WO2020152976A1 - Composition containing organopolysiloxane compound - Google Patents

Abstract

A composition according to the present invention, which contains (A) an organopolysiloxane compound that is represented by average formula (I) (wherein each R¹ independently represents a hydrogen atom, an alkyl group having 1-8 carbon atoms, which may be substituted by a halogen atom, or the like; R² represents an i-butyl group or an n-butyl group; R³ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an i-propyl group; a, b, c and d satisfy 0 ≤ a < 1, 0 < b ≤ 1, 0 ≤ c < 1, 0 ≤ d < 1 and (a + b + c + d) = 1; and e and f satisfy 0 < e ≤ 1 and 0 < f ≤ 1) and (B) a solvent that is represented by general formula (II) (wherein each of R⁴-R⁶ independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1-6 carbon atoms, provided that R⁵ and R⁶ are not hydrogen atoms at the same time; in cases where R⁴ is a hydrogen atom, n represents an integer of 2 or more; and in cases where R⁴ is a saturated hydrocarbon group, n represents an integer of 1 or more), contains a TX-free environmentally friendly solvent and an organopolysiloxane compound.

Description

Composition containing organopolysiloxane compound

The present invention relates to a composition containing an organopolysiloxane compound.

There is an increasing demand for environmentally friendly paints in consideration of environmental problems and safety to the human body. For that purpose, paints that do not contain specific VOCs (volatile organic compounds) such as toluene, xylene, and benzene, which have a high environmental load such as the occurrence of photochemical smog and cause allergies such as sick house syndrome. Is required.
In this respect, generally, for a coating containing an organosiloxane, a TX solvent such as toluene or xylene is often used from the viewpoint of solubility, drying property and easy handling.
However, the TX solvent has a high load on the human body and the environment, and has a risk of fire and explosion due to flammability and electrification. Further, it has a problem that cracks and coating unevenness are likely to occur in the coating film because of its high volatility.

　Environmentally friendly ethylene glycol is a TX-free solvent that has recently been used in increasing amounts because it has a low impact on people and nature and is easy to handle. Further, it has an advantage that it has a high boiling point and has little adverse effect on the human body due to exposure to solvent gas. Furthermore, since it has low volatility, it is excellent in workability, and cracks and uneven coating are unlikely to occur in the coating film, and therefore it is suitable as a solvent for paints.

On the other hand, as an organopolysiloxane having a polymerizable functional group, an organopolysiloxane having a divalent or trivalent siloxane bond as a skeleton is often used as a main raw material of a coating material from the viewpoint of hardness and flexibility. A trivalent siloxane bond is essential from the viewpoint of the adhesiveness between the base and the base.
Further, the state of the coating film surface after coating varies depending on the molecular weight of the organopolysiloxane. When the molecular weight is small, the ratio of the number of polymerizable functional groups is large, which causes the occurrence of cracks over time.When the molecular weight is large, the ratio of the number of polymerizable functional groups is small, which leads to deterioration in adhesion. It causes low hardness and low scratch resistance.

Organopolysiloxanes generally have an alkoxy group at the end, and alcohol is generated when a coating film is formed. Organopolysiloxanes having a methoxy group at the end are widely used from the viewpoint of ease of production and production cost, but since highly toxic methanol is generated by polymerization of organopolysiloxane, it has an impact on the environment and the human body. There is a demand for an organopolysiloxane having an ethoxy group or a butoxy group at the terminal, in which ethanol or butanol is taken into consideration.

Specifically, Patent Document 1 discloses an example of a low-VOC aqueous latex paint using a low-polymerization ethylene glycol derivative as a solvent. In this paint, the low-polymerization ethylene glycol is both a film-forming solvent and a thawing stabilizer. It is said that a coating film having excellent scratch resistance can be obtained.
Further, Patent Document 2 discloses that good adhesion and hardness are obtained in a coating film of a silicone resin composition hydrolyzed in isobutanol.

Japanese Patent Publication No. 2008-537007 Japanese Patent No. 4883269

The present invention has been made in view of the above circumstances, and is a composition containing a TX-free environment-friendly solvent and an organopolysiloxane compound, as well as excellent in coatability, crack resistance, adhesion, and smooth. An object of the present invention is to provide a coating agent capable of giving a cured coating, and a coated article.

The present inventors have conducted extensive studies to achieve the above objects, and as a result of using a composition containing an organopolysiloxane having a polymerizable functional group and a glycol ether solvent, found that the above problems can be solved. The present invention has been completed.

That is, the present invention is
1. (A) The following average formula (I)

(In the formula, each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be substituted with a halogen atom, an aralkyl group or an aryl group, and R ² represents i A butyl group or an n-butyl group, R ³ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an i-propyl group, and a, b, c and d each represent 0≦a< (1 and 0<b≦1, 0≦c<1, 0≦d<1, a+b+c+d=1 are satisfied, and e and f are numbers satisfying 0<e≦1 and 0<f≦1 respectively.)
100 parts by mass of an organopolysiloxane compound having a structure represented by: and (B) the following general formula (II)

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms, and R ⁵ and R ⁶ are hydrogen atoms at the same time. When R ⁴ is a hydrogen atom, n represents an integer of 2 or more, and when R ⁴ is the saturated hydrocarbon group, n represents an integer of 1 or more.)
A composition represented by 5 to 500 parts by mass of a solvent,
2. 1, wherein the organopolysiloxane compound has a weight average molecular weight of 1,000 to 500,000,
3. One or two compositions containing a curing catalyst,
4. A coating agent comprising the composition according to any one of 1 to 3,
5. A cured film of the composition of any one of 1 to 3,
6. Provided is a coated article having a substrate and a cured film of 5 formed on at least one surface of the substrate directly or through one or more other layers.

Since the composition of the present invention contains an organopolysiloxane having a polymerizable functional group and a glycol ether solvent, it reduces or alleviates the burden on the human body, ecology, and the global environment, and further cracks and uneven coating on the coating film. Since it is less likely to occur, it is useful as an environmentally friendly paint.

Hereinafter, the present invention will be described in more detail.
(1) Component (A) The component (A) used in the composition of the present invention is an organopolysiloxane compound having a structure represented by the following average formula (I).

In formula (I), R ^1's each independently represent a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms, which may be substituted with a halogen atom, an aralkyl group or an aryl group, and R ^2's are , I-butyl group or n-butyl group, preferably i-butyl group, and R ³ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an i-propyl group.

The alkyl group having 1 to 8 carbon atoms in R ¹ may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl and i-butyl. , Tert-butyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl groups, etc., but an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.
The aralkyl group preferably has 7 to 20 carbon atoms, and specific examples thereof include a benzyl group and a phenylethyl group.
The aryl group preferably has 6 to 18 carbon atoms, and specific examples thereof include unsubstituted aryl groups such as phenyl and naphthyl groups; tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptyl. Examples thereof include alkylaryl groups having 7 to 18 carbon atoms such as phenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl and dodecylphenyl groups, and the phenyl group is preferred.
In the above alkyl group, aralkyl group and aryl group, some or all of the hydrogen atoms may be replaced with halogen atoms (fluorine, chlorine, bromine, iodine atoms), and specific examples thereof include chloro. Examples thereof include a methyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, a chlorophenyl group and a bromophenyl group.

The above-mentioned a is a number satisfying 0≦a<1, but from the viewpoint of the crack suppressing effect, the range of 0≦a≦0.3 is preferable.
The above-mentioned b is a number satisfying 0<b≦1, but from the viewpoint of scratch resistance of the obtained cured product, the range of 0.2≦b≦1 is preferable.
The above-mentioned c is a number satisfying 0≦c<1, but from the viewpoint of the curability of the composition and the hardness of the obtained cured product, the range of 0≦c≦0.5 is preferable.
The above d is a number that satisfies 0≦d<1, but from the viewpoint of the curability of the composition and the hardness of the obtained cured product, 0≦d≦0.4 is preferable.
Note that a+b+c+d=1 is satisfied.

Although the above e is a number that satisfies 0<e≦1, it satisfies 0<e≦0.5 from the viewpoint of the storage stability of the composition and the crack resistance, water resistance and weather resistance of the obtained cured product. A number is preferred.
The above-mentioned f is a number satisfying 0<f≦1, but from the viewpoint of being effective in suppressing the condensation reaction due to the condensable functional group and crack resistance, water resistance and weather resistance of the obtained cured product, A number satisfying 0<f≦0.5 is preferable.

The (A) organopolysiloxane compound of the present invention may be a single composition or a mixture of a plurality of compounds having different compositions.

The weight average molecular weight of the (A) organopolysiloxane compound of the present invention is not particularly limited, but is preferably 1,000 to 500,000 in terms of polystyrene equivalent weight average molecular weight by gel permeation chromatography (GPC). , 500 to 300,000 is more preferable. When the weight average molecular weight is less than 1,000, the condensation does not proceed sufficiently, the storage stability of the organopolysiloxane compound may be low, and a condensation reaction may occur over time, resulting in poor crack resistance. .. If the polymer has a high molecular weight of more than 500,000, the organopolysiloxane compound becomes insoluble in the solvent, and there is a possibility that irregularities due to aggregates or uneven coating may occur.

Further, the organopolysiloxane compound of the present invention preferably has a nonvolatile content of 90% by mass or more excluding a solvent and the like. When the volatile content is large, the appearance may be deteriorated due to the generation of voids when the composition is cured, and the mechanical properties may be deteriorated.

The content of component (A) (solvent-free (A) component pure content) is 10 to 95% by mass in the composition, preferably 20 to 90% by mass, and more preferably 60 to 90% by mass. If the content of the component (A) (as non-volatile content) is less than 10% by mass, a cured product having a sufficient thickness may not be obtained after coating, and if it exceeds 95% by mass, a smooth cured product is not provided. There is a risk.

The (A) organopolysiloxane compound of the present invention can be manufactured according to a general method for manufacturing an organopolysiloxane. For example, the organopolysiloxane of the present invention can be obtained by hydrolyzing and condensing a silane compound having a hydrolyzable group.

The raw material for producing the organopolysiloxane is not particularly limited as long as it is a silane compound having 1 to 4 hydrolyzable chlorine or alkoxy groups on a silicon atom and having an organic substituent satisfying the above conditions. It is not something that will be done.
Specific examples thereof include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and methyltributoxysilane. , Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, Propyltrimethoxysilane, propyltriethoxysilane, butyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxy Silane, cyclohexyltrichlorosilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, propylmethyldichlorosilane, propylmethyldimethoxysilane, propylmethyldiethoxysilane, hexylmethyldichlorosilane, hexylmethyldimethoxysilane, hexylmethyldiethoxysilane, phenylmethyl Dichlorosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethylphenylchlorosilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, and partial hydrolysis products of these Among them, methoxysilane and ethoxysilane are preferable from the viewpoint of operability, easiness of distilling off by-products, and easy availability of raw materials.
The above silane compounds may be used alone or in combination of two or more.

A hydrolysis catalyst may be used in carrying out the hydrolysis.
As the hydrolysis catalyst, conventionally known catalysts can be used, but it is preferable that the aqueous solution exhibits acidity of pH 2 to 7, particularly acidic hydrogen halide, carboxylic acid, sulfonic acid, acidic or weakly acidic inorganic. Solid acids such as salts and ion exchange resins are preferred.
Specific examples of the acidic catalyst include hydrogen fluoride, hydrochloric acid, nitric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, formic acid, acetic acid, maleic acid, benzoic acid, lactic acid, phosphoric acid, sulfonic acid or carboxylic acid group on the surface. And a cation exchange resin having

The amount of the hydrolysis catalyst used is not particularly limited, but in consideration of the rapid progress of the reaction and the ease of removal of the catalyst after the reaction, 0.0002 to 1 mol of the hydrolyzable silane is used. A range of 0.5 mol is preferred.

The amount ratio of the hydrolyzable silane and the water required for the hydrolytic condensation reaction is not particularly limited, but the deactivation of the catalyst is prevented to allow the reaction to proceed sufficiently, and at the same time, to remove water after the reaction. In consideration of easiness, a ratio of water of 0.1 to 10 mol is preferable to 1 mol of hydrolyzable silane.
The reaction temperature during the hydrolytic condensation is not particularly limited, but in consideration of improving the reaction rate and preventing the decomposition of the organic functional group of the hydrolyzable silane, -10 to 150°C is preferable. preferable.

In addition, at the time of hydrolysis condensation, the solvent represented by (B) general formula (II) mentioned later may be used, and the organic solvent other than the (B) solvent may be used. Specific examples of such organic solvent include methanol, ethanol, propanol, n-butanol, i-butanol, t-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene and the like.
When an organic solvent other than the solvent (B) is used, it is preferable to remove it by a treatment such as a stripping step and replace it with the solvent represented by the general formula (II) (B).

At the time of hydrolysis and condensation, an appropriate reaction condition is selected by using an alcohol solvent such as ethanol, propanol, n-butanol, i-butanol, t-butanol, etc. It can be substituted with an alkoxy group such as a group, a propoxy group, an n-butoxy group, an i-butoxy group and a t-butoxy group.

(2) Component (B) The component (B) used in the composition of the present invention is a glycol ether solvent represented by the following general formula (II). Even if these glycol ether solvents are used alone, You may use suitably combining 2 or more types.

In the formula (II), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms, but R ⁵ and R ⁶ are the same. It does not become a hydrogen atom. When R ⁴ is a hydrogen atom, n represents an integer of 2 or more, and when R ⁴ is a saturated hydrocarbon group, n represents an integer of 1 or more. The upper limit of n is not particularly limited, but is preferably 10 or less.

The saturated hydrocarbon group having 1 to 6 carbon atoms may be linear, branched or cyclic and may be methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, tert-butyl, neopentyl, n. -A straight-chain or branched alkyl group such as hexyl; and a cyclic alkyl group such as a cyclopropyl, cyclopentyl, and cyclohexyl group, and the like, and a straight-chain or branched alkyl group having 1 to 6 carbon atoms is preferable.
Particularly, R ⁴ is preferably a hydrogen atom or a methyl group.

Specific examples of the solvent represented by the general formula (II) include diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, diethylene glycol monoisobutyl. Ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene Glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monophenyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, di Propylene glycol dimethyl ether and the like can be mentioned.
Among these, diethylene glycol diethyl ether and dipropylene glycol dimethyl ether are preferable.

The content of the component (B) is 10% by mass or more in the composition, preferably 15 to 40% by mass. If the content of the component (B) is less than 10% by mass of the composition, a smooth cured product may not be obtained.

The composition of the present invention preferably contains substantially no TX solvent. The TX solvent refers to an aromatic hydrocarbon solvent such as toluene or xylene. The term "substantially free from" means that the content of the TX solvent is 2.0% by mass or less in the composition, but it is preferably 0.5% by mass or less, and may be 0% by mass.

In addition, an arbitrary additive can be appropriately added to the composition of the present invention as long as the effect of the present invention is not impaired.
Specific examples of the additive include non-reactive silicone oil, reactive silicone oil, adhesion promoter such as silane coupling agent, antiaging agent, anticorrosive agent, colorant, surfactant, rheology modifier, and UV absorption. Agents, infrared absorbers, fluorescent agents, abrasives, fragrances, fillers, fillers, dyes and pigments, leveling agents, reactive diluents, non-reactive polymer resins, antioxidants, ultraviolet absorbers, light stabilizers, quenchers Examples thereof include foaming agents, dispersants, antistatic agents, thixotropy imparting agents, and the like. Each of these may be used alone or in combination of two or more and used in an appropriate amount.

The viscosity of the composition of the present invention is not particularly limited, but in consideration of improving the workability of molding or coating and suppressing the generation of uneven streaks, the viscosity at 25° C. measured by a rotational viscometer is The viscosity is preferably 100,000 mPa·s or less, more preferably 20,000 mPa·s or less. The lower limit is not particularly limited, but is preferably about 10 mPa·s.

The composition of the present invention can form a film by drying under room temperature and heating conditions, but a curing catalyst such as a condensation curing catalyst is added to accelerate the curing rate or to obtain excellent coating properties. You may.

The curing catalyst can be appropriately selected and used from known catalysts, and examples thereof include organic metal compounds such as organic tin compounds, organic titanium compounds, organic zirconium compounds and organic aluminum compounds; inorganic acids such as hydrochloric acid and sulfuric acid; p. -Toluenesulfonic acid, various organic acids such as aliphatic or aromatic carboxylic acids; ammonia; inorganic bases such as sodium hydroxide, tributylamine, 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) and the like organic bases and the like, and these may be used alone or in combination of two or more.

In the composition of the present invention, among these, organotin compounds, organometallic compounds selected from organotitanium compounds and organoaluminum compounds are preferable, and specifically, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyl. Tin dilaurate, dioctyl tin dioctate, dioctyl tin diacetate, dibutyl tin bis acetyl acetate, dioctyl tin bis acetyl laurate, tetrabutyl titanate, tetranonyl titanate, tetrakis ethylene glycol methyl ether titanate, tetrakis ethylene glycol ethyl ether titanate, bis(acetyl Acetonyl)dipropyl titanate, acetylacetone aluminum, aluminum bis(ethylacetoacetate)mononormal butyrate, aluminum ethylacetoacetate dinormalbutyrate, aluminum tris(ethylacetoacetate) and the like are preferable, and particularly, reactivity and dissolution. From the viewpoint of properties, tetrabutyl titanate, aluminum ethyl acetoacetate dinormal butyrate, aluminum bis(ethyl acetoacetate) mononormal butyrate and hydrolysates thereof are preferable.

The content of the curing catalyst is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the (A) organopolysiloxane compound.

The composition of the present invention can be produced, for example, by mixing the above-mentioned components (A) and (B) and optional components.
The proportion of the solvent represented by the general formula (II) is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 100% by mass, based on the whole solvent constituting the composition. ..

The composition of the present invention described above can be suitably used as a coating agent and the like, and can be particularly suitably used as an outer wall paint, but its application is not limited to the coating agent.
When used as a coating agent, for example, by applying the composition of the present invention to at least one surface of a substrate directly or through one or more other layers, and curing the composition to form a film. Thus, a coated article having a cured film of the composition of the present invention on at least one surface of the substrate can be obtained.

The substrate is not particularly limited, and examples thereof include glass, silicon wafer, metal, plastic molded body, ceramics, and composites thereof.
Further, the surface of these base materials is a chemical conversion treatment, a corona discharge treatment, a plasma treatment, a base material treated with an acid or an alkaline liquid, or a decorative plywood whose surface layer is coated with a different type of paint. Can also be used. Examples of other layers include those obtained by polyester resin coating, polyurethane resin coating, aminoalkyd resin coating, lacquer coating, spray coating, and water-based wax coating.

The method for applying the coating agent to the substrate may be appropriately selected from known methods, for example, flow coating, spin coating, bar coater, wire bar, brush coating, spraying, dipping, roll coating, curtain coating, knife. Various coating methods such as coating can be used. The coating amount is not particularly limited, but it is usually an amount such that the thickness of the coating film after drying is 0.1 to 1,000 μm, and preferably 1 to 100 μm.

Examples of the method for curing the composition include room temperature curing and heat curing.
The heating temperature is not particularly limited, but is preferably 100 to 300°C, more preferably 150 to 250°C.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
In the following, the nonvolatile content is a value measured according to JIS C2133, and the weight average molecular weight is GPC (gel permeation chromatography, HLC-8220 manufactured by Tosoh Corporation) and tetrahydrofuran (THF) is used as a developing solvent. Is the value measured as. The values of a to f in the average formula (I) were calculated from the results of ¹ H-NMR and ²⁹ Si-NMR measurements.

[1] Production of Composition [Example 1-1]
681.0 g (5.0 mol) of methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.), 396.6 g (2.0 mol of phenyltrimethoxysilane (KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.) ), dimethyldimethoxysilane (KBM-22, manufactured by Shin-Etsu Chemical Co., Ltd.) 240.4 g (2.0 mol), diphenyldimethoxysilane (KBM-202, manufactured by Shin-Etsu Chemical Co., Ltd.) 244.4 g (1.0 mol) ), 564.3 g of i-butanol and 47.0 g of a cation exchange resin (Levacit K2629, manufactured by LANXESS Co., Ltd.) were mixed in a reactor, and when uniform, 291.6 g of ion exchanged water was added, and the mixture was heated to 80° C. And stirred for 3 hours. After pressure filtration, 134.4 g of dipropylene glycol dimethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) was added. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was carried out to obtain a composition A.
The composition A thus obtained was a viscous liquid at 25° C. having a viscosity of 3,560 mPa·s, a non-volatile content of 86.4% by mass, and a weight-average molecular weight of the silicone component excluding the solvent of 22,200. The values of a to f in the average formula (I) were a=0, b=0.72, c=0.28, d=0, e=0.07, and f=0.06, respectively.

[Example 1-2]
Methyltrimethoxysilane (KBM-13, Shin-Etsu Chemical Co., Ltd.) 1,021.5 g (7.5 mol), dimethyldimethoxysilane (KBM-22, Shin-Etsu Chemical Co., Ltd.) 300.6 g (2. 5 mol), 413.2 g of i-butanol, and 34.4 g of a cation exchange resin (Levacit K2629, manufactured by LANXESS Co., Ltd.) were mixed in a reactor, and when uniform, 297.0 g of ion-exchanged water was added, and 80 The mixture was stirred at °C for 3 hours. After pressure filtration, 98.4 g of dipropylene glycol dimethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) was added. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed to obtain a composition B.
The composition B thus obtained was a viscous liquid at 25° C. having a viscosity of 2,200 mPa·s, a non-volatile content of 84.7 mass% and a weight average molecular weight of the silicone component excluding the solvent of 6,850. The values of a to f in the average formula (I) were a=0, b=0.76, c=0.24, d=0, e=0.08, and f=0.10.

[Example 1-3]
Methyltrimethoxysilane (KBM-13, Shin-Etsu Chemical Co., Ltd.) 817.2 g (6.0 mol), dimethyldimethoxysilane (KBM-22, Shin-Etsu Chemical Co., Ltd.) 120.2 g (1.0 mol) , Diphenyldimethoxysilane (KBM-202, manufactured by Shin-Etsu Chemical Co., Ltd.) 244.4 g (1.0 mol), hexamethyldisiloxane 162.4 g (1.0 mol), i-butanol 502.5 g, cation exchange resin ( 41.9 g of Levatit K2629 (manufactured by LANXESS Co., Ltd.) was blended in the reactor, and when uniform, 237.6 g of ion-exchanged water was added and stirred at 80° C. for 3 hours. After pressure filtration, 119.6 g of dipropylene glycol dimethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) was added. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was carried out to obtain a composition C.
The composition C thus obtained was a viscous liquid at 25° C. having a viscosity of 1,880 mPa·s, a non-volatile content of 83.9 mass %, and a weight average molecular weight of the silicone component excluding the solvent of 5,800. The values of a to f in the average formula (I) were a=0, b=0.62, c=0.22, d=0.16, e=0.09, and f=0.08, respectively. ..

[Example 1-4]
Tetraethoxysilane 10.4 g (0.05 mol), methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.) 681.0 g (5.0 mol), phenyltrimethoxysilane (KBM-103, Shin-Etsu Chemical Co., Ltd.) 29.8 g (0.15 mol), dimethyldimethoxysilane (KBM-22, Shin-Etsu Chemical Co., Ltd.) 336.6 g (2.8 mol), diphenyldimethoxysilane (KBM-202, Shin-Etsu Chemical Co., Ltd.) (Manufactured by K.K.) 488.8 g (2.0 mol), i-butanol 577.29 g, and cation exchange resin (Levacit K2629, manufactured by LANXESS Co., Ltd.) 48.1 g were mixed in a reactor, and when uniform, Ion-exchanged water (272.7 g) was added, and the mixture was stirred at 80° C. for 3 hours. After pressure filtration, 137.5 g of dipropylene glycol dimethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) was added. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was carried out to obtain a composition D.
The composition D thus obtained was a viscous liquid at 25° C. having a viscosity of 7,860 mPa·s, a non-volatile content of 87.2 mass %, and a weight-average molecular weight of the silicone component excluding the solvent of 26,300. The values of a to f in the average formula (I) were a=0.01, b=0.67, c=0.32, d=0, e=0.06, and f=0.08, respectively. ..

[Example 1-5]
To 100 parts by mass of the composition A prepared in Example 1-1, 5 parts by mass of a curing catalyst (DX-9740, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred at room temperature to obtain a composition E.

[Comparative Example 1-1]
681.0 g (5.0 mol) of methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.), 396.6 g (2.0 mol of phenyltrimethoxysilane (KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.) ), dimethyldimethoxysilane (KBM-22, manufactured by Shin-Etsu Chemical Co., Ltd.) 240.4 g (2.0 mol), diphenyldimethoxysilane (KBM-202, manufactured by Shin-Etsu Chemical Co., Ltd.) 244.4 g (1.0 mol) ), 564.3 g of i-butanol and 47.0 g of a cation exchange resin (Levacit K2629, manufactured by LANXESS Co., Ltd.) were mixed in a reactor, and when uniform, 291.6 g of ion exchanged water was added, and the mixture was heated to 80° C. And stirred for 3 hours. After pressure filtration, volatile components such as methanol were distilled off under reduced pressure. After the addition of 134.4 g of toluene, pressure filtration was carried out to obtain a composition F.
The composition F thus obtained was a viscous liquid having a viscosity of 390 mPa·s, a nonvolatile content of 81.6% by mass, and a weight average molecular weight of the silicone component excluding the solvent of 21,800 at 25° C. The values of a to f in the average formula (I) were a=0, b=0.71, c=0.29, d=0, e=0.07, and f=0.06, respectively.

[Comparative Example 1-2]
Methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.) 1,021.5 g (7.5 mol), dimethyldimethoxysilane (KBM-22, manufactured by Shin-Etsu Chemical Co., Ltd.) 300.6 g (2. 5 mol), 41-3.2 g of i-butanol, and 34.4 g of a cation exchange resin (Levacit K2629, manufactured by LANXESS Co., Ltd.) were mixed in a reactor, and when uniform, 297.0 g of ion-exchanged water was added to obtain 80. The mixture was stirred at °C for 3 hours. After pressure filtration, volatile components such as methanol were distilled off under reduced pressure. After adding 98.4 g of toluene, pressure filtration was performed to obtain a composition G.
The composition G obtained was a viscous liquid at 25° C. having a viscosity of 280 mPa·s, a non-volatile content of 82.2 mass %, and a weight average molecular weight of 7,700 of the silicone component excluding the solvent. The values of a to f in the average formula (I) were a=0, b=0.78, c=0.22, d=0, e=0.07, and f=0.10.

[Comparative Example 1-3]
Methyltrimethoxysilane (KBM-13, Shin-Etsu Chemical Co., Ltd.) 817.2 g (6.0 mol), dimethyldimethoxysilane (KBM-22, Shin-Etsu Chemical Co., Ltd.) 120.2 g (1.0 mol) , Diphenyldimethoxysilane (KBM-202, manufactured by Shin-Etsu Chemical Co., Ltd.) 244.4 g (1.0 mol), hexamethyldisiloxane 162.4 g (1.0 mol), i-butanol 502.5 g, cation exchange resin ( 41.9 g of Levatit K2629 (manufactured by LANXESS Co., Ltd.) was blended in the reactor, and when uniform, 237.6 g of ion-exchanged water was added and stirred at 80° C. for 3 hours. After pressure filtration, volatile components such as methanol were distilled off under reduced pressure. After adding 119.6 g of toluene, pressure filtration was performed to obtain a composition H.
The composition H thus obtained was a viscous liquid at 25° C. having a viscosity of 330 mPa·s, a non-volatile content of 81.1% by mass, and a weight-average molecular weight of the silicone component excluding the solvent of 5,600. The values of a to f in the average formula (I) were a=0, b=0.60, c=0.21, d=0.19, e=0.10, f=0.08, respectively. ..

[Comparative Example 1-4]
Tetraethoxysilane 10.4 g (0.05 mol), methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.) 681.0 g (5.0 mol), phenyltrimethoxysilane (KBM-103, Shin-Etsu Chemical Co., Ltd.) 29.8 g (0.15 mol), dimethyldimethoxysilane (KBM-22, Shin-Etsu Chemical Co., Ltd.) 336.6 g (2.8 mol), diphenyldimethoxysilane (KBM-202, Shin-Etsu Chemical Co., Ltd.) (Manufactured by K.K.) 488.8 g (2.0 mol), i-butanol 577.29 g, and cation exchange resin (Levacit K2629, manufactured by LANXESS Co., Ltd.) 48.1 g were mixed in a reactor, and when uniform, Ion-exchanged water (272.7 g) was added, and the mixture was stirred at 80° C. for 3 hours. After pressure filtration, volatile components such as methanol were distilled off under reduced pressure. After adding 137.5 g of toluene, pressure filtration was performed to obtain a composition I.
The composition I thus obtained was a viscous liquid at 25° C. having a viscosity of 380 mPa·s, a non-volatile content of 82.2% by mass, and a weight-average molecular weight of the silicone component excluding the solvent of 23,200. The values of a to f in the average formula (I) were a=0.01, b=0.65, c=0.35, d=0, e=0.08, and f=0.07, respectively. ..

[Comparative Example 1-5]
5 parts by mass of a curing catalyst (DX-9740, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts by mass of the composition F prepared in Comparative Example 1-1, and the mixture was stirred at room temperature to obtain a composition J.

[2] Production of cured film and coated article [Examples 2-1 to 2-5, Comparative examples 2-1 to 2-5]
The compositions A to J obtained in the above Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5 were applied onto a polished steel material by flow coating and heated in a dryer at 200° C. for 2 hours. Then, printing was performed. The content of the component (B) in each composition of the examples is 10% by mass or more.
With respect to the obtained coated article, the appearance of the coating film was visually evaluated and the adhesiveness was measured. The results are shown in Table 1.
(1) Appearance of coating film Visually, a film having a uniform coating surface and no irregularities or cracks due to agglomerates was OK, and those having irregularities due to cracks or aggregates were NG.
(2) Adhesion test A cross-cut test with 25 masses was performed according to JIS K5600-5-6, and the result was expressed as (number of masses remaining without peeling)/25.

As shown in Table 1, in Examples 2-1 to 2-5 using the compositions A to E containing the solvent represented by the general formula (II), no irregularities or cracks due to aggregates were generated. A coated article having a cured film that is uniform and has good adhesion has been obtained, suggesting the superiority of the organopolysiloxane compound of the present invention.

Claims (6)

1. (A) The following average formula (I)
   

   

   (In the formula, each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be substituted with a halogen atom, an aralkyl group or an aryl group, and R ² represents i A butyl group or an n-butyl group, R ³ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an i-propyl group, and a, b, c and d each represent 0≦a< (1 and 0<b≦1, 0≦c<1, 0≦d<1, a+b+c+d=1 are satisfied, and e and f are numbers satisfying 0<e≦1 and 0<f≦1 respectively.)
   100 parts by mass of an organopolysiloxane compound having a structure represented by: and (B) the following general formula (II)
   

   

   (In the formula, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms, and R ⁵ and R ⁶ are hydrogen atoms at the same time. When R ⁴ is a hydrogen atom, n represents an integer of 2 or more, and when R ⁴ is the saturated hydrocarbon group, n represents an integer of 1 or more.)
   A composition comprising 5 to 500 parts by mass of a solvent represented by:
2. The composition according to claim 1, wherein the organopolysiloxane compound has a weight average molecular weight of 1,000 to 500,000.
3. The composition according to claim 1 or 2, which contains a curing catalyst.
4. A coating agent comprising the composition according to any one of claims 1 to 3.
5. A cured film of the composition according to any one of claims 1 to 3.
6. A coated article having a base material and the cured film according to claim 5 formed on at least one surface of the base material directly or via one or more other layers.