiloxane (manufactured by Wako Pure Chemical Industries, Ltd.), adjust the pH to 3 with hydrochloric acid, apply it to an aluminum substrate in the same manner as in Example 1, and cure at 80 ° C. for 3 hours. A coating film was obtained. Then, the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 1.

From Table 1, the coating films using the compositions of Examples 1 to 5 had good stain resistance, weather resistance, and bending resistance.
On the other hand, the coating film using the composition of Comparative Example 1 using the polyhydroxysiloxane compound not modified with acrylic had cracks and could not even be evaluated. Further, Comparative Example 2 using acrylic urethane was inferior in antifouling property and weather resistance, and Comparative Example 3 using orthotetramethylsiloxane was inferior in bending resistance.
From the above results, it can be seen that the composition of the present embodiment is excellent in antifouling property, weather resistance, and bending resistance. From this, it is clear that the composition of the present embodiment is very useful in various industrial fields such as automobiles and buildings.

Claims (8)

A composition containing an acrylic-modified polysiloxane compound (A) having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

[M is a natural number of 1 or more, R ¹ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is represented by the following general formula (3). Indicates a binding group. ]

[N represents a natural number of 3 or more, R ⁴ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ]

[P and q are independently integers of 0 to 2 (where p + q ≦ 2), R ⁵ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a methyl group or an ethyl group . R ⁷ represents a saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms. ] It has at least a structural unit formed by polymerizing a compound having at least one ethylenically unsaturated bond with a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). A composition containing an acrylic-modified polysiloxane compound (B).

[M is a natural number of 1 or more, R ¹ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is represented by the following general formula (3). Indicates a binding group. ]

[N represents a natural number of 3 or more, R ⁴ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ]

[P and q are independently integers of 0 to 2 (where p + q ≦ 2), R ⁵ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a methyl group or an ethyl group . R ⁷ represents a saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms. ] A step of preparing an acrylic-modified polysiloxane compound (A) having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

[M is a natural number of 1 or more, R ¹ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is represented by the following general formula (3). Indicates a binding group. ]

[N represents a natural number of 3 or more, R ⁴ represents a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ]

[P and q are independently integers of 0 to 2 (where p + q ≦ 2), R ⁵ is a phenyl group or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a methyl group or an ethyl group . R ⁷ represents a saturated or unsaturated divalent hydrocarbon group having 1 to 20 carbon atoms. ]
A step of polymerizing the acrylic-modified polysiloxane compound (A) and a compound having at least one ethylenically unsaturated bond.
A method for producing a composition comprising. A cured product obtained by curing the composition according to claim 1 or 2. A substrate coated with the composition according to claim 1 or 2. A substrate with a cured product, which is obtained by curing the composition according to claim 5. A vehicle to which the composition according to claim 1 or 2 is applied. A vehicle with a cured product, which is obtained by curing the composition according to claim 7.