JP4395680B2 - Silicon-containing compound and method for producing the same - Google Patents

Description

【００１０】
【化８】

【００１１】
【化９】

【００１２】
［２］前記式（２）に示す化合物が、２，４−体及び／又は２，６−体である前記［１］に記載のケイ素含有化合物。
【００１３】
［３］下記式（４）又は（５）に示す化合物と、イソホロンジイソシアネート、又は２，４−トリレンジイソシアネート及び／もしくは２，６−トリレンジイソシアネート、並びに下記式（６）に示すアルコキシシラン化合物とを反応させることを特徴とする前記［１］又は［２］に記載のケイ素含有化合物の製造方法。
【００１４】
【化１０】

【００１５】
【化１１】

【００１６】
【化１２】

【００１７】
【発明の実施の形態】
以下、本発明の実施の形態について具体的に説明する。
本発明のケイ素含有化合物は、前記式（１）、（２）又は（３）に示す化合物（以下、それぞれ「第１のケイ素含有化合物」、「第２のケイ素含有化合物」及び「第３のケイ素含有化合物」ということがある）である。
以下、各ケイ素含有化合物ごとに具体的に説明する。
【００１８】
１．第１のケイ素含有化合物
第１のケイ素含有化合物は、前記式（４）に示す化合物（以下、「反応性化合物（４）」ということがある）と、イソホロンジイソシアネート（ＩＰＤＩ）と前記式（６）に示す化合物（以下、「反応性化合物（６）」ということがある）とを触媒の存在下で反応させることによって製造することができる。
【００１９】
反応性化合物（４）と反応性化合物（６）との配合量は、ＩＰＤＩに対してそれぞれ等モルとすることが好ましい。
【００２０】
第１のケイ素含有化合物の製造においては、化合物（４）の３級水酸基とＩＰＤＩのイソシアネート基との反応を防ぐという理由から、ＩＰＤＩと反応性化合物（６）との付加反応を行った後、ＩＰＤＩと反応性化合物（６）との付加体と、反応性化合物（４）とを反応させることが好ましい。
【００２１】
第１のケイ素含有化合物の製造において、第１のケイ素含有化合物の純度は、８０％以上が好ましく、９０％以上がさらに好ましい。
【００２２】
２．第２のケイ素含有化合物
第２のケイ素含有化合物は、反応性化合物（４）と、２，４−トリレンジイソシアネート（２，４−ＴＤＩ）又は／及び２，６−トリレンジイソシアネート（２，６−ＴＤＩ）並びに反応性化合物（６）とを触媒の存在下で反応させることによって製造することができる。
【００２３】
反応性化合物（４）と反応性化合物（６）との配合量は、ＴＤＩに対してそれぞれ等モルとすることが好ましい。
【００２４】
第２のケイ素含有化合物の製造においては、化合物（４）の３級水酸基とＴＤＩのイソシアネート基との反応を防ぐという理由から、ＴＤＩと反応性化合物（６）との付加反応を行った後、ＴＤＩと反応性化合物（６）の付加体と、反応性化合物（４）とを反応させることが好ましい。
【００２５】
第２のケイ素含有化合物の製造において、第２のケイ素含有化合物の純度は、８０％以上が好ましく、９０％以上がさらに好ましい。
【００２６】
３．第３のケイ素含有化合物
第３のケイ素含有化合物は、前記式（５）に示す化合物（以下、「反応性化合物（５）」ということがある）と、ＩＰＤＩ及び反応性化合物（６）とを触媒の存在下で反応させることによって製造することができる。
【００２７】
反応性化合物（５）と反応性化合物（６）との配合量は、ＩＰＤＩに対してそれぞれ等モルとすることが好ましい。
【００２８】
第３のケイ素含有化合物の製造においては、ＩＰＤＩと反応性化合物（５）との付加反応を行った後、ＩＰＤＩと反応性化合物（５）の付加体と、反応性化合物（６）とを反応させることが好ましい。この順序を逆にしたり、３成分を同時に添加して反応させると、目的とするケイ素含有化合物を純度よく得られないことがある。
【００２９】
第３のケイ素含有化合物の製造において、第３のケイ素含有化合物の純度は、８０％以上が好ましく、９０％以上がさらに好ましい。
【００３０】
本発明に用いられる反応性化合物（４）としては、例えば、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オンを挙げることができる。
上記化合物の市販品としては、チバスペシャルティケミカルズ（株）製 商品名：イルガキュア２９５９を挙げることができる。
【００３１】
本発明に用いられる反応性化合物（５）としては、例えば、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オンを挙げることができる。
上記化合物の市販品としては、チバスペシャルティケミカルズ（株）製 商品名：ダロキュア１１７３を挙げることができる。
【００３２】
本発明に用いられる反応性化合物（６）としては、例えば、γ−メルカプトプロピルトリメトキシシランを挙げることができる。
上記化合物の市販品としては、東レ・ダウ・コーニング・シリコーン（株）製
商品名：ＳＨ６０６２を挙げることができる。
【００３３】
上記第1〜第３のケイ素含有化合物の製造方法において、反応温度は、通常−２０〜１００℃、好ましくは０〜６０℃である。
【００３４】
また、反応は、不活性溶媒、例えば、トルエン、キシレン、ヘキサン、ヘプタン等の炭化水素系溶剤、塩化メチレン、クロロホルム、クロロベンゼン等のハロゲン化炭化水素系溶剤、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系溶剤、テトラヒドロフラン、ジオキサン、トリオキサン、ジグライム等のエーテル系溶剤、又はこれらの混合溶媒中で行ってもよい。これらの溶剤の使用量は、ジイソシアネート１モルに対して、通常、１０００ｍｌ以下、好ましくは５００ｍｌ以下、さらに好ましくは１００ｍｌ以下である。溶剤の使用量が１０００ｍｌを超えると反応が十分に進行しないことがある。
【００３５】
本発明において用いられる触媒としては、塩基性触媒及び酸性触媒のいずれであってもよく、また塩基性触媒と酸性触媒とを併用してもよい。
塩基性触媒としては、例えば、ピリジン、ピロール、トリエチルアミン、ジエチルアミン、ジブチルアミン、アンモニア等のアミン類、トリブチルホスフィン、トリフェニルホスフィン等のホスフィン類を挙げることができる。中でも、ピリジン、トリエチルアミン等の３級アミンが好ましい。
酸触媒としては、例えば、ナフテン酸銅、ナフテン酸コバルト、ナフテン酸亜鉛、ＤＡＢＣＯ、メチルＤＡＢＣＯ、トリブトキシアルミニウム、チタニウムテトラブトキシド、ジルコニウムテトラブトキシド等の金属アルコキシド類、３フ化ホウ素ジエチルエーテラート、塩化アルミニウム等のルイス酸類、２−エチルへキサン酸スズ、オクチルスズトリラウレート、ジブチルスズジラウレート、オクチルスズジアセテート等のスズ化合物を挙げることができる。中でも、オクチルスズトリラウレート、ジブチルスズジラウレート、オクチルスズジアセテート等のスズ化合物が好ましい。
塩基性触媒と酸性触媒を併用する場合、アミン類とスズ化合物との併用が好ましく、ピリジン、トリエチルアミン等の３級アミンとオクチルスズトリラウレート、ジブチルスズジラウレート、オクチルスズジアセテート等のスズ化合物との併用がさらに好ましい。
【００３６】
上記触媒の中では、塩基性触媒と酸性触媒を併用する場合が好ましく、アミン類とスズ化合物との併用がさらに好ましく、ピリジン、トリエチルアミン等の３級アミンとオクチルスズトリラウレート、ジブチルスズジラウレート、オクチルスズジアセテート等のスズ化合物との併用が特に好ましい。
【００３７】
これら触媒の添加量は、ジイソシアネート化合物１００重量部に対して０．０１〜５重量部であり、好ましくは０．１〜３重量部である。０．０１重量部未満であると反応が十分に進行しないことがあり、５重量部を超えると生成物の保存安定性が低下することがある。
【００３８】
本発明のケイ素含有化合物は、反応性粒子（表面活性粒子）の表面修飾剤として有用である。すなわち、本発明のケイ素含有化合物は、アルコキシシラン基を有するため、種々の反応性粒子との反応により、この粒子表面にラジカル重合開始機能を付与することができるため、反応性粒子の表面修飾剤として有用である。
【００３９】
【実施例】
以下、本発明を実施例によってさらに具体的に説明するが、本発明はこれら実施例に何ら制限を受けるものではない。なお、以下において、部、％は特に記載しない限り、それぞれ重量部、重量％を示す。
【００４０】
実施例１（第１のケイ素含有化合物の合成）
乾燥空気中、イソホロンジイソシアネート３４．３部、ジブチルスズジラウレート０．５部からなる溶液に対し、γ−メルカプトプロピルトリメトキシシラン３０．４部を攪拌しながら２０℃で１時間かけて滴下後、６０℃で１時間攪拌した。これにトリエチルアミン０．１部を添加し、６０℃で１時間撹拌した後の中間体中の残存イソシアネート量を分析したところ、１０％であった。反応前の全イソシアネート量は、２０％であり、この値から求められるイソシアネート反応率は５０％で、イソホロンジイソシアネート中１個のイソシアネート基とγ−メルカプトプロピルトリメトキシシランのチオール基との反応がほぼ定量的に終了したことを確認した。さらに１−［４−（２−ヒドロキシエトキシ）フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン３４．７部を添加後、６０℃で３時間加熱攪拌することで第１のケイ素含有化合物を得た。
生成物中の残存イソシアネート量を分析したところ、０．１％以下であり、反応がほぼ定量的に終了したことを確認した。
【００４１】
図１に、得られた第１のケイ素含有化合物のＩＲ吸収曲線を示す。
【００４２】
¹Ｈ−ＮＭＲスペクトルデータを以下に示す。
¹Ｈ−ＮＭＲ；ＣＤＣ１₃・４００ＭＨｚ
δｐｐｍ；０．６０−１．３５（ｍ，１７Ｈ），１．４０−１．９０（ｍ，１０Ｈ），２．８０−３．２０（ｍ，４Ｈ），３．５６（ｓ，９Ｈ），３．９０−４１９（ｍ，１Ｈ），４．２０−４．３０（ｍ，２Ｈ），４．３８−４．５０（ｍ，２Ｈ），６．９５（ｄ，２Ｈ），８．０６（ｄ，２Ｈ）
【００４３】
実施例２（第２のケイ素含有化合物の合成）
乾燥空気中、２，４−トリレンジイソシアネート２９．２部、ジブチルスズジラウレート０．１部からなる溶液に対し、γ−メルカプトプロピルトリメトキシシラン３３．０部を攪拌しながら２０℃で１時間かけて滴下後、３０℃、６０℃でそれぞれ１時間攪拌した。この中間体中の残存イソシアネート量を分析したところ、１１．３％であり、反応がほぼ定量的に終了したことを確認した。さらに、１−［４−（２−ヒドロキシエトキシ）フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン３７．７部を添加後、６０℃で３時間加熱攪拌することで第２のケイ素含有化合物を得た。
生成物中の残存イソシアネート量を分析したところ、０．１％以下であり、反応がほぼ定量的に終了したことを示した。
【００４４】
図２に、得られた第２のケイ素含有化合物のＩＲ吸収曲線を示す。
【００４５】
¹Ｈ−ＮＭＲスペクトルデータを以下に示す。
¹Ｈ−ＮＭＲ；ＣＤＣｌ₃・４００ＭＨｚ
δｐｐｍ；０．７４（ｔ，２Ｈ），１．６３（ｓ，６Ｈ），１．７７（ｑ，２Ｈ），２．１９（ｄ，３Ｈ），２．９８（ｔ，２Ｈ），３．５７（ｓ，９Ｈ），４．２７−４．３１（ｍ，２Ｈ），４．５０−４．５７（ｍ，２Ｈ），６．５５（ｓ，１Ｈ），６．９８−７．３５（ｍ，４Ｈ），７．８４（ｓ，１Ｈ），８．０７（ｄ，２Ｈ）
【００４６】
実施例３（第３のケイ素含有化合物の合成）
乾燥空気中、イソホロンジイソシアネート３８．１部、ジブチルスズジラウレート０．１部からなる溶液に対し、２−ヒドロキシー２−メチル−１−フェニル−プロパン−１−オン２８．１部を攪拌しながら２０℃で１時間かけて滴下後、３０℃、６０℃でそれぞれ１時間攪拌した。この中間体中の残存イソシアネート量を分析したところ、１０．９％であり、反応がほぼ定量的に終了したことを確認した。さらに、γ−メルカプトプロピルトリメトキシシラン３３．６部、トリエチルアミン０．１部を添加後、６０℃で３時間加熱攪拌することで第３のケイ素含有化合物を得た。
生成物中の残存イソシアネート量を分析したところ、０．１％以下であり、反応がほぼ定量的に終了したことを示した。
【００４７】
図３に、得られた第３のケイ素含有化合物のＩＲ吸収曲線示す。
【００４８】
¹Ｈ−ＮＭＲスペクトルデータを以下に示す。
¹Ｈ−ＮＭＲ；ＣＤＣｌ₃，４００ＭＨｚ
δｐｐｍ；０．５７−１．２０（ｍ，１７Ｈ），１．５９−１．８５（ｍ，１０Ｈ），２．８０−３．０５（ｍ，４Ｈ），３．５７（ｓ，９Ｈ），７．３４−７．５８（ｍ，３Ｈ），８．００−８．１１（ｍ，２Ｈ）
【００４９】
【発明の効果】
以上説明したように、本発明によって、各種基材の表面に塗膜（硬化膜）を形成し得る樹脂組成物に用いられる反応性粒子の表面修飾用剤として有用なラジカル重合開始基を有する新規なケイ素含有化合物及びその効率的な製造方法を提供することができる。
本発明のケイ素含有化合物によって表面修飾された反応性粒子を用いた樹脂組成物は、優れた硬化物生産性を有するとともに、硬化物としたときに優れた高耐擦傷性、高透明性、低カール性及び耐汚染性を有するものとなる。
【００５０】
【図面の簡単な説明】
【図１】本発明の実施例で得られた第１のケイ素含有化合物のＩＲ吸収曲線示すグラフである。
【図２】本発明の実施例で得られた第２のケイ素含有化合物のＩＲ吸収曲線示すグラフである。
【図３】本発明の実施例で得られた第３のケイ素含有化合物のＩＲ吸収曲線示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel silicon-containing compound and a method for producing the same. More specifically, a silicon-containing compound having a novel radical polymerization initiating group useful as a surface modifier for reactive particles used in a resin composition capable of forming a coating film (cured film) on the surface of various substrates and its efficiency Relates to a typical manufacturing method. The resin composition using the reactive particles surface-modified with the silicon-containing compound of the present invention has excellent cured product productivity, and also has excellent scratch resistance, high transparency, low It has curling properties and stain resistance.
[0002]
[Prior art]
Conventionally, silane coupling agents have been used to chemically modify the surface of inorganic fine particles, and these surface-modified inorganic fine particles have been tried to be used in various organic / inorganic composite materials.
[0003]
For example, Japanese Examined Patent Publication No. 62-21815 proposes the use of a composition of particles and acrylate, in which the surface of colloidal silica is modified with methacryloxysilane, as a radiation (light) curable coating material. Has been. This type of radiation curable composition has recently been widely used due to its excellent cured product productivity.
However, since the radiation curable composition usually forms a cured film by radical polymerization, there is a problem that the obtained cured film is not sufficiently cured due to the influence of dissolved oxygen in the atmosphere or in the polymerization system. there were.
[0004]
As a means for solving insufficient curing due to oxygen inhibition, there is an increase in the amount of a photoradical initiator or a combined use of a photoradical initiator that is less susceptible to oxygen inhibition. However, this means is not always satisfactory because the amount of the unreacted photoradical initiator in the cured product is increased and adverse effects such as coloring of the cured film and a decrease in scratch resistance are caused.
[0005]
Methods for solving this include the use of a polymeric initiator and the introduction of an initiator into the crosslinking system. As an example, Japanese Patent Application Laid-Open No. 9-328522 discloses a photocuring composed of silica fine particles having radical polymerization initiating groups and an acrylic monomer obtained by reacting the surface of silica fine particles with an alkoxysilane compound having a radical polymerization initiating group at the terminal. A functional coating material is disclosed.
However, even with this method, the problem of a decrease in scratch resistance of the cured film cannot be sufficiently solved.
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above-mentioned problems, and is a novel useful as a surface modifier for reactive particles used in a resin composition capable of forming a coating film (cured film) on the surface of various substrates. An object of the present invention is to provide a silicon-containing compound having a radical polymerization initiating group and an efficient production method thereof.
The resin composition using the reactive particles surface-modified with the silicon-containing compound of the present invention has excellent cured product productivity, and also has excellent scratch resistance, high transparency, low It has curling properties and stain resistance.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found a novel silicon-containing compound having a radical polymerization initiating group in its chemical structure, which is useful as a surface modifier for reactive particles. Completed. That is, the present invention provides the following silicon-containing compounds and methods for producing the same.
[0008]
[1] A silicon-containing compound represented by the following formula (1), (2) or (3).
[0009]
[Chemical 7]

[0010]
[Chemical 8]

[0011]
[Chemical 9]

[0012]
[2] The silicon-containing compound according to [1], wherein the compound represented by the formula (2) is a 2,4-isomer and / or a 2,6-isomer.
[0013]
[3] A compound represented by the following formula (4) or (5) and isophorone diisocyanate, or 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate, and an alkoxysilane compound represented by the following formula (6) The method for producing a silicon-containing compound as described in [1] or [2] above, wherein
[0014]
Embedded image

[0015]
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[0016]
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[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be specifically described.
The silicon-containing compound of the present invention is a compound represented by the above formula (1), (2) or (3) (hereinafter referred to as “first silicon-containing compound”, “second silicon-containing compound” and “third”, respectively). Sometimes referred to as a “silicon-containing compound”.
Hereinafter, each silicon-containing compound will be specifically described.
[0018]
1. First silicon-containing compound The first silicon-containing compound includes a compound represented by the above formula (4) (hereinafter sometimes referred to as “reactive compound (4)”), isophorone diisocyanate (IPDI), and the above formula (6). ) (Hereinafter sometimes referred to as “reactive compound (6)”) in the presence of a catalyst.
[0019]
The blending amounts of the reactive compound (4) and the reactive compound (6) are preferably equimolar with respect to IPDI.
[0020]
In the production of the first silicon-containing compound, since the reaction between the tertiary hydroxyl group of the compound (4) and the isocyanate group of IPDI is prevented, after the addition reaction of IPDI and the reactive compound (6), It is preferable to react the adduct of IPDI and the reactive compound (6) with the reactive compound (4).
[0021]
In the production of the first silicon-containing compound, the purity of the first silicon-containing compound is preferably 80% or more, and more preferably 90% or more.
[0022]
2. Second silicon-containing compound The second silicon-containing compound comprises a reactive compound (4) and 2,4-tolylene diisocyanate (2,4-TDI) or / and 2,6-tolylene diisocyanate (2,6 -TDI) as well as the reactive compound (6) can be produced in the presence of a catalyst.
[0023]
The blending amounts of the reactive compound (4) and the reactive compound (6) are preferably equimolar with respect to TDI.
[0024]
In the production of the second silicon-containing compound, for the purpose of preventing the reaction between the tertiary hydroxyl group of the compound (4) and the isocyanate group of TDI, after performing an addition reaction between TDI and the reactive compound (6), It is preferable to react the adduct of TDI and the reactive compound (6) with the reactive compound (4).
[0025]
In the production of the second silicon-containing compound, the purity of the second silicon-containing compound is preferably 80% or more, and more preferably 90% or more.
[0026]
3. Third silicon-containing compound The third silicon-containing compound comprises a compound represented by the formula (5) (hereinafter sometimes referred to as “reactive compound (5)”), IPDI and reactive compound (6). It can be produced by reacting in the presence of a catalyst.
[0027]
The compounding amounts of the reactive compound (5) and the reactive compound (6) are preferably equimolar with respect to IPDI.
[0028]
In the production of the third silicon-containing compound, after the addition reaction between IPDI and the reactive compound (5), the adduct of IPDI and the reactive compound (5) is reacted with the reactive compound (6). It is preferable to make it. If this order is reversed or the three components are added and reacted at the same time, the target silicon-containing compound may not be obtained with high purity.
[0029]
In the production of the third silicon-containing compound, the purity of the third silicon-containing compound is preferably 80% or more, and more preferably 90% or more.
[0030]
Examples of the reactive compound (4) used in the present invention include 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one. it can.
As a commercial item of the said compound, Ciba Specialty Chemicals Co., Ltd. brand name: Irgacure 2959 can be mentioned.
[0031]
Examples of the reactive compound (5) used in the present invention include 2-hydroxy-2-methyl-1-phenyl-propan-1-one.
As a commercial item of the said compound, Ciba Specialty Chemicals Co., Ltd. brand name: Darocur 1173 can be mentioned.
[0032]
Examples of the reactive compound (6) used in the present invention include γ-mercaptopropyltrimethoxysilane.
As a commercial item of the said compound, Toray Dow Corning Silicone Co., Ltd. brand name: SH6062 can be mentioned.
[0033]
In the manufacturing method of the said 1st-3rd silicon containing compound, reaction temperature is -20-100 degreeC normally, Preferably it is 0-60 degreeC.
[0034]
In addition, the reaction is carried out by using an inert solvent, for example, a hydrocarbon solvent such as toluene, xylene, hexane or heptane, a halogenated hydrocarbon solvent such as methylene chloride, chloroform or chlorobenzene, a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. The reaction may be carried out in an organic solvent, an ether solvent such as tetrahydrofuran, dioxane, trioxane, diglyme, or a mixed solvent thereof. The amount of these solvents used is usually 1000 ml or less, preferably 500 ml or less, more preferably 100 ml or less, per 1 mol of diisocyanate. If the amount of solvent used exceeds 1000 ml, the reaction may not proceed sufficiently.
[0035]
The catalyst used in the present invention may be either a basic catalyst or an acidic catalyst, or a basic catalyst and an acidic catalyst may be used in combination.
Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Of these, tertiary amines such as pyridine and triethylamine are preferable.
Examples of the acid catalyst include metal alkoxides such as copper naphthenate, cobalt naphthenate, zinc naphthenate, DABCO, methyl DABCO, tributoxyaluminum, titanium tetrabutoxide, zirconium tetrabutoxide, boron trifluoride diethyl etherate, and chloride. Examples thereof include Lewis acids such as aluminum and tin compounds such as tin 2-ethylhexanoate, octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. Among these, tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate are preferable.
When a basic catalyst and an acidic catalyst are used in combination, a combination of an amine and a tin compound is preferable, and a tertiary amine such as pyridine or triethylamine and a tin compound such as octyltin trilaurate, dibutyltin dilaurate, or octyltin diacetate The combined use is more preferable.
[0036]
Among the above-mentioned catalysts, it is preferable to use a basic catalyst and an acidic catalyst in combination, more preferably a combination of amines and a tin compound, tertiary amines such as pyridine and triethylamine, octyltin trilaurate, dibutyltin dilaurate, octyl. The combined use with a tin compound such as tin diacetate is particularly preferred.
[0037]
The addition amount of these catalysts is 0.01-5 weight part with respect to 100 weight part of diisocyanate compounds, Preferably it is 0.1-3 weight part. If it is less than 0.01 part by weight, the reaction may not proceed sufficiently. If it exceeds 5 parts by weight, the storage stability of the product may be lowered.
[0038]
The silicon-containing compound of the present invention is useful as a surface modifier for reactive particles (surface active particles). That is, since the silicon-containing compound of the present invention has an alkoxysilane group, it can impart a radical polymerization initiating function to the particle surface by reaction with various reactive particles. Useful as.
[0039]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, parts and% are parts by weight and% by weight, respectively, unless otherwise specified.
[0040]
Example 1 (Synthesis of first silicon-containing compound)
To a solution consisting of 34.3 parts of isophorone diisocyanate and 0.5 parts of dibutyltin dilaurate in dry air, 30.4 parts of γ-mercaptopropyltrimethoxysilane was added dropwise over 1 hour at 20 ° C. with stirring, and then 60 ° C. For 1 hour. 0.1 parts of triethylamine was added thereto, and the amount of residual isocyanate in the intermediate after stirring at 60 ° C. for 1 hour was analyzed. As a result, it was 10%. The total amount of isocyanate before the reaction is 20%, and the isocyanate reaction rate determined from this value is 50%. The reaction between one isocyanate group in isophorone diisocyanate and the thiol group of γ-mercaptopropyltrimethoxysilane is almost complete. It was confirmed that the process was quantitatively completed. Further, after adding 34.7 parts of 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, the mixture was first heated and stirred at 60 ° C. for 3 hours. A silicon-containing compound was obtained.
When the amount of residual isocyanate in the product was analyzed, it was 0.1% or less, and it was confirmed that the reaction was almost quantitatively completed.
[0041]
FIG. 1 shows an IR absorption curve of the obtained first silicon-containing compound.
[0042]
¹ H-NMR spectrum data is shown below.
_{^{1 H-NMR; CDC1 3 ·}} 400MHz
δ ppm; 0.60-1.35 (m, 17H), 1.40-1.90 (m, 10H), 2.80-3.20 (m, 4H), 3.56 (s, 9H), 3.90-419 (m, 1H), 4.20-4.30 (m, 2H), 4.38-4.50 (m, 2H), 6.95 (d, 2H), 8.06 ( d, 2H)
[0043]
Example 2 (Synthesis of second silicon-containing compound)
In a dry air, with stirring 23.0 parts of 2,4-tolylene diisocyanate and 0.1 parts of dibutyltin dilaurate, 33.0 parts of γ-mercaptopropyltrimethoxysilane is stirred at 20 ° C. over 1 hour. After dropping, the mixture was stirred at 30 ° C. and 60 ° C. for 1 hour. When the amount of residual isocyanate in this intermediate was analyzed, it was 11.3%, and it was confirmed that the reaction was almost quantitatively completed. Furthermore, after adding 37.7 parts of 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, the mixture was heated and stirred at 60 ° C. for 3 hours. Two silicon-containing compounds were obtained.
When the amount of residual isocyanate in the product was analyzed, it was 0.1% or less, indicating that the reaction was almost quantitatively completed.
[0044]
FIG. 2 shows an IR absorption curve of the obtained second silicon-containing compound.
[0045]
¹ H-NMR spectrum data is shown below.
¹ H-NMR; CDCl ₃ · 400 MHz
δ ppm; 0.74 (t, 2H), 1.63 (s, 6H), 1.77 (q, 2H), 2.19 (d, 3H), 2.98 (t, 2H), 3.57 (S, 9H), 4.27-4.31 (m, 2H), 4.50-4.57 (m, 2H), 6.55 (s, 1H), 6.98-7.35 (m , 4H), 7.84 (s, 1H), 8.07 (d, 2H)
[0046]
Example 3 (Synthesis of third silicon-containing compound)
A solution of 38.1 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate in dry air was stirred at 20 ° C. with 28.1 parts of 2-hydroxy-2-methyl-1-phenyl-propan-1-one. After dropwise addition over 1 hour, each was stirred at 30 ° C. and 60 ° C. for 1 hour. When the amount of residual isocyanate in this intermediate was analyzed, it was 10.9%, and it was confirmed that the reaction was almost quantitatively completed. Further, after adding 33.6 parts of γ-mercaptopropyltrimethoxysilane and 0.1 part of triethylamine, a third silicon-containing compound was obtained by heating and stirring at 60 ° C. for 3 hours.
When the amount of residual isocyanate in the product was analyzed, it was 0.1% or less, indicating that the reaction was almost quantitatively completed.
[0047]
FIG. 3 shows an IR absorption curve of the obtained third silicon-containing compound.
[0048]
¹ H-NMR spectrum data is shown below.
¹ H-NMR; CDCl ₃ , 400 MHz
δ ppm; 0.57-1.20 (m, 17H), 1.59-1.85 (m, 10H), 2.80-3.05 (m, 4H), 3.57 (s, 9H), 7.34-7.58 (m, 3H), 8.00-8.11 (m, 2H)
[0049]
【The invention's effect】
As described above, according to the present invention, a novel radical polymerization initiating group useful as a surface modification agent for reactive particles used in a resin composition capable of forming a coating film (cured film) on the surface of various substrates. A silicon-containing compound and an efficient production method thereof can be provided.
The resin composition using the reactive particles surface-modified with the silicon-containing compound of the present invention has excellent cured product productivity and excellent scratch resistance, high transparency, low It has curling properties and stain resistance.
[0050]
[Brief description of the drawings]
FIG. 1 is a graph showing an IR absorption curve of a first silicon-containing compound obtained in an example of the present invention.
FIG. 2 is a graph showing an IR absorption curve of a second silicon-containing compound obtained in an example of the present invention.
FIG. 3 is a graph showing an IR absorption curve of a third silicon-containing compound obtained in an example of the present invention.

Claims (3)

A silicon-containing compound represented by the following formula (1), (2) or (3).

The silicon-containing compound according to claim 1, wherein the compound represented by the formula (2) is a 2,4-isomer and / or a 2,6-isomer. A compound represented by the following formula (4) or (5) is reacted with isophorone diisocyanate, or 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate, and an alkoxysilane compound represented by the following formula (6). The method for producing a silicon-containing compound according to claim 1 or 2, wherein:

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