JP2012136677A - Additive for use in coating agent, and coating agent containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additive for use in coating agents which is, even in a very small load, capable of imparting the excellent-uniformity, transparency, solvent resistance, stain resistance, and water repellency, to the cured coating layer; and to provide a coating agent that includes this additive for use in coating agents.SOLUTION: This additive for use in coating agents includes a copolymer (A) that includes a hydroxy group and a group having a specific carbosiloxane dendrimer structure; and this coating agent includes this additive for use in coating agents.

Description

The present invention is excellent in compatibility with a resin, particularly an acrylic resin cured by an isocyanate-based curing agent, and has excellent uniformity, transparency, solvent resistance, resistance to a cured coating layer even with a very small addition amount. The present invention relates to an additive for a coating agent that can impart contamination and water repellency. Furthermore, the present invention relates to a coating agent comprising the coating agent additive.

Conventionally, a silicone-modified vinyl resin made of a vinyl polymer having a linear polyorganosiloxane group in the side chain is known. This resin is obtained by copolymerizing a linear polyorganosiloxane having a polymerizable group at one end with a vinyl compound (Patent Document 1). Such silicone-modified vinyl resins are excellent in stain resistance and water repellency due to the effect of the side chain polyorganosiloxane group, and are blended in various coating agents to impart these functions.

However, when a linear polyorganosiloxane having a polymerizable group at one end and a vinyl compound are polymerized in a solution, if the molecular weight of the polyorganosiloxane used is increased, the linear organopolysiloxane having a polymerizable group at one end is used. Due to the problem that the polymerizability of siloxane is reduced and the main chain structure is not easily incorporated, and the resin solution after polymerization becomes cloudy and becomes a non-uniform resin solution. There was a problem. In addition, when polyorganosiloxane having a low molecular weight is used, the resin solution after polymerization becomes transparent, but the organosiloxane is low in compatibility with various materials, so that it is difficult to be incorporated into the curing system. A coating agent using a resin has a problem that the coating film after coating is not sufficiently contaminated and water repellent.

On the other hand, in Patent Documents 2-6, it has been studied to use a vinyl polymer containing a carbosiloxane dendrimer structure as an additive in a coating agent. There was a drawback that it could not be incorporated and the solvent resistance was low.

JP-A-61-78806 JP 2000-160025 A JP 2000-198939 A JP 2001-192424 A JP 2000-119351 A Japanese Patent Laid-Open No. 2002-256034

The object of the present invention is excellent in compatibility with various curable resin solutions, and can impart excellent uniformity, transparency, solvent resistance, stain resistance and water repellency to the coating layer after curing. It is to provide an additive for a coating agent and a coating agent.

The inventors of the present invention have arrived at the present invention as a result of intensive studies in order to solve the above problems. That is, the object of the present invention is solved by an additive for a coating agent containing a copolymer (A) containing a specific carbosiloxane dendrimer structure and a hydroxyl group in the molecule, and a coating agent containing the same. The copolymer (A) is obtained by copolymerizing an unsaturated monomer having a carbosiloxane dendrimer structure, an unsaturated monomer containing a hydroxyl group, and optionally an unsaturated monomer not containing a hydroxyl group. Can be obtained.

Such a copolymer (A) has a carbosiloxane dendrimer structure excellent in compatibility with the curable resin solution in the molecule, and a reactive hydroxyl group is introduced into the curable resin. For this reason, by using it as an additive for coating agents, it is not only efficiently introduced into the curing system of the resin, but also with a very small amount of addition, a sufficient phase derived from the carbosiloxane dendrimer structure in the cured coating layer. Solubility, solvent resistance, stain resistance and water repellency can be imparted.

That is, the object is “[1] Additive for coating agent containing a copolymer (A) containing a group having a carbosiloxane dendrimer structure represented by the following formula (1) and a hydroxyl group in the molecule.

｛式中、Ｚは、２価の有機基であり、pは、０又は１であり、Ｒ¹及びＲ²は、それぞれ独立して、炭素原子数１〜１０のアルキル基、アリール基又はアラルキル基であり、Ｌ¹は、i=１とした場合の下記構造式（２）で示されるシリルアルキル基

{In the formula, Z is a divalent organic group, p is 0 or 1, and R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group. L ¹ is a silylalkyl group represented by the following structural formula (2) when i = 1

（式中、Ｚ及びｐは、前記と同じであり、Ｒ¹及びＲ²は、前記と同じであり、iは、前記シリルアルキル基の総階層数を示す１〜１０の整数であり、Ｌⁱ⁺¹は、水素原子、炭素原子数１〜１０のアルキル基、アリール基、アラルキル基及び前記シリルアルキル基からなる群から選択される基であり、但し、ｉ＝ｃ（ｃは前記シリルアルキル基の階層を示す１〜１０の整数である）の場合は、Ｌⁱ⁺¹は水素原子、炭素原子数１〜１０のアルキル基、アリール基又はアラルキル基であり、i＜cの場合は前記シリルアルキル基であり、aⁱは０〜３の整数である）である｝[2] 共重合体（Ａ）が、下記（ａ１）および（ａ２）の不飽和単量体を、各々、少なくとも１種類以上ずつ共重合させてなる共重合体である、[1]に記載のコーティング剤用添加剤。（ａ１） 分子中に１以上の水酸基を含有する不飽和単量体（ａ２） 下記式（１´）で示されるラジカル重合可能な不飽和単量体

Wherein Z and p are the same as above, R ¹ and R ² are the same as above, i is an integer of 1 to 10 indicating the total number of layers of the silylalkyl group, and L ^{i + 1} is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group and the silylalkyl group, provided that i = c (c is the silylalkyl group). L ^{i + 1} represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and when i <c, Is a silylalkyl group, a ⁱ is an integer of 0 to 3)} [2] The copolymer (A) contains at least each of the following unsaturated monomers (a1) and (a2): The additive for coating agent according to [1], which is a copolymer obtained by copolymerizing one or more types. (A1) Unsaturated monomer containing one or more hydroxyl groups in the molecule (a2) Unsaturated monomer capable of radical polymerization represented by the following formula (1 ′)

（式中、Ｙはラジカル重合可能な不飽和含有基であり、Ｚ、p、Ｒ¹、Ｒ²、Ｌ¹及びaⁱは前記と同じである）[3] 上記式（１´）で示されるラジカル重合可能な不飽和単量体において、ラジカル重合可能な不飽和含有基Ｙが、一般式：

(Wherein Y is an unsaturated group capable of radical polymerization, and Z, p, R ¹ , R ² , L ¹ and a ⁱ are the same as above) [3] Shown by the above formula (1 ′) In the radically polymerizable unsaturated monomer, the radically polymerizable unsaturated group Y has the general formula:

（式中、Ｒ⁴は水素原子若しくはメチル基であり、Ｒ⁵は炭素原子数１〜１０のアルキレン基である。）、

(Wherein R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkylene group having 1 to 10 carbon atoms),

（式中、Ｒ⁴及びＲ⁵は前記と同じである。）で示されるアクリル基若しくはメタクリル基含有有機基、一般式：

(Wherein R ⁴ and R ⁵ are as defined above), an acrylic group or methacryl group-containing organic group represented by the general formula:

（式中、Ｒ⁶は水素原子若しくはメチル基であり、Ｒ⁷は炭素原子数１〜１０のアルキル基であり、Ｒ⁸は炭素原子数１〜１０のアルキレン基であり、bは０〜４の整数であり、cは０又は１である。）で示されるアルケニルアリール基含有有機基および炭素原子数２〜１０のアルケニル基からなる群から選択される基である、[2]に記載のコーティング剤用添加剤。[4] 前記共重合体（Ａ）が、更に、少なくとも１種以上の（ａ３）分子中に水酸基を含有しない不飽和単量体 を共重合させてなる共重合体である、[2]に記載のコーティング剤用添加剤。[5] 前記共重合体（Ａ）がその構成単位として、前記の不飽和単量体（ａ１）、（ａ２）および任意で（ａ３）を共重合させてなる共重合体であり、当該共重合体を構成する不飽和単量体（ａ１）〜（ａ３）の質量の和が１００質量部であるとき、その質量比が、（ａ１）：（ａ２）：（ａ３）＝０．５〜５０．０：０．５〜５０．０：０〜９９．０の範囲にあることを特徴とする、[2]〜[4]のいずれか１項に記載のコーティング剤用添加剤。[6] 前記共重合体（Ａ）を構成する不飽和単量体（ａ１）が、アクリル酸ヒドロキシエチル，メタクリル酸ヒドロキシエチル，アクリル酸ヒドロキシプロピルおよびメタクリル酸ヒドロキシプロピルからなる群から選択される１種類以上の水酸基を含有する不飽和単量体である、[1]〜[5]のいずれか１項に記載のコーティング剤用添加剤。[7] [1]〜[6]のいずれか１項に記載のコーティング剤用添加剤を含有するコーティング剤。[8] [1]〜[6]のいずれか１項に記載のコーティング剤用添加剤とアクリル系樹脂（ただし、該アクリル系樹脂はカルボシロキサンデンドリマー構造を側鎖に含有しない）および硬化剤を含有するコーティング剤。[9] 前記アクリル系樹脂が、水酸基を１分子中に２個以上含有するものである[8]に記載のコーティング剤。[10] 前記硬化剤が、イソシアネート基を有する化合物である[8]に記載のコーティング剤。[11] [1]〜[6]のいずれか１項に記載のコーティング剤用添加剤、アクリル系樹脂（ただし、該アクリル系樹脂はカルボシロキサンデンドリマー構造を側鎖に含有しない）およびイソシアネート基を有する化合物からなる硬化剤を含有するコーティング剤であって、コーティング剤中の水酸基１当量に対し、イソシアネート化合物中のＮＣＯ基の物質量が０．１〜２．０の範囲内にあるコーティング剤。」により達成される。

Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is an alkyl group having 1 to 10 carbon atoms, R ⁸ is an alkylene group having 1 to 10 carbon atoms, and b is 0 to 4 The alkenylaryl group-containing organic group represented by (2) and a group selected from the group consisting of alkenyl groups having 2 to 10 carbon atoms are represented by [2]: Additive for coating agent. [4] The copolymer (A) is a copolymer obtained by copolymerizing at least one or more (a3) unsaturated monomers not containing a hydroxyl group in the molecule. The additive for coating agents as described. [5] The copolymer (A) is a copolymer obtained by copolymerizing the unsaturated monomer (a1), (a2) and optionally (a3) as a structural unit. When the sum of the masses of the unsaturated monomers (a1) to (a3) constituting the polymer is 100 parts by mass, the mass ratio is (a1) :( a2) :( a3) = 0.5 to The additive for a coating agent according to any one of [2] to [4], which is in the range of 50.0: 0.5 to 50.0: 0 to 99.0. [6] The unsaturated monomer (a1) constituting the copolymer (A) is selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. The additive for coating agent according to any one of [1] to [5], which is an unsaturated monomer containing at least one kind of hydroxyl group. [7] A coating agent containing the additive for a coating agent according to any one of [1] to [6]. [8] The coating agent additive according to any one of [1] to [6], an acrylic resin (however, the acrylic resin does not contain a carbosiloxane dendrimer structure in the side chain), and a curing agent. Contains coating agent. [9] The coating agent according to [8], wherein the acrylic resin contains two or more hydroxyl groups in one molecule. [10] The coating agent according to [8], wherein the curing agent is a compound having an isocyanate group. [11] The additive for a coating agent according to any one of [1] to [6], an acrylic resin (however, the acrylic resin does not contain a carbosiloxane dendrimer structure in the side chain) and an isocyanate group A coating agent comprising a curing agent comprising a compound having an amount of NCO groups in the isocyanate compound within a range of 0.1 to 2.0 with respect to 1 equivalent of hydroxyl group in the coating agent. Is achieved.

According to the present invention, a coating agent that has excellent compatibility with various curable resin solutions and can impart excellent uniformity, transparency, solvent resistance, stain resistance, and water repellency to the coating layer after curing. Additives and coatings can be provided.

Hereinafter, the additive for a coating agent and the coating agent of the present invention will be described in detail.

The additive for a coating agent according to the present invention is characterized by containing a copolymer (A) containing a specific carbosiloxane dendrimer structure and a hydroxyl group in the molecule. Such a copolymer (A) is a copolymer obtained by copolymerizing an unsaturated monomer having a carbosiloxane dendrimer structure in a molecule and an unsaturated monomer having a hydroxyl group in the molecule. A system polymer is preferably exemplified. Here, a group having a carbosiloxane dendrimer structure or a functional group having a hydroxyl group is introduced into the side chain of a chain-like molecular main chain comprising unsaturated polymerized units. The additive for a coating agent according to the present invention is preferably a vinyl copolymer having a vinyl polymer unit as a main chain and a side chain having a carbosiloxane dendrimer structure and a hydroxyl group.

The copolymer (A) according to the present invention is characterized by containing a group having a carbosiloxane dendrimer structure as a first feature. Here, the carbosiloxane dendrimer structure means a high molecular weight group that is highly regularly branched radially from one nucleus. As the carbosiloxane dendrimer having such a structure, there is a highly branched siloxane / silalkylene copolymer (see JP-A No. 11-1530). In the present invention, the carbosiloxane dendrimer structure in the vinyl polymer is a group represented by the following formula (1).

Formula (1):

In the formula (1), Z is a divalent organic group, and the number of repeating units p is 0 or 1. Although the divalent organic group which is Z is not specifically limited, an alkylene group, an arylene group, an aralkylene group, an ester-containing divalent organic group, an ether-containing divalent organic group, a ketone-containing divalent organic group, an amide A group-containing divalent organic group is exemplified. Among these, an organic group represented by the following formula is preferable.

In the above formula, R ⁹ is an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, a methylene group and a propylene group are preferable. R ¹⁰ is an alkyl group having 1 to ¹⁰ carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a methyl group is preferable. R ¹¹ is an alkylene group having 1 to 10 carbon atoms, and examples thereof include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, an ethylene group is preferable. d is an integer of 0 to 4, and e is 0 or 1.

R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, A linear or branched alkyl group having 1 to 30 carbon atoms such as a heptyl group and an octyl group; a cyclic alkyl group having 3 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a phenyl group, a tolyl group, An aryl group having 6 to 10 carbon atoms such as a xylyl group; an aralkyl group having 7 to 10 carbon atoms such as a benzyl group; and a hydrogen atom bonded to the carbon atom of these groups is at least partially halogen such as fluorine. Atom or carbinol group, epoxy group, glycidyl group, acyl group, carboxyl group, amino group, methacryl group, mercapto group, amide group, oxyal And a group substituted with an organic group containing a xylene group. The alkyl group, aryl or aralkyl group is preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and is an unsubstituted alkyl group or aryl group having 1 to 6 carbon atoms. More preferred is a methyl group, an ethyl group, or a phenyl group.

L ¹ is a silylalkyl group represented by the following formula (2) when i = 1.

式中、Ｚ及びｐは、前記と同じであり、Ｒ¹及びＲ²は、前記と同じであり、iは、前記シリルアルキル基の総階層数を示す１〜１０の整数であり、合成の見地から、１〜５が好ましく、１〜３がより好ましい。一方、本発明に係る硬化性組成物を硬化させてなる硬化層の硬度、耐溶剤性、耐汚染性、撥水性等の特性の見地から、ｉは２以上であることが好ましく、ｉが２または３である、第２世代型および第３世代型のカルボシロキサンデンドリマー構造は、本発明の特に好適な実施形態に包含される。

In the formula, Z and p are the same as above, R ¹ and R ² are the same as above, i is an integer of 1 to 10 indicating the total number of layers of the silylalkyl group, From the viewpoint, 1 to 5 is preferable, and 1 to 3 is more preferable. On the other hand, from the standpoint of properties such as hardness, solvent resistance, stain resistance, and water repellency of the cured layer obtained by curing the curable composition according to the present invention, i is preferably 2 or more, and i is 2 Second generation and third generation carbosiloxane dendrimer structures, or 3, are included in particularly preferred embodiments of the present invention.

L ^{i + 1} is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group and the silylalkyl group, provided that i = c (c is the silyl group) In the case of an integer of 1 to 10 indicating the hierarchy of the alkyl group, 1 to 5 is preferred, 1 to 3 is still more preferred, and 1 or 2 is still more preferred) ^{Li + 1} is a hydrogen atom or a carbon atom An alkyl group, an aryl group or an aralkyl group of formulas 1 to 10; if i <c, the silylalkyl group; a ⁱ is an integer of 0 to 3, preferably 0 to 2; It is preferably 0 to 1, and more preferably 0).

The carbosiloxane dendrimer structure is a chemical structure highly branched radially from one silicon atom, and i indicating the total number of layers of the silylalkyl group indicates the degree of branching. For example, when the total number of layers i is 1 and L ^{i + 1} is, for example, a methyl group, the carbosiloxane dendrimer structure means the following structure.

（式中、Ｚ、ｐ、Ｒ¹及びＲ²は前記と同じであり、ａ^１は０〜３の整数である）

(In the formula, Z, p, R ¹ and R ² are the same as above, and a ¹ is an integer of 0 to 3).

Similarly, when the hierarchy i is 2 and L ^{i + 1} is, for example, a methyl group, the carbosiloxane dendrimer structure means the following structure (where p = 1). The carbosiloxane dendrimer structure represented by the following structure is sometimes referred to as “second generation type”, and the copolymer (A) according to the present invention particularly preferably has a group having the carbosiloxane dendrimer structure. is there.

（式中、Ｚ、Ｒ¹及びＲ²は前記と同じであり、ａ^１及びａ²は０〜３の整数である）

(In the formula, Z, R ¹ and R ² are the same as described above, and a ¹ and a ² are integers of 0 to 3).

Furthermore, when the hierarchy i is 3 and L ^{i + 1} is, for example, a methyl group, the carbosiloxane dendrimer structure means the following structure (where p = 1). The carbosiloxane dendrimer structure represented by the following structure may be referred to as “third generation type”, and the copolymer (A) according to the present invention particularly preferably has a group having the carbosiloxane dendrimer structure. is there.

（式中、Ｚ、Ｒ¹及びＲ²は前記と同じであり、ａ^１、ａ²及びａ³は０〜３の整数である）

(In the formula, Z, R ¹ and R ² are the same as described above, and a ¹ , a ² and a ³ are integers of 0 to 3)

As the carbosiloxane dendrimer structure, the following are preferable. In particular, the carbosiloxane dendrimer structure represented by the formula (2-5) is preferable from the viewpoint of the coating layer hardness, solvent resistance, stain resistance, water repellency and the like.

（式中、Ｚ及びＲ²は前記と同じである）

(Wherein Z and R ² are the same as above)

（式中、Ｚ及びＲ²は前記と同じである）

(Wherein Z and R ² are the same as above)

The group having a carbosiloxane dendrimer structure has a structure in which carbosiloxane units are spread in a dendrimer form, so that it is more compatible with a curable resin than a linear or mere branched polysiloxane unit. It is a functional group that is excellent and can impart high water repellency (high water resistance) to the coating layer and suppresses the coating surface from being extremely smooth. Moreover, since the group having the carbosiloxane dendrimer structure is chemically stable, it can be used in combination with a wide range of coating agents.

The group having a carbosiloxane dendrimer structure is obtained by copolymerizing (a2) a radical polymerizable unsaturated monomer represented by the following formula (1 ′) with another unsaturated monomer. To be introduced.

｛式中、Ｙはラジカル重合可能な不飽和含有基であり、Ｚ、p、Ｒ¹、Ｒ²、Ｌ¹及びaⁱは前記と同じである）

(In the formula, Y is an unsaturated group capable of radical polymerization, and Z, p, R ¹ , R ² , L ¹ and a ⁱ are the same as above)

The unsaturated group is not limited as long as it has an unsaturated bond capable of radical polymerization, and examples thereof include a vinyl group, an allyl group, and a (meth) acryl group.

In the formula (1 ′), Y is a general formula:

（式中、Ｒ⁴は水素原子若しくはメチル基であり、Ｒ⁵は炭素原子数１〜１０のアルキレン基である。）、若しくは、

(Wherein R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkylene group having 1 to 10 carbon atoms), or

（式中、Ｒ⁴及びＲ⁵は前記と同じである。）で示されるアクリル基若しくはメタクリル基含有有機基、一般式：

(Wherein R ⁴ and R ⁵ are as defined above), an acrylic group or methacryl group-containing organic group represented by the general formula:

（式中、Ｒ⁶は水素原子若しくはメチル基であり、Ｒ⁷は炭素原子数１〜１０のアルキル基であり、Ｒ⁸は炭素原子数１〜１０のアルキレン基であり、bは０〜４の整数であり、cは０又は１である。）で示されるアルケニルアリール基含有有機基、及び、炭素原子数２〜１０のアルケニル基からなる群から選択される基を有するものが好ましい。

Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is an alkyl group having 1 to 10 carbon atoms, R ⁸ is an alkylene group having 1 to 10 carbon atoms, and b is 0 to 4 And an alkenylaryl group-containing organic group represented by (2) and a group selected from the group consisting of alkenyl groups having 2 to 10 carbon atoms.

As such a component (a2), for example, the following formula

で示されるものが挙げられる。

The thing shown by is mentioned.

These unsaturated monomers having a carbosiloxane dendrimer structure are, for example, according to the method for producing a branched siloxane / silalkylene copolymer described in JP-A No. 11-1530 (Japanese Patent Application No. 9-171154). Can be manufactured.

The copolymer (A) according to the present invention is characterized by having a hydroxyl group in the molecule in addition to the carbosiloxane dendrimer structure. Hydroxyl group (—OH) is a component that is reactive with resins, particularly acrylic resins that are cured by isocyanate curing agents. When the curable resin is cured mainly by a condensation reaction, it is shared with the resin curing system. A polymer (A) is taken in efficiently. As a result, the copolymer (A) according to the product of the present invention has improved affinity for the curable resin, and improved compatibility at the time of curing and transparency (uniformity) of the coating layer.

Here, the hydroxyl group (—OH) may be directly bonded to the main chain of the copolymer (A) or may be bonded like —Z—OH via the divalent organic group (Z). May be. Z is exemplified by the same divalent organic group as described above.

The hydroxyl group is introduced into the copolymer by copolymerizing (a1) an unsaturated monomer containing one or more hydroxyl groups in the molecule with another unsaturated monomer. Examples of such component (a1) include vinyl monomers having a hydroxyl group in the molecule, acrylates having a hydroxyl group in the molecule, methacrylates having a hydroxyl group in the molecule, and a hydroxyl group in the molecule. Allyl compounds having a hydroxyl group in the molecule, unsaturated carboxylic acid amide compounds having a hydroxyl group in the molecule, unsaturated fatty acids having a hydroxyl group in the molecule, unsaturated fatty acid esters having a hydroxyl group in the molecule, and Examples include monomers obtained by addition reaction of various hydroxyl group-containing monomers with ε-caprolactone adduct. These can be used alone or in combination of two or more.

Specific examples of the component (a1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl. (Meth) acrylate, methyl (2-hydroxymethyl) acrylate, ethyl (2-hydroxymethyl) acrylate, butyl (2-hydroxymethyl) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, glycerin mono (meth) (Meth) acrylic acid esters such as acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate; allyl alcohol, 2-hydro Allyl compounds such as cyethyl allyl ether; vinyl ether compounds such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and 6-hydroxyhexyl vinyl ether; unsaturated carboxylic acids such as N-methylol (meth) acrylamide and N-methylolcrotonamide Acid amide compounds; hydroxyl group-containing unsaturated fatty acids such as ricinoleic acid; hydroxyl group-containing unsaturated fatty acid esters such as alkyl ricinoleate and a single amount obtained by addition reaction of these hydroxyl group-containing monomers with an ε-caprolactone adduct Examples include the body.

As the component (a1), acrylic acid esters or methacrylic acid esters having a hydroxyalkyl group in the molecule can be preferably exemplified, and more specifically, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate. , 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, a hydroxyl group-containing vinyl monomer.

The copolymer (A) according to the present invention has a carbosiloxane dendrimer structure and a hydroxyl group in the molecule, and is obtained by copolymerizing the components (a1) and (a2). However, it may be a copolymer obtained by optionally using (a3) an unsaturated monomer that does not contain a hydroxyl group in the molecule. In particular, the unsaturated monomer which is the component (a3) is suitable as a part of the main chain of the copolymer (A), and if desired, a different functional group can be added to the copolymer ( Suitable as a means to be introduced into A). Further, by using these monomers in combination, a cost-effective copolymer can be obtained while imparting desired properties such as blocking resistance and leveling properties to the coating layer. In some cases, properties such as solubility can be further improved by selecting a saturated monomer.

(A3) The unsaturated monomer which is a component is a vinyl-type monomer, Comprising: The thing which does not have a hydroxyl group can be illustrated suitably. Specifically, lower alkyl acrylates or methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate; acrylic acid Glycidyl, glycidyl methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, Lower acrylate or methacrylate having a C _1-6 lower alkyl group such as n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate; acrylic Higher acrylates or methacrylates such as 2-ethylhexyl acid, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate; lower grades such as vinyl acetate and vinyl propionate Fatty acid vinyl ester; higher fatty acid ester such as vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate; styrene, vinyl toluene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, Aromatic vinyl monomers such as vinyl pyrrolidone; dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl Amino group-containing vinyl monomers such as acrylate and diethylaminoethyl methacrylate; acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N Amide group-containing vinyl monomers such as methoxymethylmethacrylamide, isobutoxymethoxyacrylamide, isobutoxymethoxymethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide; acrylic acid, methacrylic acid, itaconic acid , Crotonic acid, fumaric acid, maleic acid and other carboxylic acid-containing vinyl monomers; tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, butoxyethyl Ether-based vinyl monomers such as polyacrylate, butoxyethyl methacrylate, cetyl vinyl ether, 2-ethylhexyl vinyl ether; polydimethylsiloxane containing an acrylic or methacrylic group at one end, and a polydimethylsiloxane containing an alkenylaryl group at one end Unsaturated group-containing silicone compounds such as dimethylsiloxane; butadiene; vinyl chloride; vinylidene chloride; acrylonitrile, methacrylonitrile; dibutyl fumarate; maleic anhydride; dodecyl succinic anhydride; acrylic glycidyl ether, methacryl glycidyl ether; 4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid Radical polymerizable unsaturated carboxylic acid alkali metal salts, ammonium salts, organic amine salts, radical polymerizable unsaturated monomers having a sulfonic acid group such as styrene sulfonic acid, and their alkali metal salts, ammonium salts, organic Amine salts; quaternary ammonium salts derived from acrylic acid or methacrylic acid such as 3-methacryloxypropyltrimethylammonium chloride, methacrylic acid esters of alcohols having tertiary amine groups such as diethylamine ester of methacrylic acid and their 4 A quaternary ammonium salt is exemplified. A lower acrylate or methacrylate having a C _1-6 lower alkyl group is preferred.

Such a component (a3) may be an unsaturated monomer having a silicon atom-bonded alkoxy group. Specifically, methacryloxypropyltriethoxysilane, acryloxypropyltriethoxysilane, methacryloxy Examples include propyltrimethoxysilane, acryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (2-methoxyethoxy) silane.

Moreover, a polyfunctional vinyl-type monomer can also be used as (a3) component, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butane. Diol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trioxyethyl acrylate , Trimethylolpropane trioxyethyl methacrylate, and unsaturated group-containing silicone compounds such as polydimethylsiloxane blocked with alkenyl aryl groups at both ends of the molecular chain .

Further, a vinyl monomer containing a fluorinated organic group may be used as the component (a3). The vinyl monomer containing the fluorinated organic group is preferably represented by the general formula: CH ₂ = CR ¹⁵ COOR ^f . In the formula, R ¹⁵ is a hydrogen atom or a methyl group, R ^f is a fluorinated organic group, and examples thereof include a fluoroalkyl group and a fluoroalkyloxyfluoroalkylene group as described above. Specific examples of such component (a3) include compounds represented by the following formulae. In the following formula, z is an integer of 1 to 4. CH ₂ = CCH ₃ COO-CF ₃ , CH ₂ = CCH ₃ COO-C ₂ F ₅ , CH ₂ = CCH ₃ COO-nC ₃ F ₇ , CH ₂ = CCH ₃ COO-CF (CF ₃ ) ₂ , CH ₂ = CCH ₃ COO-nC ₄ F ₉ , CH ₂ = CCH ₃ COO-CF ₂ CF (CF ₃ ) ₂ , CH ₂ = CCH ₃ COO-nC ₅ F ₁₁ , CH ₂ = CCH ₃ COO-nC ₆ F ₁₃ , CH ₂ = CCH ₃ COO-nC ₈ F ₁₇ , CH ₂ = CCH ₃ COO-CH ₂ CF ₃ , CH ₂ = CCH ₃ COO-CH (CF ₃ ) ₂ , CH ₂ = CCH ₃ COO-CH ₂ CH (CF ₃ ) ₂ , CH ₂ = CCH ₃ COO-CH ₂ (CF ₂ ) ₂ F, CH ₂ = CCH ₃ COO-CH ₂ (CF ₂ ) ₃ F, CH ₂ = CCH ₃ COO-CH ₂ (CF ₂ ) ₄ F, CH ₂ = CCH ₃ COO-CH ₂ (CF ₂ ) ₆ F, CH ₂ = CCH ₃ COO-CH ₂ (CF ₂ ) ₈ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CF ₃ , CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₂ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₃ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₄ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₆ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₈ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ ( CF ₂ ) ₁₀ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₁₂ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₁₄ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₁₆ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CH ₂ CF ₃ , CH ₂ = CCH ₃ COO-CH ₂ CH ₂ C H ₂ (CF ₂ ) ₂ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CH ₂ (CF ₂ ) ₂ H, CH ₂ = CCH ₃ COO-CH ₂ (CF ₂ ) ₄ H, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₃ H, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _z -OC ₃ F ₇ , CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CF ₂ CF _2- [OCF ₂ CF (CF ₃ )] _z -OC ₃ F ₇ CH ₂ = CHCOO-CF ₃ , CH ₂ = CHCOO-C ₂ F ₅ , CH ₂ = CHCOO- nC ₃ F ₇ , CH ₂ = CHCOO-CF (CF ₃ ) ₂ , CH ₂ = CHCOO-nC ₄ F ₉ , CH ₂ = CHCOO-CF ₂ CF (CF ₃ ) ₂ , CH ₂ = CHCOO-nC ₅ F ₁₁ , CH ₂ = CHCOO-nC ₆ F ₁₃ , CH ₂ = CHCOO-nC ₈ F ₁₇ , CH ₂ = CHCOO-CH ₂ CF ₃ , CH ₂ = CHCOO-CH (CF ₃ ) ₂ , CH ₂ = CHCOO-CH ₂ CH (CF ₃ ) ₂ , CH ₂ = CHCOO-CH ₂ (CF ₂ ) ₂ F, CH ₂ = CHCOO-CH ₂ (CF ₂ ) ₃ F, CH ₂ = CHCOO-CH ₂ (CF ₂ ) ₄ F, CH ₂ = CHCOO-CH ₂ (CF ₂ ) ₆ F, CH ₂ = CHCOO-CH ₂ (CF ₂ ) ₈ F, CH ₂ = CHCOO-CH ₂ CH ₂ CF ₃ , CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₂ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₃ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₄ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₆ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₈ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₁₀ F, CH ₂ = CHCOO -CH ₂ CH ₂ (CF ₂ ) ₁₂ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₁₄ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₁₆ F, CH ₂ = CHCOO-CH ₂ CH ₂ CH ₂ CF ₃ , CH ₂ = CHCOO-CH ₂ CH ₂ CH ₂ (CF ₂ ) ₂ F, CH ₂ = CHCOO-CH ₂ CH ₂ CH ₂ (CF ₂ ) ₂ H, CH ₂ = CHCOO-CH ₂ (CF ₂ ) ₄ H, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₃ H, CH ₂ = CHCOO-CH ₂ CH ₂ CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _{z- OC 3 F 7, CH 2 =} CHCOO-CH 2 CH 2 CF 2 CF 2 - [OCF 2 CF (CF 3)] z -OC 3 F 7.

Among these, a vinyl monomer represented by the following formula is preferable. CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₆ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₈ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF
_{2) 6 F, CH 2 =} CCH 3 COO-CH 2 CH 2 (CF 2) 8 F, CH 2 = CHCOO-CH 2 CF 3, CH 2 = CCH 3 COO-CH 2 CF 3. In particular, a vinyl monomer represented by the following formula is more preferable. _{CH 2 = CHCOO-CH 2 CF} 3, CH 2 = CCH 3 COO-CH 2 CF 3.

The copolymer (A) is a copolymer obtained by copolymerizing the unsaturated monomers (a1), (a2) and optionally (a3), and the copolymerization ratio is arbitrary. When the mass of all unsaturated monomers, which is the sum of the masses of unsaturated monomers (a1) to (a3), is 100 parts by mass, the mass ratio of each component is (a1) :( a2): (A3) = 0.1-99.9: 0.1-99.9: 0 can be appropriately set within the range of 0-99.8, and (a1) :( a2) :( a3) = 0. It is preferable that it exists in the range of 5-50.0: 0.5-80.0: 0-99.0, (a1) :( a2) :( a3) = 3.0-30.0: 2.0 More preferably, it is in the range of ˜70.0: 0 to 95.0, and (a1) :( a2) :( a3) = 5.0 to 20.0: 7.0 to 60.0: 20.0 ~ 88.0 range It is particularly preferred in the. Further, the copolymer (A) satisfying the condition of {mass of component (a2)} ≧ {mass of component (a1)} is particularly preferable.

The copolymer (A) obtained at the above polymerization ratio is particularly excellent in solubility in the curable resin because the group having a carbosiloxane dendrimer structure and the hydroxyl group are introduced into the main chain at a predetermined ratio. In the synthesis in a solvent, it is not cloudy and is in a transparent state, and it is useful in that it is particularly excellent in the stability over time of the additive for coating agents and the blending stability with respect to any coating agent. In addition, the coating layer after curing has excellent uniformity, transparency, solvent resistance, stain resistance and water repellency even with a very small addition amount compared to a copolymer containing no hydroxyl group and carbosiloxane dendrimer structure. There is an advantage that can be imparted.

As the copolymerization method, a radical polymerization method or an ionic polymerization method is used. Among them, the radical polymerization method is preferable, and the solution polymerization method is particularly preferably used. This solution polymerization is performed by reacting each unsaturated monomer in a solvent in the presence of a radical initiator at a temperature of 50 to 150 ° C. for 3 to 20 hours. Solvents used here include aliphatic hydrocarbons such as hexane, octane, decane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane; acetone and methyl ethyl ketone , Ketones such as methyl isobutyl ketone and diisobutyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate; alcohols such as methanol, ethanol, isopropyl alcohol and butanol; octamethylcyclotetrasiloxane and decamethylcyclo Illustrative are organosiloxane oligomers such as pentasiloxane, hexamethyldisiloxane and octamethyltrisiloxane. As the radical initiator, conventionally known compounds generally used in radical polymerization methods are used. Specifically, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methyl) is used. Azobis compounds such as butyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate); benzoyl peroxide, lauroyl peroxide And organic peroxides such as tert-butylperoxybenzoate and tert-butylperoxy-2-ethylhexanoate. This radical initiator may be used individually by 1 type, and may mix and use 2 or more types. It is preferable that the usage-amount of a radical initiator is the range of 0.1-5 mass parts with respect to a total of 100 mass parts of said (a1) component-(a3) component. Moreover, a chain transfer agent can be added at the time of superposition | polymerization. Specific examples of this chain transfer agent include mercapto compounds such as 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, and polydimethylsiloxane having a mercaptopropyl group; methylene chloride, chloroform, four Halides such as carbon chloride, butyl bromide and 3-chloropropyltrimethoxysilane are exemplified.

After the polymerization, a method of removing the remaining unreacted vinyl monomer by treating under reduced pressure with heating, or no bromination by hydrogenation reaction in the absence of solvent or solvent in the presence of a hydrogenation catalyst. It can be purified using a method of treating and contacting nitrogen gas under reduced pressure to distill off the light matter. In particular, such refined products are preferably used when used for external preparations that require reduction in odor and compatibility with other cosmetic ingredients. In the hydrogenation reaction and stripping step, the solvent, reaction conditions, reduced pressure conditions and the like used for purification of a known organopolysiloxane copolymer can be used and selected without particular limitation.

The number average molecular weight of the copolymer (A) used in the present invention is preferably 3,000 to 2,000,000, and more preferably 5,000,000, in view of ease of blending as a raw material for the coating agent. 000-800,000. Examples of the property include liquid, gum, paste, solid, and powder, and a solution or dispersion by dilution of a solvent is preferable.

The additive for a coating agent according to the present invention can be blended in a desired coating agent. The main component of the coating agent is composed of an organic resin capable of thermosetting or room temperature curing that can be used for a paint or a coating agent, and a curing agent, and a curing catalyst may be added as necessary. More specifically, the organic resin is an organic resin selected from alkyd resins, acrylic resins, polyester resins, polyurethane resins, and mixtures thereof, and is a copolymer used in the present invention. The thing which does not correspond to (A) is illustrated.

The additive for a coating agent according to the present invention is particularly compatible with a coating agent containing an acrylic resin, particularly compatibility, uniformity with respect to a cured coating layer, transparency, solvent resistance, stain resistance, repellent properties. The effect of improving aqueous properties is remarkable. The acrylic resin that is the main component of the coating agent does not correspond to the copolymer (A) used in the present invention, and is an acrylic resin that does not contain a carbosiloxane dendrimer structure in the side chain.

The coating agent according to the present invention preferably contains an additive for a coating agent containing the copolymer (A), an acrylic resin, and a curing agent, and further, if necessary, a curing catalyst. It may be added. The copolymer (A), the acrylic resin, and the curing agent may be used in combination of two or more components.

Preferred acrylic resins are those obtained by polymerizing monomers that are mainly acrylic acid esters or acrylic acid esters among the above unsaturated monomers, and preferably one molecule of hydroxyl group. The thing which contains 2 or more inside can be mentioned. Such acrylic resins include acrylic monomers or acrylic esters among the unsaturated monomers, acrylic esters having a hydroxyl group in the molecule, and methacrylic groups having a hydroxyl group in the molecule. It can be obtained by polymerizing an unsaturated monomer having a hydroxyl group in the molecule such as an acid ester. In addition, such an acrylic resin having a hydroxyl group may be referred to as an “acrylic polyol resin”, and commercially available products such as “Acridic (trademark), Bernock (trademark)” manufactured by Dainippon Ink and Chemicals, Inc. Etc. Such acrylic resins can be used alone or in combination of two or more.

Examples of the curing agent include isocyanate compounds and melamine compounds. Specific examples of the isocyanate compound include aliphatic xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or polyhydric alcohol addition type, burette type, trimer type, aromatic tolylene diisocyanate, diphenylmethane diisocyanate and other polyisocyanates. Compounds, and blocked isocyanate compounds. Commercially available isocyanate compounds include, for example, “Bernock (trademark)” manufactured by Dainippon Ink and Chemicals, “Sumijour (trademark)” manufactured by Bayer Sumitomo Urethane Co., Ltd., and Takeda Pharmaceutical Co., Ltd. "Takenate (trademark)", Nippon Polyurethane Industry Co., Ltd. "Coronate (trademark)", Asahi Kasei Kogyo Co., Ltd. "Duranate (trademark)", etc. are mentioned. An isocyanate compound can be used individually by 1 type, and can also be used in combination of 2 or more type.

Specific examples of the melamine compound include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, isobutyl ether type melamine, and n-butyl ether type melamine. These melamine compounds can be used alone or in combination of two or more. As for the usage-amount of this melamine compound, 1-30 mass parts is preferable with respect to 100 mass parts of resin components of a coating agent.

The coating agent of the present invention particularly preferably contains a compound having an isocyanate group as the curing agent. This is because the copolymer (A) has a hydroxyl group and thus has excellent reactivity with respect to an isocyanate group, and reacts with the curing agent to be efficiently incorporated into the curing system of the coating agent. Suitable curing agents are the same as the aforementioned isocyanate compounds.

In the coating agent of the present invention, the amount of the curing agent used can be selected as desired, but when the curing agent is a compound having an isocyanate group, it is equivalent to 1 equivalent of a hydroxyl (—OH) group in the coating agent. On the other hand, the amount of the isocyanate (—NCO) group of the isocyanate compound is preferably in the range of 0.1 to 2.0. Here, the hydroxyl group in the coating agent is mainly the sum of the hydroxyl groups contained in the acrylic resin having a hydroxyl group and the copolymer (A) which is the additive for coating agent according to the present invention. Particularly, the equivalent ratio of —OH / —NCO is 1.0 / 0.00 in the range in which the isocyanate group is 0.5 to 1.5 equivalents with respect to 1 equivalent of the hydroxyl group in the coating agent. A range of 5 to 1.0 / 1.5 is preferable. More preferably, it is in the range of the equivalent ratio of 1 / 0.7 to 1.2. Within this range, the coating agent containing an acrylic resin can be cured stably without causing foaming or poor curing. On the other hand, when the amount of isocyanate group used is less than 0.1 mol per mol of hydroxyl group, the coating layer obtained after curing may not have sufficient stain resistance, water repellency and non-adhesiveness. Moreover, when the usage-amount of the isocyanate group with respect to 1 mol of hydroxyl groups exceeds 2 mol, the workability of the coating layer obtained after hardening may become inferior. In addition, each usage-amount can be calculated by a well-known and usual method from the hydroxyl value of a copolymer (A) and acrylic resin, and content of the isocyanate group of an isocyanate compound.

The curing catalyst can be optionally blended, and examples thereof include organometallic compounds, amine compounds, and acidic compounds. Specific examples of the organometallic compound include tin octylate, di-n-butyltin dioctate, di-n-butyltin dilaurate, di-n-octyltin bis (isooctylthioglycolate), and di-n-butyltin. Organic tin compounds such as sulfide and di-n-octyltin oxide; Organic titanium compounds such as tetraisopropoxy titanium, tetra-n-butoxy titanium, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate; aluminum isopropylate And organoaluminum compounds such as aluminum tris (acetylacetonate); zinc octylate, magnesium naphthenate and the like. Examples of the amine compound include triethylamine, ethylenediamine, diethylenetriamine, dimethylaminoethanol, and isophoronediamine. Examples of the acidic compound include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, phthalic acid, phthalic anhydride, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, and these organic amine block compounds. These curing catalysts can be used alone or in combination of two or more as required. It is preferable that the usage-amount of this curing catalyst shall be 0.001-5 mass parts with respect to 100 mass parts of resin components of a coating agent.

Additives include dehydrating agents, pigments, dispersants, antifoaming agents, thickeners, anti-settling agents, anti-sagging agents, leveling agents, matting agents, anti-scratch agents, UV absorbers, light stabilizers, and antioxidants. An agent, an antibacterial agent, etc. are mentioned, These can use 1 or more types.

Examples of dehydrating agents include dimethoxymethane, 1,1-dimethoxyethane, 1,1-dimethoxypropane, 1,1-dimethoxybutane, 1,1-dimethoxycyclohexane, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, orthoacetic acid. Ethyl, dimethyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ- Examples include hydrolysable esters such as aminopropyltriethoxysilane, methyl silicate, and ethyl silicate. By adding this, water in the system can be removed, and the storage stability can be further improved. It is preferable that the usage-amount of this dehydrating agent shall be 0.1-50 mass parts with respect to 100 mass parts of resin components of a coating agent.

There is no restriction | limiting in particular in the usage-amount of another additive, According to a use, it can add and use the usage-amount of a well-known usual additive with respect to curable resin coating agent.

As a method for applying the coating agent of the present invention to a substrate, a known and commonly used application method for the curable resin coating agent can be selected without particular limitation depending on the shape of the substrate and the purpose of coating. Specifically, any of bar coater method, roll coater method, blade coater method, gravure coater method, beat coater method, curtain flow coater method, dip coating method and spray coating method may be used. It can be applied on both sides, part or all.

After coating, it can be cured at any temperature from room temperature to 300 ° C., but it is preferable to heat and dry at a temperature of 60 to 250 ° C. for 5 seconds to 60 minutes in order to promote the volatilization of the solvent and the crosslinking reaction. . The higher the curing temperature, the shorter the curing time, and the curing time can be further shortened by using a curing catalyst in combination. Moreover, in order to accelerate | stimulate a crosslinking reaction, the coating material after application | coating drying can also be cured for 1 to 7 days at the temperature of 30-120 degreeC.

The thickness of the coating film when applying the coating agent of the present invention can be selected without particular limitation depending on the shape of the substrate and the purpose of coating, but is usually in the range of 0.1 to 100 μm, 0.5 ˜50 μm is preferred.

Examples of the material to which the coating agent of the present invention is applied include metals, inorganic materials, plastics, and composite materials. Examples of the metal include stainless steel, aluminum, tinplate, tin, mild steel plate, copper, brass, various plated steel plates, and titanium. A metal substrate subjected to a surface treatment such as a chemical conversion treatment or an alumite treatment can also be suitably used. Examples of the inorganic material include glass, mortar, slate, concrete, and tile. Examples of the plastic include molded products such as polypropylene, polyethylene, acrylic, polycarbonate, polystyrene, polyethylene terephthalate, nylon, polyester, rubber, and elastomer subjected to surface treatment, and products obtained by processing these into a film. Examples of the composite material include fiber reinforced thermosetting plastic (FRP), fiber reinforced thermoplastic plastic (FRTP), a laminated plate, a sandwich material in which a metal and an organic material are pressure-bonded, and a metal vapor deposited film plastic.

The coating layer formed by curing the coating agent of the present invention is excellent in uniformity, transparency, solvent resistance, stain resistance, water repellency, etc., for example, oil stains, dust and dirt in the air, exhaust gas, Prevents various contaminants such as dirt, graffiti, and stickers mixed in rainwater; effective in preventing snow accretion, icing and adhesion of aquatic organisms. Specific applications include prevention of oil stains around kitchen ranges, storage doors, ventilation fans and lighting covers; prevention of dirt on the outer walls of concrete, tiles, etc .; prevention of dirt from exhaust gases such as road tunnels and highway noise barriers; outer walls , Prevention of adhesion of graffiti and stickers on public telephone boxes, telephone poles, public toilets, etc .; prevention of snow and icing on roofs, electric wires, etc .; prevention of adhesion of barnacles adhering to the bottom of general ships;

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. The viscosity is a measured value at 25 ° C., and various properties of the copolymer (A) were measured by the following methods.

[Method for Measuring Viscosity of Copolymer] The kinematic viscosity of the copolymer was measured by a capillary viscosity measurement method using an Ubbelohde viscometer. [Method of measuring molecular weight and degree of dispersion of copolymer] The molecular weight and degree of dispersion of the copolymer were measured by gel permeation chromatography (GPC). The molecular weight of the obtained copolymer was shown by the number average molecular weight in terms of polystyrene. [Method for Measuring Copolymer Solid Content Concentration] After weighing 1 g of the silicone-modified vinyl copolymer obtained in each example in an aluminum dish, it was heated in an oven at 150 ° C. for 2 hours, The solid content concentration was calculated from the volatile content (g).

[Example 1] 355 g of butyl acetate was charged in a 1000 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, and heated and stirred at 70 ° C under a nitrogen atmosphere. To this butyl acetate, (a-3-1) 102.5 g of methyl methacrylate, (a-3-2) 22.5 g of n-butyl acrylate, (a-1-1) 25 g of 2-hydroxyethyl methacrylate, (A-2-1) 100 g of a vinyl monomer having a carbosiloxane dendrimer structure represented by the following formula,

およびラジカル重合開始剤 Ｖ−６０１（和光純薬（株）製）２．５ｇを２時間かけて滴下した。滴下終了後、７０℃で６時間反応させたところ、ポリスチレン換算数平均分子量が８２００、分散度９．２４、動粘度１０８．２６ｍｍ^２／ｓ、固形分濃度３６．９％のシリコーン変性ビニル系共重合体（Ａ１）を含有するコーティング剤用添加剤を得た。

And 2.5 g of radical polymerization initiator V-601 (made by Wako Pure Chemical Industries, Ltd.) was dripped over 2 hours. After the completion of addition, it was allowed to react for 6 hours at 70 ° C., a polystyrene-reduced number-average molecular weight of 8200 and a dispersity 9.24, kinematic viscosity 108.26mm ² / s, a solid content concentration 36.9% of silicone-modified vinyl copolymer The additive for coating agents containing a polymer (A1) was obtained.

[Example 2] Instead of the component (a-2-1) in Example 1, (a-2-2) a vinyl monomer having a carbosiloxane dendrimer structure represented by the following formula

を用いた以外は、実施例１と同様にして、ポリスチレン換算数平均分子量が２５３００、分散度６．９２、動粘度４２２．６９ｍｍ^２／ｓ、固形分濃度４０．４％のシリコーン変性ビニル系共重合体（Ａ２）を含有するコーティング剤用添加剤を得た。

In the same manner as in Example 1, a silicone-modified vinyl copolymer having a polystyrene-equivalent number average molecular weight of 25300, a dispersity of 6.92, a kinematic viscosity of 422.69 mm ² / s, and a solid content concentration of 40.4% was used. The additive for coating agents containing a polymer (A2) was obtained.

[Comparative Example 1] In Example 1, instead of the component (a-2-1), the formula:

で表される直鎖状ポリシロキサン構造を有するビニル系単量体を用いた以外は、実施例１と同様にして、ポリスチレン換算数平均分子量が１２９００、分散度９．０４、動粘度４０４．９３ｍｍ^２／ｓ、固形分濃度３９．１％のシリコーン変性ビニル共重合体（Ｂ１）を含有するコーティング剤用添加剤を得た。

The number average molecular weight in terms of polystyrene was 12900, the degree of dispersion was 9.04, and the kinematic viscosity was 404.93 mm, except that a vinyl monomer having a linear polysiloxane structure represented by the following formula was used. An additive for a coating agent containing a silicone-modified vinyl copolymer (B1) having a ² / s solid content concentration of 39.1% was obtained.

[Comparative Example 2] In Example 1, instead of the component (a-2-1), the formula:

で表される直鎖状ポリシロキサン構造を有するビニル系単量体を用いた以外は、実施例１と同様にして、ポリスチレン換算数平均分子量が２７００、分散度９．９４、動粘度２１．６７ｍｍ^２／ｓ、固形分濃度３１．７％の白濁したシリコーン変性ビニル系共重合体（Ｂ２）を含有するコーティング剤用添加剤を得た。

The number average molecular weight in terms of polystyrene was 2700, the degree of dispersion was 9.94, and the kinematic viscosity was 21.67 mm, except that a vinyl monomer having a linear polysiloxane structure represented by An additive for coating agent containing a cloudy silicone-modified vinyl copolymer (B2) having a solid content concentration of ² / s and a solid content of 31.7% was obtained.

[Comparative Example 3] In Example 1, instead of the component (a-2-1), the formula:

で表される直鎖状ポリシロキサン構造を有するビニル系単量体を用いた以外は、実施例１と同様にして、ポリスチレン換算数平均分子量が６９００、分散度７．６３、動粘度２０５２．７９ｍｍ^２／ｓ、固形分濃度３７．８％の白濁したシリコーン変性ビニル系重合体（Ｂ３）を含有するコーティング剤用添加剤を得た。

The number average molecular weight in terms of polystyrene was 6900, the degree of dispersion was 7.63, and the kinematic viscosity was 2052.79 mm, except that a vinyl monomer having a linear polysiloxane structure represented by the following formula was used. An additive for a coating agent containing a cloudy silicone-modified vinyl polymer (B3) having a solid content concentration of 37.8% at ² / s was obtained.

Evaluation of the coating agent containing the silicone-modified vinyl polymer obtained in Examples 1 and 2 and Comparative Examples 1 to 3 was performed as follows. In each experimental example, the amount of the silicone-modified vinyl polymer added is 1 mol% with respect to the amount of all hydroxyl groups in the acrylic polyol resin (hereinafter referred to as “total polyol”). did.

[Evaluation of Coating Agent] 16.1 g of coating agent additive (OH number 43.2) adjusted to a concentration of 3 wt% using butyl acetate (amount that is 1 mol% based on the total polyol), acrylic polyol resin {"Acridick (trademark) A-829" manufactured by Dainippon Ink & Chemicals, Inc. (solid content concentration 60 wt%, OH number 44)} 78.3 g, polyisocyanate compound {manufactured by Dainippon Ink & Chemicals, Inc. "Bernock (trademark) D-950" (solid content concentration 75%, NCO content 12.5%)} 25.0 g and diluting solvent (butyl acetate) 101.3 g were stirred and mixed. A coating agent (molar ratio: NCO / OH = 1.5) containing a polymer was obtained.

The above coating agent is applied to an aluminum plate (JIS H 4000.5 × 50 × 150 mm) with a Meyer bar, heated at 150 ° C. for 15 minutes to be cured, and the coating layer (coating film) has a dry film thickness of 10 μm. An aluminum plate was obtained. Using the coated aluminum plate thus obtained, each characteristic was evaluated according to the following criteria. The results are shown in Table 1.

[Appearance] The appearance of the obtained coating film was visually observed and evaluated according to the following criteria. ○: A transparent coating film. Δ: The coating film has slight turbidity or unevenness. X: The coating film is cloudy. [Solvent resistance] A rubbing tester (manufactured by Ohira Rika Kogyo Co., Ltd.) is attached with felt soaked in xylene, applied with a load of 1.2 kg, and visually observed the state of the coating film after rubbing the coating film surface 100 times. And evaluated according to the following criteria. ○: No change in surface appearance △: Little change in surface appearance ×: Change in surface appearance [Contamination resistance] Marked with a blue ink pen (Magic ink, manufactured by Pentel Co., Ltd.) on the cured coating film for 10 minutes After air drying, it was wiped off with a Kimwipe. The method of repelling and wiping off the magic ink during marking was visually observed and evaluated according to the following criteria. ○: Magic ink is repelled and can be easily wiped off. X: There is no repelling of the magic ink, and it is difficult to wipe off the printed portion. [Water contact angle] A water drop was brought into contact with the cured coating film, and the contact angle of water was measured with a contact angle meter (DM-700, manufactured by Kyowa Interface Chemical Co., Ltd.). [Pencil hardness] Measured by a method according to the pencil scratch test according to JIS K5400, paragraphs 6 and 14. [Friction coefficient] Using a friction tester (Haydon-14 type, manufactured by Shinto Kagaku Co., Ltd.), measurement was performed under the conditions of a 10φ × 15 mm SUS cylinder, a load of 50 g, and a tensile speed of 100 mm / min.

With an additive for a coating agent having an existing linear polysiloxane, even when the addition amount is as small as 1 mol% based on the total polyol, the appearance of the coating film becomes cloudy and a uniform coating film cannot be obtained. On the other hand, the additive for coating agent of the present invention has a characteristic that it is excellent in compatibility with the curable resin component which is the main component of the coating agent, and a uniform and transparent coating film can be obtained. Further, by using the silicone-modified vinyl copolymer (A1) having the second-generation carbosiloxane dendrimer structure shown in Example 1, in addition to the above properties, a coating having stain resistance, water repellency, etc. It was confirmed that a coating agent having excellent layer characteristics can be obtained.

The additive for a coating agent of the present invention is a copolymer having a carbosiloxane dendrimer structure and a hydroxyl group in the side chain, and can be made into a transparent resin solution. In addition, the coating agent containing the additive for a coating agent of the present invention has a solvent resistance, stain resistance, and repellency to the coating layer (coating film) obtained after curing even with a very small amount of addition due to the effect of the carbosiloxane dendrimer structure. Water and the like are imparted. For this reason, the coating agent of the present invention can impart stain resistance as a surface protecting agent by applying it to various articles, such as oil stains, dirt and dust in the air, exhaust gas, dirt mixed in rainwater, etc. Can be used for a wide variety of soil types. The additive for coating agents according to the present invention is also useful as a compounding ingredient in general paints and coating agents, and other silicones that are water repellent while suppressing smoothness, such as painting on floors of gymnasiums. This is also effective when it is desired to impart the above characteristics.

Claims (11)

The additive for coating agents containing the copolymer (A) which contains the group which has a carbosiloxane dendrimer structure shown by following formula (1) in a molecule | numerator, and a hydroxyl group.

{In the formula, Z is a divalent organic group, p is 0 or 1, and R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group. L ¹ is a silylalkyl group represented by the following structural formula (2) when i = 1

Wherein Z and p are the same as above, R ¹ and R ² are the same as above, i is an integer of 1 to 10 indicating the total number of layers of the silylalkyl group, and L ^{i + 1} is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group and the silylalkyl group, provided that i = c (c is the silylalkyl group). L ^{i + 1} represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and when i <c, A silylalkyl group and a ⁱ is an integer of 0 to 3)} The coating agent according to claim 1, wherein the copolymer (A) is a copolymer obtained by copolymerizing at least one kind of each of the following unsaturated monomers (a1) and (a2). Additives. (A1) Unsaturated monomer containing one or more hydroxyl groups in the molecule (a2) Unsaturated monomer capable of radical polymerization represented by the following formula (1 ′)

(Wherein Y is a radically polymerizable unsaturated group, and Z, p, R ¹ , R ² , L ¹ and a ⁱ are the same as above) In the radically polymerizable unsaturated monomer represented by the above formula (1 ′), the radically polymerizable unsaturated group Y has a general formula:

(Wherein R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkylene group having 1 to 10 carbon atoms),

(Wherein R ⁴ and R ⁵ are as defined above), an acrylic group or methacryl group-containing organic group represented by the general formula:

Wherein R ⁶ is a hydrogen atom or a methyl group, R ⁷ is an alkyl group having 1 to 10 carbon atoms, R ⁸ is an alkylene group having 1 to 10 carbon atoms, and b is 0 to 4 Is an integer selected from the group consisting of an alkenylaryl group-containing organic group represented by (2) and an alkenyl group having 2 to 10 carbon atoms. Additive for coating agent. The coating according to claim 2, wherein the copolymer (A) is a copolymer obtained by copolymerizing at least one or more kinds of (a3) unsaturated monomers not containing a hydroxyl group in the molecule. Additive for pharmaceuticals. The copolymer (A) is a copolymer obtained by copolymerizing the unsaturated monomers (a1), (a2) and optionally (a3) as the structural unit. When the sum of the masses of the unsaturated monomers (a1) to (a3) constituting is 100 parts by mass, the mass ratio is (a1) :( a2) :( a3) = 0.5 to 50.0. The additive for a coating agent according to any one of claims 2 to 4, wherein the additive is in the range of 0.5 to 50.0: 0 to 99.0. The unsaturated monomer (a1) constituting the copolymer (A) is at least one selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. The additive for coating agents according to any one of claims 1 to 5, which is an unsaturated monomer containing a hydroxyl group. The coating agent containing the additive for coating agents of any one of Claims 1-6. The coating agent containing the additive for coating agents of any one of Claims 1-6, acrylic resin (however, this acrylic resin does not contain a carbosiloxane dendrimer structure in a side chain), and a hardening | curing agent. The coating agent according to claim 8, wherein the acrylic resin contains two or more hydroxyl groups in one molecule. The coating agent according to claim 8, wherein the curing agent is a compound having an isocyanate group. Curing comprising the additive for a coating agent according to any one of claims 1 to 6, an acrylic resin (however, the acrylic resin does not contain a carbosiloxane dendrimer structure in a side chain) and a compound having an isocyanate group. A coating agent comprising an agent, wherein the amount of NCO groups in the isocyanate compound is within a range of 0.1 to 2.0 with respect to 1 equivalent of a hydroxyl group in the coating agent.