JP6067206B2 - Curable composition and article having a cured layer of the composition - Google Patents

Description

The present invention relates to a curable composition that forms a cured layer having high hardness and excellent uniformity, transparency, solvent resistance, stain resistance, and water repellency. Furthermore, the present invention relates to an article having a cured layer formed by curing the curable composition.

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 the molecular weight of the polyorganosiloxane is increased, the compatibility of the resin with various materials is greatly reduced, and when incorporated into a curing system, the appearance becomes cloudy, resulting in insufficient contamination and water repellency. However, there is a problem that the hardness is remarkably lowered. For this reason, this resin has a problem that it is difficult to use it for the use of articles that require contamination resistance, hardness, and durability, and it can be applied only to limited use by itself.

JP-A-61-78806

An object of the present invention is to provide a curable composition that provides a cured layer having excellent uniformity, transparency, solvent resistance, stain resistance, water repellency, and high hardness. Furthermore, this invention aims at providing the articles | goods which have a hardened layer which shows said characteristic.

As a result of intensive studies to solve the above problems, the present inventors have a specific carbosiloxane dendrimer structure that gives properties such as high water repellency in the molecule, and are reactive to the resin. By using the copolymer (A) having a hydroxyl group introduced as a functional group as a main component of a curable composition of an isocyanate / melamine curing system having reactivity with a hydroxyl group, the copolymer has excellent transparency, stain resistance, and water repellency. The inventors have found that a curable composition having high hardness can be obtained, and have reached the present invention.

That is, an object of the present invention is to provide a copolymer (A) containing a specific carbosiloxane dendrimer structure and a hydroxyl group in the molecule, and one or more curing agents (B) selected from the group consisting of isocyanate compounds and melamine compounds. This is solved by a curable composition containing a curable composition containing. Moreover, the subject of this invention is solved by the article | item which has a hardened layer formed by hardening | curing the said curable composition.

That is, the above object is selected from the group consisting of [1] a copolymer having a carbosiloxane dendrimer structure represented by the following formula (1) and a hydroxyl group-containing copolymer (A) and an isocyanate compound and a melamine compound. A curable composition containing one or more kinds of curing agents (B).

｛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

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, and a ⁱ is 0 )} [2] The copolymer (A) comprises at least one or more of the following unsaturated monomers (a1) and (a2): The curable composition according to [1], which is a copolymer obtained by copolymerization. (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]に記載の硬化性組成物。[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]に記載の硬化性組成物。[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項に記載の硬化性組成物。[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項に記載の硬化性組成物。[7] 前記硬化剤が、１種類以上のイソシアネート化合物（Ｂ１）である[1]に記載の硬化性組成物。[8] 前記硬化剤が、１種類以上のポリイソシアネート化合物（Ｂ１−２）である[1]または[7]に記載の硬化性組成物。[9] 前記共重合体（Ａ）中の水酸基１当量に対し、前記硬化剤（Ｂ）中のＮＣＯ基の物質量が０．１〜２．０の範囲内にある[1]〜[8]に記載の硬化性組成物。[10] [1]〜[9]のいずれか１項に記載の硬化性組成物を硬化させてなる、厚さ０．１〜１０μｍの硬化層を有する物品。[11] 板状またはシート状部材である、[10]に記載の物品。」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]: Curable composition. [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 curable composition 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 curable composition according to any one of [2] to [4], which is in a 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 curable composition according to any one of [1] to [5], which is an unsaturated monomer containing at least one kind of hydroxyl group. [7] The curable composition according to [1], wherein the curing agent is one or more isocyanate compounds (B1). [8] The curable composition according to [1] or [7], wherein the curing agent is at least one polyisocyanate compound (B1-2). [9] The amount of NCO group in the curing agent (B) is in the range of 0.1 to 2.0 with respect to 1 equivalent of the hydroxyl group in the copolymer (A). ] The curable composition as described in above. [10] An article having a cured layer having a thickness of 0.1 to 10 μm obtained by curing the curable composition according to any one of [1] to [9]. [11] The article according to [10], which is a plate-like or sheet-like member. Is achieved.

An object of the present invention is to provide a curable composition that provides a cured layer having excellent uniformity, transparency, solvent resistance, stain resistance, water repellency, and high hardness. Furthermore, the present invention can provide an article having a cured layer exhibiting the above properties.

Hereinafter, the curable composition of the present invention and an article having a cured layer made of the composition will be described in detail.

The curable composition according to the present invention contains a copolymer (A) containing a specific carbosiloxane dendrimer structure and a hydroxyl group in the molecule as a main component. 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 copolymer (A) according to the present invention is preferably a vinyl copolymer having a vinyl polymer unit as a main chain and having a carbosiloxane dendrimer structure and a hydroxyl group in its side chain.

The copolymer (A) contains a group having a carbosiloxane dendrimer structure. 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 viewpoint of properties such as hardness, stain resistance, water repellency and the like 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 or 3. Second generation and third generation carbosiloxane dendrimer structures 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, and when i <c, the silylalkyl group, and a ⁱ is 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である）

(Wherein, Z, p, R ¹ and R ² are the same as described above, and a ¹ is 0 )

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 0 )

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である）

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

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 properties of the cured layer such as hardness, stain resistance, and water repellency.

（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 spread in a dendrimer form, so that a hardened layer having a much higher hardness than a linear or mere branched polysiloxane unit is formed. It is a hydrophobic functional group that can be formed, can impart properties such as high water repellency (high water resistance) to the cured layer, and suppresses extremely smooth coating surface. In addition, since the group having the carbosiloxane dendrimer structure is chemically stable, it can be stored for a long time without causing problems such as decomposition of the curable composition over time.

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 isocyanate-based curing agents. When the curable resin is cured mainly by a condensation reaction, the copolymer (A) is efficiently incorporated into the resin curing system. It is captured. As a result, the copolymer (A) according to the product of the present invention has improved affinity for the curable resin, and improved compatibility during curing and transparency (uniformity) of the cured 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. And hydroxyl group-containing vinyl monomers such as 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate.

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 monomer, Comprising: The thing which does not have a hydroxyl group in a molecule | numerator 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 -Methoxymethyl methacrylamide,
Amide group-containing vinyl monomers such as isobutoxymethoxyacrylamide, isobutoxymethoxymethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid , Carboxylic acid-containing vinyl monomers such as maleic acid; ethers such as tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, ethoxydiethylene glycol acrylate, ethoxydiethylene glycol methacrylate, cetyl vinyl ether, 2-ethylhexyl vinyl ether Bond-containing vinyl monomer; polydimethylsiloxane containing an acrylic or methacrylic group at one end, alkene at one end Unsaturated silicone compounds such as polydimethylsiloxane containing ruaryl groups; butadiene; vinyl chloride; vinylidene chloride; acrylonitrile, methacrylonitrile; dibutyl fumarate; maleic anhydride; dodecyl succinic anhydride; Methacrylic glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate: alkalis of radically polymerizable unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid 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; Examples include quaternary ammonium salts derived from acrylic acid or methacrylic acid such as oxypropyltrimethylammonium chloride, methacrylic acid esters of alcohols having a tertiary amine group such as diethylamine methacrylate and quaternary ammonium salts thereof. The 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 has a group having a carbosiloxane dendrimer structure and a hydroxyl group introduced into the main chain at a predetermined ratio, so when used as a main agent, the hardness of the cured layer, Excellent uniformity, transparency, solvent resistance, stain resistance, and water repellency. Also, when synthesized in a solvent, it does not become cloudy and is in a transparent state. And it is useful in that it is particularly excellent in blending stability with respect to an arbitrary coating agent.

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 copolymer (A) used in the present invention is the main component of the curable composition, and from the viewpoint of ease of blending as a raw material and coating properties of the obtained curable composition, its number average molecular weight. Is preferably 3,000 to 2,000,000, and more preferably 5,000 to 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.

In the curable composition according to the present invention, the copolymer (A) is converted into one or more curing agents selected from the group consisting of an isocyanate compound and a melamine compound, which are curing agents reactive with hydroxyl groups. It is characterized by being cured by B). The hydroxyl group (—OH) of the copolymer (A) is reactive with an isocyanate-based or melamine-based curing agent. When the curable resin is cured mainly by a condensation reaction, it is co-polymerized with the resin curing system. A polymer (A) is taken in efficiently. Thereby, the affinity at the time of hardening of the whole composition is improved, and the hardness, transparency (uniformity) and stain resistance of the cured layer are improved.

The curing agent (B) may be an isocyanate compound (B1), a melamine compound (B2), or a mixture thereof, and two or more kinds of compounds can be used in combination. That is, the curable composition according to the present application can use an isocyanate-based, melamine-based, or a combination of these curing systems without any particular limitation. However, from the viewpoint of reactivity with the copolymer (A), the curing agent preferably contains at least one isocyanate compound (B1), and preferably contains at least one polyisocyanate compound (B1-2). It is particularly preferable to contain Needless to say, even when these isocyanate-based curing agents are selected, a melamine-based curing agent can be optionally used in combination. Moreover, a curing catalyst can be added as needed.

In the curable composition of the present invention, the amount of the curing agent (B) used is not particularly limited, and is 100 parts by mass of the resin component of the curable composition comprising the component (A) and the component (B). It is common to use in the range of 1-50 mass parts with respect to it.

On the other hand, in the curable composition of the present invention, from the viewpoint of various properties of the cured layer, there is a more preferable range than the above general range for the amount and type of the curing agent (B). That is, the curing agent (B) contains one or more isocyanate compounds (B1), and the isocyanate (—NCO) in the curing agent with respect to 1 equivalent of the hydroxyl (—OH) group in the polymer (A). An amount in which the amount of the group is within the range of 0.1 to 2.0 is preferable. Further, the isocyanate group has a range of 0.5 to 1.5 equivalents relative to 1 equivalent of the hydroxyl group in the copolymer (A), that is, the equivalent ratio of —OH / —NCO is 1. The range of 0 / 0.5 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. When the amount of isocyanate group used is less than 0.1 mol relative to 1 mol of the hydroxyl group in the copolymer (A), the cured layer 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 content of the isocyanate group of an isocyanate compound.

Specific examples of the isocyanate compound (B1) as a curing agent include aliphatic xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or their polyhydric alcohol addition type, burette type, trimer type, aromatic tolylene diisocyanate. , Polyisocyanate compounds such as diphenylmethane diisocyanate, and blocked isocyanate compounds. From the viewpoint of curability, a polyisocyanate compound (B1-2) is preferable, and a hexamethylene diisocyanate polyisocyanate compound is particularly preferable. Moreover, these isocyanate compounds can be used alone or in combination of two or more.

Examples of commercially available isocyanate compounds (B1) include “Barnock (trademark)” manufactured by Dainippon Ink and Chemicals, “Sumijoule (trademark)” manufactured by Bayer Sumitomo Urethane Co., Ltd., Takeda Pharmaceutical ( “Takenate (trademark)” manufactured by Nihon Polyurethane Industry Co., Ltd., “Coronate (trademark)” manufactured by Asahi Kasei Kogyo Co., Ltd., and the like.

Specific examples of the melamine compound (B2) which is a curing agent include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, isobutyl ether type melamine, n-butyl ether type melamine and the like. These melamine compounds can be used alone or in combination of two or more.

If necessary, the curable composition of the present invention can further contain a curing catalyst. Examples of the curing catalyst 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 curable composition.

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, moisture in the system can be removed, and the storage stability of the curable composition according to the present invention 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 curable composition.

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 and usual additive with respect to curable resin coating agent.

Although the curable composition of the present invention can be cured as it is, it is particularly excellent in uniformity, transparency, solvent resistance, stain resistance and water repellency on the substrate by being applied to the substrate and cured. In addition, it is preferable to form a hardened layer having a high hardness.

As a method for applying the curable composition 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. In order to accelerate the crosslinking reaction, the cured layer after coating and drying can be subjected to curing treatment at a temperature of 30 to 120 ° C. for 1 to 7 days.

The thickness of the coating film when applying the curable composition of the present invention can be selected without particular limitation depending on the shape of the substrate and the purpose of the coating, but usually after curing, in order to exert the function of the cured layer The thickness is preferably in the range of 0.1 to 100 μm, particularly preferably in the range of 0.5 to 50 μm.

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 cured layer formed by curing the curable composition of the present invention is excellent in uniformity, transparency, solvent resistance, stain resistance, water repellency, and high hardness. For example, oil stains, dust in the air Prevention of various pollutants such as dirt, dust, exhaust gas, dirt mixed in rainwater, graffiti, sticker paper, etc .; effective in preventing snow accretion, icing, and attachment of aquatic organisms.

The article having a cured layer according to the present invention is not particularly limited, and has kitchen and household items such as a kitchen range, storage door, ventilation fan, lighting cover, etc., having a cured layer for the purpose of preventing oil stains; Building materials such as concrete and tiles with a hardened layer for the purpose of prevention; Buildings such as road tunnels and highway soundproof walls with a hardened layer to prevent contamination by exhaust gas; For the purpose of preventing adhesion of graffiti, stickers, etc. Outdoor walls such as exterior walls, telephone booths, utility poles, public toilets, etc. that have a hardened layer; roofs that have a hardened layer to prevent snow and ice accretion, houses such as electric wires; hardened layers to prevent adhesion such as barnacles General ships having underwater, underwater structures and the like.

In addition, a plate-like or sheet-like base material made of metal, inorganic material, plastic, composite material, etc., and having the hardened layer of the present invention has a function of exhibiting high hardness, water repellency and stain resistance on the surface. Since the coating film is formed, it is extremely useful as a highly functional material.

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.

[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 of measuring solid content concentration of copolymer] After weighing 1 g of the silicone-modified vinyl copolymer obtained in each synthesis example in an aluminum pan, the sample was heated in an oven at 150 ° C for 2 hours to evaporate the solvent. The solid content concentration was calculated from the minute (g).

Synthesis Example 1 355 g of butyl acetate was charged into 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. in 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 completion of the dropwise addition, the mixture was reacted at 70 ° C. for 6 hours. As a result, a silicone-modified vinyl copolymer having a polystyrene-equivalent number average molecular weight of 8200, a dispersity of 9.24, a kinematic viscosity of 108.26 mm ² / s, and a solid content concentration of 36.9% was obtained. A polymer (A1) was obtained.

[Synthesis Example 2] In Synthesis Example 1, instead of the above component (a-2-1), (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. A polymer (A2) was obtained.

[Comparative Synthesis Example 1] In Synthesis 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（Ｃ１）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. ² / s, a silicone-modified vinyl copolymer (C1) having a solid content concentration of 39.1% was obtained.

[Comparative Synthesis Example 2] In Synthesis 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（Ｃ２）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 A cloudy silicone-modified vinyl copolymer (C2) having a solids concentration of 31.7% at ² / s was obtained.

[Comparative Synthesis Example 3] In Synthesis 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共重合体（Ｃ３）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. A cloudy silicone-modified vinyl copolymer (C3) having a solids concentration of 37.8% at ² / s was obtained.

Evaluation of the coating agent containing the silicone-modified vinyl polymer obtained in the synthesis example and the comparative synthesis example was performed as follows. Sumijoule (trademark) N3300 used as a curing agent is a polyfunctional isocyanate compound mainly composed of hexamethylene diisocyanate trimer (= polyisocyanate compound).

[Example 1] Silicone-modified vinyl copolymer (A1) of Synthesis Example 1 (solid content concentration 36.9%, OH value 43.2) 15 g, polyfunctional isocyanate compound (B1) {Bayer Sumitomo Urethane Co., Ltd. Sumijoule (trademark) N3300, NCO content 25%} 1.07 g, dibutyltin dilaurate (0.1 wt% butyl acetate solution) 1.32 g and dilute solvent butyl acetate 4.64 g are uniformly mixed, The curable composition (NCO / OH = 1.5) of Example 1 was obtained. This curable composition was applied to an aluminum plate (JIS H 4000.5 × 50 × 150 mm) with a Meyer bar, heated at 150 ° C. for 15 minutes, and cured to obtain a coated aluminum plate having a dry film thickness of 10 μm.

[Example 2] Silicone-modified vinyl copolymer (A2) of Synthesis Example 2 (solid content concentration 40.4%, OH number 43.2) 15 g, polyfunctional isocyanate compound (B1) {Bayer Sumitomo Urethane Co., Ltd. Sumijoule (trademark) N3300, NCO content 25%} 1.18 g, 1.45 g of dibutyltin dilaurate (0.1 wt% butyl acetate solution) and 6.50 g of butyl acetate as a diluting solvent were mixed uniformly. The curable composition of Example 2 (NCO / OH = 1.5) was obtained. This curable composition was applied to an aluminum plate (JIS H 4000.5 × 50 × 150 mm) with a Meyer bar, heated at 150 ° C. for 15 minutes, and cured to obtain a coated aluminum plate having a dry film thickness of 10 μm.

[Comparative Example 1] Silicone modified vinyl copolymer (C1) of Comparative Synthesis Example 1 (solid content concentration 39.1%, OH value 43.2) 15 g, polyfunctional isocyanate compound (B1) {Bayer Sumitomo Urethane Co., Ltd. ) Sumijoule (trademark) N3300, NCO content 25%} 1.14 g, 1.40 g of dibutyltin dilaurate (0.1 wt% butyl acetate solution) and 5.81 g of butyl acetate as a diluent solvent, A curable composition (NCO / OH = 1.5) containing a silicone-modified vinyl resin was obtained. This curable composition was applied to an aluminum plate (JIS H 4000.5 × 50 × 150 mm) with a Meyer bar, heated at 150 ° C. for 15 minutes, and cured to obtain a coated aluminum plate having a dry film thickness of 10 μm.

[Comparative Example 2] Silicone-modified vinyl copolymer (C2) of Comparative Synthesis Example 2 (solid content concentration 31.7%, OH value 43.2) 15 g, polyfunctional isocyanate compound (B1) {Bayer Sumitomo Urethane Co., Ltd. ) Sumijoule (trademark) N3300, NCO content 25%} 0.92 g, 1.14 g of dibutyltin dilaurate (0.1 wt% butyl acetate solution) and 1.87 g of butyl acetate as a diluent solvent, A curable composition (NCO / OH = 1.5) containing a silicone-modified vinyl resin was obtained. This curable composition was applied to an aluminum plate (JIS H 4000.5 × 50 × 150 mm) with a Meyer bar, heated at 150 ° C. for 15 minutes, and cured to obtain a coated aluminum plate having a dry film thickness of 10 μm.

[Comparative Example 3] Silicone-modified vinyl copolymer (C3) of Comparative Synthesis Example 3 (solid content concentration 37.8%, OH number 43.2) 15 g, polyfunctional isocyanate compound (B1) {Bayer Sumitomo Urethane Co., Ltd. ) Sumijoule (trademark) N3300, NCO content 25%} 1.10 g, 1.35 g of dibutyltin dilaurate (0.1 wt% butyl acetate solution) and 5.12 g of butyl acetate as a diluent solvent, A curable composition (NCO / OH = 1.5) containing a silicone-modified vinyl resin was obtained. This curable composition was applied to an aluminum plate (JIS H 4000.5 × 50 × 150 mm) with a Meyer bar, heated at 150 ° C. for 15 minutes, and cured to obtain a coated aluminum plate having a dry film thickness of 10 μm.

The following characteristics were evaluated using the coated aluminum plate obtained as described above, and 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. X: The coating film is cloudy. [Contamination resistance] The cured coating film was marked with a blue ink pen [Magic ink, manufactured by Pentel Co., Ltd.], air-dried for 10 minutes, and then wiped off with 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.

As shown in Table 1, the curable composition of the present invention not only exhibits high compatibility, stain resistance, and water repellency, but also has a higher hardness than a curable composition containing a linear polysiloxane. It is what has. In particular, in Example 1 using the silicone-modified vinyl copolymer (A1) of Synthesis Example 1 having a second generation carbosiloxane dendrimer structure, it was confirmed that the effect was particularly remarkable.

The curable composition of the present invention is mainly composed of a copolymer having a carbosiloxane dendrimer structure and a hydroxyl group, and can be made into a transparent resin solution. Moreover, the curable composition obtained by making the copolymer of this invention react with an isocyanate compound as a main ingredient shows high transparency, hardness, and stain | pollution resistance by the effect of a carbosiloxane dendrimer structure. For this reason, the curable composition of the present invention can impart stain resistance as a surface protective agent when applied to various articles, and is mixed in oil stains, dust and dust in the air, exhaust gas, and rainwater. It can be used for a wide variety of dirt types such as dirt. In addition, an article having a cured layer formed by curing the curable composition according to the present invention is extremely useful as a highly functional material because it has a coating film with high hardness and functionality.

Claims (11)

A copolymer having a carbosiloxane dendrimer structure represented by any of the following formulas (2-1) to (2-3) in the molecule and a hydroxyl group-containing copolymer (A);
A curable composition containing one or more curing agents (B) selected from the group consisting of isocyanate compounds and melamine compounds.

(In the formula, Z is a divalent organic group,
p 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, and a ¹ is 0)

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

(In the formula, Z, R ¹ and R ² are the same as above, and a ¹ , a ² and a ³ are 0) The curable composition 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). Composition.
(A1) Unsaturated monomer containing one or more hydroxyl groups in the molecule (a2) Unsaturated monomer capable of radical polymerization represented by any of the following formulas (2-1 ′) to (2-3 ′) body

(In the formula, Y is a radical-polymerizable unsaturated group,
Z is a divalent organic group,
p 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, and a ¹ is 0)

(Wherein Y, Z, R ¹ and R ² are the same as above, and a ¹ and a ² are 0)

(Wherein, Y, Z, R ¹ and R ² are the same as above, and a ¹ , a ² and a ³ are 0)
In the radically polymerizable unsaturated monomer represented by any one of the above formulas (2-1 ′) to (2-3 ′), the radically polymerizable unsaturated group Y is
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,
General formula:

Wherein R6 is a hydrogen atom or a methyl group, R7 is an alkyl group having 1 to 10 carbon atoms, R8 is an alkylene group having 1 to 10 carbon atoms, and b is an integer of 0 to 4. And c is 0 or 1. The curable composition according to claim 2, which is a group selected from the group consisting of an alkenylaryl group-containing organic group and an alkenyl group having 2 to 10 carbon atoms. object. The curable composition according to claim 2, wherein the copolymer (A) is obtained by further copolymerizing at least one or more kinds of (a3) unsaturated monomers not containing a hydroxyl group in the molecule. 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 copolymer is 100 parts by mass, the mass ratio is
(A1) :( a2) :( a3) = 0.5 to 50.0: 0.5 to 50.0: 0 to 99.0
The curable composition according to claim 3 or 4, wherein the curable composition is in the range of. 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 curable composition according to any one of claims 1 to 5, which is an unsaturated monomer containing a hydroxyl group. The curable composition according to claim 1, wherein the curing agent is one or more isocyanate compounds (B1). The curable composition according to claim 1 or 7, wherein the curing agent is at least one polyisocyanate compound (B1-2). To 1 equivalent of hydroxyl group in the copolymer (A), any one of the claims 1 to 8 substance amount of NCO groups in the curing agent (B) is within the range of 0.1 to 2.0 the curable composition according to item. An article having a cured layer with a thickness of 0.1 to 10 µm obtained by curing the curable composition according to any one of claims 1 to 9. The article according to claim 10, which is a plate-like or sheet-like member.