JPH05222198A - Silicone compound, vinyl copolymer therewith and coating composition made by using it - Google Patents
Silicone compound, vinyl copolymer therewith and coating composition made by using itInfo
- Publication number
- JPH05222198A JPH05222198A JP4023447A JP2344792A JPH05222198A JP H05222198 A JPH05222198 A JP H05222198A JP 4023447 A JP4023447 A JP 4023447A JP 2344792 A JP2344792 A JP 2344792A JP H05222198 A JPH05222198 A JP H05222198A
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- compound
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- vinyl
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、耐候性、耐酸性、耐溶
剤性、耐汚染性、平滑性等に優れた塗料、コーティング
剤、シーリング剤、接着剤などの原料として有用なシリ
コーン系化合物、その共重合体及びそれを用いた塗料組
成物に関する。The present invention relates to a silicone compound useful as a raw material for paints, coating agents, sealing agents, adhesives, etc., which are excellent in weather resistance, acid resistance, solvent resistance, stain resistance, smoothness, etc. , A copolymer thereof, and a coating composition using the same.
【0002】[0002]
【従来の技術】分子末端、あるいは側鎖にアルコキシシ
リル基を有するビニル系重合体、及びそれを用いた塗料
組成物は、例えば特開昭54−36395号公報、特開
昭54−40893号公報、特開昭54−123129
号公報等で公知である。2. Description of the Related Art A vinyl polymer having an alkoxysilyl group at a molecular end or a side chain and a coating composition using the same are disclosed, for example, in JP-A-54-36395 and JP-A-54-40893. JP-A-54-123129
It is well known in Japanese Patent Publication No.
【0003】[0003]
【発明が解決しようとする課題】しかしながら、最近、
建築分野、自動車分野、金属塗装分野等においては、例
えば耐候性、耐酸性、耐溶剤性、耐汚染性、平滑性等の
性能面で更に性能の優れた塗料原料が求められている。[Problems to be Solved by the Invention] However, recently,
In the fields of construction, automobiles, metal coatings, etc., there is a demand for coating materials having further excellent performance in terms of performance such as weather resistance, acid resistance, solvent resistance, stain resistance and smoothness.
【0004】[0004]
【課題を解決するための手段】本発明者らは、重合性二
重結合を有する特定構造のシリコーン系化合物、及びそ
の共重合体を創出し、かつそれを塗料に応用することに
より上記課題を解決しうることを見出し、本発明を完成
するに到った。即ち、本発明は(1)分子構造中に下記
一般式(A)と(B)で表される構造を併せ有し、
(2)末端基としてケイ素に結合する場合がR2 −O−
および酸素に結合する場合がR2 −の構造をとり(R2
は炭素数1〜18の直鎖または分岐アルキル基、または
フェニル基)、(3)数平均分子量800〜20000
0、かつ(4)R1/R2 比が0.8〜10であること
を特徴とするシリコーン系化合物〔化合物−I〕、The present inventors have solved the above problems by creating a silicone compound having a specific structure having a polymerizable double bond, and a copolymer thereof, and applying it to a coating material. They have found that they can be solved, and have completed the present invention. That is, the present invention has both the structures represented by the following general formulas (A) and (B) in the molecular structure (1),
(2) When bonded to silicon as an end group, R 2 —O—
And the case of binding to oxygen has a structure of R 2 — (R 2
Is a linear or branched alkyl group having 1 to 18 carbon atoms, or a phenyl group), (3) number average molecular weight 800 to 20,000
0, and (4) R 1 / R 2 ratio is 0.8 to 10, a silicone-based compound [compound-I],
【0005】[0005]
【化4】 [Chemical 4]
【0006】及び(1)分子構造中に下記一般式(C)
と(D)で表される構造を併せ有し、(2)末端基とし
てケイ素に結合する場合がR2 −O−および酸素に結合
する場合がR2 −の構造をとり(R2 は炭素数1〜18
の直鎖または分岐アルキル基、またはフェニル基)、
(3)R1 /R2 比が0.8〜10であるシリコーン系
官能基を少なくとも1つの側鎖中に持つことを特徴とす
る数平均分子量1000〜200000のビニル系共重
合体〔共重合体−I〕、And (1) in the molecular structure, the following general formula (C)
And (D), and (2) has a structure of R 2 —O— when bound to silicon as an end group and R 2 — when bound to oxygen (R 2 is a carbon atom). Number 1-18
Linear or branched alkyl group, or phenyl group),
(3) A vinyl-based copolymer having a number average molecular weight of 1,000 to 200,000 having a silicone-based functional group having an R 1 / R 2 ratio of 0.8 to 10 in at least one side chain [copolymer] Combined-I],
【0007】[0007]
【化5】 [Chemical 5]
【0008】及び上記ビニル系共重合体を主成分とする
ことを特徴とする塗料組成物である。上記〔化合物−
I〕で示されるシリコーン系化合物は、例えば特願平2
−12718号公報、特願平2−12720号公報、特
願平3−43382号公報に記載されているように、分
子構造中に下記一般式(E)と(F)で表はされる構造
を併せ有し、かつ末端基としてケイ素末端に結合する場
合がR2 −O−、酸素末端に結合する場合がR2 −(R
2 は前出R2 と同じものを示す)なる構造を有し、かつ
R1 /R2 比が0.8〜10なるヒドロシリコーン系化
合物〔化合物−II〕が有するSi−H基に炭素−炭素
不飽和結合化合物を付加させること(ヒドロシリル化反
応)により得られる。A coating composition comprising the above vinyl-based copolymer as a main component. [Compound-
The silicone compound represented by the formula [I] is disclosed in, for example, Japanese Patent Application No.
As described in Japanese Patent Application No. 12718, Japanese Patent Application No. 2-12720 and Japanese Patent Application No. 3-43382, a structure represented by the following general formulas (E) and (F) in the molecular structure. R 2 —O— when bonded to the silicon terminal as an end group and R 2 — (R
2 has the same structure as the above R 2 ) and has a R 1 / R 2 ratio of 0.8 to 10 in which the Si-H group contained in the hydrosilicone compound [Compound-II] has carbon- It can be obtained by adding a carbon unsaturated bond compound (hydrosilylation reaction).
【0009】[0009]
【化6】 [Chemical 6]
【0010】この〔化合物−II〕は上記出願に記載さ
れているように、例えばジオキサン等の溶媒中で、トリ
クロルシラン、又はトリクロルシラン/オルガノトリク
ロルシラン混合物と水を反応させて加水分解縮重合し、
その後アルコールと反応して得られる。このようにして
得られた〔化合物−II〕の構造はR6 が水素、R2 が
メチル基(Me)の場合を例にとって代表的なものを比
較的低分子量で例示すると以下の(G)、(H)及び
(Q)式で示されるような化合物である。This [Compound-II] is hydrolyzed and polycondensed by reacting trichlorosilane or a trichlorosilane / organotrichlorosilane mixture with water in a solvent such as dioxane as described in the above-mentioned application. ,
It is then obtained by reacting with alcohol. The structure of [Compound-II] thus obtained is as follows. A typical example of the case where R 6 is hydrogen and R 2 is a methyl group (Me) with a relatively low molecular weight is as follows: , (H) and (Q).
【0011】[0011]
【化7】 [Chemical 7]
【0012】[0012]
【化8】 [Chemical 8]
【0013】[0013]
【化9】 [Chemical 9]
【0014】この〔化合物−II〕に付加させるべき炭
素−炭素不飽和結合化合物の例としては、例えば、 プロピレン、1−ブテン、1−ヘキセン、1−オク
テン、イソブテン、5−メチル−1−ブテン、2−ヘキ
セン、シクロヘキセンの如きオレフィン類、 酢酸アリル、プロピオン酸アリル、2−エチルヘキ
サン酸アリル、安息香酸アリル等のアリルエステル類、 アリルメチルエーテル、アリルエチルエーテル、ア
リル−n−ヘキシルエーテル、アリルシクロヘキシルエ
ーテル、アリル−2−エチルヘキシルエーテル、アリル
フェニルエーテル、アリルグリシジルエーテル等のアリ
ルエーテル類 (メタ)アクリル酸メチル、(メタ)アクリル酸エ
チル、(メタ)アクリル酸ブチル、(メタ)アクリル酸
−2−エチルヘキシル、(メタ)アクリル酸シクロヘキ
シル、(メタ)アクリル酸フェニル等の(メタ)アクリ
ル酸エステル類、 酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ス
テアリン酸ビニル、安息香酸ビニル等のカルボン酸ビニ
ルエステル類、 メチルビニルエーテル、エチルビニルエーテル、ブ
チルビニルエーテル、イソブチルビニルエーテル、シク
ロヘキシルビニルエーテル等のビニルエーテル類、 スチレン、(メタ)アクリロニトリル、クロトン酸
エステル類等の他の炭素−炭素不飽和結合化合物等が挙
げられる。Examples of the carbon-carbon unsaturated bond compound to be added to this [compound-II] include, for example, propylene, 1-butene, 1-hexene, 1-octene, isobutene, 5-methyl-1-butene. Olefins such as 2-hexene and cyclohexene, allyl acetates such as allyl acetate, allyl propionate, allyl 2-ethylhexanoate and allyl benzoate, allyl methyl ether, allyl ethyl ether, allyl-n-hexyl ether, allyl Allyl ethers such as cyclohexyl ether, allyl-2-ethylhexyl ether, allyl phenyl ether, allyl glycidyl ether, etc. Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid-2 -Ethylhexyl, (meth) a (Meth) acrylic acid esters such as cyclohexyl acrylate and phenyl (meth) acrylate, carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate and vinyl benzoate, methyl vinyl ether, ethyl vinyl ether , Vinyl ethers such as butyl vinyl ether, isobutyl vinyl ether, and cyclohexyl vinyl ether; and other carbon-carbon unsaturated bond compounds such as styrene, (meth) acrylonitrile, and crotonic acid esters.
【0015】これらのうち、1−ヘキセン、1−オクテ
ン等の末端オレフィン類、アリルエステル類、アリルエ
ーテル類が反応性の面で好ましい。 更に、〔化合物−I〕で示されるシリコーン系化合
物へのエポキシ基導入のための炭素−炭素不飽和結合化
合物としては、例えばアリルグリシジルエーテル、(メ
タ)アクリル酸グリシジル等の炭素−炭素不飽和結合と
エポキシを1分子中に併せ持つ化合物が挙げられる。こ
の中でアリルグリシジルエーテルが好ましく用いられ
る。 また、〔化合物−I〕で示されるシリコーン系化合
物への重合性二重結合導入のための炭素−炭素不飽和結
合化合物としては、例えば(メタ)アクリル酸アリル、
ジアリルエーテル、ジアリルフタレート(メタ)アクリ
ル酸ビニル、クロトン酸ビニル、桂皮酸ビニル、エチレ
ングリコールジ(メタ)アクリル酸エステル、ブチレン
グリコールジ(メタ)アクリル酸エステル等の2個以上
の二重結合基を1分子中に併せ持つ化合物が挙げられ
る。これらのうち、特に好ましいものとして(メタ)ア
クリル酸アリルが挙げられる。Of these, terminal olefins such as 1-hexene and 1-octene, allyl esters and allyl ethers are preferable from the viewpoint of reactivity. Furthermore, examples of the carbon-carbon unsaturated bond compound for introducing an epoxy group into the silicone compound represented by [Compound-I] include carbon-carbon unsaturated bond such as allyl glycidyl ether and glycidyl (meth) acrylate. And a compound having both epoxy in one molecule. Of these, allyl glycidyl ether is preferably used. Further, as the carbon-carbon unsaturated bond compound for introducing the polymerizable double bond into the silicone compound represented by [Compound-I], for example, allyl (meth) acrylate,
Two or more double bond groups such as diallyl ether, diallyl phthalate (meth) acrylic acid vinyl, vinyl crotonic acid vinyl, cinnamic acid vinyl, ethylene glycol di (meth) acrylic acid ester, butylene glycol di (meth) acrylic acid ester A compound which has both in one molecule is mentioned. Of these, allyl (meth) acrylate is particularly preferable.
【0016】本発明の〔化合物−II〕と不飽和結合化
合物との反応に際し、第VIII白金系触媒を使用する
ことが好ましい。この第VIII族白金系触媒として
は、例えば白金の単体、塩化白金酸、アルコール変性塩
化白金酸、塩化白金−オレフィン錯体、アルミナ、シリ
カ等の担体に固体白金を担持させたもの、ロジウム−オ
レフィン錯体など、コバルト、パラジウムおよびニッケ
ルから選ばれたVIII族の金属化合物等が有効に使用
される。その使用量は、通常反応物に対して1〜100
0ppmの量が用いられる。In the reaction of [Compound-II] of the present invention with the unsaturated bond compound, it is preferable to use a platinum group VIII catalyst. Examples of the Group VIII platinum-based catalyst include platinum simple substance, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum chloride-olefin complex, solid platinum supported on a carrier such as alumina and silica, and rhodium-olefin complex. For example, a Group VIII metal compound selected from cobalt, palladium and nickel is effectively used. The amount used is usually 1 to 100 with respect to the reaction product.
An amount of 0 ppm is used.
【0017】このヒドロシリン化反応は、50〜150
℃の温度で反応時間は1〜5時間で達成される。反応温
度が50℃以下の場合は反応速度が遅くなり実用的でな
い。また、反応温度が150℃以上になると一部高分子
量物が生成したりゲル化反応が起こるので好ましくな
い。本発明において〔化合物−II〕と炭素−炭素不飽
和結合化合物とを反応させる時のモル比は、目標とする
反応生成物により変わるが、通常、Si−H基1モルに
対して、不飽和結合化合物を0.1〜50モルの範囲が
好ましい。This hydrosylation reaction is carried out at 50 to 150
At a temperature of ° C a reaction time of 1 to 5 hours is achieved. When the reaction temperature is 50 ° C. or lower, the reaction rate becomes slow, which is not practical. Further, if the reaction temperature is 150 ° C. or higher, some high molecular weight products are generated and a gelling reaction occurs, which is not preferable. In the present invention, the molar ratio at the time of reacting [Compound-II] with the carbon-carbon unsaturated bond compound varies depending on the target reaction product, but is usually unsaturated with respect to 1 mol of Si-H groups. The binding compound is preferably in the range of 0.1 to 50 mol.
【0018】この反応において、溶媒を用いてもよい。
用いられる溶媒としては、ラダ−型ヒドロシリコ−ン化
合物と不飽和結合化合物をともに溶解する溶媒が好まし
い。通常、トルエン、キシレン等の有機溶媒が用いられ
る。溶媒を使用する場合は、反応に用いられる原料1重
量部に対して0.1〜10重量部を用いることが好まし
い。A solvent may be used in this reaction.
The solvent used is preferably a solvent that dissolves both the ladder-type hydrosilicone compound and the unsaturated bond compound. Usually, an organic solvent such as toluene or xylene is used. When a solvent is used, it is preferable to use 0.1 to 10 parts by weight with respect to 1 part by weight of the raw material used in the reaction.
【0019】かくして得られたシリコ−ン系化合物〔化
合物−I〕は、分子内に環状シリコ−ン構造、及び/又
はラダ−型シリコ−ン構造、加水分解性アルコキシシリ
ル基を有し、かつ重合性二重結合、又はエポキシ基、又
は重合性二重結合及びエポキシ基を併せ持っており、塗
料原料、コ−ティング剤原料、シ−リング剤原料、接着
剤原料として有用である。The silicone compound [Compound-I] thus obtained has a cyclic silicone structure and / or a ladder-type silicone structure, a hydrolyzable alkoxysilyl group in the molecule, and It has a polymerizable double bond, an epoxy group, or a polymerizable double bond and an epoxy group, and is useful as a coating material, a coating material, a sealing material, and an adhesive material.
【0020】この重合性二重結合を有する〔化合物−
I〕は、これと共重合可能な他の重合性ビニルモノマ−
と共重合することにより、側鎖に〔化合物−I〕の残基
を有するビニル系共重合体〔共重合体−I〕を形成す
る。共重合させるべきビニルモノマ−類としては、例え
ば上記のハイドロシリレ−ションに用いた炭素−炭素不
飽和結合化合物〜を使用することが可能であるが、
特に(メタ)アクリル酸メチル、(メタ)アクリル酸エ
チル、(メタ)アクリル酸−n−ブチル、(メタ)アク
リル酸−第三ブチル、(メタ)アクリル酸ヘキシル、
(メタ)アクリル酸シクロヘキシル、(メタ)アクリル
酸−2−エチルヘキシル、(メタ)アクリル酸ラウリ
ル、(メタ)アクリル酸ステアリル、(メタ)アクリル
酸フェニル、(メタ)アクリル酸グリシジル、(メタ)
アクリル酸−2−ヒドロキシエチル、(メタ)アクリル
酸−3−(トリメトキシシリル)プロピル、(メタ)ア
クリル酸−3−(メチルジメトキシシリル)プロピル、
(メタ)アクリル酸−3−(トリエトキシシリル)プロ
ピル、(メタ)アクリル酸イソボルニル等の(メタ)ア
クリル酸エステル類、(メタ)アクリル酸、スチレン等
が好ましく使用される。Having this polymerizable double bond [Compound-
I] is another polymerizable vinyl monomer copolymerizable therewith.
A vinyl-based copolymer [copolymer-I] having a residue of [compound-I] on the side chain is formed by copolymerization with the above. As the vinyl monomers to be copolymerized, it is possible to use, for example, the carbon-carbon unsaturated bond compound used in the above hydrosilation.
In particular, methyl (meth) acrylate, ethyl (meth) acrylate, -n-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate,
Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, glycidyl (meth) acrylate, (meth)
2-hydroxyethyl acrylate, -3- (trimethoxysilyl) propyl (meth) acrylate, -3- (methyldimethoxysilyl) propyl (meth) acrylate,
(Meth) acrylic acid esters such as 3- (triethoxysilyl) propyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid, styrene and the like are preferably used.
【0021】共重合に際しては常法通り、過酸化物、ア
ゾ系化合物等の重合開始剤の存在下、有機溶媒を用いた
溶液重合が好ましく用いられる。溶剤としてはベンゼ
ン、トルエン、キシレン等の芳香族炭化水素、酢酸エチ
ル、酢酸ブチル、酢酸−2−エチルヘキシル等のエステ
ル類、アセトン、メチルエチルケトン、メチルイソブチ
ルケトン等のケトン類等が通常用いられる。また、メル
カプタン化合物類、ハロゲン化炭化水素類等の連鎖移動
剤の使用も可能である。Upon copolymerization, solution polymerization using an organic solvent in the presence of a polymerization initiator such as a peroxide or an azo compound is preferably used in a conventional manner. As the solvent, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate, butyl acetate and 2-ethylhexyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone are usually used. It is also possible to use chain transfer agents such as mercaptan compounds and halogenated hydrocarbons.
【0022】重合の温度は、重合開始剤の種類、量によ
りそれぞれ異なるが、通常は常温〜150℃程度の範囲
から選ばれる。得られる共重合体の分子量は開始剤及び
連鎖移動剤の種類、量及び重合温度により制御が可能で
あり、数平均分子量1000〜200000の範囲から
選択される。The polymerization temperature varies depending on the type and amount of the polymerization initiator, but is usually selected from the range of room temperature to 150 ° C. The molecular weight of the obtained copolymer can be controlled by the types and amounts of the initiator and the chain transfer agent and the polymerization temperature, and is selected from the range of the number average molecular weight of 1,000 to 200,000.
【0023】かくして得られたビニル系共重合体は少な
くとも一つの側鎖に、特定のシリコ−ン構造、加水分解
性アルコキシシリル基を併せ有し、かつ必要に応じてエ
ポキシ基をも有しており、熱硬化、湿気硬化、触媒硬化
等が可能であり、塗料原料、コ−ティング剤原料、シ−
リング剤原料、接着剤原料として有用な新規共重合体で
ある。The vinyl copolymer thus obtained has a specific silicone structure and a hydrolyzable alkoxysilyl group in at least one side chain, and also has an epoxy group if necessary. It is possible to heat cure, moisture cure, catalyst cure, etc.
It is a novel copolymer useful as a raw material for a ring agent and an adhesive.
【0024】本発明により得られる特定構造を有する樹
脂を塗料に適用する場合、必要に応じ非プロトン系の溶
剤で希釈して塗布硬化させる。硬化に際しては、促進触
媒を用いることが好ましい。かかる硬化触媒として代表
的なものを挙げれば、例えば モノメチル錫トリアセテ−ト、ジメチル錫ジアセテ
−ト、ジブチル錫ジアセテ−ト、ジブチル錫ジ2−エチ
ルヘキサノエ−ト、ジブチル錫ジラウレ−ト、ジフェニ
ル錫ジオクテ−ト、ビス(ジブチル錫モノラウレ−ト)
サルファイド、モノブチル錫ジラウレ−トハイドロクロ
ライド、2−エチルヘキサン酸錫、ジブチル錫オキシド
等の錫系化合物、 ヘキサン酸亜鉛、2−エチルヘキサン酸亜鉛、亜鉛
アセチルアセトナ−ト、ビス(亜鉛モノアセト酢酸塩)
オキサイド、ビス(亜鉛モノ酢酸塩)オキサイド、亜鉛
ジベンゾイルメタン等の亜鉛系化合物、 ヘキサン酸鉛、2−エチルヘキサン酸鉛、鉛アセチ
ルアセトナ−ト等の鉛系化合物、 ジイソプロポキシ・ビス(エチルアセトアセテ−
ト)チタネ−ト、ジイソプロポキシ・ビス(アセチルア
セテ−ト)チタネ−トまたはジイソプロポキシ・ビス
(アセチルアセトン)チタネ−トの如きチタニウムキレ
−ト化合物、 ジイソプロピレ−トエチルアセトアセテ−トアルミ
ニウム、トリス(エチルアセテ−ト)アルミニウム、ト
リス(n−プロピルアセトアセテ−ト)アルミニウム、
トリス(イソプロピルアセトアセテ−ト)アルミニウ
ム、トリス(n−ブチルアセトアセテ−ト)アルミニウ
ム、トリス(アセチルアセトナ−ト)アルミニウム、ト
リス(エチルアセトナ−ト)アルミニウム、ジイソプロ
ピレ−トエチルアセトナ−トアルミニウム、モノアセチ
ルアセトナ−ト・ビス(エチルアセトナ−ト)アルミニ
ウム、モノエチルアセトアセテ−トビス(アセチルアセ
トナ−ト)アルミニウム、トリス(イソプロピレ−ト)
アルミニウム、トリス(sec−ブチレ−ト)アルミニ
ウム、ジイソプロピレ−トモノ−sec−プトキシアル
ミニウムまたはトリスアセチルアセトンアルミニウムの
如きアルミニウムキレ−ト化合物、 テトラキス(アセチルアセトン)ジルコニウム、テ
トラキス(n−プロピルアセトアセテ−ト)ジルコニウ
ム、テトラキス(アセチルアセトナ−ト)ジルコニウム
またはテトラキス(エチルアセトアセテ−ト)ジルコニ
ウムの如きジルコニウム化合物、 トリエチルアミン、トリブチルアミン、N,N,
N′,N′−トリメチルエチレンジアミン、エチレンジ
アミン、ジエチレントリアミン、ジアザビシクロオクタ
ン、ダイマ−酸のポリアミドポリアミン、イソホロンジ
アミン、キシリレンジアミン、ジアミノジフェニルメタ
ン、無水フタル酸、テトラヒドロ無水フタル酸、無水ピ
ロメリット酸、無水トリメリット酸、フェノ−ルノボラ
ック、ポリメルカプタン、ポリサルファイド、2−メチ
ル−4−エチルイミダゾ−ル等のエポキシ硬化剤等が挙
げられる。When the resin having a specific structure obtained by the present invention is applied to a coating material, it is diluted with an aprotic solvent if necessary and then applied and cured. Upon curing, it is preferable to use an accelerating catalyst. Typical examples of such a curing catalyst include, for example, monomethyltin triacetate, dimethyltin diacetate, dibutyltin diacetate, dibutyltin di2-ethylhexanoate, dibutyltin dilaurate, diphenyltin. Dioctate, bis (dibutyltin monolaurate)
Tin compounds such as sulfide, monobutyltin dilaurate hydrochloride, tin 2-ethylhexanoate and dibutyltin oxide, zinc hexanoate, zinc 2-ethylhexanoate, zinc acetylacetonate, bis (zinc monoacetoacetate) )
Zinc compounds such as oxide, bis (zinc monoacetate) oxide, zinc dibenzoylmethane, lead hexanoate, lead 2-ethylhexanoate, lead acetylacetonate, etc., diisopropoxy bis ( Ethyl acetoacetate
Titanium), a titanium chelate compound such as diisopropoxy bis (acetylacetate) titanate or diisopropoxy bis (acetylacetone) titanate, diisopropylate ethylacetoacetate aluminum, Tris (ethylacetate) aluminum, tris (n-propylacetoacetate) aluminum,
Tris (isopropylacetoacetate) aluminum, tris (n-butylacetoacetate) aluminum, tris (acetylacetonate) aluminum, tris (ethylacetonate) aluminum, diisopropylethylethylacetonate aluminum, monoacetylacetate. Naat bis (ethylacetonate) aluminum, monoethylacetoacetate bis (acetylacetonate) aluminum, tris (isopropylate)
Aluminum chelate compounds such as aluminum, tris (sec-butyrate) aluminum, diisopropyl mono-sec-ptoxy aluminum or tris acetylacetone aluminum, tetrakis (acetylacetone) zirconium, tetrakis (n-propylacetoacetate) zirconium Zirconium compounds such as tetrakis (acetylacetonate) zirconium or tetrakis (ethylacetoacetate) zirconium, triethylamine, tributylamine, N, N,
N ', N'-trimethylethylenediamine, ethylenediamine, diethylenetriamine, diazabicyclooctane, dimer acid polyamide polyamine, isophoronediamine, xylylenediamine, diaminodiphenylmethane, phthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, anhydrous Examples of the epoxy curing agent include trimellitic acid, phenol novolac, polymercaptan, polysulfide, and 2-methyl-4-ethylimidazole.
【0025】これら触媒は、適宜混合して用いても良
い。触媒の添加量は通常樹脂に対し、0.005%〜5
重量%の範囲から選ばれる。硬化温度は被塗物の性状、
塗装目的により自由に設定可能であるが、一般的には大
気温度下の自然乾燥から220℃程度の焼き付け硬化の
範囲で選択すれば良い。塗料化の際、必要に応じて酸化
防止剤、光安定剤、粘性制御剤等の添加物、着色のため
の顔料、アルミペ−スト等の金属粉等を添加可能なこと
は勿論である。These catalysts may be appropriately mixed and used. The addition amount of the catalyst is usually 0.005% to 5 with respect to the resin.
It is selected from the range of weight%. The curing temperature depends on the nature of the object to be coated,
It can be freely set according to the purpose of coating, but generally, it may be selected in the range of natural drying at atmospheric temperature to bake hardening at about 220 ° C. It is needless to say that an additive such as an antioxidant, a light stabilizer, a viscosity controlling agent, a pigment for coloring, a metal powder such as an aluminum paste or the like can be added, if necessary, when forming a coating material.
【0026】[0026]
【実施例】以下、実施例に従い本発明を更に詳細に説明
するが、本発明は実施例によりなんら限定されるもので
はない。実施例中のNMR分析は日本電子(株)PMX
60Si、赤外吸光スペクトル(IR)は日本分光
(株)FT/IR−5300を用いた。また分子量測定
はゲルパ−ミエ−ションクロマトグラフィ−(GPC)
により行ったが、製造例1においては東ソ−TSKゲル
G5000HXL+G2500HXL、また実施例にお
いてはShodex KF−805+KF−804+K
F−802のカラム系を用いた。EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples. The NMR analysis in the examples is JMX PMX.
60Si, infrared absorption spectrum (IR) used JASCO Corporation FT / IR-5300. The molecular weight is measured by gel permeation chromatography (GPC).
In the production example 1, Toso-TSK gel G5000HXL + G2500HXL, and in the examples Shodex KF-805 + KF-804 + K.
A column system of F-802 was used.
【0027】塗膜性能評価は下記の方法に従い行った。 1)光 沢 :JIS K5400−7.6(60
°) ○:鏡面光沢度=85%以上 2)表面平滑性:表面粗さ形状測定器“サ−フコム−5
54AD”(東京精密(株)製)を用いて測定。表面性
(良)○>△>×(不良) 3)ゲル分率 :硬化塗膜をアセトンに浸漬し、20℃
×24時間放置後の塗膜重量残存率(%) 4)鉛筆硬度 :JIS K5400−8.4.1(す
り傷評価) 5)付 着 性:JIS K5400−8.5.2.
○:10〜8点、△:6〜4点、×:2〜0点 6)屈曲性 :JIS K5400−8.1 ○:
2mmφ合格、△:3〜6mmφ合格 ×:8mmφ
以上 7)耐汚染性 :JIS K5400−8.10
○:変化無し、 △:軽微な変化 ×:著しい変化 8)耐酸性 :JIS K5400−8.22 9)耐アルカリ性:JIS K5400−8.21(5
%NaOH水溶液で試験) 10)耐溶剤性:JIS K5400−8.24 (ト
ルエン) 11)耐候性 :ASTM G−53 ○:2500
時間暴露で光沢保持率=95%以上 ×:2500時間
暴露で光沢保持率=90%以下The coating film performance was evaluated according to the following method. 1) Mitsuzawa: JIS K5400-7.6 (60)
°) ◯: Specular glossiness = 85% or more 2) Surface smoothness: Surface roughness profile measuring device "Surfcom-5"
54AD "(manufactured by Tokyo Seimitsu Co., Ltd.) Surface property (good) ○>△> × (poor) 3) Gel fraction: The cured coating film is immersed in acetone at 20 ° C.
X Coating weight residual rate (%) after standing for 24 hours 4) Pencil hardness: JIS K5400-8.4.1 (Scratch evaluation) 5) Adhesion: JIS K5400-8.5.2.
○: 10 to 8 points, △: 6 to 4 points, ×: 2 to 0 points 6) Flexibility: JIS K5400-8.1 ○:
2mmφ pass, △: 3-6mmφ pass x: 8mmφ
Above 7) Contamination resistance: JIS K5400-8.10.
◯: No change, Δ: Minor change x: Significant change 8) Acid resistance: JIS K5400-8.22 9) Alkali resistance: JIS K5400-8.21 (5
% NaOH aqueous solution) 10) Solvent resistance: JIS K5400-8.24 (toluene) 11) Weather resistance: ASTM G-53 ◯: 2500
Gloss retention after time exposure = 95% or more x: Gloss retention after exposure to 2500 hours = 90% or less
【0028】[0028]
【製造例1】 〔化合物−II〕の合成 温度計、攪拌用回転子、冷却管を取付けた2リットルの
4口フラスコにジオキサン1200gとトリクロロシラ
ン1molを仕込み攪拌した。水18gとジオキサン1
8gを入れた滴下ロ−トを上記4口フラスコに取付け、
25〜30℃に保ちながら滴下した。滴下後、さらに3
0分間攪拌を続けた後エタノ−ル3molを入れた滴下
ロ−トを取付け、25〜30℃に保ちながら滴下した。
その後さらに120分間攪拌した。反応液を取り出し、
約60℃以下減圧下で溶媒を完全に溜去したところ7
9.3gの低粘度シリコ−ン化合物が得られた。この液
体をクロロホルムに溶解し、この溶液をゲルパ−ミエ−
ションクロマトグラフィ−(以下、GPC法と略記)に
より分子量を測定した。その結果、数平均分子量(以
下、MNと略記)840、重量平均分子量(以下、MW
と略記)1600であった。 1H−NMRによりSi−
H/OC2 H5 は約1.2であった。又、このシリコ−
ン化合物を2N−NaOH中に添加し、発生する水素ガ
スにより、Si−Hの含有量を測定したところ11.5
mmol/gの水素ガスが発生した。[Production Example 1] Synthesis of [Compound-II] 1200 g of dioxane and 1 mol of trichlorosilane were charged and stirred in a 2-liter four-necked flask equipped with a thermometer, a stirring rotor and a cooling tube. 18g water and 1 dioxane
A dropping funnel containing 8 g was attached to the 4-neck flask,
The solution was added dropwise while maintaining the temperature at 25 to 30 ° C. 3 more after dropping
After continuing stirring for 0 minutes, a dropping funnel containing 3 mol of ethanol was attached and dropping was performed while maintaining the temperature at 25 to 30 ° C.
Then, the mixture was stirred for another 120 minutes. Remove the reaction solution,
When the solvent was completely distilled off under reduced pressure below about 60 ° C, 7
9.3 g of low-viscosity silicone compound was obtained. This liquid was dissolved in chloroform, and this solution was added to gel permeation solution.
The molecular weight was measured by ion chromatography (hereinafter abbreviated as GPC method). As a result, a number average molecular weight (hereinafter, abbreviated as MN) 840, a weight average molecular weight (hereinafter, MW)
1600). Si- by 1 H-NMR
H / OC 2 H 5 was about 1.2. Also, this silicone
1H was measured by adding hydrogen chloride compound to 2N-NaOH and measuring the hydrogen gas generated.
Hydrogen gas of mmol / g was generated.
【0029】[0029]
【実施例I−1】 〔化合物−I〕の合成 温度計、攪拌用回転子、冷却管、チッ素供給用導入管を
取付けた200ミリリットル4口フラスコに、8%の塩
化白金酸を含むイソプロパノ−ル溶液0.32g、メタ
クリル酸アリル3.41g、アリルグリシジルエ−テル
27.69g、トルエン50.8gを仕込んだ。又、滴
下ロ−トに製造例1で得られたシリコ−ン化合物19.
9gを入れ上記4口フラスコに取付けた。少量(5ミリ
リットル/分程度)のチッ素を流し攪拌、加熱昇温を行
った。フラスコ内温が70℃に昇温したとき、シリコ−
ン化合物の滴下を開始し、80〜85℃に保ちながら全
量滴下した。滴下終了後80〜85℃の温度で3時間攪
拌した。反応終了後、反応液をガスクロマトグラフィ−
により分析したところメタクリル酸アリルの反応率70
%、アクリルグリシジルエ−テルの反応率77%であっ
た。Example I-1 Synthesis of [Compound-I] A 200 ml four-necked flask equipped with a thermometer, a stirring rotor, a cooling tube, and a nitrogen supply introduction tube was charged with isopropanol containing 8% chloroplatinic acid. Solution 0.32 g, allyl methacrylate 3.41 g, allyl glycidyl ether 27.69 g, and toluene 50.8 g were charged. In addition, the silicone compound (19.) obtained in Production Example 1 was added to the dropping funnel.
9 g was put and attached to the above 4-necked flask. A small amount (about 5 ml / min) of nitrogen was poured, and the mixture was stirred and heated to raise the temperature. When the temperature inside the flask was raised to 70 ° C, the silicone
The entire amount of the compound was added while maintaining the temperature at 80 to 85 ° C. After completion of dropping, the mixture was stirred at a temperature of 80 to 85 ° C. for 3 hours. After the reaction is completed, the reaction solution is subjected to gas chromatography.
When analyzed by, the reaction rate of allyl methacrylate was 70
%, And the reaction rate of acrylic glycidyl ether was 77%.
【0030】反応液は、50℃以下減圧下で溶媒を溜去
したところ40.7gの淡黄色透明液体が得られた。こ
の液体をGPC法により分子量を測定したところMN1
900であった。又、この液体を2N−NaOHに添加
し残存Si−Hの測定を行ったところSi−Hの反応率
は、76%であった。また、IR分析(赤外吸収スペク
トル)では、1720cm-1にカルボン酸エステルの吸
収、1640cm-1にビニル基の吸収があった。IRス
ペクトルを図1に示す。When the solvent was distilled off from the reaction solution under reduced pressure at 50 ° C. or lower, 40.7 g of a pale yellow transparent liquid was obtained. When the molecular weight of this liquid was measured by the GPC method, MN1
It was 900. When this liquid was added to 2N-NaOH and the residual Si-H was measured, the reaction rate of Si-H was 76%. Further, in the IR analysis (infrared absorption spectrum), there was absorption of a carboxylic acid ester at 1720 cm −1 and absorption of a vinyl group at 1640 cm −1 . The IR spectrum is shown in FIG.
【0031】[0031]
【実施例I−2】 〔化合物−I〕の合成 温度計、攪拌用回転子、冷却管、チッ素供給用導入管を
取付けた200ミリリットルの4口フラスコ内をチッ素
で充分置換し白金黒0.5gを入れ、その後、製造例1
のシリコ−ン化合物19.2g、1−ヘキセン16.9
g、メタクリル酸アリル4.85g、トルエン40.9
gの混合液を添加した。攪拌、加熱を開始し、80〜8
5℃へ昇温した。そのまま80〜85℃に保ち3時間攪
拌した。反応液を取り出し濾過し白金黒を除いた後、約
60℃の減圧下で溶媒を完全に溜去したところ30.8
gの回収物を得た。反応液のガスクロマトグラフィ−に
より、1−ヘキセンの反応率57%、メタクリル酸アリ
ルの反応率90%、Si−Hの反応率73%であり、M
Nは1700であった。Example I-2 Synthesis of [Compound-I] Platinum black was prepared by thoroughly replacing the inside of a 200 ml four-necked flask equipped with a thermometer, a stirring rotor, a cooling tube, and a nitrogen supply introduction tube with nitrogen. 0.5g was put, and then Production Example 1
Silicon compound of 19.2 g, 1-hexene 16.9
g, allyl methacrylate 4.85 g, toluene 40.9
g mixture was added. Start stirring and heating, 80 ~ 8
The temperature was raised to 5 ° C. The temperature was kept at 80 to 85 ° C. and stirred for 3 hours. The reaction solution was taken out and filtered to remove platinum black, and then the solvent was completely distilled off under reduced pressure of about 60 ° C. to obtain 30.8.
g of recovered material was obtained. By gas chromatography of the reaction liquid, the reaction rate of 1-hexene was 57%, the reaction rate of allyl methacrylate was 90%, and the reaction rate of Si—H was 73%.
N was 1700.
【0032】[0032]
【実施例I−3】 〔化合物−I〕の合成 実施例I−1と同様な装置に、8%の塩化白金酸を含む
イソプロパノ−ル溶液0.10g、酢酸アリル7.5
g、製造例1で得られたシリコ−ン化合物8.3g、キ
シレン15.8gを仕込み、温度80〜85℃で2時間
攪拌した。その後メタクリル酸アリル6.3gを滴下
し、80〜85℃、2時間反応させた。反応液を約45
℃減圧下で溶媒を溜去したところ15.2gの回収物を
得た。反応液のガスクロ分析の結果、酢酸アリルの反応
率95%、メタクリル酸アリルの反応率19%であっ
た。GPC法により分子量を測定したところMN260
0であった。又、Si−Hの反応率は85%であった。Example I-3 Synthesis of [Compound-I] In a device similar to that of Example I-1, 0.10 g of isopropanol solution containing 8% of chloroplatinic acid and allyl acetate 7.5.
g, 8.3 g of the silicone compound obtained in Production Example 1, and 15.8 g of xylene were charged, and the mixture was stirred at a temperature of 80 to 85 ° C. for 2 hours. After that, 6.3 g of allyl methacrylate was added dropwise and reacted at 80 to 85 ° C. for 2 hours. The reaction solution is about 45
When the solvent was distilled off under reduced pressure at ° C, 15.2 g of a recovered product was obtained. As a result of gas chromatography analysis of the reaction liquid, the reaction rate of allyl acetate was 95% and the reaction rate of allyl methacrylate was 19%. When the molecular weight was measured by the GPC method, MN260
It was 0. The reaction rate of Si-H was 85%.
【0033】1H−NMR分析結果、5.4〜6.4p
pmにCH2 =C1 −基が0.5〜1.1ppmにSi
−CH2 −基があることがわかる。この 1H−NMRス
ペクトルを図3に示す。IR分析の結果、1750cm
-1にカルボン酸エステルの吸収が強く有り、1640c
m-1 にビニル基の吸収があった。このIRスペクトル
を図2に示す。 1 H-NMR analysis result, 5.4 to 6.4 p
CH 2 = C 1 -group in pm is Si in 0.5 to 1.1 ppm
It can be seen that there is a —CH 2 — group. This 1 H-NMR spectrum is shown in FIG. IR analysis result, 1750 cm
-1 has strong absorption of carboxylic acid ester, 1640c
There was absorption of vinyl group at m -1 . This IR spectrum is shown in FIG.
【0034】[0034]
【実施例I−4〜I−5】 〔化合物−I〕の合成 実施例I−2と同様にして、触媒、製造例1で得られた
シリコ−ン化合物、メタクリル酸アリル化合物(AMA
と略記)、トルエンを反応器に仕込み、反応温度80〜
85℃で反応を行った。Examples I-4 to I-5 Synthesis of [Compound-I] In the same manner as in Example I-2, the catalyst, the silicone compound obtained in Production Example 1 and the allyl methacrylate compound (AMA) were used.
Abbreviated as "), toluene was charged into the reactor, and the reaction temperature was 80 to
The reaction was carried out at 85 ° C.
【0035】その結果を表1に示す。The results are shown in Table 1.
【0036】[0036]
【表1】 [Table 1]
【0037】[0037]
【実施例II−1】 〔共重合体−I〕の合成 温度計、攪拌用回転子、冷却管、チッ素供給用導入管を
取付けた300ミリリットル4口フラスコに、トルエン
70gを仕込んだ。一方、滴下ロ−トにメタクリル酸メ
チル36g、アクリル酸n−ブチル23g、3−メタク
リロキシプロピルトリメトキシシラン12g、実施例I
−1で得られたシリコ−ン系化合物29g、トルエン3
0g、アゾビスイソブチロニトリル(AIBN)1.0
g、n−ドデシルメルカプタン(LSH)2.0gの混
合液を仕込み、上記4口フラスコに取付けた。4口フラ
スコ内にチッ素を供給し、反応装置内を充分チッ素で置
換した。攪拌、加熱を行い4口フラスコ内を80℃に保
ちながら混合液を滴下した。滴下終了後温度80℃で5
時間攪拌した。Example II-1 Synthesis of [Copolymer-I] 70 g of toluene was charged into a 300 ml four-necked flask equipped with a thermometer, a stirring rotor, a cooling tube, and a nitrogen supply introducing tube. On the other hand, 36 g of methyl methacrylate, 23 g of n-butyl acrylate, 12 g of 3-methacryloxypropyltrimethoxysilane were added to the dropping funnel, and Example I was used.
29 g of the silicon-based compound obtained in -1 and toluene 3
0 g, azobisisobutyronitrile (AIBN) 1.0
A mixed solution of 2.0 g of g and n-dodecyl mercaptan (LSH) was charged and attached to the 4-necked flask. Nitrogen was supplied into the 4-neck flask, and the inside of the reactor was sufficiently replaced with nitrogen. The mixture was added dropwise while stirring and heating to keep the inside of the 4-neck flask at 80 ° C. After the dropping is completed, the temperature is 80 ° C and the temperature is 5
Stir for hours.
【0038】反応終了後、反応液のガスクロ分析の結
果、(メタ)アクリルモノマ−の反応率は、メタクリル
酸メチル100%アクリル酸n−ブチル94%、メタク
リロキシプロピルトリメトキシシラン99%であった。
GPC法による分析結果MN5800、MW67000
であった。反応液の一部を取り、60℃減圧下で濃縮し
た後、同重量のトルエンを加え50%溶液とした。この
溶液のIR分析において1640cm-1 のビニル基の
吸収はなかった。IRスペクトルを図4に示す。After completion of the reaction, gas chromatographic analysis of the reaction solution revealed that the reaction rate of the (meth) acrylic monomer was 100% methyl methacrylate, 94% n-butyl acrylate, and 99% methacryloxypropyltrimethoxysilane. ..
Analysis results by GPC method MN5800, MW67000
Met. A part of the reaction solution was taken and concentrated under reduced pressure at 60 ° C., and then toluene of the same weight was added to obtain a 50% solution. In the IR analysis of this solution, there was no absorption of a vinyl group at 1640 cm -1 . The IR spectrum is shown in FIG.
【0039】[0039]
【実施例II−2〜II−5】 〔共重合体−I〕の合成 実施例II−1と同様に、4口フラスコにトルエン20
gを仕込み、滴下ロ−トにて下記の混合液を80℃で滴
下した。その後80℃で5時間反応させた。 メタクリル酸メチル (MMA) 19.9g アクリル酸n−ブチル (BA) 12.6g 3−メタクリロキシ プロピルトリメトキシシラン 7.0g 実施例I−2〜I−5のシリコ−ン系化合物 15.5g AIBN 0.55g n−C12H25SH 1.10g トルエン 35g 表2にその結果を示す。Examples II-2 to II-5 Synthesis of [Copolymer-I] Toluene 20 was placed in a 4-neck flask in the same manner as in Example II-1.
Then, the following mixture was added dropwise at 80 ° C. with a dropping funnel. Then, the mixture was reacted at 80 ° C. for 5 hours. Methyl methacrylate (MMA) 19.9 g n-butyl acrylate (BA) 12.6 g 3-methacryloxypropyltrimethoxysilane 7.0 g Silicone compounds of Examples I-2 to I-5 15.5 g AIBN 0 to .55g n-C 12 H 25 SH 1.10g toluene 35g table 2 shows the results.
【0040】[0040]
【表2】 [Table 2]
【0041】[0041]
【実施例II−6〜II−9】 〔共重合体−I〕の合成 実施例II−1同様に、4口フラスコにトルエン70g
を仕込み、滴下ロ−トに表3の組成液を仕込み、実施例
II−1と同様に反応させた。表3に仕込み組成及びそ
の結果を示す。Examples II-6 to II-9 Synthesis of [Copolymer-I] 70 g of toluene was placed in a 4-neck flask in the same manner as in Example II-1.
Was charged, and the composition liquid of Table 3 was charged into the dropping funnel and reacted in the same manner as in Example II-1. Table 3 shows the charged composition and the result.
【0042】[0042]
【表3】 [Table 3]
【0043】[0043]
【製造例2】実施例II−1と同様に、4口フラスコに
トルエン70gを仕込み、滴下ロ−トにて下記の混合液
を80℃で滴下した。その後温度80℃で5時間反応さ
せた。 メタクリル酸メチル 54g アクリル酸−n−ブチル 34g 3−メタクリロキシ プロピルトリメトキシシラン 12g AIBN 1.0g n−C12H25SH 2.0g この結果、得られたポリマ−分子量(MN)5500で
あった。[Production Example 2] In the same manner as in Example II-1, 70 g of toluene was charged into a 4-necked flask, and the following mixed solution was added dropwise at 80 ° C. with a dropping funnel. Then, the reaction was carried out at a temperature of 80 ° C. for 5 hours. Methyl methacrylate 54 g-n-butyl acrylate 34 g 3-methacryloxypropyltrimethoxysilane 12 g AIBN 1.0 g n-C 12 H 25 SH 2.0 g As a result, the obtained polymer molecular weight (MN) was 5500.
【0044】[0044]
【実施例III−1〜9】実施例II−1〜8で得られ
た樹脂溶液に硬化触媒(a=アルミニウムアセチルアセ
テ−ト,b=ジブチル錫ジラウレ−ト)を対樹脂分1重
量%配合した後、酢酸エチル/キシレン(40/60)
(重量%)の混合溶剤をシンナ−としてフォ−ドカップ
♯4で15秒に粘度調整し塗装し、150℃×30分加
熱硬化させて得られた塗膜の性能評価を行った。結果を
表4に示す。Examples III-1 to 9: A curing catalyst (a = aluminum acetyl acetate, b = dibutyltin dilaurate) was added to the resin solutions obtained in Examples II-1 to 8 in an amount of 1% by weight of the resin content. After that, ethyl acetate / xylene (40/60)
The viscosity of the mixed solvent (wt%) was used as a thinner to adjust the viscosity of the paint in a cup # 4 for 15 seconds, and the coating was performed, followed by heat curing at 150 ° C. for 30 minutes to evaluate the performance of the coating film. The results are shown in Table 4.
【0045】[0045]
【比較例1】一方、製造例2で得られた、本願発明の特
定構造の側鎖を持たない樹脂を、実施例II−1〜9と
同様に塗装、硬化、評価して比較例とした。結果を表4
に併せて示した。Comparative Example 1 On the other hand, the resin having no side chain of the specific structure of the present invention obtained in Production Example 2 was coated, cured and evaluated in the same manner as in Examples II-1 to 9 to give a comparative example. .. The results are shown in Table 4.
Are also shown.
【0046】[0046]
【表4】 [Table 4]
【0047】[0047]
【発明の効果】かくして得られた塗料組成物は低粘度で
希釈有機溶剤の使用量の低減化が可能であり、得られた
硬化塗膜は非常に優れた光沢と表面平滑性を有する卓越
した外観を提供すると共に、優れた耐候性、耐酸性、耐
アルカリ性、耐溶剤性、撥水性、耐汚染性を発揮する
為、例えば、新車中塗及び上塗り、自動車補修、建築外
装、建材、プラスチック、各種金属製品、木工等の種々
の分野に適用可能な高性能塗料として使用される。The coating composition thus obtained has a low viscosity and can reduce the amount of diluted organic solvent used, and the obtained cured coating film has excellent gloss and surface smoothness. In addition to providing appearance, it also exhibits excellent weather resistance, acid resistance, alkali resistance, solvent resistance, water repellency, and stain resistance, so for example, new car middle coating and top coating, automobile repair, building exterior, building materials, plastic, various Used as a high-performance paint applicable to various fields such as metal products and woodworking.
【図1】本発明の実施例I−1で得られた化合物のIR
スペクトルを示す。FIG. 1 is the IR of the compound obtained in Example I-1 of the present invention.
The spectrum is shown.
【図2】本発明の実施例I−3で得られた化合物のIR
スペクトルを示す。FIG. 2 is the IR of the compound obtained in Example I-3 of the present invention.
The spectrum is shown.
【図3】本発明の実施例I−3で得られた化合物のNM
Rスペクトルを示す。FIG. 3 is an NM of the compound obtained in Example I-3 of the present invention.
The R spectrum is shown.
【図4】本発明の実施例II−1で得られた化合物のI
Rスペクトルを示す。FIG. 4 I of the compound obtained in Example II-1 of the present invention
The R spectrum is shown.
Claims (3)
(B)で表される構造を併せ有し、(2)末端基として
ケイ素に結合する場合がR2 −O−および酸素に結合す
る場合がR2 −の構造をとり(R2 は炭素数1〜18の
直鎖または分岐アルキル基、またはフェニル基)、
(3)数平均分子量800〜200000、かつ(4)
R1 /R2 比が0.8〜10であることを特徴とするシ
リコーン系化合物。 【化1】 1. A compound having the structures represented by the following general formulas (A) and (B) in the molecular structure (1), and (2) in the case of being bonded to silicon as an end group, R 2 —O— and When bonded to oxygen, it has a structure of R 2 — (R 2 is a linear or branched alkyl group having 1 to 18 carbon atoms, or a phenyl group),
(3) Number average molecular weight of 800 to 200,000, and (4)
A silicone compound having an R 1 / R 2 ratio of 0.8 to 10. [Chemical 1]
(D)で表される構造を併せ有し、(2)末端基として
ケイ素に結合する場合がR2 −O−および酸素に結合す
る場合がR2 −の構造をとり(R2 は炭素数1〜18の
直鎖または分岐アルキル基、またはフェニル基)、
(3)R1 /R2 比が0.8〜10であるシリコーン系
官能基を少なくとも1つの側鎖中に持つことを特徴とす
る数平均分子量1000〜200000のビニル系共重
合体。 【化2】 2. A compound having the structures represented by the following general formulas (C) and (D) in the molecular structure (1), and (2) in the case of being bonded to silicon as an end group, R 2 —O— and When bonded to oxygen, it has a structure of R 2 — (R 2 is a linear or branched alkyl group having 1 to 18 carbon atoms, or a phenyl group),
(3) A vinyl-based copolymer having a number average molecular weight of 1,000 to 200,000, having a silicone-based functional group having an R 1 / R 2 ratio of 0.8 to 10 in at least one side chain. [Chemical 2]
(D)で表される構造を併せ有し、(2)末端基として
ケイ素に結合する場合がR2 −O−および酸素に結合す
る場合がR2 −の構造をとり(R2 は炭素数1〜18の
直鎖または分岐アルキル基、またはフェニル基)、
(3)R1 /R2 比が0.8〜10であるシリコーン系
官能基を少なくとも1つの側鎖中に持つ数平均分子量1
000〜200000のビニル系共重合体を主成分とす
ることを特徴とする塗料組成物。 【化3】 3. (1) The compound has the structures represented by the following general formulas (C) and (D) in the molecular structure, and (2) in the case of being bonded to silicon as an end group, R 2 —O— and When bonded to oxygen, it has a structure of R 2 — (R 2 is a linear or branched alkyl group having 1 to 18 carbon atoms, or a phenyl group),
(3) Number average molecular weight 1 having a silicone functional group having an R 1 / R 2 ratio of 0.8 to 10 in at least one side chain
A coating composition comprising 000 to 200,000 vinyl-based copolymer as a main component. [Chemical 3]
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JP04023447A JP3115928B2 (en) | 1992-02-10 | 1992-02-10 | Silicone compound, vinyl copolymer thereof, and coating composition using the same |
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JP04023447A JP3115928B2 (en) | 1992-02-10 | 1992-02-10 | Silicone compound, vinyl copolymer thereof, and coating composition using the same |
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JPH05222198A true JPH05222198A (en) | 1993-08-31 |
JP3115928B2 JP3115928B2 (en) | 2000-12-11 |
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ID=12110762
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