JP2020063444A - Monomer and oligomer resin for one drop fill sealant - Google Patents

Abstract

To provide a resin system for sealant material having excellent adhesiveness and moisture barrier properties and excellent liquid crystal resistance (less contamination).SOLUTION: The present invention provides a novel curable resin and prepolymer, having a structure of the following formula, and a production method and a composition produced therefrom. Particularly useful applications thereof include a one drop fill sealant for a liquid crystal assembly. The resin and prepolymer, and composition of the inventions are particularly useful for assembly of an LCD panel.SELECTED DRAWING: None

Description

  The present invention relates to monomers and oligomers useful as sealants, especially one drop fill sealants for liquid crystal applications. In particular, the present invention enables the assembly of LCD panels without transferring the sealant resin to the liquid crystal upon curing of the LCD assembly and / or resin, and vice versa.

<Simple explanation of related technology>
One Drop Fill (“ODF”) process (liquid crystal dropping method) has replaced the conventional vacuum injection technology and has become the main process of LCD panel assembly in display applications to meet the requirements of high speed manufacturing process. There is. In the ODF process, first, a sealant is dispensed on a substrate with electrodes to form a frame of a display element, and liquid crystal is dropped inside the frame. The next step in the assembly is to bond the substrates with the other electrodes under vacuum. The sealant then undergoes a curing process, either by a combination of UV and heat, or by a heat only process.

  The ODF method has some problems such as the uncured sealant material coming into contact with the liquid crystal during the assembly process. This can cause degradation of the electro-optical properties of the liquid crystal due to migration of the resin into the liquid crystal or vice versa, or ionic impurities that may be present. Therefore, the design of a resin system for sealant materials that exhibits good liquid crystal resistance (less contamination) along with good adhesion and moisture barrier properties remains a challenge.

<Outline>
The present invention relates to unique resins and ODF compositions made therefrom.

  In one aspect of the invention, a resin having structure I is included.

式中、
Ｑは、

In the formula,
Q is

または

Or

から選択されてもよく、
式中、
Ｒは、直鎖または分枝アルキル、直鎖または分枝シクロアルキル、アルキレン、シクロアルキレン、ビシクロアルキレン、トリシクロアルキレン、直鎖または分枝アルキレン、直鎖または分枝シクロアルキレン、直鎖または分枝アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンまたはヘテロシクロアリーレンから選択される多価ヒドロカルビル連結基であり、アルキル、シクロアルキル、アルキレン、シクロアルキレン、アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンおよびヘテロシクロアリーレンは、任意にＯまたはＳまたはヒドロキシル基を含むことができ、
Ｒ_１は、メチルまたはＨであり、
Ｘは、ＣＨ_２、

May be selected from
In the formula,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R ₁ is methyl or H,
X is CH ₂ ,

または

Or

ｎ、ｎ_１、ｎ_２、ｎ_３は、それぞれ独立して１〜１０であり、
Ｙは、アリーレン、アルキレン、アルケニレン、アラルキレン、シクロアルキレン、ビシクロアルキレンまたはトリシクロアルキレンである。

n, n ₁ , n ₂ , and n ₃ are each independently 1 to 10,
Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene.

  Another aspect of the invention includes a resin having structure II.

式中、
Ｒは、直鎖または分枝アルキル、直鎖または分枝シクロアルキル、アルキレン、シクロアルキレン、ビシクロアルキレン、トリシクロアルキレン、直鎖または分枝アルキレン、直鎖または分枝シクロアルキレン、直鎖または分枝アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンまたはヘテロシクロアリーレンから選択される多価ヒドロカルビル連結基であり、アルキル、シクロアルキル、アルキレン、シクロアルキレン、アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンおよびヘテロシクロアリーレンは、任意にＯまたはＳまたはヒドロキシル基を含むことができ、
Ｒ_１およびＲ_２は、それぞれ独立して、メチルまたはＨであり、
ｎ_１およびｎ_２は、それぞれ独立して１〜１０であり、および
Ｘ_１およびＸ_２は、それぞれ独立して、ＣＨ_２、

In the formula,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R ₁ and R ₂ are each independently methyl or H,
n ₁ and n ₂ are each independently 1 to 10, and X ₁ and X ₂ are each independently CH ₂ ,

および

and

から選択され、
式中、
ｎ_３は、１〜１０であり、
Ｙは、アリーレン、アルキレン、アルケニレン、アラルキレン、シクロアルキレン、ビシクロアルキレンまたはトリシクロアルキレンである。

Selected from
In the formula,
n ₃ is 1 to 10,
Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene.

  Yet another aspect of the invention includes a resin having structure III.

式中、
Ｘ_１およびＸ_２は、独立して、任意に１個以上のヘテロ原子を有する官能化または非官能化脂環式基から選択される３〜１０員環基であり、
ｎは、１〜１０であり、
Ｒは、直鎖または分枝アルキル、直鎖または分枝シクロアルキル、アルキレン、シクロアルキレン、ビシクロアルキレン、トリシクロアルキレン、直鎖または分枝アルキレン、直鎖または分枝シクロアルキレン、直鎖または分枝アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンまたはヘテロシクロアリーレンから選択される多価ヒドロカルビル連結基であり、アルキル、シクロアルキル、アルキレン、シクロアルキレン、アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンおよびヘテロシクロアリーレンは、任意にＯまたはＳまたはヒドロキシル基を含むことができ、
Ｒは、任意の位置でＸ_１およびＸ_２を含む環構造に連結され、
Ｘ_３は、メタクリレート基を環Ｘ_１に連結する結合または

In the formula,
X ₁ and X ₂ are independently a 3-10 membered ring group selected from functionalized or non-functionalized cycloaliphatic groups optionally having one or more heteroatoms,
n is 1 to 10,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R is linked to a ring structure containing X ₁ and X ₂ at any position,
X ₃ is a bond connecting a methacrylate group to the ring X ₁ or

または

Or

であり、
ｎ_３は、１〜１０であり、および
Ｙは、アリーレン、アルキレン、アルケニレン、アラルキレン、シクロアルキレン、ビシクロアルキレンまたはトリシクロアルキレンであり、
ただし、Ｘ_１環上のヒドロキシル基は、（メタ）アクリレートを含有するＸ_３基に隣接し、かつＸ_２環上のヒドロキシル基は、マレイミドアルカノイル基にそれぞれ隣接している。

And
n ₃ is 1 to 10 and Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene,
However, the hydroxyl group on the X ₁ ring is adjacent to the X ₃ group containing the (meth) acrylate, and the hydroxyl group on the X ₂ ring is adjacent to the maleimidoalkanoyl group.

  Yet another aspect of the invention includes a resin having structure IV.

式中、
Ｘ_１およびＸ_２は、独立して、任意に１個以上のヘテロ原子を有する官能化または非官能化脂環式基から選択される３〜１０員環基であり、
Ｒは、直鎖または分枝アルキル、直鎖または分枝シクロアルキル、アルキレン、シクロアルキレン、ビシクロアルキレン、トリシクロアルキレン、直鎖または分枝アルキレン、直鎖または分枝シクロアルキレン、直鎖または分枝アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンまたはヘテロシクロアリーレンから選択される多価ヒドロカルビル連結基であり、アルキル、シクロアルキル、アルキレン、シクロアルキレン、アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンおよびヘテロシクロアリーレンは、任意にＯまたはＳまたはヒドロキシル基を含むことができ、
Ｒは、任意の位置で環構造Ｘ_１およびＸ_２に連結されてもよく、
ただし、Ｘ_２環上のヒドロキシル基は、マレイミドアルカノイル基に隣接し、
ｎ＝１〜１０である。

In the formula,
X ₁ and X ₂ are independently a 3-10 membered ring group selected from functionalized or non-functionalized cycloaliphatic groups optionally having one or more heteroatoms,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R may be linked to the ring structures X ₁ and X ₂ at any position,
However, the hydroxyl group on the X ₂ ring is adjacent to the maleimidoalkanoyl group,
n = 1 to 10.

  In yet another aspect of the invention, a resin having structure V is included.

式中、
Ｘ_１およびＸ_２は、独立して、任意に１個以上のヘテロ原子を有する官能化または非官能化脂環式基から選択される３〜１０員環基であり、
Ｒは、直鎖または分枝アルキル、直鎖または分枝シクロアルキル、アルキレン、シクロアルキレン、ビシクロアルキレン、トリシクロアルキレン、直鎖または分枝アルキレン、直鎖または分枝シクロアルキレン、直鎖または分枝アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンまたはヘテロシクロアリーレンから選択される多価ヒドロカルビル連結基であり、アルキル、シクロアルキル、アルキレン、シクロアルキレン、アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンおよびヘテロシクロアリーレンは、任意にＯまたはＳまたはヒドロキシル基を含むことができ、
Ｒは、任意の位置で環構造Ｘ_１およびＸ_２に連結され、
Ｘ_３およびＸ_４は、それぞれ独立して、メタクリレート基を環Ｘ_１およびＸ_２に連結する結合または

In the formula,
X ₁ and X ₂ are independently a 3-10 membered ring group selected from functionalized or non-functionalized cycloaliphatic groups optionally having one or more heteroatoms,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R is linked to the ring structures X ₁ and X ₂ at any position,
X ₃ and X ₄ are each independently a bond or a bond connecting a methacrylate group to the rings X ₁ and X _2.

または

Or

であり、
ｎ_３は、１〜１０であり、および
Ｙは、アリーレン、アルキレン、アルケニレン、アラルキレン、シクロアルキレン、ビシクロアルキレンまたはトリシクロアルキレンであり、
Ｒ_１およびＲ_２は、それぞれ独立してＨまたはメチルであり、
ただし、Ｘ_１環上のヒドロキシル基は、Ｘ_３基に隣接し、かつＸ_２環上のヒドロキシル基は、Ｘ_４基に隣接する。

And
n ₃ is 1 to 10 and Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene,
R ₁ and R ₂ are each independently H or methyl,
However, the hydroxyl group on the X ₁ ring is adjacent to the X ₃ group and the hydroxyl group on the X ₂ ring is adjacent to the X ₄ group.

  Another aspect of the invention includes a resin having structure VI.

式中、
Ｒ_１およびＲ_２は、それぞれ独立して、多価ヒドロカルビル連結基である。この多価ヒドロカルビル連結基は、直鎖または分枝アルキル、直鎖または分枝シクロアルキル、アルキレン、シクロアルキレン、ビシクロアルキレン、トリシクロアルキレン、直鎖または分枝アルキレン、直鎖または分枝シクロアルキレン、直鎖または分枝アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンまたはヘテロシクロアリーレンから選択され、アルキル、シクロアルキル、アルキレン、シクロアルキレン、アルケニレン、アリーレン、アラルキレン、アリールビシクロアルキレン、アリールトリシクロアルキレン、ビシクロアルキルアリーレン、トリシクロアルキルアリーレン、ビスフェニレン、シクロアルキルアリーレン、ヘテロシクロアルキレンおよびヘテロシクロアリーレンは、任意にＯまたはＳまたはヒドロキシル基を含むことができ、
Ｘは、ジカルボン酸の骨格であり、アリーレン、アルキレン、シクロアルキレン、直鎖または分枝アルキレン、シクロアルキレン、ビシクロアルキレン、トリシクロアルキレン、直鎖または分枝アルケニレン、アリーレン、アラルキレン、シクロアルキルアリーレン、ヘテロシクロアルキレンまたはヘテロシクロアリーレンから選択され、
ｎは、１〜１０である。

In the formula,
R ₁ and R ₂ are each independently a polyvalent hydrocarbyl linking group. The polyvalent hydrocarbyl linking group is a linear or branched alkyl, a linear or branched cycloalkyl, an alkylene, a cycloalkylene, a bicycloalkylene, a tricycloalkylene, a linear or branched alkylene, a linear or branched cycloalkylene, Linear or branched alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, selected from cycloalkylarylene, heterocycloalkylene or heterocycloarylene, alkyl, cyclo Alkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkylari Ren, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
X is a skeleton of dicarboxylic acid, and is arylene, alkylene, cycloalkylene, straight chain or branched alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, straight chain or branched alkenylene, arylene, aralkylene, cycloalkylarylene, hetero. Selected from cycloalkylene or heterocycloarylene,
n is 1 to 10.

  Yet another aspect of the invention includes a resin having structure VII.

In the formula,
R ₁ and R ₂ are each independently linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched. Selected from branched cycloalkylene, straight chain or branched alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, heterocycloalkylene or heterocycloarylene. A polyvalent hydrocarbyl linking group, each optionally containing O or S or a hydroxyl group,
X is a skeleton of dicarboxylic acid, and is arylene, alkylene, cycloalkylene, straight chain or branched alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, straight chain or branched alkenylene, arylene, aralkylene, cycloalkylarylene, hetero. Selected from cycloalkylene or heterocycloarylene,
n is 1 to 10,
X ₁ and X ₂ are polymerizable groups and are independently selected from a glycidyl group or a (meth) acryloyl group, X ₁ and X ₂ may be the same when they are not a glycidyl group. .

  Yet another aspect of the invention includes a resin having structure VIII.

In the formula,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Each may optionally contain O or S or hydroxyl groups,
R ₁ is a linking group, which may be a carbonyl group, an aliphatic or an aromatic group and may contain one or more ester, ether, thioether or hydroxyl groups,
R ₂ is a substituent on the aromatic ring and can be H, halogen, alkyl, alkyl ether, thioether group,
X ₁ can be H or a polymerizable group selected from a (meth) acryloyl group and a glycidyl group.

  Yet another aspect of the invention includes a resin having structure IX.

In the formula,
R ₁ is simply a bond connecting two aromatic groups and is O, carbonyl or a polyvalent hydrocarbyl linking group. The polyvalent linking group may be linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear. Or may be selected from branched alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, heterocycloalkylene or heterocycloarylene, alkyl, Cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, Cycloalkylarylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R ₂ is an aliphatic or aromatic linking group which may contain one or more ester, ether, thioether, carbonate or hydroxyl groups,
R ₃ is a substituent on the aryl group, which may be H, halogen, alkyl, alkyl ether or thioether group,
X is a polymerizable functional group selected from H or a (meth) acryloyl or glycidyl group.

  Yet another aspect of the invention includes a resin having structure X.

In the formula,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Each optionally containing O or S or hydroxyl groups,
R ₁ is methyl or H,
n ₁ and n ₂ are each independently 1 to 10,
X is CH ₂ ,

または

Or

から選択され、
ｎ_３は、１〜１０であり、
Ｙは、アリーレン、アルキレン、アルケニレン、アラルキレン、シクロアルキレン、ビシクロアルキレンまたはトリシクロアルキレンである。

Selected from
n ₃ is 1 to 10,
Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene.

<Detailed description>
The polymers of the present invention are useful in a wide variety of applications including sealing, adhesives and coatings. One particularly desirable use is an ODF sealant for assembling LCD panels.

  The present invention includes a number of novel materials including resins, oligomers and polymers useful in preparing curable compositions that can be used in ODF sealants. The present invention also includes novel compositions made from the disclosed resins. For the purposes of the present invention, the term "resin" includes the novel materials mentioned above, namely resins, oligomers and polymers.

  One aspect of the present invention is a cured resin composition for use as an ODF sealant, which comprises a resin represented by the general structural formula shown above.

  The glycidyl ether / ester compound useful for synthesizing the resin of the present invention described in the present specification is not particularly limited, and examples of commercially available compounds are, for example, Epikote 828EL and Epikote 1004 (all Japan Epoxy Resins Co. )) Bisphenol A type epoxy resin; such as Epikote 806 and Epikote 4004 (all manufactured by Japan Epoxy Resins Co., Ltd.); bisphenol F type epoxy resin; Epiclon EXA1514 (manufactured by Dainippon Ink and Chemicals, Inc.) and Shin A Bisphenol S type epoxy resin such as SE 650 manufactured by T &C; 2,2'-diallyl bisphenol A type epoxy resin such as RE-81 ONM (manufactured by Nippon Kayaku Co., Ltd.); Epiclon EXA7015 ( Hydrogenated bisphenol type epoxy resin such as Nippon Ink Chemical Co., Ltd .; propylene oxide addition bisphenol A type epoxy resin such as EP-4000S (manufactured by ADEKA); EX-201 (manufactured by Nagase Chemtex Co., Ltd.) ) And other resorcinol type epoxy resins; Epikote YX-4000H (manufactured by Japan Epoxy Resins Co., Ltd.) and other biphenyl type epoxy resins; YSLV 50TE (manufactured by Tohto Kasei Co., Ltd.) and other sulfide type epoxy resins; YSLV 80DE (Tohto Kasei Co., Ltd.) Co., Ltd.) type epoxy resin; EP-4088S and EP4088L (made by ADEKA) dicyclopentadiene type epoxy resin; Shin AT & C SE-80, SE-90 naphthalene type epoxy resin. ; Epikot 630 (manufactured by Japan Epoxy Resins Co., Ltd.), Epiclon 430 (manufactured by Dainippon Ink and Chemicals, Inc., and TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Inc.)) and the like; ZX-1542 ( Alkyl such as Toto Kasei Co., Ltd., Epiclon 726 (manufactured by Dainippon Ink and Chemicals, Inc.), Epolight8OMFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX-611 (manufactured by Nagase ChemteX Co., Ltd.). Polyol type epoxy resin; rubber-modified epoxy resin such as YR-450, YR-207 (all manufactured by Tohto Kasei Co., Ltd.) and Epolead PB (manufactured by Daicel Chemical Industries Ltd.); Denacol EX-147 (Nagase Chemtex Co., Ltd.) Glycidyl ester compounds such as); Epik teYL-7000 (manufactured by Japan Epoxy Resin Co., Ltd.) and other bisphenol A episulfide resins; YDC-1312, YSLV-BOXY, YSLV-90CR (manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Others include Epikote 1031, Epikote 1032 (all manufactured by Japan Epoxy Resins Co., Ltd.), EXA-7120 (manufactured by Dainippon Ink and Chemicals, Inc.), TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

  Examples of commercially available phenol novolac type epoxy compounds include Epiclon N-740, N-770, N-775 (all manufactured by Dainippon Ink and Chemicals, Inc.), Epikote 152, Epikote 154 (all manufactured by Japan Epoxy Resins Co., Ltd.). ) And the like.

  Examples of commercially available cresol novolac type epoxy compounds include Epiclon N-660, N-665, N-670, N-673, N-680, N-695, N-665-EXP and N-672-EXP (all Dainippon Ink and Chemicals, Inc.), and examples of commercially available biphenyl novolac epoxy compounds include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.), and commercially available trisphenol novolac epoxy compounds. Examples include EP1032S50 and EP1032H60 (all manufactured by Japan Epoxy Resins Co., Ltd.), and examples of commercially available dicyclopentadiene novolac type epoxy compounds include XD-1000-L (manufactured by Nippon Kayaku Co., Ltd.). ) And HP-7200 (manufactured by Dainippon Ink and Chemicals, Inc.). Examples of commercially available bisphenol A type epoxy compounds are Epikote 828, Epikote 834, Epikote 1001, Epikote 1004 (all manufactured by Japan Epoxy Resins Co., Ltd.), Epiclon 850, Epiclon 860 and Epiclon 4055 (all Dainippon Ink and Chemicals Inc.). Examples of commercially available bisphenol F type epoxy compounds include Epikote 807 (manufactured by Japan Epoxy Resins Co., Ltd.) and Epiclon 830 (manufactured by Dainippon Ink and Chemicals, Inc.), and commercially available 2,2′- Examples of the diallyl bisphenol A type epoxy compound include RE-81ONM (manufactured by Nippon Kayaku Co., Ltd.), and examples of commercially available hydrogenated bisphenol type epoxy compounds include ST-5080. (Manufactured by Tohto Kasei Co., Ltd.), and examples of commercially available polyoxypropylene bisphenol A type epoxy compounds include EP-4000 and EP-4005 (both manufactured by ADEKA).

  HP4032 and Epiclon EXA-4700 (all manufactured by Dainippon Ink and Chemicals, Inc.); Epiclon N-770 (manufactured by Dainippon Ink and Chemicals, Inc.) and other phenol novolac type epoxy resins; Epiclon N-670-EXP -S (manufactured by Dainippon Ink and Chemicals Incorporated) and other ortho-cresol novolac type epoxy resins; Epiclon HP7200 (manufactured by Dainippon Ink and Chemicals Incorporated) and other dicyclopentadiene novolac type epoxy resins; Biphenyl novolac type epoxy resin such as Yakuhin Co., Ltd .; naphthalene phenol novolac type epoxy resin such as ESN-165S (manufactured by Toto Kasei Co., Ltd.) and the like.

  Examples of alicyclic epoxy compounds useful for synthesizing the resin of the present invention include, but are not limited to, at least one alicyclic ring obtained by epoxidizing a cyclohexene ring- or cyclopentene ring-containing compound and Mention may be made of polyglycidyl ethers of polyhydric alcohols with cyclohexene oxide or cyclopentene oxide containing compounds. Specific examples include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexane. Carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane Carboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane Carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) Cyclohexane Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis (3,4- Epoxy cyclohexane carboxylate), dioctyl epoxy hexahydrophthalate and di-2-ethylhexyl epoxy hexahydrophthalate.

  Some of the above cycloaliphatic epoxy resins are; UVR-6100, UVR-6105, UVR-6110, UVR-6128 and UVR-6200 (products of Dow Corporation); CELLOXIDE 2021, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 2000, CELLOXIDE 3000, CYCLMERM A200, CYCLMER M100, CYCLMER M101, CYCLMER M101, EPOLEAD GT-301, EPOLEAD GT 300, EPOLEAD GT and EPOLEAD GT, EPOLEAD GT, EPOLEAD 401, EPOLEAD 401, EPOLEAD 401, EPOLEAD 401, and EPOLEAD 401, EPOLEAD 401, and EPOLEAD 401. ); KRM- 2110 and KRM-2199 (product of ADEKA).

  In addition to the curable polymer of the present invention, the ODF sealant composition may also include a free radical initiator (heat or UV generating) and a curing agent. Curing of the ODF composition can be accomplished by thermal and / or UV mechanisms. In embodiments where an epoxide ring is present, a latent epoxy hardener can also be used.

Useful thermal free radical initiators include, for example, organic peroxides and azo compounds known in the art.
Examples include AIBN (azodiisobutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2 , 2'-azobis (2-ethylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,11-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [ Azo free radical initiators such as N- (2-propenyl) -2-methylpropionamide; Dialkyl peroxide free radical initiators such as 1,1-di- (butylperoxy-3,3,5-trimethylcyclohexane) Alkyl perester free radical initiators such as TBPEH (t-butylper-2-ethylhexanoate); benzoic peroxide Diacyl peroxide free radical initiators such as ethyl; peroxydicarbonate radical initiators such as ethylhexyl percarbonate; methyl ethyl ketone peroxide, bis (t-butyl peroxide) diisopropylbenzene, t-butyl perbenzoate, t-butyl peroxy Ketone peroxide initiators such as neodecanoate, and combinations thereof.

  Further examples of organic peroxide free radical initiators include dilauroyl peroxide, 2,2-di (4,4-di (tert-butylperoxy) cyclohexyl) propane, di (tert-butylperoxyisopropyl) benzene. , Di (4-tert-butylcyclohexyl) peroxydicarbonate, dicetylperoxydicarbonate, dimyristylperoxydicarbonate, 2,3-dimethyl-2,3-diphenylbutane, dicumyl peroxide, dibenzoylper Oxide, diisopropyl peroxydicarbonate, tert-butyl monoperoxy maleate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperoxy-2-ethylhexyl carbonate, tert- Milperoxy-2-ethylhexanoate, tert-amylperoxypivalate, tert-amylperoxy 2-ethylhexyl carbonate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 2 , 5-dimethyl-2,5-di- (tert-butylperoxy) hexpe-3, di (3-methoxybutyl) peroxydicarbonate, diisobutylperoxide, tert-butylperoxy-2-ethylhexanoate ( Trigonox 21 S), 1,1-di (tert-butylperoxy) cyclohexane, tert-butylperoxy neodecanoate, tert-butylperoxypivalate, tert-butylperoxy neoheptanoate, tert-butyl. Peroxydiethyla Tate, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane , Di (3,5,5-trimethylhexanoyl) peroxide, tert-butylperoxy-3,5,5-trimethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, tert-butylperoxy 3,5,5-trimethylhexanoate, cumylperoxy neodecanoate, di-tert- Butyl peroxide, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxybenzoate, di (2-ethyl) Hexyl) peroxydicarbonate, tert- butylperoxy acetate, isopropyl cumyl hydroperoxide, and tert- butyl cumyl peroxide and the like.

  Usually, a thermal free radical initiator having a higher decomposition rate is preferable because it can easily generate a free radical at a general curing temperature (80 to 130 ° C.) and has a high curing rate, and thus a liquid resin and a liquid crystal can be used. The contact time with can be shortened, and the liquid crystal contamination can be reduced. On the other hand, if the initiator decomposition rate is too high, it affects the viscosity stability at room temperature, thereby shortening the working life of the sealant.

  A convenient way to describe the rate of decomposition of an initiator at a particular temperature is its half-life, ie the time required to decompose half of the naturally occurring peroxide. To compare the reactivity of different initiators, the temperature at which each initiator has a half-life (T1 / 2) of 10 hours is used. The most reactive (fastest) initiator would be the one with a T1 / 2 temperature of at least 10 hours.

  In the present invention, a thermal free radical initiator having a T1 / 2 temperature of 30 to 80 ° C. for 10 hours is preferable, and a thermal free radical initiator having a T1 / 2 temperature of 10 hours of 40 to 70 ° C. is more preferable.

  In order to balance the reactivity and viscosity stability of the composition, the thermal free radical initiator used in the resin composition is usually 100 parts by weight of the resin of the present invention in the curable composition of the present invention. Based on 0.01 to 3 parts by weight, preferably 0.5 to 2 parts by weight.

  Useful UV free radical initiators include Norrish type I cleavable photoinitiators commercially available from CIBA and BASF. These photoinitiators are used in the formulation in amounts of about 0.1-5% by weight, more preferably about 0.2-3% by weight.

  Examples of useful epoxy hardeners include Ajicure series hardeners available from Ajinomoto Fine-Techno Co .; Amicure series hardeners available from Air products and JERCURE (R) products available from Mitsubishi Chemical. Is mentioned. These hardeners are used in amounts of about 1 to about 50% by weight of the total composition, more preferably about 5 to about 20% by weight of the total composition.

  The curable composition may optionally contain a further component capable of a photopolymerization reaction such as a vinyl ether compound, if desired. In addition, the curable composition may further include additives for improving or modifying fluidity, dispensing, printability, storability, curability, physical properties after curing, resin components and the like.

  For example, organic or inorganic fillers, thixotropic agents, silane coupling agents, diluents, modifiers, colorants such as pigments and dyes, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers. Various additives such as a leveling agent may be contained in the composition, but the present invention is not limited thereto. In particular, the composition preferably comprises an additive selected from the group consisting of organic or inorganic fillers, thixotropic agents, and silane coupling agents. These additives may be present in an amount of about 0.1 to about 50% by weight of the total composition, more preferably about 2 to about 10% by weight.

  Fillers include, but are not limited to, silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, gypsum, calcium silicate. , Inorganic fillers such as talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride; while poly (methyl) methacrylate, poly (ethyl) methacrylate, poly (propyl) methacrylate, poly (butyl) methacrylate , Butyl acrylate-methacrylic acid- (methyl) methacrylate copolymer, polyacrylonitrile, polystyrene, polybutadiene, polypentadiene, polyisoprene, polyisopropylene, and other organic fillers. These can be used alone or in combination. These fillers may be present in amounts of about 1 to about 80% by weight of the total composition, more preferably about 5% to about 30%.

  Examples of the thixotropic agent include talc, fumed silica, surface-treated ultrafine calcium carbonate, fine particle alumina, plate-like alumina, layered compound such as montmorillonite, needle-like compound such as aluminum borate whiskers, and the like. Not limited. Of these, talc, fumed silica, and fine-grained alumina are particularly preferable. These agents may be present in amounts of about 1 to about 50% by weight of the total composition, more preferably about 1 to about 30%.

  Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. .

The curable composition of the present invention can be obtained by mixing the above components with a mixer having, for example, a stirring blade and a three-roll mill. The composition is a liquid under ambient conditions having a viscosity of 200-400 Pa · s (25 ° C.) at 1.5 s ⁻¹ shear rate, which allows it to be easily dispensed.

Also provided is a method of manufacturing a liquid crystal display having a liquid crystal layer between a first substrate and a second substrate by a liquid crystal one drop fill process. The method comprises the following steps:
(A) applying the curable composition according to the present invention to the seal area around the surface of the first substrate;
(B) Dropping liquid crystal into a central region surrounded by the seal region on the surface of the first substrate;
(C) a step of stacking the second substrate on the first substrate;
(D) optionally partially curing the curable composition by UV irradiation;
(E) A step of performing final curing by heating the curable composition is included.

  The first substrate and the second substrate used in the present invention are usually transparent glass substrates. Generally, a transparent electrode, an active matrix element (TFT or the like), an alignment film, a color filter and the like are formed on at least one opposing surface of both substrates. These configurations can be changed depending on the type of LCD. It is considered that the manufacturing method of the present invention can be applied to any type of LCD.

  In the step (a), the curable composition is applied to the peripheral portion of the surface of the first substrate in a frame shape so as to surround the periphery of the substrate. A portion where the curable composition is applied in a frame shape is referred to as a seal area. The curable composition can be applied by a known method such as screen printing or dispensing.

  Next, in step (b), liquid crystal is dropped onto the central region surrounded by the frame-shaped seal region on the surface of the first substrate. This step is preferably performed under reduced pressure.

  Next, in step (c), the second substrate is placed on the first substrate, and UV irradiation is performed in step (d). Upon irradiation with UV, the curable composition is partially cured and exhibits a strength that does not cause displacement when handled, and both substrates are temporarily fixed. In general, the irradiation time is preferably short, for example 5 minutes or less, preferably 3 minutes or less, more preferably 1 minute or less.

  In step (e), the curable composition is heated to obtain the final cure strength and finally the two substrates are bonded together. The heat curing in step (e) is generally carried out at a temperature of 80 to 130 ° C, preferably 100 to 120 ° C, with a heating time of 30 minutes to 3 hours, typically 1 hour.

  This process completes most of the LCD panel.

<Performance data of ODF formulation>
Table I below shows ODF Formulations 2-7 of the invention and Control Formulation 1 containing the commercially available Uvacure 1561, a partially acrylated BPA diglycidyl ether. Irgacure 651 is a commercially available photoinitiator; A-187 is an adhesion promoter; EH-4357S is an epoxy hardener; SO-E2 is a silica filler.

As shown in Table I, some inventive formulations exhibit improved moisture barrier properties and adhesion (measured as corner strength).
<Synthesis>

General procedure for glycidyl ether ring opening with (meth) acrylic acid and 6-maleimidocaproic acid>
Epoxy resin and appropriate stoichiometry of methacrylic acid or 6-maleimidocaproic acid were placed in toluene in a round bottom flask equipped with mechanical stirrer and nitrogen inlet. Methylhydroquinone (1000-3000 ppm) and Hycat 2000S epoxy ring-opening catalyst (1 wt%) were added and the mixture was stirred at 60 ° C. for about 24 hours. After cooling to room temperature (room temperature), an appropriate amount of ethyl acetate was added and the mixture was washed twice with aqueous NaHCO ₃ solution and several times with deionized water. After drying over anhydrous Na ₂ SO ₄ , the solvent was passed through a silica column. Another 500 ppm of methylhydroquinone was added and the solvent was evaporated to give a partially or fully ring-opened epoxy- (meth) acrylate or epoxy-maleimide resin.

<General procedure for chain extension of diglycidyl ether using dicarboxylic acid to obtain epoxy-terminated oligomer and capping with methacrylic acid>
Diglycidyl ether (2 eq), dicarboxylic acid (1 eq), Hycat 2000S epoxy ring-opening catalyst (1 wt%) in a mixture of toluene and tetrahydrofuran (THF) (2: 1) in a multi-necked flask equipped with mechanical stirrer. I put it in. The mixture was stirred at 60 ° C for 15 hours and at 70 ° C for 12 hours to obtain a chain-extended epoxy resin. The resin can be capped in the same reaction vessel by adding methacrylic acid. After cooling to room temperature, ethyl acetate was added and the mixture was washed twice with aqueous NaHCO ₃ solution and several times with deionized water. After drying over anhydrous Na ₂ SO ₄ , the organic layer was passed through a silica column and the solvent was evaporated to give a chain extended epoxy resin. The molecular weight of the resulting oligomer can be changed by changing the dicarboxylic acid ratio of the diglycidyl ether.

<Synthesis of Resin of the Present Invention>

<Preparation of Resin 1 of the Present Invention>
In a 1 L 4-neck flask equipped with mechanical stirrer and nitrogen inlet, EP4088S (123.6 g, 400 mmol), methacrylic acid (86.2 g, 1000 mmol), MeHQ (100 mg, 500 ppm), Hycat 2000S (2.1 g, 1% by weight) and toluene (200 mL) were added. The mixture was stirred at 60 ° C. overnight. After cooling to room temperature, 500 mL of ethyl acetate was added and the mixture was washed twice with aqueous NaHCO ₃ solution and several times with deionized water. After drying over anhydrous Na ₂ SO ₄ , the solvent was passed through a silica column. Another 500 ppm MeHQ was added and the solvent was evaporated to give dimethacrylate resin 1 (182 g, 87%).

<Preparation of Resin 2 of the Present Invention>
EP4088S (101 g, 327 mmol) and 6-maleimidocaproic acid (96.8 g, 458 mmol), methylhydroquinone (100 mg, 500 ppm) in a 500 mL four-necked flask equipped with mechanical stirrer and nitrogen inlet (130 mL). I put it in. 2g of Hycat 2000S (1 wt%) was added and the mixture was stirred at 60 ° C for about 16 hours. After cooling to room temperature, ethyl acetate was added and the product was washed twice with aqueous NaHCO ₃ solution to remove residual maleimidocaproic acid. The organic layer was then washed several times with deionized water and dried over anhydrous Na ₂ SO ₄ . The organic layer was then passed through a silica column and the solvent was evaporated to give hybrid epoxy-maleimide resin 2 (170g, 85%).

<Preparation of Resin 3 of the Present Invention>
In a 500 mL four-necked flask equipped with a mechanical stirrer, Tactix 756 (70.6 g per epoxy, 280 mmol), methacrylic acid (16.03 g, 186 mmol), Hycat 2000S (0.86 g, 1 wt%) and toluene (100 mL). ) Was put. 500 ppm methylhydroquinone (40 mg) was added and the mixture was stirred at 60 ° C. overnight. After cooling to room temperature, 300 mL of ethyl acetate was added and the organic layer was washed twice with aqueous NaHCO ₃ solution and several times with deionized water. After drying over anhydrous Na ₂ SO ₄ , the organic layer was passed through a column containing silica gel. 200 mg methylhydroquinone (2000 ppm) was added and the solvent was evaporated to give dimethacrylate resin 3 (brown solid) (62 g, 72%, yield due to difficulty in removing all solid material from the flask). Has decreased).

<Preparation of Resin 4 of the Present Invention>
Tactix 756 (92.5 g, 366 mmol, relating to epoxy functional groups), 6-maleimidocaproic acid (25.8 g, 122 mmol), methylhydroquinone (63 mg, 500 ppm) were placed in a 500 mL four-necked flask equipped with mechanical stirrer. . Toluene (200 mL) was added and the mixture was stirred at 60 ° C until homogeneous. Hycat 2000S was added (1.26 g, 1 wt%) and the mixture was stirred at the same temperature for about 16 hours. After cooling to room temperature, 400 mL of ethyl acetate was added, and the organic layer was washed twice with an aqueous NaHCO ₃ solution and several times with deionized water. After drying over anhydrous Na ₂ SO ₄ , the organic layer was passed through a silica column and the solvent was evaporated to give a hybrid epoxy-maleimide resin 4 (92 g, 78%).

<Preparation of Resin 5 of the Present Invention>
Bisphenol A diglycidyl ether (121 g, 355 mmol), 6-maleimidocaproic acid (105 g, 497 mmol) and methylhydroquinone (110 mg, 500 ppm) were placed in toluene (200 mL) of a 1 L four-necked flask equipped with a mechanical stirrer. . The mixture was stirred at 60 ° C until homogeneous. Hycat 2000S (2.2 g, 1 wt%) was added and the mixture was stirred at the same temperature overnight. After cooling to room temperature, 1 L of ethyl acetate was added, and the organic layer was washed twice with an aqueous NaHCO ₃ solution and several times with deionized water. After drying over anhydrous Na ₂ SO ₄ , the organic layer was passed through a silica column and the solvent was evaporated to give a hybrid epoxy maleimide resin 5 (175 g, 77%).

<Preparation of Resin 6 of the Present Invention>
Resorcinol diglycidyl ether (101 g, 454 mmol), methacrylic acid (54.8 g, 636 mmol), 3-maleimidopropanoic acid (50 g, 295 mmol), methyl in toluene (200 mL) in a 500 mL four-necked flask equipped with a mechanical stirrer. Hydroquinone (100 mg, 500 ppm) and Hycat 2000S (2 g, 1 wt%) were added and the mixture heated at 60 ° C. overnight. After cooling to room temperature, 500 mL of ethyl acetate was added, and the organic layer was washed twice with an aqueous NaHCO ₃ solution and several times with deionized water. After drying over anhydrous Na ₂ SO ₄ , the organic layer was passed through a silica column. 500 ppm of methylhydroquinone was added and the solvent was evaporated to give RDGE hybrid maleimide-methacrylate resin 6 as a viscous liquid (165 g, 80%).

<Preparation of Resin 7 of the Present Invention>
In a toluene (200 mL) of a 500 mL four-necked flask equipped with a mechanical stirrer, resorcinol diglycidyl ether (93.2 g, 419 mmol), acrylic acid (33.2 g, 251 mmol), methacrylic acid (39.7 g, 251 mmol). , Methylhydroquinone (130 mg, 1000 ppm) and Hycat 2000s (1.3 g, 1 wt%) were added and the mixture was heated at 60 ° C. overnight. After cooling to room temperature, 500 mL of ethyl acetate was added, the organic layer was washed twice with aqueous NaHCO ₃ solution and several times with deionized water, and dried over anhydrous Na ₂ SO ₄ . The organic layer was passed directly through a column of silica gel, 500 ppm methylhydroquinone was added and the solvent was evaporated to give a hybrid acrylate-methacrylate resin 7 (123 g, 92%).

<Preparation of Resin 8 of the Present Invention>
EP4088S epoxy resin (133.3 g, 432 mmol), isophthalic acid (35.9 g, 216 mmol), Hycat 2000S in a mixture of toluene (200 mL) and THF (100 mL) in a 500 mL three-necked flask equipped with a magnetic stirrer. (1.7 g, 1% by weight) was added. The mixture was stirred at 60 ° C. for 15 hours and 70 ° C. for 12 hours. After cooling to room temperature, 500 mL of ethyl acetate was added and the mixture was washed twice with aqueous NaHCO ₃ solution and several times with deionized water. After drying over anhydrous Na ₂ SO ₄ , the organic layer was passed through a silica column and the solvent was evaporated to give a viscous liquid chain extended EP 4088S epoxy resin 8 (132 g, 78%). The molecular weight of the chain extender resin can be changed by changing the ratio of diacid to diglycidyl ether.

<Preparation of Resin 9 of the Present Invention>
EP4088S (168 g, 545 mmol) isophthalic acid (45.33 g, 272 mmol) was placed in a mixture of toluene (200 g) and THF (100 mL) in a 500 mL three-necked flask equipped with a mechanical stirrer. The mixture was stirred at 60 ° C. for 15 minutes. Hycat 2000S (2.1 g, 1 wt%) is added and the mixture is stirred at the same temperature for about 12 hours and 70 ° C. for 8 hours, at which time the mixture becomes homogeneous. Methacrylic acid (56.3 g, 654 mmol) and additional Hycat (2.1 g, 1 wt%) were added and the mixture was stirred overnight further. The THF was evaporated and 700 mL of ethyl acetate was added. The organic layer was washed twice with aqueous NaHCO ₃ and several times with deionized water. The organic layer was passed through a silica column and the solvent was evaporated to give a highly viscous liquid methacrylate endcap chain extended DCPD oligomer (Resin 9) (160 g, 78%).

<Preparation of Resin 10 of the Present Invention>
Tris (2,3-epoxypropyl) isocyanurate (62 g, 209 mmol) and methacrylic acid (35.9 g, 418 mmol) were placed in toluene (200 mL) in a 500 mL round bottom flask equipped with a magnetic stir bar and nitrogen inlet. It was 1000 ppm methylhydroquinone and Hycat 2000 S (1 g, 1 wt%) were added and the mixture was heated at 60 ° C. overnight. After cooling to room temperature, ethyl acetate was added and the organic layer was washed twice with saturated aqueous bicarbonate solution and then several times with deionized water. After drying over anhydrous Na ₂ SO ₄ , the organic layer was passed through a silica column and the solvent was evaporated. This provided a viscous liquid epoxy dimethacrylate resin 10 (73 g, 74%).

<Preparation of Resin 11 of the Present Invention>
RDGE (93.4 g, 420 mmol), 6-maleimidocaproic acid (124.2 g, 588 mmol), methylhydroquinone (100 mg, 500 ppm) were placed in a toluene (200 mL) of a 500 mL four-necked flask equipped with a mechanical stirrer, The mixture was heated at 60 ° C until homogeneous. Hycat 2000S (2.05 g, 1 wt%) was added and the mixture was stirred at 60 ° C. overnight. Next morning, after cooling to room temperature, 500 mL of ethyl acetate was added, and the organic layer was washed twice with aqueous NaHCO ₃ solution and several times with deionized water. After drying over anhydrous Na ₂ SO ₄ , the organic layer was passed through a silica column and the solvent was evaporated. 500 ppm MeHQ was added and the solvent was evaporated to give a light brown viscous liquid of Resin 11 (158 g, 73%).

<Preparation of Resin 12 of the Present Invention>
A 100 mL round bottom flask was charged with 20.0 g of Tactix 756 (Huntsman Advanced Materials) and 20.0 g of SR833 (Sartomer). The mixture was heated to 100 ° C. in air with stirring. A homogeneous solution was obtained in about 30 minutes. The reaction was cooled to 70 ° C. and 6.62 g of 2-carboxyethyl acrylate (CEA) and 0.45 g of 2- (dimethylamino) ethyl acrylate (DMAEA) were added. The reaction continued in air for 4 hours. ¹ H NMR showed complete consumption of acid. The formation of adducts was further confirmed by mass spectroscopy.

<Preparation of Resin 13 of the Present Invention>
Trimellitic anhydride (154 g, 802 mmol) was placed in a mixture of DMF (500 mL) and xylene (100 mL) in a 1 L four-necked flask equipped with a mechanical stirrer. To this was added tricyclodecanediamine (Oxea chemicals, 78 g, 401 mmol) and the mixture was stirred at room temperature until nearly homogenous. The mixture is heated and when the temperature reaches about 130 ° C. the reflux of the mixture is started. The mixture was refluxed for 1 hour, the mixture was concentrated and the solvent mixture was evaporated. The distillation starts at about 138 ° C and the pot temperature gradually rises to about 172 ° C. After distilling off most of the solvent, excess water was poured into the mixture and stirred for 2 hours. It takes a while for the gel-like material to solidify. The white precipitate obtained was filtered off and the filter cake was washed twice with water. The solid was dried to give a white powder of Resin 13 (174 g, 80%).

<Preparation of Resin 14 of the Present Invention>
Imidedioic acid resin 13 (57.5 g, 105 mmol) and glycidyl methacrylate (28.6 g, 201 mmol) were placed in THF (150 mL) in a 500 ml four-necked flask equipped with a mechanical stirrer and a condenser. Hycat 2000S (0.9 g, 1 wt%) was added and the mixture was stirred at 60 ° C. overnight. The THF was evaporated and 600 mL ethyl acetate was added. The organic layer was washed twice with aqueous NaHCO ₃ and several times with deionized water and passed through a silica column. Another 1000 ppm MeHQ was added and the solvent was evaporated to give a light green solid resin 14 (90%).

<Preparation of Resin 15 of the Present Invention>
4,4′-Hexafluoroisopropylidene diphthalic anhydride (100 g, 225 mmol) was placed in a mixture of DMF (400 mL) and xylene (80 mL) in a 1 L 3-neck flask equipped with mechanical stirrer and heating mantle. . Ethanolamine (31 g, 506 mmol) was added in one portion (slight exotherm as temperature rose to about 45 ° C). At the beginning of the azeotropic distillation, the reaction temperature gradually increased to about 139 ° C and the mixture was heated to 170 ° C. Eventually the temperature rose to about 160 ° C in about 30 minutes. At this point the reaction was stopped and IR showed the imidization was complete. After cooling, 500 mL of water was added and stirred for 30 minutes. The precipitated solid was filtered off, washed with water several times and dried to give a light orange solid imidodiol resin 15 (101 g, 85%).

<Preparation of Resin 16 of the Present Invention>
Imidediol 15 (42 g, 79 mmol), methacrylic acid (17 g, 198 mmol), PTSA monohydrate (1.5 g, 7.9 mmol) in toluene (300 mL) in a 1 L 3-neck flask equipped with mechanical stirrer and water condenser. ), 4-methoxyphenol (60 mg, 1000 ppm). The mixture was refluxed by azeotropic distillation of water for about 7 hours. After cooling to room temperature, the mixture was diluted with ethyl acetate, washed twice with aqueous NaHCO ₃ solution, and washed with deionized water until the ionic conductivity was about 2 μS. The organic layer was passed through a silica column containing a short plug of silitin between the silica layers. Another 500 ppm of 4-methoxyphenol was added and the solvent was evaporated on a rotary evaporator to give Resin 16 (43 g, 81%).

<Preparation of Resin 17 of the Present Invention>
4,4′-Oxydiphthalic anhydride (104 g, 335 mmol) was placed in a mixture of DMF (400 mL) and xylene (100 mL) in a 1 L 3-neck flask equipped with mechanical stirrer and heating mantle. Ethanolamine (47 g, 769 mmol) was added in one portion (slight exotherm as the temperature rose to about 48 ° C). At the beginning of the azeotropic distillation, the reaction temperature gradually increased to about 139 ° C and the mixture was heated to 170 ° C. Eventually the temperature rose to about 170 ° C in about 30 minutes. After most of the solvent had evaporated, the mixture was cooled to room temperature. 500 mL of water was added and well stirred for 30 minutes. The white solid that precipitated was filtered off, washed several times with water, and dried to give an off-white solid imide diol resin 17 (108 g, 81%).

<Preparation of Resin 18 of the Present Invention>
Imidediol 17 (38 g, 95 mmol), methacrylic acid (20.63 g, 239 mmol), PTSA monohydrate (1. 3 g) in toluene (300 mL) in a 1 L three-necked flask equipped with mechanical stirrer and water condenser. 8 g, 9.5 mmol) and 4-methoxyphenol (60 mg, 1000 ppm) were added. The mixture was refluxed by azeotropic distillation of water for about 7 hours. After cooling to room temperature, the mixture was diluted with ethyl acetate, washed twice with aqueous NaHCO ₃ solution, and washed with deionized water until the ionic conductivity was about 2 μS. The organic layer was passed through a silica column containing a short plug of silitin between the silica layers. Another 500 ppm of 4-methoxyphenol was added and the solvent was evaporated on a rotary evaporator to give a brown viscous liquid of Resin 18 (44.1 g, 85%).

Claims (30)

A resin that includes the following structures.

(In the formula,
Q is

and

May be selected from
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R ₁ is methyl or H,
X is CH ₂ ,

Or

n, n ₁ , n ₂ , and n ₃ are each independently 1 to 10,
Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene. ) A resin that includes the following structures.

(In the formula,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R ₁ and R ₂ are each independently methyl or H,
n ₁ and n ₂ are each independently 1 to 10, and X ₁ and X ₂ are each independently CH ₂ ,

and

Selected from
n ₃ is 1 to 10,
Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene. ) A resin that includes the following structures.

(In the formula,
X ₁ and X ₂ are independently a 3-10 membered ring group selected from functionalized or non-functionalized cycloaliphatic groups optionally having one or more heteroatoms,
n is 1 to 10,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R is linked to a ring structure containing X ₁ and X ₂ at any position,
X ₃ is a bond connecting a methacrylate group to the ring X ₁ or

Or

And
n ₃ is 1 to 10 and Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene,
However, the hydroxyl group on the X ₁ ring is adjacent to the X ₃ group containing the (meth) acrylate, and the hydroxyl group on the X ₂ ring is adjacent to the maleimidoalkanoyl group. ) A resin that includes the following structures.

(In the formula,
X ₁ and X ₂ are independently a 3-10 membered ring group selected from functionalized or non-functionalized cycloaliphatic groups optionally having one or more heteroatoms,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R may be linked to the ring structures X ₁ and X ₂ at any position,
However, the hydroxyl group on the X ₂ ring is adjacent to the maleimidoalkanoyl group,
n = 1 to 10. ) A resin that includes the following structures.

(In the formula,
X ₁ and X ₂ are independently a 3-10 membered ring group selected from functionalized or non-functionalized cycloaliphatic groups optionally having one or more heteroatoms,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R is linked to the ring structures X ₁ and X ₂ at any position,
X ₃ and X ₄ are each independently a bond or a bond connecting a methacrylate group to the rings X ₁ and X _2.

Or

May be
n ₃ is 1 to 10 and Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene,
R ₁ and R ₂ are each independently H or methyl,
However, the hydroxyl group on the X ₁ ring is adjacent to the X ₃ group and the hydroxyl group on the X ₂ ring is adjacent to the X ₄ group. ) A resin that includes the following structures.

(In the formula,
R ₁ and R ₂ are each independently linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched. Selected from branched cycloalkylene, straight chain or branched alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, heterocycloalkylene or heterocycloarylene. Is a polyvalent hydrocarbyl linking group, alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltri Kuroarukiren, bicycloalkyl arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
X is a skeleton of dicarboxylic acid, and is arylene, alkylene, cycloalkylene, straight chain or branched alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, straight chain or branched alkenylene, arylene, aralkylene, cycloalkylarylene, hetero. Selected from cycloalkylene or heterocycloarylene,
n is 1 to 10. ) A resin that includes the following structures.

(In the formula,
R ₁ and R ₂ are each independently linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched. Selected from branched cycloalkylene, straight chain or branched alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, heterocycloalkylene or heterocycloarylene. Is a polyvalent hydrocarbyl linking group, alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltri Kuroarukiren, bicycloalkyl arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
X is a skeleton of dicarboxylic acid, and is arylene, alkylene, cycloalkylene, straight chain or branched alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, straight chain or branched alkenylene, arylene, aralkylene, cycloalkylarylene, hetero. Selected from cycloalkylene or heterocycloarylene,
n is 1 to 10,
X ₁ and X ₂ are polymerizable groups and are independently selected from a glycidyl group or a (meth) acryloyl group, X ₁ and X ₂ may be the same when they are not a glycidyl group. . ) A resin that includes the following structures.

(In the formula,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R ₁ is a linking group, which may be a carbonyl group, an aliphatic or an aromatic group and may contain one or more ester, ether, thioether or hydroxyl groups,
R ₂ is a substituent on the aromatic ring and can be H, halogen, alkyl, alkyl ether, thioether group,
X ₁ can be H or a polymerizable group selected from a (meth) acryloyl group and a glycidyl group. ) A resin that includes the following structures.

(In the formula,
R ₁ is a bond that simply connects two aromatic groups, and is O, carbonyl or straight-chain or branched alkyl, straight-chain or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, straight-chain. Or branched alkylene, linear or branched cycloalkylene, linear or branched alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, hetero A polyvalent hydrocarbyl linking group selected from cycloalkylene or heterocycloarylene, which is alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbiene. Cycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloarylene can optionally include O or S or a hydroxyl group,
R ₂ is an aliphatic or aromatic linking group which may contain one or more ester, ether, thioether, carbonate or hydroxyl groups,
R ₃ is a substituent on the aryl group, which may be H, halogen, alkyl, alkyl ether or thioether group,
X is a polymerizable functional group selected from H or a (meth) acryloyl or glycidyl group. ) A resin that includes the following structures.

(In the formula,
R is linear or branched alkyl, linear or branched cycloalkyl, alkylene, cycloalkylene, bicycloalkylene, tricycloalkylene, linear or branched alkylene, linear or branched cycloalkylene, linear or branched Alkenylene, arylene, aralkylene, aryl bicycloalkylene, aryltricycloalkylene, bicycloalkylarylene, tricycloalkylarylene, bisphenylene, cycloalkylarylene, a polyvalent hydrocarbyl linking group selected from heterocycloalkylene or heterocycloarylene, Alkyl, cycloalkyl, alkylene, cycloalkylene, alkenylene, arylene, aralkylene, arylbicycloalkylene, aryltricycloalkylene, bicycloalkyl Arylene, tricycloalkyl arylene, bisphenylene, cycloalkylarylene, heterocycloalkylene and heterocycloalkyl arylene may optionally contain O or S, or hydroxyl group,
R ₁ is methyl or H,
n ₁ and n ₂ are each independently 1 to 10,
X is CH ₂ ,

and

Selected from
n ₃ is 1 to 10,
Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene. )   An ODF sealant composition comprising the resin of claim 1 and a material selected from the group consisting of free radical initiators, hardeners, fillers and combinations thereof.   In addition, photoinitiators, thixotropic agents, silane coupling agents, diluents, modifiers, colorants, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, tougheners and The ODF sealant composition according to claim 11, comprising a material selected from the group consisting of these combinations.   An ODF sealant composition comprising the resin of claim 2 and a material selected from the group consisting of free radical initiators, hardeners, fillers and combinations thereof.   In addition, photoinitiators, thixotropic agents, silane coupling agents, diluents, modifiers, colorants, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, tougheners and 14. The ODF sealant composition of claim 13, comprising a material selected from the group consisting of these combinations.   An ODF sealant composition comprising the resin of claim 3 and a material selected from the group consisting of free radical initiators, hardeners, fillers and combinations thereof.   In addition, photoinitiators, thixotropic agents, silane coupling agents, diluents, modifiers, colorants, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, tougheners and 16. The ODF sealant composition of claim 15, comprising a material selected from the group consisting of these combinations.   An ODF sealant composition comprising the resin of claim 4 and a material selected from the group consisting of free radical initiators, hardeners, fillers and combinations thereof.   In addition, photoinitiators, thixotropic agents, silane coupling agents, diluents, modifiers, colorants, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, tougheners and 18. The ODF sealant composition of claim 17, comprising a material selected from the group consisting of these combinations.   An ODF sealant composition comprising the resin of claim 5 and a material selected from the group consisting of free radical initiators, hardeners, fillers and combinations thereof.   In addition, photoinitiators, thixotropic agents, silane coupling agents, diluents, modifiers, colorants, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, tougheners and 20. The ODF sealant composition of claim 19, comprising a material selected from the group consisting of these combinations.   An ODF sealant composition comprising the resin of claim 6 and a material selected from the group consisting of free radical initiators, hardeners, fillers and combinations thereof.   In addition, photoinitiators, thixotropic agents, silane coupling agents, diluents, modifiers, colorants, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, tougheners and 22. The ODF sealant composition of claim 21, comprising a material selected from the group consisting of these combinations.   An ODF sealant composition comprising the resin of claim 7 and a material selected from the group consisting of free radical initiators, hardeners, fillers and combinations thereof.   In addition, photoinitiators, thixotropic agents, silane coupling agents, diluents, modifiers, colorants, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, tougheners and 24. The ODF sealant composition of claim 23, comprising a material selected from the group consisting of these combinations.   An ODF sealant composition comprising the resin of claim 8 and a material selected from the group consisting of free radical initiators, hardeners, fillers and combinations thereof.   In addition, photoinitiators, thixotropic agents, silane coupling agents, diluents, modifiers, colorants, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, tougheners and 26. The ODF sealant composition of claim 25, comprising a material selected from the group consisting of these combinations.   An ODF sealant composition comprising the resin of claim 9 and a material selected from the group consisting of free radical initiators, hardeners, fillers and combinations thereof.   In addition, photoinitiators, thixotropic agents, silane coupling agents, diluents, modifiers, colorants, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, tougheners and 28. The ODF sealant composition of claim 27, comprising a material selected from the group consisting of these combinations.   An ODF sealant composition comprising the resin of claim 10 and a material selected from the group consisting of free radical initiators, hardeners, fillers and combinations thereof.   In addition, photoinitiators, thixotropic agents, silane coupling agents, diluents, modifiers, colorants, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, tougheners and 30. The ODF sealant composition of claim 29, comprising a material selected from the group consisting of these combinations.