JP4594955B2 - Method for producing composite fine particles - Google Patents

Description

  The present invention relates to a method for producing composite fine particles for obtaining a cured film or a cured product having high transparency and hardness.

A film-forming resin composition is used for the purpose of forming a film on the surface of a metal material such as iron, stainless steel or aluminum; an inorganic material such as mortar or slate; or an organic material such as plastic, wood or paper. This film-formable resin composition contains a film-formable resin as a main component and has a film-forming performance. However, since the resulting film has low hardness, it is used for reinforcing inorganic fillers such as silica fine particles in applications where hardness is required. It is used by further adding an agent. However, conventional reinforcing inorganic fillers such as silica fine particles have a drawback that they are difficult to disperse in the resin, and have problems in film performance and storage stability.
In order to solve such problems, the present inventors have developed composite fine particles in which an organic polymer is integrated with inorganic fine particles. In the composite fine particles, since the organic polymer integrated with the inorganic fine particles has an affinity for the film-forming resin composed of acrylic polyol and isocyanate, the dispersibility of the inorganic fine particles in the film-forming resin can be greatly improved. The film-forming composition containing the composite fine particles is extremely excellent in film performance and stability, and the obtained coating film has excellent weather resistance and contamination resistance (see, for example, Patent Document 1). .)

However, as a result of subsequent research, the film obtained from this film-forming composition has a limit to hardening because the matrix of the film is formed only by the reaction of acrylic polyol and isocyanate, and has a scratch resistance. Low. Although it is conceivable to increase the amount of the composite fine particles to increase the hardness, the coating is fragile and insufficient in toughness.
JP 7-178335 A

In order to improve this problem, the present applicant has selected a compound containing a polymerizable functional group as a film forming component to be blended with the composite fine particles (Japanese Patent Application No. 9-42576). In other words, the hardness of the matrix portion was increased by bringing a high crosslink density structure into the matrix. Since the matrix is polymerizable, this curable resin composition can be used for applications other than film formation.
However, in order to obtain a cured product having higher hardness, a cured film or a cured product having higher transparency, other devices are required.
That is, the problem to be solved by the present invention is to provide a method for producing composite fine particles that not only has excellent weather resistance and stain resistance, but also provides a cured film or cured product having high transparency and hardness. .

In order to solve the above-mentioned problems, the present inventors have devised an improvement on the previously developed composite fine particles. Then, focusing on imparting addition reactivity to the composite fine particles, various experiments and researches were repeated, and the present invention was completed.
That is, the method for producing composite fine particles according to the present invention includes:
It is composed of an organic chain and a polysiloxane group, and at least one Si—OR ¹ group (R ¹ is a hydrogen atom, an optionally substituted alkyl group, and an acyl group) in the polysiloxane group. a seed group, when R ¹ are a plurality in one molecule, a plurality of R ¹ may be identical to each other, a may be different.) silicon-containing polymer having a (P), alone, Or a step of hydrolysis / condensation with a hydrolyzable metal compound (G);
Reacting a hydrolysis / condensation product with a coupling agent having an ethylenically unsaturated group;
It is a manufacturing method containing.

  The method for producing composite fine particles according to the present invention provides a cured film and a cured product having not only excellent dispersibility, rich addition polymerization, excellent weather resistance and stain resistance, but also high transparency and hardness. It is possible to easily produce composite fine particles that can be produced.

[Composite fine particles]
The composite fine particles according to the present invention are fine particles obtained by integrating an organic polymer with inorganic fine particles, and further contain an ethylenically unsaturated group. This ethylenically unsaturated group has a function of imparting addition reactivity to the composite fine particles. The ethylenically unsaturated group is bonded to the inorganic fine particles and / or the organic polymer directly or indirectly through a divalent organic group. Among these, when the ethylenically unsaturated group is indirectly bonded via a divalent organic group, it is easy to produce. The bonding site of the ethylenically unsaturated group may be the surface of the inorganic fine particle, or the main chain and / or the side chain of the organic polymer. Among these, when the ethylenically unsaturated group is bonded to the surface of the inorganic fine particle, the addition reactivity on the surface of the inorganic fine particle is increased.

Specific examples of the ethylenically unsaturated group include, for example, a terminal vinyl group, an allyl group, a (meth) acryl group, an α-substituted methacryl group, an ethylene group, an acetylene group, and the like. Can coexist.
Specific examples of the divalent organic group include, for example, a linear or branched alkylene group such as methylene, ethylene, isopropylene group, or a substituted alkylene group; a phenylene group, a substituted phenylene group; a carbon chain of the alkylene group. An oxyalkylene group in which any carbon atom is replaced with an oxygen atom or the like can be mentioned, and these can be used alone or in combination of two or more.
There is no limitation in particular about content of the ethylenically unsaturated group contained in composite microparticles, Preferably it is 0.01-100 mmol / g per 1g of composite microparticles, More preferably, it is 0.05-50 mmol / g. If it is out of the above range, the addition reactivity due to the ethylenically unsaturated group may not be sufficiently exhibited.

The method for introducing an ethylenically unsaturated group into the composite fine particles is generally a method of reacting a coupling agent having an ethylenically unsaturated group, which will be described later, but is not limited to this method.
The integration of the inorganic fine particles and the organic polymer may be achieved by fixing the organic polymer to the inorganic fine particles. As described later, a silicon-containing polymer (P) that is a siloxane compound having an organic part and an inorganic part is used. The inorganic fine particles may be formed by hydrolysis and condensation, and at the same time, integration with the organic polymer may be achieved. In the above description, fixing does not mean temporary adhesion or adhesion, but means that organic polymer is not detected in the washing liquid when the composite fine particles are washed with a solvent. It strongly suggests that chemical bonds are formed between the fine particles.

The inorganic fine particles may be fine particles substantially composed of an inorganic substance, and any kind of constituent elements may be used, but inorganic oxides are preferably used. The shape of the inorganic fine particles is arbitrary such as a spherical shape, a needle shape, a plate shape, a scale shape, and a crushed particle shape.
The average particle size of the composite fine particles is not particularly limited, and is preferably 5 to 200 nm, more preferably 5 to 100 nm, and most preferably 5 to 50 nm. When the average particle diameter of the composite fine particles is less than 5 nm, the surface energy of the composite fine particles is increased, and the composite fine particles are easily aggregated. If the average particle size of the composite fine particles exceeds 200 nm, the transparency of the coating may be reduced.

The coefficient of variation (particle size distribution) of the composite fine particles is not particularly limited and is preferably 50% or less, more preferably 40% or less, and most preferably 30% or less. This is because if the particle size distribution of the composite fine particles is too wide, that is, if the coefficient of variation of the particle size exceeds 50%, the unevenness of the coating surface becomes severe and the smoothness of the coating is lost.
The inorganic oxide is defined as various oxygen-containing metal compounds in which a metal element mainly forms a three-dimensional network through bonds with oxygen atoms. As the metal element constituting the inorganic oxide, for example, an element selected from Group II to VI of the Periodic Table of Elements is preferable, and an element selected from Group III to V is more preferable. Among these, an element selected from Si, Al, Ti, and Zr is particularly preferable. Silica fine particles whose metal element is Si are the most preferred inorganic fine particles because they are easy to produce and easily available. The inorganic oxide may contain an organic group or a hydroxyl group in its structure. These groups may contain various groups derived from the metal compound (G) as a raw material to be described later. The organic group is, for example, at least one selected from the group consisting of an optionally substituted alkyl group having 20 or less carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group. The inorganic oxide constituting the inorganic fine particles need not be only one type, and may be two or more types.

The inorganic fine particles can contain an alkoxy group. The content of alkoxy groups is preferably 0.01 to 50 mmol per 1 g of composite fine particles. The alkoxy group represents an R ^m O group bonded to a metal element constituting the skeleton of the inorganic fine particles. Here, R ^m is an alkyl group which may be substituted, when R m ^O group is more, R m ^O group may be different it may be the same. Specific examples of R ^m include methyl, ethyl, n-propyl, iso-propyl, n-butyl and the like. The alkoxy group supplementarily improves the affinity of the inorganic fine particles with the organic medium and the dispersibility in the organic medium.
The organic polymer is usually present on the surface of the inorganic fine particles, but a part of the organic polymer may be included in the inorganic fine particles. When a part of the organic polymer is included in the inorganic fine particles, moderate flexibility and toughness can be imparted to the inorganic fine particles. The presence or absence of the organic polymer in the inorganic fine particles can be determined, for example, by measuring the specific surface area of the inorganic fine particles after the composite fine particles are heated at 500 to 700 ° C. to thermally decompose the organic fine particles. This can be confirmed by comparing with the theoretical value of the specific surface area calculated from the diameter. That is, when an organic polymer is included in the inorganic fine particles, a large number of pores are generated in the inorganic fine particles due to the thermal decomposition of the organic polymer. The calculated value is much larger than the theoretical value of the specific surface area.

  The organic polymer contributes to improving the dispersibility of the composite fine particles in the resin and the affinity with the organic medium, and the organic polymer itself may contribute as a binder or a matrix. The structure of the organic polymer is arbitrary, such as a straight chain, a branched chain, or a crosslinked structure. Specific examples of the resin constituting the organic polymer include acrylic resins, polystyrene, polyvinyl acetate, polyolefins such as polyethylene and polypropylene, polyesters such as polyvinyl chloride, polyvinylidene chloride, and polyethylene terephthalate, and copolymers thereof. There may be a resin in which these are partially modified with a functional group such as an amino group, an epoxy group, a hydroxyl group, or a carboxyl group. Among these, organic polymers containing acrylic units such as acrylic resins, acrylic-styrene resins, and acrylic-polyester resins have a film-forming ability and are suitable for film-forming composition applications such as paints. Examples of the acrylic unit include a highly polar side such as a methyl (meth) acrylate unit, an ethyl (meth) acrylate unit, and a methacrylate unit having a hydroxyl group such as a (meth) acrylate unit having a hydroxyl group such as a polyethylene glycol side chain. Examples include units having a chain, and these units improve the stain resistance of the coating.

As described above, the integration of the inorganic fine particles and the organic polymer in the composite fine particles may be performed simultaneously with the formation of the inorganic fine particles when the siloxane compound having the organic portion and the inorganic portion is hydrolyzed and condensed. As such a siloxane compound, a silicon-containing polymer (P) described later having a structure composed of an organic chain and a polysiloxane group and having at least one Si-OR ¹ group in the polysiloxane group is preferable. Can be mentioned. In this case, the organic polymer is derived from the organic chain of the silicon-containing polymer (P).
The organic polymer may have a functional group other than the ethylenically unsaturated group. It is preferable that the functional group is a perfluoroalkyl group and / or a silicone group because the stain resistance of the coating is improved. Specific examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorodecyl group, a perfluorododecyl group, A perfluorotetradecyl group etc. are mentioned. It is preferable that the perfluoroalkyl group is at least one of a perfluoromethyl group and a perfluoroethyl group because introduction into an organic polymer is easy. Some of the fluorine atoms in the perfluoroalkyl group may be substituted with other atoms such as a chlorine atom as long as the effects of the present invention are not impaired. Only one perfluoroalkyl group may be used, or two or more perfluoroalkyl groups may be appropriately combined. Specific examples of the silicone group include a dimethyl silicone group, a diphenyl silicone group, a methyl phenyl silicone group, a diethyl silicone group, and a methyl ethyl silicone group. It is preferable that the silicone group is at least one of a dimethyl silicone group and a diphenyl silicone group because introduction into an organic polymer is easy. Only one type of silicone group may be used, or two or more types may be appropriately combined. The molecular weight of the perfluoroalkyl group and the silicone group is not particularly limited, but is preferably 50,000 or less and more preferably 10,000 or less from the viewpoint of easy introduction into the organic polymer. . The bonding form of the main chain of the organic polymer and the perfluoroalkyl group and / or the silicone group is not particularly limited. In addition to those in which these groups and the main chain of the organic polymer are directly bonded, an ester group (—COO It may be bonded via —) or an ether group (—O—). The content of perfluoroalkyl groups and / or silicone groups in the organic polymer is not particularly limited, but is preferably 0.01 to 50%, more preferably 0.5 to 10% of the total weight. When the content is less than 0.01%, it is difficult for the composite fine particles to migrate to the surface of the coating during coating formation. On the other hand, if it exceeds 50%, the composite fine particles may fall off from the surface of the coating, and the contamination resistance of the coating may be reduced.

The average molecular weight of the organic polymer is not particularly limited, but it is preferably 200,000 or less, more preferably 50,000 or less, considering the solubility in organic solvents and the ease of producing composite fine particles. .
The ratio between the inorganic fine particles and the organic polymer in the composite fine particles is not particularly limited, but it is advantageous to increase the content of the inorganic fine particles as much as possible in order to more effectively exhibit the properties such as hardness and heat resistance of the inorganic fine particles. From such a viewpoint, the content of the inorganic fine particles is preferably 5 to 99.5% by weight. The lower limit of the content of the inorganic fine particles is more preferably 30% by weight, and most preferably 50% by weight.

The composite fine particles of the present invention can be dispersed in water and / or an organic solvent described later and handled as a dispersion containing the composite fine particles.
The composite fine particles of the present invention can be produced by any method, but the production method of the present invention described in detail below is a preferred example, and is not limited to this production method.
[Production method of composite fine particles]
The method for producing composite fine particles according to the present invention includes a hydrolysis / condensation step and a coupling agent reaction step. The hydrolysis / condensation step is a step of integrating the inorganic fine particles and the organic polymer to obtain integrated fine particles as a hydrolysis / condensate, and the coupling agent reaction step is a cup having an ethylenically unsaturated group. This is a step of reacting the ring agent with the integrated fine particles to bond the ethylenically unsaturated group to the surface of the inorganic fine particles.

The hydrolysis / condensation step is composed of an organic chain and a polysiloxane group, and at least one Si-OR ¹ group (R ¹ is a hydrogen atom and an optionally substituted alkyl group in the polysiloxane group, A silicon-containing polymer having at least one group selected from acyl groups and having a plurality of R ¹ groups in the molecule, the R ¹ groups may be the same or different from each other. This is a step of hydrolyzing and condensing P) alone or together with the hydrolyzable metal compound (G). Detailed description of the silicon-containing polymer (P) and the hydrolyzable metal compound (G) will be described later.
The hydrolysis / condensation method is not particularly limited, but it is preferably performed in a solution because the reaction can be easily performed. A solution here is a liquid which uses an organic solvent and / or water as a medium. Specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, iso-butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate , Esters such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone; tetrahydrofuran, dioxane, ethyl ether, Ethers such as di-n-butyl ether; methanol, ethanol, iso-propyl alcohol, n-butanol, ethylene glycol, ethyl Alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether; halogenated hydrocarbons such as methylene chloride and chloroform Etc., and one or more of these are used. Among these, it is preferable to use alcohols, ketones, and ethers that are soluble in water.

  The above hydrolysis / condensation can be carried out without a catalyst, but if necessary, one or more of an acidic catalyst or a basic catalyst can be used as a catalyst. Specific examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as acetic acid, propionic acid, oxalic acid, and p-toluenesulfonic acid; and acidic ion exchange resins. Specific examples of the basic catalyst include ammonia; organic amine compounds such as triethylamine and tripropylamine; sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, sodium hydroxide, hydroxide Examples include alkali metal compounds such as potassium; basic ion exchange resins and the like. When a basic catalyst is used, the inorganic fine particles obtained by hydrolysis / condensation have a stronger skeleton. Therefore, the basic catalyst is preferable to the acidic catalyst.

  The raw material composition at the time of hydrolysis / condensation is not particularly limited, but the amount of each raw material relative to the total amount of the raw material composition consisting of silicon-containing polymer (P), metal compound (G), organic solvent, water, catalyst or the like. The blending ratio is as follows. The silicon-containing polymer (P) is preferably 0.1 to 80% by weight, and more preferably 0.5 to 30% by weight. 0-80 weight% is preferable and, as for a metal compound (G), 0-50 weight% is more preferable. The organic solvent is preferably 0 to 99.9% by weight, and more preferably 20 to 99% by weight. The catalyst is preferably 0 to 20% by weight, and more preferably 0 to 10% by weight. The amount of water used for hydrolysis / condensation is not particularly limited as long as it is an amount sufficient to form silicon-containing polymer (P) or silicon-containing polymer (P) and metal compound (G) by hydrolysis / condensation. In order to perform hydrolysis / condensation more sufficiently and strengthen the skeleton of the particles, the larger the amount of water, the better. Specifically, the molar ratio of water to the hydrolyzable group to be hydrolyzed / condensed is 0.1 or more, preferably 0.5 or more, more preferably 1 or more.

  In the silicon-containing polymer (P), the organic chain and the polysiloxane group are chemically bonded through Si-C bond, Si-O-C bond, etc., but this bonding site is not easily subjected to hydrolysis, Since it is difficult to receive an unfavorable reaction such as a reaction, it is preferably composed of Si—C bonds. The specific structure of the silicon-containing polymer (P) is not limited as long as it is soluble in an organic solvent or water. For example, a polymer in which a polysiloxane group is grafted to an organic chain, or a polysiloxane group is an organic chain. A polymer bonded to one or both ends of the polymer, and a polysiloxane group as a core, and a plurality of organic chains (the plurality of organic chains may be the same or different) in this core are linear or branched Examples thereof include polymers bonded in a shape. Here, the organic chain refers to a portion other than the polysiloxane group in the silicon-containing polymer (P). The main chain in the organic chain is mainly composed of carbon, and carbon atoms participating in the main chain bond occupy 50 to 100 mol% of the main chain, and the remainder is an element such as N, O, S, Si, P or the like. It is preferable for reasons such as easy availability.

Specific examples of the resin constituting the organic chain include those described above for the organic polymer constituting the composite fine particles.
The polysiloxane group is a group formed by connecting two or more Si atoms in a linear or branched manner by a polysiloxane bond (Si—O—Si bond). The number of Si atoms possessed by the polysiloxane group is not particularly limited, but is preferably an average of 4 or more per polysiloxane group in that it can contain a large amount of the R ¹ O groups described above. 11 or more are more preferable. The R ¹ O group in ^one Si-OR group is a functional group that can be hydrolyzed and / or condensed, and preferably has an average of 5 or more per molecule of silicon-containing polymer (P), and has 20 or more. Is more preferable. As the number of R ¹ O groups increases, the number of reaction points for hydrolysis and condensation increases, and inorganic fine particles having a stronger skeleton can be obtained. The number of carbon atoms of the alkyl group and acyl group corresponding to R ¹ is not particularly limited, but is preferably 1 to 5 because the hydrolysis rate of the R ¹ O group is high. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec-butyl group, tert-butyl group, and pentyl group. Specific examples of the acyl group having 1 to 5 carbon atoms include an acetyl group and a propionyl group. As the substituted alkyl group and acyl group, one or more of the hydrogen atoms of the alkyl group or acyl group is an alkoxy group such as a methoxy group or an ethoxy group; an acyl group such as an acetyl group or a propionyl group A group formed by substitution with halogen such as chlorine and bromine. R ¹ is preferably a hydrogen atom, a methyl group, or an ethyl group, and most preferably a methyl group, because the hydrolysis / condensation rate of the R ¹ O group is further increased.

Specific examples of the polysiloxane group include a polymethylmethoxysiloxane group, a polyethylmethoxysiloxane group, a polymethylethoxysiloxane group, a polyethylethoxysiloxane group, a polyphenylmethoxysiloxane group, and a polyphenylethoxysiloxane group. All of the Si atoms in the polysiloxane group are preferably bonded only to the R ¹ O group, except for being bonded to an organic chain or a polysiloxane bond (Si—O—Si bond). As a result, the ionicity of the Si atom is further increased. As a result, the hydrolysis / condensation rate of the R ¹ O group is increased, and the reactive sites in the silicon-containing polymer (P) are increased. It is because it is obtained. Specific examples of such polysiloxane groups include polydimethoxysiloxane groups, polydiethoxysiloxane groups, polydiiso-propoxysiloxane groups, poly n-butoxysiloxane groups, and the like.

The average molecular weight of the silicon-containing polymer (P) is not particularly limited, but is preferably 200,000 or less, and more preferably 50,000 or less. If the molecular weight is too high, it may not dissolve in the organic solvent, which is not preferable.
The silicon-containing polymer (P) can be produced by a known method. Although the following method is mentioned as the example, It is not limited to these methods.
(1) After radical (co) polymerizing a radical polymerizable monomer in the presence of a silane coupling agent having a double bond group or a mercapto group, the obtained (co) polymer and a silane compound described below and / or its A method of obtaining a macropolymer (hereinafter abbreviated as polymerizable polysiloxane) by cohydrolyzing and condensing a derivative.

(2) A method of radical (co) polymerizing a radical polymerizable monomer in the presence of the polymerizable polysiloxane obtained as described above.
(3) A silane coupling agent having a reactive group such as a double bond group, an amino group, an epoxy group, or a mercapto group is reacted with a polymer having a group that reacts with the reactive group. A method of cohydrolyzing and condensing a silane compound and / or a derivative thereof described later.
(4) After co-hydrolyzing / condensing the silane coupling agent having the reactive group and the silane compound and / or derivative thereof, the resultant reaction product is reacted with a polymer having a group that reacts with the reactive group. How to make.

Of the above four methods, method (2) is preferred. This is because the silicon-containing polymer (P) can be obtained more easily.
The silicon-containing polymer (P) includes (i) a perfluoroalkyl group and / or a silicone group (hereinafter sometimes referred to as (i) group), and (ii) a perfluoroalkyl group and / or a silicone group. It may further include at least one group of functional groups that can be introduced (hereinafter, also referred to as (ii) functional groups). Specific examples of the group (i) include the groups described in the organic polymer of composite fine particles. (Ii) Specific examples of functional groups include hydroxyl, carboxyl, amino, epoxy, mercapto, oxazoline and aldehyde groups. When the silicon-containing polymer (P) contains a functional group (ii), a compound containing a group that reacts with the functional group and a perfluoroalkyl group and / or a silicone group is selected from the above (1) to (4). A perfluoroalkyl group and / or a silicone group can be introduced into the silicon-containing polymer (P) by reacting with a hydrolysis / condensation product in the course of the method. (Ii) The group that reacts with the functional group varies depending on the type of the functional group, but when the functional group is a hydroxyl group, it is an oxazoline group, a carboxyl group, and an epoxy group, and when the functional group is a carboxyl group, the oxazoline Group, hydroxyl group, epoxy group and mercapto group, when the functional group is epoxy group, it is oxazoline group, carboxyl group, hydroxyl group, amino group and mercapto group, and when functional group is amino group, oxazoline group An epoxy group and a vinyl group, an amino group when the functional group is a vinyl group, an epoxy group, a carboxyl group, a hydroxyl group, an amino group and a mercapto group when the functional group is an oxazoline group, Oxazoline group, epoxy group, carboxyl group and epoxy group when the functional group is a mercapto group A.

Specific examples of the silane compound include methyltriacetoxysilane, dimethyldiacetoxysilane, trimethylacetoxysilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetraiso-propoxysilane, tetrabutoxysilane, methyltrimethoxysilane, phenyl Examples include trimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, and dimethoxydiethoxysilane. Examples of these derivatives include hydrolysis / condensation products thereof. Of the above, alkoxysilane compounds are preferred because they are readily available as raw materials. When the silane compound and / or derivative thereof is Si (OR ² ) ₄ and its derivative (R ² will be described later), composite particles having a stronger skeleton are obtained with a high hydrolysis / condensation rate.

The metal compound (G) can form a three-dimensional network by hydrolysis and further condensation. Specific examples of such a metal compound (G) include metal halides, metal nitrates, metal sulfates, metal ammonium salts, organometallic compounds, alkoxy metal compounds, and derivatives thereof. The metal compound (G) can be used alone or in combination of two or more.
As the metal compound (G), it is preferable that the metal element is selected from elements of Group III, Group IV, and Group V of the Periodic Table. Among them, the following general formula (1)
(R ² O) _m MR ³ _nm (1)
(In the general formula (1), M is at least one metal element selected from the group consisting of Si, Al, Ti, and Zr, and R ² is selected from a hydrogen atom, an optionally substituted alkyl group, and an acyl group. At least one group, R ³ is an optionally substituted alkyl group, cycloalkyl group, aryl group, aralkyl group, n is the valence of the metal element M, m is 1 to When there are a plurality of integers of n, R ² and / or R ³ in one molecule, the plurality of R ² and / or R ³ may be the same or different from each other. More preferred is at least one metal compound selected from the derivatives. As for R ² , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a sec-butyl group, a tert-butyl group, and a pentyl group, and the acyl group includes an acetyl group. And propionyl group. R ² is preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a methyl group. This is because the hydrolysis / condensation rate of the R ² O group is fast. For R ³ , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a sec-butyl group, a tert-butyl group, and a pentyl group, and the cycloalkyl group includes a cyclohexyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include a benzyl group. The substituted alkyl group, cycloalkyl group, aryl group, and aralkyl group are one or more hydrogen atoms of the alkyl group, cycloalkyl group, aryl group, and aralkyl group, which are a methoxy group or an ethoxy group. A group substituted with a functional group such as an alkoxy group such as amino group, nitro group, epoxy group, or halogen. Specific examples of the metal compound (G) represented by the general formula (1) include methyltriacetoxysilane, dimethyldiacetoxysilane, trimethylacetoxysilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, and tetraiso-proxysilane. , Tetrabutoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, dimethoxydiethoxysilane, aluminum trimethoxy Aluminum triethoxide, aluminum triiso-propoxide, aluminum tributoxide, dimethylaluminum methoxide, tetra Toxytitanium, tetraethoxytitanium, tetraiso-propoxytitanium, tetrabutoxytitanium, tetra (2-ethylhexyloxy) titanium, diethoxysibutoxytitanium, iso-proxytitanium trioctarate, diiso-propoxytitanium diacrylate, tributoxy Examples thereof include titanium stearate, zirconium acetate, tetramethoxyzirconium, tetraethoxyzirconium, tetraiso-propoxyzirconium, and tetrabutoxyzirconium. Specific examples of the derivative of the metal compound (G) represented by the general formula (1) include diiso-propoxytitanium diacetylacetonate, oxytitanium diacetylacetonate, dibutoxytitanium bistriethanolamate, dihydroxytitanium dilactoate, zirconium. Examples include acetylacetonate, acetylacetone zirconium butoxide, triethanolamine zirconium butoxide, aluminum acetylacetonate and the like. At least selected from silane compounds and derivatives thereof in which M is Si in the general formula (1) because they are easily available industrially and do not contain halogens or the like that adversely affect the physical properties of the production apparatus and final product. It is more preferable to use one type.

Next, the coupling agent reaction step is obtained by reacting the coupling agent having an ethylenically unsaturated group with the integrated fine particles obtained by integrating the inorganic fine particles and the organic polymer obtained in the hydrolysis / condensation step. This is a step of bonding an ethylenically unsaturated group to the surface of the inorganic fine particles.
If the coupling agent used in the coupling agent reaction step has an ethylenically unsaturated group in the molecule and has a hydrolyzable group that can react with inorganic fine particles to form a chemical bond, There is no particular limitation. Specific examples of such a coupling agent include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxy. Examples thereof include silicon-based coupling agents such as silane; titanium-based coupling agents such as isopropyldi (meth) acrylic isostearoyl titanate, and these are used alone or in combination of two or more.

The method of reacting the coupling agent is not particularly limited, but for the reason that the reaction can be easily performed, in the same manner as the hydrolysis / condensation step described above, in a solution containing an organic solvent and / or water, Preference is given to using a catalyst. As the catalyst, a basic catalyst is more preferable.
The raw material composition in the reaction of the coupling agent reaction is not particularly limited, but the blending ratio of each raw material with respect to the total amount of the raw material composition including integrated fine particles, coupling agent, organic solvent and / or water, and catalyst is as follows It is. The integrated fine particles are preferably 0.05 to 20% by weight, and more preferably 0.5 to 8% by weight. The coupling agent is preferably 0.001 to 5% by weight, and more preferably 0.005 to 1% by weight. The organic solvent and / or water is preferably 80 to 99.9% by weight, more preferably 90 to 99% by weight. The catalyst is preferably 5% by weight or less, and more preferably 0.01 to 2% by weight.

Examples of other methods for producing the composite fine particles of the present invention include the following methods (a) and (b).
(A) In the hydrolysis / condensation step, hydrolysis / condensation is performed using a silicon-containing polymer (P) having a functional group capable of reacting with an acid group such as an amino group in the side chain to form a chemical bond. . Next, a method of reacting the functional group with a compound having an acid group such as (meth) acrylic acid and an ethylenically unsaturated group.
(B) A method in which terminal hydroxyl group-containing unsaturated polyester and polyalkoxysiloxane are reacted, and the resulting silicon-containing polymer (P) is used for hydrolysis and condensation.

[Core-shell type composite particles]
The core-shell type composite particle according to the present invention is obtained by seed polymerization of an unsaturated monomer using the composite fine particle as a core. Here, seed polymerization is emulsion polymerization in which an unsaturated monomer is polymerized in the presence of composite fine particles as a seed (seed) for initiating polymerization, and is usually performed using an emulsifier and a radical polymerization initiator. The core-shell type composite particle has a structure in which the core of the composite fine particle is covered with a shell obtained by polymerizing an unsaturated monomer. Without increasing the strength of the resulting coating.

Examples of the unsaturated monomer include acrylic monomers, fluorine monomers, silicone monomers, and the like, and one or more of these are used.
Examples of acrylic monomers include acrylic carboxylic acids such as (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylic such as isopropyl, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl tridecyl (meth) acrylate Acid ester; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylic acid ester (for example, trade name Plaxel FM, manufactured by Daicel Industries), phthalic acid and propylene (Meth) acrylic ester diols obtained from glycols Hydroxyl group-containing (meth) acrylic acid esters such as acid monoesters; Epoxy group-containing (meth) acrylic acid esters such as (meth) acrylic acid glycidyl; (meth) acrylonitrile, (meth) acrylamide, N-methylolacrylamide, N-butoxy Other acrylic monomers such as methyl acrylamide, diacetone acrylamide, ethyl (meth) acrylate 2-ethyl sulfonate and salts thereof can be used, and these are used alone or in combination of two or more.

  As a fluorine-type monomer, the monomer etc. which have the following perfluoroalkyl group and polymerizable double bond group can be mentioned, for example. Examples of the perfluoroalkyl group include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, perfluorododecyl group, A fluorotetradecyl group etc. can be mentioned, These are used 1 type or 2 types or more. Among these, when the perfluoroalkyl group is a perfluoromethyl group and / or a perfluoroethyl group, core-shell type composite particles can be easily obtained. A part of the fluorine atom in the perfluoroalkyl group may be substituted with another atom such as a chlorine atom as long as the effects of the present invention are not impaired.

As a silicone type monomer, the monomer etc. which have the following silicone group and a polymerizable double bond group can be mentioned, for example. Examples of the silicone group include a dimethyl silicone group, a diphenyl silicone group, a methyl phenyl silicone group, a diethyl silicone group, a methyl ethyl silicone group, and the like, and one or more of these are used. Among these, when the silicone group is a dimethyl silicone group and / or a diphenyl silicone group, core-shell type composite particles can be easily obtained.
The molecular weight of the perfluoroalkyl group or the silicone group is not particularly limited, but is preferably 200 to 50,000, and more preferably 200 to 10,000, for example.

Core-shell type composite particles having a perfluoroalkyl group and / or a silicone group are composed of a composite fine particle as a core and an unsaturated monomer containing a fluorine monomer and / or a silicone monomer as an essential component. It may be produced by emulsion polymerization in the presence of fine particles, and has a reactive functional group (a) and is obtained by emulsion polymerization, and a core-shell type composite particle, a perfluoroalkyl group and / or a silicone group And a compound having a reactive functional group (b) that reacts with the reactive functional group (a) may be reacted with each other.
Along with the unsaturated monomer, other monomers include aromatic monomers such as styrene, vinyltoluene, 1-methylstyrene, chloromethylstyrene, styrenesulfonic acid and salts thereof; vinyl acetate, vinyl propionate, Vinyl monomers such as vinyl stearate, vinyl chloride, vinylidene chloride, vinyl sulfonic acid and salts thereof; allyl monomers such as allyl acetate, diallyl adipate and diallyl itaconate; fats such as ethylene, propylene and isoprene Group monomers; other unsaturated monomers such as diethyl maleate, crotonic acid, itaconic acid, maleic acid and maleic anhydride may be used in combination for emulsion polymerization.

Examples of general emulsifiers used in emulsion polymerization include anionic surfactants, nonionic surfactants, cationic surfactants, and polymer surfactants. Species or two or more are used.
Examples of the anionic surfactant include alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate; ammonium alkyl sulfates such as ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinoate; Alkyl sulfonates such as alkali metal salts and ammonium salts of sulfonated paraffins; fatty acid salts such as sodium laurate, triethanolamine oleate, and triethanolamine abiates; sodium dodecylbenzene sulfonate, alkali metal sulfates of alkali phenol hydroxyethylene, etc. Alkyl aryl sulfonates; higher alkyl naphthalene sulfonic acids; naphths Ren acid formalin condensate; dialkyl sulfosuccinate, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylaryl sulfate salts and the like can be mentioned, it is used alone or in combination.

Nonionic surfactants include, for example, polyoxyethylene alkyl ethers; polyoxyethylene alkyl aryl ethers; sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; fatty acid monoglycerides such as monolaurate of glycerol; oxyethylene-oxypropylene Copolymers: Condensation products of ethylene oxide and aliphatic amines, amides or acids can be mentioned, and these are used alone or in combination of two or more.
Examples of the polymer surfactant include polyvinyl alcohol; sodium poly (meth) acrylate, potassium poly (meth) acrylate, ammonium poly (meth) acrylate, polyhydroxyethyl (meth) acrylate, polyhydroxypropyl (meth) ) Acrylate; copolymer of two or more polymerizable monomers that are constituent units of these polymers; copolymer of a polymerizable monomer that is a constituent unit of these polymers with another monomer A polymer etc. can be mentioned, These are 1 type (s) or 2 or more types used.

As the emulsifier used in the emulsion polymerization, a so-called phase transfer catalyst such as a crown ether can also be used.
The use of a reactive emulsifier described in detail below as the emulsifier used in emulsion polymerization is preferable because water-soluble substances during film formation can be reduced and the water resistance of the coating is increased.
As such a reactive emulsifier, a terminal alkyl group-containing polymer and / or a salt thereof described below is particularly preferable. Here, the terminal alkyl group-containing polymer is a water-soluble polymer having an acid value of 200 mgKOH / g or more obtained by polymerizing a monomer component containing an unsaturated carboxylic acid in the presence of an alkyl mercaptan having 6 to 18 carbon atoms. It is a polymer having water dispersibility and containing an alkyl group at the terminal.

By using the terminal alkyl group-containing polymer and / or a salt thereof as an emulsifier, the film has excellent initial drying properties, and excellent weather resistance, gloss, sharpness, and the like.
The terminal alkyl group-containing polymer has an acid value of 200 mgKOH / g or more in order to improve performance such as polymerization stability during emulsion polymerization, water resistance, solvent resistance, strength and the like of a film obtained from the film-forming composition. And must have water solubility or water dispersibility. When the acid value is less than 200 mgKOH / g, the emulsifying ability is not sufficient, the polymerization stability becomes poor, aggregates are generated, and the storage stability of the film-forming composition is low.
Although there is no limitation in particular about the molecular weight of a terminal alkyl group containing polymer, Preferably it is 300-7000, More preferably, it is 400-4000. When the molecular weight is out of the above range, the polymerization stability during emulsion polymerization may be lowered.

The unsaturated carboxylic acid used for the synthesis of the terminal alkyl group-containing polymer is not particularly limited as long as it is a compound having a carboxyl group and / or a salt thereof and a polymerizable unsaturated group in the molecule. Examples of unsaturated carboxylic acids include monounsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid and itaconic acid and salts thereof; divalent unsaturated carboxylic acids such as maleic acid and fumaric acid; esters thereof and the like A salt etc. can be mentioned, These are 1 type (s) or 2 or more types used.
By polymerizing a monomer component containing an unsaturated carboxylic acid, a carboxyl group is introduced into the resulting terminal alkyl group-containing polymer to impart hydrophilicity. The carboxyl group also exhibits an effect of curing the film forming composition.

  Although the said monomer component may contain only unsaturated carboxylic acid, it may contain monomers other than unsaturated carboxylic acid as needed. The monomer is not particularly limited as long as it is a compound copolymerizable with the unsaturated carboxylic acid, and examples thereof include styrene, vinyltoluene, α-methylstyrene, chloromethylstyrene, styrenesulfonic acid, and salts thereof. (Meth) acrylamide, (meth) acrylamide, N-monomethyl (meth) acrylamide, (meth) acrylamide derivatives such as N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide; methyl (meth) acrylate, ( (Meth) acrylic acid and 1 to 1 carbon atoms such as ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, iso-butyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. (Meth) a synthesized by ester formation reaction with 18 alcohols Rylic acid esters; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl; hydroxy group-containing compounds synthesized by ester formation reaction of (meth) acrylic acid with polypropylene glycol or polyethylene glycol ( (Meth) acrylic acid esters; (meth) acrylic acid 2-ethyl sulfonate and salts thereof, vinyl sulfonic acid and salts thereof, vinyl acetate, (meth) acrylonitrile, and the like. used.

Monomers other than the unsaturated carboxylic acid contained in the monomer component are used in such a range that the acid value of the terminal alkyl group-containing polymer does not become less than 200 mgKOH / g. The type and amount of the monomer other than the unsaturated carboxylic acid are determined in consideration of compatibility with the core-shell type composite particles obtained by emulsion polymerization using the terminal alkyl group-containing polymer.
The alkyl mercaptan used for the synthesis of the terminal alkyl group-containing polymer is not particularly limited as long as it has 6 to 18 carbon atoms. For example, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan , Cetyl mercaptan, stearyl mercaptan, and the like, and these may be used alone or in combination. In the alkyl mercaptan having 5 or less carbon atoms, the polymerization stability at the time of emulsion polymerization is lowered, and the storage stability of the film-forming composition is lowered.

Alkyl mercaptan acts as a molecular weight modifier and is used to introduce an alkyl group at the end of the polymer. By polymerizing in the presence of this alkyl mercaptan, the molecular weight of the terminal alkyl group-containing polymer can be adjusted to a range of 300 to 7000, and surface activity can be imparted to the terminal alkyl group-containing polymer. .
The amount of the alkyl mercaptan used is determined based on the molecular weight of the desired terminal alkyl group-containing polymer, and is usually 2 to 300 parts by weight with respect to 100 parts by weight of the monomer component.
The method for polymerizing the monomer component is not particularly limited, and various conventionally known polymerization methods such as bulk polymerization, solution polymerization, and suspension polymerization can be employed.

The terminal alkyl group-containing polymer may be produced using a conventionally known radical polymerization initiator such as an oil-soluble polymerization initiator or a water-soluble polymerization initiator. The amount of the radical polymerization initiator used is not particularly limited, and in order to efficiently produce a terminal alkyl group-containing polymer, 1 mol or less of the radical polymerization initiator is preferable with respect to 1 mol of the alkyl mercaptan. The following is more preferable. The polymerization reaction may be performed using a solvent, and the solvent is not particularly limited as long as it can dissolve the monomer component, alkyl mercaptan and radical polymerization initiator and does not inhibit the polymerization reaction. Absent.
There is no limitation in particular about reaction temperature at the time of manufacturing a terminal alkyl group content polymer, and 50-150 ° C is preferred. Moreover, although reaction time is suitably set according to the kind etc. of the said monomer component, alkyl mercaptan, and radical polymerization initiator, 1-8 hours are preferable.

The terminal alkyl group-containing polymer has sufficient surface activity, but when emulsion polymerization is carried out, a part or all of the carboxyl groups in the terminal alkyl group-containing polymer are neutralized with a neutralizing agent. preferable. By neutralizing the carboxyl group, the polymerization stability during emulsion polymerization and the storage stability of the film-forming composition are enhanced.
Examples of the neutralizing agent include alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide and calcium carbonate; ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine And water-soluble organic amines such as monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and diethylenetriamine. These may be used alone or in combination.

  When the terminal alkyl group-containing polymer and / or salt thereof is used as an emulsifier for emulsion polymerization, the unsaturated monomer that is a raw material for the core-shell type composite particles further comprises a functional group-containing monomer. It is preferable to include. The functional group-containing monomer is not particularly limited as long as it is a monomer having a functional group reactive to the carboxyl group in the terminal alkyl group-containing polymer. For example, glycidyl (meth) acrylate , Epoxy group-containing monomers such as 2-methylglycidyl (meth) acrylate and allyl glycidyl ether; monomers containing aziridinyl groups such as (meth) acryloylaziridine and 2-aziridinylethyl (meth) acrylate Oxazoline-containing monomers such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline, and the like may be used alone or in combination of two or more.

Although there is no limitation in particular about the weight ratio of the functional group containing monomer in an unsaturated monomer, Preferably it is 0.5 to 40 weight%, More preferably, it is 0.5 to 15 weight%. When the weight ratio of the functional group-containing monomer is less than 0.5% by weight, the carboxyl group in the terminal alkyl group-containing polymer remains in an unreacted state, and the core-shell type composite particles are sufficiently crosslinked. There is a possibility that it may not be performed, and the initial drying property, water resistance, solvent resistance and strength of the coating may be inferior. On the other hand, when the weight ratio of the functional group-containing monomer exceeds 40% by weight, the polymerization stability at the time of emulsion polymerization is lowered, and the storage stability of the film-forming composition is lowered.
As reactive emulsifiers used in emulsion polymerization, in addition to terminal alkyl group-containing polymers and / or salts thereof, anionic having radical polymerizable functional groups such as allyl group, propenyl group, acryloyl group, methacryloyl group, maleoyl group, etc. Alternatively, a nonionic polymerizable functional group-containing emulsifier can also be used. By using this polymerizable functional group-containing emulsifier, water resistance during film formation can be reduced, so that water resistance is enhanced. Examples of the hydrophilic group of the anionic emulsifier include a sulfuric acid group, a sulfonic acid group, a phosphoric acid group, and a carboxyl group. Examples of the hydrophobic group of the anionic emulsifier include an alkyl group having 6 to 60 carbon atoms, an alkenyl group, an aralkyl group, an alkylaryl group, and an aryl group.

  As the polymerizable functional group-containing emulsifier, for example, the trade name “Eleminol JS-2” (manufactured by Sanyo Kasei Co., Ltd.) containing a compound of the following general formula (2) or general formula (3)

(However, R ^a is a hydrogen atom or a methyl group, R ^b is an organic group having an optionally substituted hydrocarbon group or oxyalkylene group, A ¹ is an alkylene group having 2 to 4 carbon atoms, and n ₁ is An integer greater than or equal to 0, M ¹ is an alkali metal, alkaline earth metal, ammonium, organic amine salt or organic quaternary ammonium base);
Trade name “Latemul S-180” (manufactured by Kao Corporation) containing the compound of the following general formula (4) or the following general formula (5)

(However, R ^a is a hydrogen atom or a methyl group, R ^c is a hydrocarbon group which may have a substituent, A ¹ is an alkylene group having 2 to 4 carbon atoms, n ₂ is an integer of 0 to 100, M ² Is a monovalent or divalent cation);
A trade name “ADEKA rear soap SE-10N” (manufactured by Asahi Denka Kogyo Co., Ltd.) containing a compound of the following general formula (6)

(However, R ^a is a hydrogen atom or a methyl group, R ^d is a hydrocarbon group or acyl group having 8 to 24 carbon atoms, A ¹ is an alkylene group having 2 to 4 carbon atoms, n ₂ is an integer of 0 to 100, m ₁ is an integer of 0 to 50, and M ³ is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or an organic amine base).
Product name “AQUALON HS-10” (Daiichi Kogyo Seiyaku Co., Ltd.) containing the compound of the following general formula (7)

(Where R ^e is an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R ^f is hydrogen, an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R ^g is a hydrogen or propenyl group, A ¹ is an alkylene group having 2 to 4 carbon atoms, n ₃ is an integer of 1 to 200, and M ⁴ is an alkali metal, ammonium or alkanolamine residue.);
Product name “Antox MS-60” (manufactured by Nippon Emulsifier Co., Ltd.) containing the compound of the following general formula (8)

^(However, R h, ^{R i} is a hydrogen atom or an alkyl group having 1 to 25 carbon ^atoms, R j, ^{R k} is an alkyl group having 1 to 25 carbon atoms, a benzyl group or styrene group, _{m 2} is 0 to 2 integer R ^a is a hydrogen atom or a methyl group, A ² is an alkylene group having 2 or 3 carbon atoms, n ₄ is an integer of 1 or more, and M ⁵ is an alkali metal, alkaline earth metal, ammonium or amine cation).
A trade name “RA-1120” (manufactured by Nippon Emulsifier Co., Ltd.) containing a compound of the following general formula (9)

(Wherein R ¹ is a hydrocarbon group, A ² is an alkylene group having 2 or 3 carbon atoms, n ₄ is an integer of 1 or more, and M ⁵ is an alkali metal, alkaline earth metal, ammonium or amine cation);
A trade name “ADEKA rear soap NE-30” (manufactured by Asahi Denka Kogyo Co., Ltd.) containing a compound of the following general formula (10)

(However, R ^a is a hydrogen atom or a methyl group, R ^d is a hydrocarbon group or acyl group having 8 to 24 carbon atoms, A ¹ is an alkylene group having 2 to 4 carbon atoms, n ₂ is an integer of 0 to 100, m ₁ is an integer from 0 to 50);
Trade names “AQUALON RN-50”, “AQUALON RN-30” and “AQUALON RN-20” (Daiichi Kogyo Seiyaku Co., Ltd.) containing the compound of the following general formula (11)

(Where R ^e is an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R ^f is hydrogen, an alkyl group having 6 to 18 carbon atoms, an alkenyl group or an aralkyl group, R ^g is a hydrogen or propenyl group, A ¹ is an alkylene group having 2 to 4 carbon atoms, and n ₃ is an integer of 1 to 200.);
A trade name “RMA-506” (manufactured by Nippon Emulsifier Co., Ltd.) containing a compound of the following general formula (12)

(However, R ^a is a hydrogen atom or a methyl group, R ¹ is a hydrocarbon group, A ² is an alkylene group having 2 or 3 carbon atoms, and n ₂ is an integer of 0 to 100.)
These may be used alone or in combination of two or more.
Examples of radical polymerization initiators used in emulsion polymerization include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; organic peroxides such as tert-butyl peroxide, benzoyl peroxide, and peracetic acid; 2 Azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylpropionamidine) dihydrochloride; hydrogen peroxide, etc., and these may be one or more used. The amount of radical polymerization initiator used is not particularly limited. A reducing agent such as sodium bisulfite or L-ascorbic acid may be used in combination with the radical polymerization initiator to form a redox initiator.

There is no particular limitation on the method for producing core-shell type composite particles by emulsion polymerization of unsaturated monomers in the presence of composite fine particles. For example, there are methods listed in (1) to (3) below. A combination of these methods or a complicated combination of these methods may be used.
(1) A batch polymerization method in which a composite emulsion, an unsaturated monomer, an emulsifier, and a solvent are added to a reaction vessel to prepare a pre-emulsion, and a radical polymerization initiator is added to the pre-emulsion to perform emulsion polymerization.
(2) A pre-emulsion is prepared by mixing an unsaturated monomer and an emulsifier in advance, and this pre-emulsion and a radical polymerization initiator are added dropwise to a solvent containing composite fine particles in a reaction vessel to conduct emulsion polymerization. Pre-emulsion dripping method.

(3) An unsaturated monomer dropping method in which a solvent, an emulsifier and composite fine particles are mixed in a reaction vessel, and an unsaturated monomer and a radical polymerization initiator are dropped.
The production of the core-shell type composite particles may be performed by a multistage polymerization method such as power feed polymerization. In this case, the particles can be structured in a different phase.
As the solvent, those containing water as an essential component and appropriately containing the aforementioned organic solvent are used.
In carrying out the emulsion polymerization, for the purpose of adjusting the molecular weight, in addition to the above-described components, emulsion polymerization may be carried out together with a chain transfer agent such as n-dodecyl mercaptan or lauryl methyl mercaptan.

About emulsion polymerization temperature, it is 0-100 degreeC normally, Preferably it is 40-95 degreeC.
The core-shell type composite particles obtained after the emulsion polymerization may usually be handled as an aqueous dispersion containing the core-shell type composite particles without isolation from the reaction mixture.
The average particle size of the core-shell type composite particles is not particularly limited, but is preferably 5 nm to 100 μm, more preferably 20 nm to 500 nm. When the average particle diameter of the core-shell type composite particles is less than 5 nm, the surface energy of the composite particles becomes high and aggregation tends to occur. On the other hand, when the average particle diameter exceeds 100 μm, the film formability may be lowered.

[Film-forming composition]
The film-forming composition according to the present invention is a composition containing the composite fine particles and / or core-shell composite particles as essential components. This film-forming composition usually contains the aforementioned organic solvent and / or water, and the composite fine particles and core-shell type composite particles are dispersed in the organic solvent and / or water. Specific examples of the organic solvent contained in the film-forming composition include the organic solvents described in the above-described method for producing composite fine particles.
The film-forming composition according to the present invention preferably contains a film-forming compound that may contain a polymerizable functional group. The film-forming compound is a component having film-forming performance and imparting weather resistance to the resulting film, and a film-forming compound containing a polymerizable functional group and a film-forming compound containing no polymerizable functional group It is divided roughly. The types of film-forming compounds containing a polymerizable functional group include monomers, oligomers, and polymers, whereas the types of film-forming compounds that do not contain a polymerizable functional group are only polymers. Although it does not specifically limit as a kind of polymeric functional group, A radically polymerizable group is preferable and what has a monofunctional radically polymerizable group is a monomer (the above-mentioned unsaturated monomer), and a polyfunctional radically polymerizable group is What has is a monomer, an oligomer, and a polymer (polyfunctional radically polymerizable compound). The film-forming compound containing a polymerizable functional group contains a polymerizable functional group in the molecule, and therefore has polymerizability, and can be used for applications other than film formation. In combination with the above-mentioned composite fine particles containing, a film having high transparency and excellent stain resistance, high hardness and excellent scratch resistance can be obtained.

When the film-forming compound is an unsaturated monomer, the boiling point is generally low, which causes odor problems, is monofunctional, has low reactivity, and deteriorates physical properties. It is preferable to leave. As the method, it is preferable to select composite fine particles as the particle component and polymerize them in advance.
Hereinafter, the film-forming compound will be described in detail in the order of a film-forming compound containing a polymerizable functional group and a film-forming compound not containing a polymerizable functional group.
The film-forming compound containing a polymerizable functional group is not particularly limited as long as it has a film-forming ability and has a polymerizable functional group in the molecule, but the radically polymerizable compound described below is an essential component. Are preferably included, and may further contain a cationically polymerizable compound described below.

  Examples of the radical polymerizable compound include urethane (meth) acrylate, polyfunctional (meth) acrylate, (meth) acrylic acid ester polymer or copolymer side chain (meth) acryloyl group-containing acrylic resin (hereinafter, Multifunctional radical polymerizable compounds (polyfunctional radical polymerizable polymers, oligomers, monomers) such as (meth) acryloyl group-containing acrylic resins), epoxy (meth) acrylates, polyester (meth) acrylates, etc .; unsaturated A monomer etc. can be mentioned and these are used 1 type or 2 types or more. As the polyfunctional radical polymerizable polymer, oligomer, and monomer, urethane (meth) acrylate, polyfunctional (meth) acrylate, and (meth) acryloyl group-containing acrylic resin are preferable from the viewpoint of weather resistance and scratch resistance.

  As a urethane (meth) acrylate, the compound obtained by making hydroxyl group containing (meth) acrylate and polyisocyanate react can be mentioned, for example. Here, the hydroxyl group-containing (meth) acrylate is 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane diacrylate, and the like, and these can be used alone or in combination. As a mixture comprising two or more kinds of hydroxyl group-containing (meth) acrylates, for example, “A-TMM · 3L” (made by Shin-Nakamura Chemical Co., Ltd.), which is a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, “DPHA” (manufactured by Nippon Kayaku Co., Ltd.), which is a mixture of dipentaerythritol pentaacrylate and hexaacrylate. The polyisocyanate may be any of aliphatic, aromatic, and alicyclic polyisocyanates. For example, methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4, -trimethylhexamethylene diisocyanate, Examples thereof include isophorone diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and methylene bisphenyl diisocyanate. These can be used alone or in combination of two or more. Among the above polyisocyanates, those that are non-yellowing urethane are preferably used. The combination of hydroxyl group-containing (meth) acrylate and polyisocyanate is not particularly limited, but a combination of 2-hydroxyethyl acrylate and isophorone diisocyanate, 2-hydroxyethyl acrylate and 2,2,4, -trimethylhexamethylene diisocyanate. Combinations of "A-TMM 3L" and isophorone diisocyanate, "A-TMM 3L" and tolylene diisocyanate, "DPHA" and isophorone diisocyanate, "DPHA" and methylenebisphenyl diisocyanate In order to increase reactivity and adhesion, it is preferable. As a method for producing urethane (meth) acrylate, for example, the ratio (hydroxyl group: isocyanate group) of hydroxyl group in hydroxyl group-containing (meth) acrylate and isocyanate group in polyisocyanate is 1: 0 in molar ratio. .8 to 1: 1 and weighed into a reaction vessel, added a catalytic amount of an organic tin compound such as dibutyltin laurate, and further added a polymerization inhibitor such as hydroquinone, and a reaction temperature of 30 to 120 ° C., preferably Can mention the method of heating and stirring at 50-90 degreeC. The reaction temperature is preferably raised stepwise. The reaction product may contain an oligomerized urethane (meth) acrylate. Examples of commercially available urethane (meth) acrylates include UA-306H, UF-8001, and UF-8003 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.); M-1100, M-1200, M-1210, M -1310, M-1600 (above, manufactured by Toa Gosei Chemical Co., Ltd.); Photomer-6008, Photomer-6210 (above, manufactured by San Nopco); U-4HA, U-6HA (above, Shin-Nakamura Chemical Co., Ltd.) And the like).

  The polyfunctional (meth) acrylate is not particularly limited as long as it has two or more (meth) acrylate groups in the molecule. For example, 1,6-hexanediol di (meth) acrylate, 1,4-butane Diol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, poly (Butanediol) di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, triisopropylene glycol di (meth) acrylate, polyethylene glycol di (meth) Di (meth) acrylates such as acrylate and bisphenol A di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, and trimethylolpropane triethoxytri (meth) acrylate (Meth) acrylates; tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate and di-trimethylolpropane tetra (meth) acrylate; penta (meth) acrylate such as dipentaerythritol (monohydroxy) penta (meth) acrylate ) Acrylates and the like, and one or more of these can be used.

  As (meth) acryloyl group-containing acrylic resin, for example, addition of (meth) acrylic acid to a copolymer containing epoxy group-containing (meth) acrylate and / or oxazonyl group-containing (meth) acrylate as a constituent component Body: an adduct obtained by adding an epoxy group-containing (meth) acrylate and / or an oxazonyl group-containing (meth) acrylate to a copolymer having (meth) acrylic acid as a constituent component; constituting a hydroxyl group-containing (meth) acrylate An adduct obtained by adding an adduct of a hydroxyl group-containing (meth) acrylate and a polyisocyanate to a copolymer as a component; a copolymer having an isocyanate group-containing (meth) acrylate as a constituent component, a hydroxyl group-containing ( Examples include adducts to which (meth) acrylate is added. It can be used alone or in combination.

Specific examples of the unsaturated monomer include those exemplified in the above-mentioned core-shell type composite particle, and the unsaturated monomer includes the acrylic monomer described above. preferable.
Next, examples of the cationic polymerizable compound include an epoxy group-containing compound, a vinyl ether group-containing compound, a cyclic imino group-containing compound, a cyclic ether group-containing compound, a lactone, a spiro orthoester, and a bicyclo orthoester. These can be used alone or in combination of two or more. Among these cationically polymerizable compounds, at least one selected from an epoxy group-containing compound and a vinyl ether group-containing compound is preferable.

  As an epoxy group containing compound, an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, etc. can be mentioned, These can use 1 type (s) or 2 or more types. Here, the aromatic epoxy compound is a polyglycidyl ether or an epoxy novolac of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, and the polyglycidyl ether includes bisphenol A. Or the glycidyl ether obtained by making the alkylene oxide adduct and epichlorohydrin react can be mentioned. As the alicyclic epoxy compound, a polyglycidyl ether, a cyclohexene ring-containing compound or a cyclopentene ring-containing compound of a polyhydric alcohol having at least one alicyclic ring or an alkylene oxide adduct thereof, and a suitable compound such as hydrogen peroxide, peracid, etc. A cyclohexene oxide-containing compound or a cyclopentene oxide-containing compound obtained by epoxidation with an oxidizing agent is preferred. Here, the polyglycidyl ether is glycidyl ether obtained by reacting hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin. Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyglycidyls of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols. Ethers, monoglycidyl ethers of higher aliphatic alcohols and the like are preferable. Examples of commercially available aliphatic epoxy compounds include Denacol (product numbers: EX-611, 612, 614, 614B, 622, 651, 651A, 512, 521, 411, 421, 301, 313, 314, 321, 201, 211, 212,810,811,850,851,821,830,832,841,861,911,941,920,921,922,931,2000,4000,111,121,141,145,146,171,192; Nagase Kasei Kogyo Co., Ltd.).

  Examples of vinyl ether group-containing compounds include tripropylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, cyclohexane-1,4-dimethylol divinyl ether, bisphenol A divinyl ether, dodecyl vinyl ether, Reaction product of propenyl ether propylene carbonate, hydroxybutyl vinyl ether, polyol compound, polyisocyanate and hydroxyl group-containing vinyl ether compound (for example, hydroxybutyl vinyl ether, tripropylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, 4-hydroxycyclohexyl monovinyl ether) Polyurethane polyvinyl ether etc. which are It can, and they can be used alone or in combination of two or more. The method for producing the vinyl ether group-containing compound is not particularly limited, and examples thereof include a method of reacting a di-, tri- or tetrafunctional polyol, acetylene and a base catalyst under high pressure.

Next, the film-forming compound that does not contain a polymerizable functional group will be described. Examples of the film-forming compound that does not contain a polymerizable functional group include a polymer obtained by polymerizing the unsaturated monomer described in the section of the core-shell type composite particle. The film-forming compound that does not contain a polymerizable functional group will be described in detail in the film-forming composition (3) described later.
The film-forming composition of the present invention is not particularly limited as long as it is a composition containing the composite fine particles and / or core-shell type composite particles as an essential component. (1) to (3) can be mentioned.
Film-forming composition (1): A composition containing a polyfunctional radically polymerizable compound as a film-forming compound and composite fine particles.

Film-forming composition (2): A composition containing an unsaturated monomer as a film-forming compound and composite fine particles, wherein the unsaturated monomer and the composite fine particles are previously polymerized.
Film-forming composition (3): A composition that contains composite fine particles and / or core-shell composite particles as essential components and may contain a film-forming compound that does not contain a polymerizable functional group.
Hereinafter, the film forming compositions (1) to (3) will be described in detail.
The film-forming composition (1) contains the polyfunctional radical polymerizable compound described above in detail and composite fine particles as essential components, and usually further contains an organic solvent. The amount of the organic solvent used is not particularly limited.

The mixing ratio of the composite fine particles in the film-forming composition (1) is not particularly limited, but is preferably 0.1 to 99% by weight, more preferably 15 to 70% by weight of the whole film-forming composition (1). %. When the compounding ratio of the composite fine particles is less than 0.1% by weight, the transparency, stain resistance, scratch resistance and surface hardness of the coating film are lowered. On the other hand, when the compounding ratio of the composite fine particles exceeds 99% by weight, the adhesion and toughness of the coating film are lowered.
Depending on the type of film-forming compound and the curing method, the film-forming composition (1) is, for example, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, acetyl peroxide, propionyl peroxide. , Isobutyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, tertiary butyl peroxide, tertiary butyl hydroxide, tertiary butyl cumyl peroxide, diisopropyl peroxide, di-n-propyl peroxy carbonate, Harden organic peroxides such as dimethoxypropyl peroxycarbonate and radical polymerizable compounds such as azobisisobutyronitrile. 1-hydroxy-cyclohexyl-phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-dimethyl-1-propan-1-one, 2-methyl-1- [ UV curing catalyst for curing radically polymerizable compounds such as 4- (methylthio) phenyl] -2-monforinopropanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one; ammonium salt It may further contain a cationic polymerization initiator for curing a cationically polymerizable compound such as a compound, a sulfonium salt compound, a phosphonium salt compound, or an iodonium salt compound.

  The film-forming composition (1) is a leveling agent generally used in film-forming compositions such as paints; chrome lead, molybdate orange, bitumen, cadmium pigments, titanium white, complex oxide pigments, transparent iron oxide , Carbon black, cyclic higher pigments, soluble azo pigments, copper phthalocyanine pigments, dyed pigments, pigment intermediates, pigments; pigment dispersants; UV absorbers; antioxidants; viscosity modifiers; Deactivator; Peroxide decomposing agent; Filler; Reinforcing agent; Plasticizer; Lubricant; Anticorrosive agent; Rust preventive agent; Emulsifier; Mold demolding agent; It may further contain additives such as flame retardants; anti-dripping agents; melt flow modifiers; antistatic agents and the like. In addition, when hardening the composition (1) for film-forming with an ultraviolet-ray, it cannot be overemphasized that the compounding quantity of a ultraviolet absorber is selected so that hardening may not be inhibited.

  The method of curing the film-forming composition (1) is not particularly limited, and examples thereof include a method of curing by heating, irradiation with active energy rays such as ultraviolet rays and electron beams. The active energy rays may be ionizing radiation such as α rays, β rays, γ rays, microwaves, high frequencies, visible rays, infrared rays, laser rays, etc., and any energy species that generate radical active species or cationic active species. Good. Examples of sources of such active energy rays include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and the like, which are selected in consideration of the wavelength at which the curing reaction occurs. .

Since the film-forming composition (1) contains a polyfunctional radical polymerizable compound as a film-forming compound, when the film-forming composition (1) further contains the thermosetting catalyst or the ultraviolet curing catalyst, It can be cured by heating or irradiation with ultraviolet rays. When the film-forming compound further contains a cationic polymerizable compound, if the film-forming composition (1) further contains a cationic polymerization initiator, it can be cured by heating, irradiation with ultraviolet rays or electron beams.
When the film-forming composition (1) is cured by heating, the heating temperature is appropriately selected depending on the type of base material to be coated. For example, when the material is plastic, the material is heated to a temperature (curing acceleration temperature) at which the thermosetting catalyst is decomposed and curing is sufficiently accelerated within the range of the deformation temperature or lower. When the plastic is polycarbonate, for example, the curing acceleration temperature is 80 to 150 ° C, preferably 100 to 130 ° C.

The method of curing the film-forming composition (1) by irradiation with ultraviolet rays varies depending on conditions such as the type of light source that generates ultraviolet rays and the distance between the light source and the coating surface. For example, ultraviolet rays having a wavelength of 1000 to 8000 angstroms are used. A method of irradiating usually several seconds or at most several tens of seconds can be mentioned.
As a method for curing the film-forming composition (1) by electron beam irradiation, for example, an electron beam is usually used at an acceleration voltage of 50 to 1000 keV, preferably 100 to 300 keV so that the absorbed dose is about 1 to 20 Mrad. The irradiation method can be mentioned. The electron beam irradiation may be performed in the atmosphere, but is preferably performed in an inert gas such as nitrogen. The absorbed dose can be irradiated until the radically polymerizable functional group remaining in the coating does not affect the physical properties of the coating.

After ultraviolet irradiation or electron beam irradiation, if necessary, heating can be performed to complete the curing.
Film-forming composition (1) is, for example, aluminum, stainless steel, tin, tinplate, steel plate, concrete, mortar, slate, glass and other inorganic materials; wood, polycarbonate, polymethyl methacrylate, polyethylene terephthalate and other plastics, paper, etc. It can be applied to a substrate made of an organic material or a base material such as a film to form a film. Application can be carried out by conventional methods such as dipping, spraying, brushing, curtain flow coater, roll coating, spin coating, bar coating, electrostatic coating and the like.

Next, the film-forming composition (2) is a composition containing an unsaturated monomer and composite fine particles, and the unsaturated monomer and the composite fine particles are polymerized in advance.
Although the compounding ratio of the composite fine particles in the film-forming composition (2) is not particularly limited, it is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight based on the whole film-forming composition (2). %. When the compounding ratio of the composite fine particles is less than 0.1% by weight, the transparency, stain resistance, scratch resistance and surface hardness of the coating film are lowered. On the other hand, when the compounding ratio of the composite fine particles exceeds 30% by weight, the adhesion and toughness of the coating film are lowered.
The unsaturated monomer that is prepolymerized with the composite fine particles is preferably an acrylic monomer because of its high film-forming ability, and the acrylic monomer contains a hydroxyl group-containing (meth) acrylic acid ester as an essential component. However, since it can be combined with a curing agent that reacts with a hydroxyl group, which will be described later, the film properties such as film strength, flexibility, and solvent resistance are further improved. When the unsaturated monomer polymerized in advance with the composite fine particle is an acrylic monomer containing a hydroxyl group-containing (meth) acrylic acid ester as an essential component, the organic polymer of the composite fine particle has a hydroxyl group-containing (meth) acrylate unit It is preferable to contain.

The unsaturated monomer that is prepolymerized with the composite fine particle is an acrylic monomer containing a hydroxyl group-containing (meth) acrylic ester as an essential component, or the organic polymer of the composite fine particle contains a (meth) acrylate unit having a hydroxyl group In the case where the film-forming composition (2) further contains at least one compound selected from a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin as a curing agent that reacts with a hydroxyl group, the storage stability is improved. It is favorable and can provide a film having good film properties such as stain resistance, flexibility, weather resistance, storage stability, and the like.
Examples of the polyfunctional isocyanate compound include aliphatic, alicyclic, aromatic and other polyfunctional isocyanate compounds and modified compounds thereof. Specific examples of the polyfunctional isocyanate compound include, for example, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, 2,2,4-trimethylhexylmethane diisocyanate, methylcyclohexane diisocyanate, 1, Trimers such as biuret and isocyanurate of 6-hexamethylene diisocyanate; produced by reaction of these polyfunctional isocyanates with polyhydric alcohols such as propanediol, hexanediol, polyethylene glycol, and trimethylolpropane Compounds in which two or more isocyanate groups remain; these polyfunctional isocyanate compounds are ethanol, hexanol, etc. Blocked polyfunctional isocyanate compounds blocked with blocking agents such as alcohols, compounds having a phenolic hydroxyl group such as phenol and cresol, oximes such as acetooxime and methylethylketoxime, and lactams such as ε-caprolactam and γ-caprolactam Can be mentioned. These polyfunctional isocyanate compounds can use 1 type, or 2 or more types of mixtures. Of these, a non-yellowing polyfunctional isocyanate compound having no isocyanate group directly bonded to the aromatic ring is preferable in order to prevent undesirable yellowing of the coating film.

Examples of the melamine compound include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, iso-butyl ether type melamine, n-butyl ether type melamine, butylated benzoguanamine and the like. These melamine compounds can use 1 type, or 2 or more types of mixtures.
Specific examples of aminoplast resins include alkyl etherified melamine resins, urea resins, benzoguanamine resins, and the like, and these aminoplast resins may be used alone or in combination of two or more.

Here, the alkyl etherified melamine resin is obtained by methylolating aminotriazine and alkyl etherifying with cyclohexanol or alkanol having 1 to 6 carbon atoms, and includes butyl etherified melamine resin, methyl etherified melamine resin, methylbutyl. Mixed melamine resins are representative. In addition, a sulfonic acid catalyst for promoting curing, for example, paratoluenesulfonic acid and its amine salt can be used.
When the film-forming composition (2) contains the curing agent, it preferably contains a curing catalyst in order to promote the crosslinking reaction. As the curing catalyst, an acidic or basic curing catalyst can be used.

Specific examples of the acidic curing catalyst include organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and dodecylbenzenesulfonic acid. Specific examples of the basic curing catalyst include amine catalysts such as triethylamine, methylimidazole, acridine, hexadecyltrimethylammonium stearate; organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, etc. Can be mentioned. One or two or more of these curing catalysts are used, and a co-catalyst may be used in combination as necessary.
The film-forming composition (2) may further contain one or more additives, and examples of the additive include those described in the film-forming composition (1).

Examples of the use and application method of the film-forming composition (2) include the use and application method described in the film-forming composition (1).
The film obtained from the film-forming composition (2) is baked and dried as necessary. For example, a film is formed by heating at a temperature in the range of room temperature to 300 ° C. for 0.2 minutes or more, and this film is a transparent and glossy excellent film. Furthermore, the film-forming composition (2) can be used in either pre-coating or post-coating.
Next, the film-forming composition (3) is a composition that contains composite fine particles and / or core-shell composite particles as essential components and may contain a film-forming compound that does not contain a polymerizable functional group. .

  The blending ratio (solid content ratio) of the composite fine particles and / or core-shell composite particles and the film-forming compound not containing a polymerizable functional group in the film-forming composition (3) is not particularly limited. However, the weight ratio [(composite fine particles and / or core-shell type composite particles) / (film-forming compound containing no polymerizable functional group)] is 100/0 to 0.1 / 99.9, preferably 98. / 2 to 1/99, more preferably 70/30 to 5/95. When there are few film forming compounds which do not contain a polymerizable functional group, there exists a possibility that the film formability of a film may fall. On the other hand, when there are many film forming compounds which do not contain a polymerizable functional group, there exists a possibility that the stain resistance and surface hardness of a film may fall.

Examples of the film-forming compound that does not contain a polymerizable functional group include a polymer obtained by polymerizing the unsaturated monomer described in the section of the core-shell type composite particle. As the unsaturated monomer, one containing the above-mentioned acrylic monomer is preferable because of its high film-forming ability, and film properties such as film strength, flexibility and solvent resistance are improved. As an acryl-type monomer, what contains a hydroxyl-containing (meth) acrylic acid ester as an essential component is still more preferable.
When the unsaturated monomer used in the production of the film-forming compound is an acrylic monomer containing a hydroxyl group-containing (meth) acrylic acid ester as an essential component, the organic polymer of the composite fine particles has a hydroxyl group ( It is preferred to include a (meth) acrylate unit.

The unsaturated monomer used in the production of the film-forming compound is an acrylic monomer containing a hydroxyl group-containing (meth) acrylic acid ester as an essential component, or the organic polymer of the composite fine particles has a hydroxyl group (meth) When the acrylate unit is included, the film-forming composition (3) further includes a curing agent that reacts with the hydroxyl group described in the film-forming composition (2), so that the storage stability is good and the A film having good physical properties such as contamination, flexibility, weather resistance, storage stability and the like can be provided, and the resulting film is also preferable because it is glossy.
When the film-forming composition (3) contains the curing agent described in the film-forming composition (2), the film-forming composition (2) is also described in order to promote the crosslinking reaction. It is preferable that it further contains a curing catalyst.

When the film-forming composition (3) contains composite fine particles as an essential component, since the composite fine particles contain an ethylenically unsaturated group, as in the film-forming composition (1), heat, ultraviolet rays, electrons An ethylenically unsaturated group can be added and reacted with a wire or the like. In this case, the film-forming composition (3) is appropriately cured by appropriately including a thermosetting catalyst, an ultraviolet curing catalyst, or the like.
The film-forming composition (3) may further contain one or more additives, and examples of the additive include those described in the film-forming composition (1).
Examples of the use and application method of the film-forming composition (3) include the use and application method described in the film-forming composition (1).

The film obtained from the film-forming composition (3) is baked and dried as necessary. For example, a film is formed by heating at a temperature in the range of room temperature to 300 ° C. for 0.2 minutes or more, and this film is a transparent and glossy excellent film. Furthermore, the film-forming composition (3) can be used in either pre-coating or post-coating.
The method for producing the film-forming composition (3) is not particularly limited. For example, a dispersion obtained by dispersing composite fine particles and / or core-shell composite particles in an organic solvent and / or water, and unsaturated The method etc. which mix a polymer etc. which superpose | polymerize a monomer by solution polymerization etc. can be mentioned. In order to improve the dispersibility of the polymer, a surfactant or the like may be further mixed. Only the dispersion may be used as the film-forming composition (3).

Examples of the present invention are shown below together with comparative examples, but prior to the description of the examples, production examples of the silicon-containing polymer (P) and the polymerizable functional group-containing compound will be described. The silicon-containing polymer (P) will be described including its preparation stage. In addition, this invention is not limited to the following Example.
In the following preparation steps, production examples, examples, and comparative examples, “part” indicates “part by weight” and “%” indicates “% by weight”.
-Synthesis of polymerizable polysiloxane (S-1)-
In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 144.5 g of tetramethoxysilane, 23.6 g of γ-methacryloxypropyltrimethoxysilane, 19 g of water, 30.0 g of methanol, Amberlyst 15 (Rohm 5.0 g of a cation exchange resin manufactured by And Hearth Japan Co., Ltd. was charged, and the charged product was stirred at 65 ° C. for 2 hours to be reacted. After the reaction mixture is once cooled to room temperature, a distillation column, a cooling tube connected to the distillation column, and an outlet are provided in place of the cooling tube, and the temperature is raised to 80 ° C. under normal pressure over 2 hours. Methanol flows out. It was kept at the same temperature until it disappeared. The reaction mixture was further maintained at the same temperature at a pressure of 200 mmHg and a temperature of 90 ° C. until methanol did not flow out, and the reaction was allowed to proceed further. The reaction mixture was cooled again to room temperature, and Amberlyst 15 was filtered off from the reaction mixture to obtain a polymerizable polysiloxane (S-1) having a number average molecular weight of 1800.

-Synthesis of silicon-containing polymer (P-1)-
Into a 0.5 liter flask equipped with a stirrer, dripping port, thermometer, cooling pipe and N ₂ gas introduction port, 140 g of butyl acetate as an organic solvent was introduced, N ₂ gas was introduced, and the temperature inside the flask was increased while stirring. Heated to 120 ° C. Next, a solution prepared by mixing 20 g of polymerizable polysiloxane (S-1), 90 g of methyl methacrylate, 90 g of butyl acrylate, and 1.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the charged product from the dropping port. It was added dropwise over time. After the addition of the above solution, the reaction mixture was continuously stirred at the same temperature for 1 hour, and then 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the reaction mixture twice every 30 minutes. The reaction mixture was further heated for 2 hours for copolymerization to obtain a solution in which the silicon-containing polymer (P-1) having a number average molecular weight of 12,000 was dissolved in methanol. The solid content of the silicon-containing polymer (P-1) contained in the obtained solution was 49.5%.

-Synthesis of silicon-containing polymer (P-2)-
Into a 0.5 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and an N ₂ gas introduction port, 168 g of ethanol as an organic solvent was charged, N ₂ gas was introduced, and the flask internal temperature was 78 while stirring. Heated to ° C. Then, a solution prepared by mixing 16 g of polymerizable polysiloxane (S-1), 56 g of methyl methacrylate, 56 g of butyl acrylate, 32 g of hydroxyethyl methacrylate, and 3.2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the dropping port. More dropwise on the charge over 2 hours. After the addition of the above solution, the reaction mixture was continuously stirred at the same temperature for 1 hour, and then 0.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the reaction mixture twice every 30 minutes. The reaction mixture was further heated for 2 hours for copolymerization to obtain a solution in which the silicon-containing polymer (P-2) having a number average molecular weight of 9,000 was dissolved in ethanol. The solid content of the silicon-containing polymer (P-2) contained in the obtained solution was 40.0%.

-Synthesis of silicon-containing polymer (P-3)-
Into a 0.5 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and an N ₂ gas introduction port, 196 g of methanol as an organic solvent was charged, N ₂ gas was introduced, and the flask internal temperature was adjusted to 65 while stirring. Heated to ° C. Next, a solution prepared by mixing 12 g of polymerizable polysiloxane (S-1), 25 g of methyl methacrylate, 78 g of acrylic acid, and 3.6 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the charged product through the dropping port. It was added dropwise over time. After the addition of the above solution, the reaction mixture was continuously stirred at the same temperature for 1 hour, and then 0.2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to the reaction mixture every 30 minutes. The reaction mixture was further heated for 2 hours for copolymerization to obtain a solution in which the silicon-containing polymer (P-3) having a number average molecular weight of 7,000 was dissolved in methanol. The solid content of the silicon-containing polymer (P-3) contained in the obtained solution was 29.5%.

The number average molecular weights of the polymerizable polysiloxane (S-1) and silicon-containing polymers (P-1) to (P-3) obtained as described above were analyzed by the following method.
Number average molecular weight measurement method The polystyrene-reduced number average molecular weight of the polymerizable polysiloxane and the silicon-containing polymer was measured by gel permeation chromatography (GPC) under the following conditions.
Preparation of sample: Using tetrahydrofuran as a solvent, 0.05 g of polymerizable polysiloxane or organic polymer (P) was dissolved in 1 g of tetrahydrofuran to prepare a sample.

Apparatus: A high-speed GPC apparatus HLC-8020 manufactured by Tosoh Corporation was used.
Column: G3000H, G2000H and GMHXL manufactured by Tosoh Corporation were used.
Standard polystyrene: TSK standard polystyrene manufactured by Tosoh Corporation was used.
Measurement conditions: Measurement was performed at a measurement temperature of 35 ° C. and a flow rate of 1 ml / min.
-Synthesis of butyl acetate solution (AC-P) of acrylic resin containing acroyl group-
300 g of butyl acetate was charged into a 1 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, and nitrogen gas was introduced and heated to 120 ° C. while stirring. 123 g of cyclohexyl methacrylate, 60 g of glycidyl methacrylate, 82 g of butyl acrylate, 3 g of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H -A mixture of 3 g of benzotriazole and 12 g of 2,2'-azobis (2-methylbutyronitrile) as an initiator was added dropwise to the charge over 4 hours, and the mixture was further heated for 2 hours after the addition. The temperature of the reaction mixture was lowered to 110 ° C., 32 g of acrylic acid, 1 g of trimethylammonium bromide and 500 ppm of methoquinone were added, and the mixture was reacted at 110 ° C. for 6 hours. A butyl acetate solution (AC-P) was obtained. The acid value was 10 mgKOH / g.

-Example A1-
Production of composite fine particle dispersion (Z-1) A liter of 507 g of methanol and 127 g of methanol were charged into a 1 liter four-necked flask equipped with a stirrer, two dripping ports (drip port i and dripping port b), and a thermometer, The internal temperature was adjusted to 20 ° C. Next, a mixed solution of 26 g of a butyl acetate solution of silicon-containing polymer (P-1) and 70 g of tetramethoxysilane (raw material solution A) was added to the charged product from 9 g of 25% aqueous ammonia, 36 g of methanol and 27 g of water. The mixed liquid (raw material liquid B) was added dropwise from the dropping port 2 over 1 hour with stirring. After the dropwise addition, the reaction mixture was stirred at the same temperature for 30 minutes, and then a mixture of 15 g of 3-methacryloxypropyltrimethoxysilane and 15 g of methanol (raw material C) was added to the reaction mixture over 15 minutes from the dropping port a. It was dripped. After further stirring the reaction mixture for 30 minutes, the temperature of the reaction mixture was gradually raised to 130 ° C., and ammonia, methanol, butyl acetate and water were distilled off until the solid content concentration of the reaction mixture reached 30%. A composite fine particle dispersion (Z-1) in which the composite fine particles were dispersed in butyl acetate was obtained. Table 1 shows the composite fine particle concentration of the obtained dispersion, the inorganic content in the composite fine particles, the average particle size and coefficient of variation of the composite fine particles, the alkoxy group content in the composite fine particles, and the stability over time.

-Example A2-
Manufacture of composite fine particle dispersion (Z-2) Ethanol 627g was charged into a 1 liter four-necked flask equipped with a stirrer, two dropping ports (dropping port A and dropping port B), and thermometer, and the internal temperature was 20 Adjusted to ° C. Next, 32 g of an ethanol solution of silicon-containing polymer (P-2) and a mixed solution of 70 g of tetramethoxysilane (raw material solution A) were mixed into this charge from a dropping port (a), 9 g of 25% aqueous ammonia, 36 g of ethanol, and 27 g of water. The liquid (raw material liquid B) was added dropwise from the dropping port over 1 hour with stirring. After the dropwise addition, the reaction mixture was stirred at the same temperature for 30 minutes, and then a mixed liquid of 10 g of 3-methacryloxypropyltrimethoxysilane and 10 g of ethanol (raw material liquid C) was added to the reaction mixture over 15 minutes from the dropping port a. It was dripped. The reaction mixture was further stirred for 30 minutes to obtain a composite fine particle dispersion (Z-2) in which composite fine particles were dispersed. Table 1 shows the composite fine particle concentration of the obtained dispersion, the inorganic content in the composite fine particles, the average particle size and coefficient of variation of the composite fine particles, the alkoxy group content in the composite fine particles, and the stability over time.

Next, in a 1 liter four-necked flask equipped with a stirrer, a dripping port and a thermometer, 400 g of the composite fine particle dispersion (Z-2) obtained above, Nonipol 200 (manufactured by Sanyo Chemical Co., Ltd.) as a surfactant ) Compound fine particle dispersion in which 20 g and 100 g of water were charged, adjusted to an internal temperature of 100 ° C., and ammonia, ethanol and methanol were distilled off until the solid content concentration of the charge reached 30%, and the composite fine particles were dispersed in water. The body (Z-2 ′) was obtained.
-Example A3-
Production of composite fine particle dispersion (Z-3) Into a 1 liter four-necked flask equipped with a stirrer, two dropping ports (dropping port A and dropping port B), and thermometer, 70 g of 25% aqueous ammonia and 294 g of methanol were added. The internal temperature was adjusted to 20 ° C. Next, 43 g of a methanol solution of silicon-containing polymer (P-3), 112 g of water, and 70 g of methanol (raw material liquid A) were added to this charge from a dripping port (a), and a mixed solution of 70 g of tetramethoxysilane and 140 g of methanol (raw material) Liquid B) was added dropwise from the dropping port over 1 hour with stirring. After the dropwise addition, the reaction mixture was stirred at the same temperature for 30 minutes, and then a mixed liquid of 8 g of vinyltrimethoxysilane and 8 g of methanol (raw material liquid C) was dropped into the reaction mixture over 15 minutes from the dropping port a. After further stirring the reaction mixture for 30 minutes, 100 g of water was added to the reaction mixture, and the temperature of the reaction mixture was gradually raised to 100 ° C., and ammonia, methanol and water were added until the solid content concentration of the reaction mixture reached 30%. Distilled to obtain a composite fine particle dispersion (Z-3) in which the composite fine particles were dispersed in water. Table 1 shows the composite fine particle concentration of the obtained dispersion, the inorganic content in the composite fine particles, the average particle size and coefficient of variation of the composite fine particles, the alkoxy group content in the composite fine particles, and the stability over time.

-Comparative Example A1-
Production of composite fine particle dispersion (Z-C1) A composite fine particle dispersion (Z) in which composite fine particles are dispersed in butyl acetate in the same manner as in Example 1 except that the raw material liquid C is not dropped into the reaction mixture. -C1) was obtained.

About the composite fine particle dispersion obtained above, the composite fine particle concentration of the obtained dispersion, the inorganic content in the composite fine particle, the average particle size and coefficient of variation of the composite fine particle, the alkoxy group content in the composite fine particle, stable over time Sex was analyzed and evaluated by the following method.
Composite fine particle concentration The composite fine particle dispersion was dried at 130 ° C. for 24 hours under a pressure of 100 mmHg, and obtained from the following formula.
Concentration of composite fine particles (% by weight) = 100 × D / W
(Where D: weight of composite fine particles after drying (g)
W: Weight of composite fine particle dispersion before drying (g))
Inorganic content in composite fine particles Elemental analysis was performed on the composite fine particle dispersion dried at 130 ° C. for 24 hours under a pressure of 100 mmHg, and ash was used as the inorganic content in the composite fine particles.
The average particle size and coefficient of variation were measured at 23 ° C. using a dynamic light scattering measurement method using the following apparatus. The measured average particle diameter is a volume average particle diameter.

Apparatus: Sub-micron particle size analyzer (manufactured by Nozaki Sangyo Co., Ltd., NICOMP MODEL 370)
Sample to be measured: Composite fine particle dispersion dispersed in tetrahydrofuran having a composite fine particle concentration of 0.1 to 2.0% by weight (if the organic polymer in the composite fine particles is not soluble in tetrahydrofuran, it is dispersed in a solvent in which the organic polymer is dissolved. Dispersion).
Coefficient of variation: The coefficient of variation is determined by the following equation.
Coefficient of variation (%)
= (Standard deviation of particle diameter of composite fine particles) / (Average particle diameter of composite fine particles)
Alkoxy group content in composite fine particles 5 g of the composite fine particle dispersion dried at 130 ° C. under a pressure of 100 mmHg for 24 hours was dispersed in a mixture of 50 g of acetone and 50 g of 2N-NaOH aqueous solution and stirred at room temperature for 24 hours. . Thereafter, the alcohol in the liquid was quantified with a gas chromatograph, and the alkoxy group content of the composite fine particles was calculated.
Stability over time The obtained dispersion was sealed in a Gardner viscosity tube and stored at 50 ° C. One month later, no particle aggregation, sedimentation or viscosity increase was observed.

-Example B1-
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen gas introduction tube, 85 g of pure water, 5 g of 20% Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution as an emulsifier and 20% Aqualon RN- 20 g (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was charged with 10 g of an aqueous solution, stirred while gently blowing nitrogen gas into the charged product, and heated to 75 ° C.
Next, 70 g of the composite fine particle dispersion (Z-2 ′) was added to the charged product, and after sufficiently stirring, a polymerizable monomer composed of 5 g of 2-ethylhexyl acrylate, 1 g of styrene, and 10 g of methyl methacrylate was further charged. To this charge, 0.6 g of 5% aqueous ammonium persulfate solution was added to initiate seed polymerization.

  A polymerizable monomer component (A) comprising 16.5 g of 2-ethylhexyl acrylate, 1 g of glycidyl methacrylate, 0.5 g of acrylic acid, 1.5 g of hydroxyethyl methacrylate, 10 g of styrene, 20 g of n-butyl methacrylate and 11 g of methyl methacrylate. To the polymerizable monomer component (A) was added 3.3 g of 20% aqualon HS-10 aqueous solution, 1.7 g of 20% aqualon RN-20 aqueous solution and 30 g of pure water, and the pre-emulsion mixture (A) and did. After 10 minutes have passed since the 5% ammonium persulfate aqueous solution was added, the pre-emulsion mixture (A) and 2.4 g of 5% ammonium persulfate aqueous solution were uniformly added dropwise over 80 minutes to a reaction temperature of 75 to 75%. The seed polymerization was carried out while maintaining at 80 ° C. After completion of the dropwise addition, the reaction mixture was aged with stirring for 30 minutes.

  Next, a polymerizable monomer component (B) comprising 14 g of 2-ethylhexyl acrylate, 1 g of glycidyl methacrylate, 1 g of hydroxyethyl methacrylate, 14 g of styrene, 5 g of n-butyl methacrylate, and 15 g of methyl methacrylate was prepared. To the body component (B), 5 g of 20% Aqualon HS-10 aqueous solution, 2.5 g of 20% Aqualon RN-20 aqueous solution and 15 g of pure water were added to obtain a pre-emulsion mixture (B). A pre-emulsion mixture (B), 3.0 g of 5% ammonium persulfate aqueous solution and 2.4 g of 2.5 sodium hydrogen carbonate aqueous solution were added dropwise to the reaction mixture over 100 minutes. During the dropping, seed polymerization was performed while maintaining the reaction temperature in the range of 75 to 80 ° C. After completion of the dropwise addition, the reaction mixture was aged with stirring for 1 hour, and the temperature of the reaction mixture was lowered to 60 ° C. Further, 2.5 g of 5% aqueous ammonia was added, and the reaction mixture was sufficiently stirred to obtain a dispersion (B1) containing core-shell type composite particles having a solid content of 42% and a viscosity of 340 mPa · s.

-Example B2-
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube was charged with 65 g of pure water and 50 g of the composite fine particle dispersion (Z-3), and while nitrogen gas was gently blown into this charge, Stir and warm to 75 ° C.
A polymerizable monomer component (A) comprising 15 g of 2-ethylhexyl acrylate, 1 g of glycidyl methacrylate, 0.5 g of acrylic acid, 1 g of hydroxyethyl methacrylate, 15 g of styrene, 1 g of n-butyl methacrylate and 15 g of methyl methacrylate was prepared in advance. 10% of this polymerizable monomer component (A) was added dropwise to the charge, followed by dropwise addition of 0.6 g of 5% aqueous ammonium persulfate solution. After 10 minutes from the addition of the aqueous ammonium persulfate solution, the remaining polymerizable monomer component (A) and 2.4 g of 5% aqueous ammonium persulfate solution are uniformly added dropwise over 80 minutes to the temperature of the reaction mixture. Was polymerized while being kept at 75-80 ° C. After completion of the dropwise addition, the reaction mixture was stirred and aged for 30 minutes to obtain a dispersion (B2) containing core-shell type composite particles having a solid content of 38.1% and a viscosity of 00 mPa · s.

-Examples B3-B5-
The composite fine particle dispersion (Z-2 ′) produced above was mixed according to the formulation shown in Table 2 to obtain a composition (B3) (Example B3).
The dispersion (B1) produced above was mixed with the formulation shown in Table 2 to obtain a composition (B4) (Example B4).
The dispersion (B1) produced above was mixed with the formulation shown in Table 2 to obtain a composition (B5) (Example B5).

U Double E-11: Nippon Shokubai Co., Ltd., Hals hybrid resin emulsion, 50% non-volatile content.
Using the compositions (B3) to (B5) obtained above as raw materials, white paints were prepared and evaluated according to the following composition.
Preparation and evaluation of white paint
Using the composition obtained above, each was mixed in the following composition.
Deionized water 64.6 parts Dispersant (Kao Corporation, Demol EP) 2.0 parts Antifoam (San Nopco, Nopco 8034) 0.3 parts Titanium oxide (rutile type) 60.0 parts Above composition 146 .7 parts
Deposition aid (Chisso, CS-12) 15.0 parts
Total 288.6 parts In addition, a viscosity modifier (Adecanol UH, manufactured by Asahi Denka Co., Ltd.) so that the viscosity measured with a Craves single viscometer KU-1 (Brookfield) is 80 to 95 (25 ° C.). The white paint was prepared by adjusting the viscosity using -420). About the obtained white coating material, 60 degree gloss, coating-film contamination A, and coating-film contamination B were measured and evaluated by the following method. The results are also shown in Table 2.

[60 degree gloss]
The paint was applied onto a glass plate using a B-type film applicator with a gap of 150 μm and dried under conditions of 23 ° C. and 65% Rh for 7 days. The obtained film was measured for specular gloss as defined in 7.6 of JIS K 5400 at a measurement angle of 60 degrees. The larger the value, the better the gloss.
[Coating Contamination A]
The paint was applied on an aluminum plate so as to have a dry film thickness of about 80 μm, and dried for 7 days under conditions of 23 ° C. and 65% Rh. The obtained coating was immersed in a 0.05% carbon aqueous solution while stirring, then washed with water, the degree of adhesion of dirt to the coating was observed, and evaluated according to the following evaluation criteria.

◎: No adhesion ○: Almost no adhesion △: Some adhesion ×: Adhesion [Coating stain B]
The coating material was applied onto the flexible board so as to have a dry film thickness of about 80 μm, and dried for 7 days under conditions of 23 ° C. and 65% Rh. The obtained film is exposed to the south (30 degrees) in Suita City, Osaka Prefecture, and according to JIS Z8730, the difference in brightness of the film after three months (ΔL ^* value) with respect to the initial brightness is calculated using the integrated spectroscopic method. Measurement was performed using a color difference meter (manufactured by JEOL Ltd.). In general, the closer the ΔL ^* value is to 0, the more dirty the coating is. The coating film contamination C was evaluated according to the following evaluation criteria.

A: ΔL ^* ≦ 5
○: 5 <ΔL ^* ≦ 10
Δ: 10 <ΔL ^* ≦ 15
×: ΔL ^* > 15
-Example C1-
Urethane (meth) acrylate, 60 parts of UV curable composite fine particle dispersion (Z-1), 100 parts of urethane acrylate (trade name: Photomer 6008, manufactured by San Nopco), UV stabilizer (trade names: Tinuvin 123, Ciba Geigy) 2 parts, UV absorber (trade name: Tinuvin 400, manufactured by Ciba Geigy), radical photoinitiator (trade name: Darocur 1173, manufactured by Ciba Geigy), leveling agent (trade name: BYK300, manufactured by Big Chemie) 0.1 The resin composition (1) was obtained by adding a part and stirring well and adjusting a viscosity. Using an applicator on a polymethylmethacrylate flat plate, a test plate (1) coated with the resin composition (1) so as to have a dry film thickness of 20 μm was obtained. The test plate (1) is dried with hot air at 80 ° C. for 30 minutes, placed on a conveyor moving at a speed of 5 m / min, and once irradiated with ultraviolet rays from a height of 20 cm using a high-pressure mercury lamp (120 W / cm). The curing test plate (1) was obtained. The cured test plate (1) was measured and evaluated for hardness, transparency, scratch resistance, stain resistance and weather resistance by the methods described below. The results are shown in Table 3.

-Example C2-
Resin composition (2) and test plate (2) were obtained in the same manner as in Example C1 except that the polyfunctional (meth) acrylate and each component shown in Table 3 were added. The test plate (2) was cured after hot air drying in the same manner as in Example C1 to obtain a cured test plate (2), and the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured by the methods described below. evaluated. The results are shown in Table 3.
-Example C3-
Polyfunctional (meth) acrylate and acryloyl group-containing acrylic resin, electron beam cured composite fine particle dispersion (Z-1) 60 parts, polyfunctional acrylate (trade name: Light acrylate TMP-6EO-3A, manufactured by Kyoeisha Chemical Industry Co., Ltd. 50 parts of EO-modified trimethylolpropane triacrylate), 100 parts of a butyl acetate solution (AC-P) of acrylic resin containing an acryloyl group, and 0.1 part of a leveling agent (trade name: BYK300, manufactured by Big Chemie) are thoroughly stirred. The resin composition (3) was obtained by adjusting the viscosity. Using an applicator on a polymethyl methacrylate flat plate, a test plate (3) coated with the resin composition (3) so as to have a dry film thickness of 20 μm was obtained. The test plate (3) was dried with hot air at 80 ° C. for 30 minutes, and then an area beam type electron beam irradiation apparatus manufactured by Nissin High Voltage Co., Ltd. was used under the conditions of an acceleration voltage of 200 kV and a dose of 10 Mrad. The test plate (3) was irradiated with an electron beam to obtain a cured test plate (3). For the cured test plate (3), the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured and evaluated by the methods described below, and the results are shown in Table 3.

-Example C4-
Resin composition (4) and test plate (4) were obtained in the same manner as in Example C3 except that urethane (meth) acrylate, polyfunctional (meth) acrylate, and each component shown in Table 3 were added. The test plate (4) was cured after hot air drying in the same manner as in Example C3 to obtain a cured test plate (4), and the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured by the methods described below. evaluated. The results are shown in Table 3.
-Example C5-
Urethane (meth) acrylate, polyfunctional (meth) acrylate and acryloyl group-containing acrylic resin, 50 parts butyl acetate solution (AC-P) of electron beam-cured acroyl group-containing acrylic resin, pigment (trade name: CR-95, Ishihara) 20 parts of Titanium Oxide manufactured by Sangyo Co., Ltd. was previously blended to prepare a paint composition A. 70 parts of the composition A prepared above, 60 parts of the composite fine particle dispersion (Z-1), 50 parts of urethane acrylate (trade name: Photomer-6008, manufactured by San Nopco), polyfunctional acrylate (trade name: light acrylate TMP) -6EO-3A, 25 parts of EO-modified trimethylolpropane triacrylate manufactured by Kyoeisha Chemical Industry Co., Ltd., and 0.1 part of a leveling agent (trade name: BYK300, manufactured by Big Chemie) were added and stirred well to adjust the viscosity. Thus, a resin composition (5) was obtained. Using an applicator on a polymethylmethacrylate flat plate, a test plate (5) coated with the resin composition (5) so as to have a dry film thickness of 20 μm was obtained. After drying the test plate (5) with hot air at 80 ° C. for 30 minutes, using an area beam type electron beam irradiation apparatus manufactured by Nisshin High Voltage Co., Ltd., under the conditions of an acceleration voltage of 200 kV and a dose of 10 Mrad. The test plate (5) was irradiated with an electron beam to obtain a cured test plate (5). With respect to the cured test plate (5), the hardness, scratch resistance, stain resistance and weather resistance were measured and evaluated by the methods described later, and the results are shown in Table 3.

-Example C6-
A resin composition (6) and a test plate (6) were obtained in the same manner as in Example C1, except that the urethane (meth) acrylate, the vinyl ether group-containing compound, and each component shown in Table 3 were added. The test plate (6) was cured after hot air drying in the same manner as in Example C1 to obtain a cured test plate (6), and the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured by the methods described below. evaluated. The results are shown in Table 3.
-Example C7-
A resin composition (7) and a test plate (7) were obtained in the same manner as in Example C1 except that the acroyl group-containing acrylic resin and epoxy group-containing compound, heat and each component shown in Table 3 were added. The test plate (7) was cured after hot air drying in the same manner as in Example C1 to obtain a cured test plate (7), and the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured by the methods described below. evaluated. The results are shown in Table 3.

-Example C8-
A resin composition (8) and a test plate (8) were obtained in the same manner as in Example C1 except that the acroyl group-containing acrylic resin and vinyl ether group-containing compound, heat and ultraviolet curing were added. The test plate (8) was cured after hot air drying in the same manner as in Example C1 to obtain a cured test plate (8), and the hardness, transparency, scratch resistance, stain resistance and weather resistance were measured by the methods described below. evaluated. The results are shown in Table 3.
-Comparative Example C1-
Urethane (meth) acrylate, UV curing As shown in Table 4, in place of the composite fine particle dispersion (Z-1), except for adding the composite fine particle dispersion (Z-C1), the same as in Example C3, A comparative resin composition (1) and a comparative test plate (1) were obtained. The comparative test plate (1) was cured after hot air drying in the same manner as in Example C3 to obtain a comparative cured test plate (1). The hardness, transparency, scratch resistance, stain resistance and weather resistance were determined by the methods described below. Measurement and evaluation. The results are shown in Table 4.

-Comparative Example C2-
Urethane (meth) acrylate and polyfunctional (meth) acrylate, as shown in Table 4, except that composite fine particle dispersion (Z-C1) is added instead of composite fine particle dispersion (Z-1). In the same manner as in Example C4, a comparative resin composition (2) and a comparative test plate (2) were obtained. The comparative test plate (2) was cured after hot-air drying in the same manner as in Example C4 to obtain a comparative cured test plate (2). Measurement and evaluation. The results are shown in Table 4.
-Comparative Example C3-
Urethane (meth) acrylate and vinyl ether group-containing compound, UV curing As shown in Table 4, Example C6 except that the composite fine particle dispersion (Z-C1) is added instead of the composite fine particle dispersion (Z-1). In the same manner as above, a comparative resin composition (3) and a comparative test plate (3) were obtained. The comparative test plate (3) was cured after hot air drying in the same manner as in Example C6 to obtain a comparative cured test plate (3). Measurement and evaluation. The results are shown in Table 4.

-Comparative Example C4-
Acroyl group-containing acrylic resin and epoxy group-containing compound , as shown in Table 4, Example C7, except that composite fine particle dispersion (Z-C1) was added instead of composite fine particle dispersion (Z-1) In the same manner as above, a comparative resin composition (4) and a comparative test plate (4) were obtained. The comparative test plate (4) was cured after hot air drying in the same manner as in Example C7 to obtain a comparative cured test plate (4). The hardness, transparency, scratch resistance, stain resistance and weather resistance were determined by the methods described below. Measurement and evaluation. The results are shown in Table 4.
Performs a pencil scratch test of hardness of JIS K5400 6.14 (pencil hardness test), were evaluated by scratches.
Transparency The total light transmittance (%) was measured using a haze meter manufactured by Nippon Denshoku Industries Co., Ltd.
Gloss retention (rubbing) after pressing a felt soaked with a scratch-resistant cleanser dispersion (concentration 5%) against the cured coating while applying a load of 200 g / cm ² and rubbing 50 times. The subsequent gloss value was divided by the gloss value before rubbing and multiplied by 100) to evaluate the scratch resistance. The greater the gloss retention, the higher the scratch resistance.
The degree of soiling on the paint film when 0.05% carbon aqueous solution was applied to the stain-resistant paint film 10 times with a brush, forcedly dried at 80 ° C. for 1 hour and then washed 30 times with a brush while washing with water I saw.

◎: No adhesion ○: Almost no adhesion △: Some adhesion
The gloss retention of the coating film after 3000 hours was measured and evaluated with a weather-resistant sunshine weather meter.

* 1 Product name: Photomer 6008, manufactured by San Nopco.
* 2 Product name: Light acrylate TMP-6EO-3A, an EO-modified trimethylolpropane triacrylate manufactured by Kyoeisha Chemical Industry Co., Ltd.
* 3 Product name: Light Ester 1.6HX-A, 1,6-hexanediol diacrylate manufactured by Kyoeisha Chemical Industry Co., Ltd.
* 4 Product name: Celoxide 2021, an alicyclic epoxy compound manufactured by Daicel Chemical Industries, Ltd.
* 5 Cyclohexane dimethanol divinyl ether manufactured by ISP Japan.

* 6 Product name: Tinuvin 400, manufactured by Ciba Geigy.
* 7 Product name: Tinuvin 123, manufactured by Ciba Geigy.
* 8 Product name: BYK300, made by Big Chemie.
* 9 Product name: CR-95, titanium oxide manufactured by Ishihara Sangyo Co., Ltd.
* 10 Product name: Darocur 1173, manufactured by Ciba Geigy.
* 11 Product name: Irgacure 184, manufactured by Ciba Geigy.
* 12 Product name: Sun-Aid SI-60L, manufactured by Sanshin Chemical Industry Co., Ltd.
-Example C9-
A 1 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling tube and a nitrogen gas inlet was charged with 165 g of butyl acetate, and heated to 120 ° C. while introducing nitrogen gas and stirring. To this preparation, 50 g of the composite fine particle dispersion (Z-1), 120 g of cyclohexyl methacrylate, 60 g of hydroxyethyl methacrylate, 99 g of butyl methacrylate, 3 g of 4-metalloyloxy-2,2,6,6-tetramethylpiperidine, 2- A mixture of 3 g of [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole and 15 g of 2,2′-azobis (2-methylbutyronitrile) as an initiator was added dropwise over 4 hours. did. After dropping, the mixture was further heated for 2 hours to obtain a copolymer solution (9) containing the composite fine particle-containing acrylic polyol. The nonvolatile content of the copolymer solution (9) was 60%. The number average molecular weight of the acrylic polyol portion of the composite fine particle-containing acrylic polyol was 5,500.

  A polyfunctional isocyanate (Sumijour N-3200, manufactured by Sumitomo Bayer Urethane Co., Ltd.) as a curing agent is added to the copolymer solution (9), a hydroxyl group in the composite fine particle-containing acrylic polyol, and an isocyanate in the polyfunctional isocyanate. The resin was mixed so that the equivalent ratio with the group was 1: 1, and a resin composition (9) having the composition shown in Table 5 was obtained. Using an applicator on a polymethyl methacrylate flat plate, a test plate (9) coated with the resin composition (9) so as to have a dry film thickness of 30 μm was obtained. The test plate (1) was dried at 80 ° C. for 2 hours to obtain a cured test plate (9). The cured test plate (9) was measured and evaluated by the above methods for hardness, transparency, scratch resistance, contamination resistance and weather resistance. The results are shown in Table 5.

-Example C10-
Into a 1 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 265 g of butyl acetate was charged, and heated to 120 ° C. while introducing nitrogen gas and stirring. To this charge, 50 g of the composite fine particle dispersion (Z-1), 120 g of cyclohexyl methacrylate, 60 g of butyl acrylate, 99 g of butyl methacrylate, 3 g of 4-metalloyloxy-2,2,6,6-tetramethylpiperidine, 2- [ 2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (3 g) and 2,2'-azobis (2-methylbutyronitrile) (15 g) as an initiator were added dropwise over 2 hours. . After dropping, the mixture was further heated for 2 hours to obtain a copolymer solution (10) containing the composite fine particle-containing acrylic lacquer. The nonvolatile content of the copolymer solution (10) was 50%. The number average molecular weight of the acrylic lacquer portion of the composite fine particle-containing acrylic lacquer was 25000.

  The copolymer solution (10) was blended to obtain a resin composition (10) having the blending composition shown in Table 5. Using an applicator on a polymethyl methacrylate flat plate, a test plate (10) coated with the resin composition (10) so as to have a dry film thickness of 30 μm was obtained. The test plate (1) was dried at 60 ° C. for 1 hour, and the test plate (10) was measured and evaluated for hardness, transparency, scratch resistance, stain resistance and weather resistance by the above methods. The results are shown in Table 5.

The method for producing composite fine particles according to the present invention provides a cured film or cured product having not only excellent dispersibility, rich addition polymerization, excellent weather resistance and stain resistance, but also high transparency and hardness. It can be conveniently used when producing composite fine particles that can be produced.

Claims (1)

It is composed of an organic chain and a polysiloxane group, and at least one Si—OR ¹ (R ¹ is a hydrogen atom, an optionally substituted alkyl group, and an acyl group) in the polysiloxane group. a group, when R ¹ are a plurality in one molecule, a plurality of R ¹ may be identical to each other, a may be different.) silicon-containing polymer having a (P), alone or A step of hydrolysis and condensation with the hydrolyzable metal compound (G),
Reacting a hydrolysis / condensation product with a coupling agent having an ethylenically unsaturated group;
A method for producing composite fine particles, comprising: