JP2008038113A5

JP2008038113A5 -

Info

Publication number: JP2008038113A5
Application number: JP2006218360A
Authority: JP
Filing date: 2006-08-10
Publication date: 2009-06-04
Anticipated expiration: 2026-08-10

Description

本発明者は、上記のような問題点を解決するために鋭意研究を重ねた結果、本発明を完成するに至った。即ち、
１）シリコーン変性剤〔Ａ〕と、少なくとも１種のカルボキシル基を持つエチレン性不飽和単量体〔Ｂ〕と、少なくとも１種の他のエチレン性不飽和単量体〔Ｃ〕とからなり、カルボキシル基を持つエチレン性不飽和単量体〔Ｂ〕と他のエチレン性不飽和単量体〔Ｃ〕の合計質量に対して、該カルボキシル基を持つエチレン性不飽和単量体〔Ｂ〕及び他のエチレン性不飽和単量体〔Ｃ〕を、それぞれ９０〜９９．５質量％及び０．５〜１０質量％用い、又、上記シリコーン変性剤〔Ａ〕を下記の式
１／５≦｛単量体〔Ｂ〕＋単量体〔Ｃ〕｝／シリコーン変性剤〔Ａ〕≦５００／１３３
で表される関係を満足する量を用いて得られることを特徴とするシリコーン含有高分子エマルジョンであって、シリコーン変性剤〔Ａ〕が、
下記式（１）： As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is,
1) A silicone modifier [A], an ethylenically unsaturated monomer [B] having at least one carboxyl group, and at least one other ethylenically unsaturated monomer [C] , The ethylenically unsaturated monomer [B] having a carboxyl group and the total mass of the ethylenically unsaturated monomer [B] having a carboxyl group and the other ethylenically unsaturated monomer [C] and Other ethylenically unsaturated monomers [C] were used in an amount of 90 to 99.5% by mass and 0.5 to 10% by mass, respectively, and the silicone modifier [A] was represented by the following formula:
1/5 ≦ {monomer [B] + monomer [C]} / silicone modifier [A] ≦ 500/133
A silicone-containing polymer emulsion obtained by using an amount satisfying the relationship represented by the following formula, wherein the silicone modifier [A] is:
Following formula (1):

２）シリコーン含有高分子エマルジョンが、シリコーン変性剤〔Ａ〕と、少なくとも１種のカルボキシル基を持つエチレン性不飽和単量体〔Ｂ〕と、少なくとも１種の他のエチレン性不飽和単量体〔Ｃ〕とを乳化重合に付して得られることを特徴とする上記１）記載の高耐久コーティング用組成物。 2) The silicone-containing polymer emulsion comprises a silicone modifier [A], at least one ethylenically unsaturated monomer having a carboxyl group [B], and at least one other ethylenically unsaturated monomer. The highly durable coating composition as described in 1) above, which is obtained by subjecting [C] to emulsion polymerization.

３）シリコーン含有高分子エマルジョンの上記シリコーン変性剤〔Ａ〕が、上記式（２）で表されるシリコーン構造を有するシラン（２）からなる群から選ばれる少なくとも１種と、上記環状シラン及び式（３）で表されるシリコーン構造を有するシラン（３）からなる群から選ばれる少なくとも１種の合計質量に対して、該式（２）で表されるシリコーン構造を有するシラン（２）からなる群から選ばれる少なくとも１種に対する、上記環状シラン及び式（３）で表されるシリコーン構造を有するシラン（３）からなる群から選ばれる少なくとも１種のモル比が少なくとも１／１００であり、又、上記式（１）で表されるシリコーン構造を有するシラン（１）からなる群より選ばれる少なくとも一種を下記の式
１／１００≦シラン（１）／｛シラン（２）＋シラン（３）｝≦１０／１
で表される関係を満足するモル比で用いることを特徴とする上記１）または２）のいずれかに記載の高耐久コーティング用組成物。 3) The silicone modifier [A] of the silicone-containing polymer emulsion is at least one selected from the group consisting of silane (2) having a silicone structure represented by the formula (2), the cyclic silane and the formula It consists of silane (2) which has a silicone structure represented by the formula (2) with respect to at least one total mass selected from the group consisting of silane (3) which has a silicone structure represented by (3). The molar ratio of at least one selected from the group consisting of the above cyclic silane and the silane (3) having a silicone structure represented by formula (3) to at least one selected from the group is at least 1/100, At least one selected from the group consisting of silane (1) having a silicone structure represented by the above formula (1) is represented by the following formula 1/100 ≦ silane (1) / {Silane (2) + Silane (3)} ≦ 10/1
The composition for high durability coating according to any one of 1) or 2) above, wherein the composition is used in a molar ratio satisfying the relationship represented by:

４）シリコーン含有高分子エマルジョンが、該シリコーン変性剤〔Ａ〕が、同じか異なった（Ａ−１）と（Ａ−２）よりなり、該カルボキシル基を持つエチレン性不飽和単量体〔Ｂ〕が、同じか異なった（Ｂ−１）と（Ｂ−２）よりなり、該他のエチレン性不飽和単量体〔Ｃ〕が、同じか異なった（Ｃ−１）と（Ｃ−２）よりなり、上記乳化重合をステップ（１）およびステップ（２）の順で行い、ステップ（１）においては、該シリコーン変性剤（Ａ−１）と、少なくとも１種の該カルボキシル基を持つエチレン性不飽和単量体（Ｂ−１）と、少なくとも１種の該他のエチレン性不飽和単量体（Ｃ−１）とを同時に乳化重合してシリコーンを含むシードエマルジョンを得、この存在下で、ステップ（２）においては該シリコーン変性剤（Ａ−２）と、少なくとも１種の該カルボキシル基を持つエチレン性不飽和単量体（Ｂ−２）と、少なくとも１種の該他のエチレン性不飽和単量体（Ｃ−２）を乳化重合して得られる重合体からなることを特徴とする上記１）〜３）のいずれかに記載の高耐久コーティング用組成物。
５）シリコーン含有高分子エマルジョンの少なくとも１種のエチレン性不飽和単量体〔Ｂ〕が、該エチレン性不飽和単量体〔Ｂ〕の質量に対して５質量％以上のアクリル酸、メタクリル酸の炭素数が５〜１２のシクロアルキルエステルを含有することを特徴とする上記１）〜４）のいずれかに記載の高耐久コーティング用組成物。 4) The silicone-containing polymer emulsion is composed of (A-1) and (A-2) in which the silicone modifier [A] is the same or different, and the ethylenically unsaturated monomer [B ] Are the same or different (B-1) and (B-2), and the other ethylenically unsaturated monomers [C] are the same or different (C-1) and (C-2). The emulsion polymerization is performed in the order of step (1) and step (2). In step (1), the silicone modifier (A-1) and ethylene having at least one carboxyl group are used. The ethylenically unsaturated monomer (B-1) and at least one other ethylenically unsaturated monomer (C-1) are simultaneously emulsion polymerized to obtain a seed emulsion containing silicone. In step (2), the silicone modifier (A 2) emulsion polymerization of at least one ethylenically unsaturated monomer (B-2) having the carboxyl group and at least one other ethylenically unsaturated monomer (C-2). The highly durable coating composition as described in any one of 1) to 3) above, which comprises a polymer obtained in the above manner.
5) At least one ethylenically unsaturated monomer [B] of the silicone-containing polymer emulsion is 5% by mass or more of acrylic acid or methacrylic acid based on the mass of the ethylenically unsaturated monomer [B]. The high-durability coating composition according to any one of 1) to 4) above, which comprises a cycloalkyl ester having 5 to 12 carbon atoms.

本発明のコーティング組成物は、シリコーン変性剤としてシラン（１）から選ばれる少なくとも１種を含み、カルボキシル基を持つエチレン性不飽和単量体〔Ｂ〕と他のエチレン性不飽和単量体〔Ｃ〕の合計質量に対して、該カルボキシル基を持つエチレン性不飽和単量体〔Ｂ〕及び他のエチレン性不飽和単量体〔Ｃ〕を、それぞれ９０〜９９．５質量％及び０．５〜１０質量％用い、又、上記シリコーン変性剤〔Ａ〕を下記の式
１／５≦｛単量体〔Ｂ〕＋単量体〔Ｃ〕｝／シリコーン変性剤〔Ａ〕≦５００／１３３
で表される関係を満足する量を用いることを特徴とするシリコーン含有高分子エマルジョンと光触媒からなり、従来のシリコーン含有高分子エマルジョンに比して、耐候性、耐汚染性に優れた塗膜を形成できる。 The coating composition of the present invention contains at least one selected from silane (1) as a silicone modifier, and has an ethylenically unsaturated monomer [B] having a carboxyl group and another ethylenically unsaturated monomer [ C] to 90-99.5% by mass and 0.005% of the ethylenically unsaturated monomer [B] having the carboxyl group and the other ethylenically unsaturated monomer [C], respectively. 5-10% by mass, and the silicone modifier [A] is represented by the following formula 1/5 ≦ {monomer [B] + monomer [C]} / silicone modifier [A] ≦ 500/133.
It consists of a silicone-containing polymer emulsion and a photocatalyst characterized by using an amount satisfying the relationship expressed by the following, and has a coating film that is superior in weather resistance and stain resistance as compared to conventional silicone-containing polymer emulsions. Can be formed.

本発明の高耐久性エマルジョンと光触媒からなるコーティング組成物の好ましい１つの態様は、カルボキシル基を持つエチレン性不飽和単量体〔Ｂ〕と他のエチレン性不飽和単量体〔Ｃ〕の合計質量に対して、該カルボキシル基を持つエチレン性不飽和単量体〔Ｂ〕及び他のエチレン性不飽和単量体〔Ｃ〕を、それぞれ９０〜９９．５質量％及び０．５〜１０質量％用い、又、上記シリコーン変性剤〔Ａ〕を下記の式
１／５≦｛単量体〔Ｂ〕＋単量体〔Ｃ〕｝／シリコーン変性剤〔Ａ〕≦５００／１３３
で表される関係を満足する量を用いることを特徴とするシリコーン含有高分子エマルジョンと光触媒を混合することによって得られる。上記式よりシリコーン変性剤量が少なければ、光触媒機能による有機成分の分解が進行し、バインダーとしての機能を劣化させ高耐久機能を発現することができない。また上記式よりシリコーン変性剤量が多ければ、シリコーン含有高分子エマルジョンの製造の際に、重合安定性を損ない、多量の乳化剤等を使用する結果、耐水性の劣るバインダーとなり高耐久機能を発現することが困難となる。本発明におけるシリコーン含有高分子エマルジョンのシリコーン変性剤〔Ａ〕のより好ましい変性量は、下記の式
１／１≦｛単量体〔Ｂ〕＋単量体〔Ｃ〕｝／シリコーン変性剤〔Ａ〕≦５００／２６７
で表される関係を満足する量である。上記式におけるシリコーン変性量では、光触媒機能による有機成分の分解を長期に渡って抑制でき、長期間の耐候性機能を付与することが可能となる。またシリコーン変性量を実用性能範囲内に設定することにより、副生アルコールの処理及び原料費のコスト上昇を抑制でき、汎用的な製品を提供可能となる。 One preferred embodiment of the coating composition comprising the highly durable emulsion and photocatalyst of the present invention is the sum of the ethylenically unsaturated monomer [B] having a carboxyl group and the other ethylenically unsaturated monomer [C]. The ethylenically unsaturated monomer [B] having the carboxyl group and the other ethylenically unsaturated monomer [C] are 90 to 99.5% by mass and 0.5 to 10% by mass, respectively. %, And the silicone modifier [A] is represented by the following formula 1/5 ≦ {monomer [B] + monomer [C]} / silicone modifier [A] ≦ 500/133.
It is obtained by mixing a silicone-containing polymer emulsion and a photocatalyst characterized by using an amount satisfying the relationship represented by: If the amount of the silicone modifier is less than the above formula, the decomposition of the organic component by the photocatalytic function proceeds, the function as a binder is deteriorated, and the high durability function cannot be expressed. If the amount of the silicone modifier is larger than the above formula, the production stability of the silicone-containing polymer emulsion is impaired, and as a result of using a large amount of an emulsifier and the like, it becomes a binder with poor water resistance and exhibits a high durability function. It becomes difficult. A more preferable modification amount of the silicone modifier [A] of the silicone-containing polymer emulsion in the present invention is represented by the following formula 1/1 ≦ {monomer [B] + monomer [C]} / silicone modifier [A]. ] ≦ 500/267
Is an amount that satisfies the relationship represented by With the silicone modification amount in the above formula, decomposition of the organic component due to the photocatalytic function can be suppressed over a long period of time, and a long-term weather resistance function can be imparted. Further, by setting the silicone modification amount within the practical performance range, it is possible to suppress the treatment of by-product alcohol and the cost increase of raw material costs, and to provide a general-purpose product.

Claims

Silicone-modified agent (A), it becomes from ethylenically unsaturated monomers having at least one carboxyl group and (B), at least one other ethylenically unsaturated monomer and (C), a carboxyl group The ethylenically unsaturated monomer [B] having the carboxyl group and the other mass with respect to the total mass of the ethylenically unsaturated monomer [B] having the above and other ethylenically unsaturated monomers [C] The ethylenically unsaturated monomer [C] is used in an amount of 90 to 99.5% by mass and 0.5 to 10% by mass, respectively, and the silicone modifier [A] is represented by the following formula:
1/5 ≦ {monomer [B] + monomer [C]} / silicone modifier [A] ≦ 500/133
A silicone-containing polymer emulsion obtained by using an amount satisfying the relationship represented by the following formula, wherein the silicone modifier [A] is:
Following formula (1):

((N, m) is a set of (1, 0) or (1, 1), and when n = 1 and m = 0, R ¹ is a phenyl group or a cyclohexyl group, and each R ³ is Each independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group, or when n = 1 and m = 1, R ¹ is a phenyl group or a cyclohexyl group, and R ² is A hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an alkyl acrylate group having 1 to 10 carbon atoms, or a 1 to 1 carbon atom Group consisting of silane (1) having a silicone structure represented by 10 alkyl methacrylate groups, and each R ³ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group. At least one kind selected from Including
Following formula (2):
CH ₃ —Si— (R ⁴ ) ₃ (2)
(Wherein each R ⁴ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group) and includes at least one selected from the group consisting of silanes (2) having a silicone structure ,
Following formula (3):
(CH ₃ ) ₂ —Si— (R ⁵ ) ₂ (3)
(Wherein each R ⁵ is independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group) and / or at least one selected from the group consisting of silanes (3) having a silicone structure Alternatively, a highly durable coating composition comprising a silicone-containing polymer emulsion containing a cyclic silane and a photocatalyst.

The silicone-containing polymer emulsion comprises a silicone modifier [A], an ethylenically unsaturated monomer [B] having at least one carboxyl group, and at least one other ethylenically unsaturated monomer [C The composition for high durability coating according to claim 1, wherein the composition is obtained by emulsion polymerization.

The silicone modifier [A] of the silicone-containing polymer emulsion is at least one selected from the group consisting of silane (2) having a silicone structure represented by the formula (2), the cyclic silane, and the formula (3 From the group consisting of silane (2) having a silicone structure represented by the formula (2), with respect to at least one total mass selected from the group consisting of silane (3) having a silicone structure represented by The molar ratio of at least one selected from the group consisting of the cyclic silane and the silane (3) having a silicone structure represented by the formula (3) to at least one selected is at least 1/100, and At least one selected from the group consisting of silane (1) having a silicone structure represented by formula (1) is represented by the following formula 1/100 ≦ silane (1) / { Run (2) + Silane (3)} ≦ 10/1
The composition for high durability coating according to claim 1 , wherein the composition is used in a molar ratio satisfying the relationship represented by:

The silicone-containing polymer emulsion comprises (A-1) and (A-2) in which the silicone modifier [A] is the same or different, and the ethylenically unsaturated monomer [B] having the carboxyl group is The same or different (B-1) and (B-2), and the other ethylenically unsaturated monomer [C] is the same or different from (C-1) and (C-2) The emulsion polymerization is carried out in the order of step (1) and step (2). In step (1), the silicone modifier (A-1) and an ethylenic polymer having at least one carboxyl group are used. The saturated monomer (B-1) and at least one other ethylenically unsaturated monomer (C-1) are simultaneously emulsion polymerized to obtain a seed emulsion containing silicone, In step (2), the silicone modifier (A-2 Obtained by emulsion polymerization of at least one ethylenically unsaturated monomer (B-2) having the carboxyl group and at least one other ethylenically unsaturated monomer (C-2). The composition for high durability coating according to any one of claims 1 to 3 , wherein the composition is made of a polymer.

At least one ethylenically unsaturated monomer [B] of the silicone-containing polymer emulsion is not less than 5% by mass of acrylic acid or methacrylic acid carbon based on the mass of the ethylenically unsaturated monomer [B]. The composition for high durability coating according to any one of claims 1 to 4, comprising a cycloalkyl ester having a number of 5 to 12.