KR100754724B1 - Insulating Interlayers for Liquid Crystal Display Element and Liquid Crystal Display Elements Using the Same - Google Patents

Abstract

The present invention is selected from the group consisting of (A) a compound represented by the following formula (A-1) (A-1), (A-2) a compound represented by the following formula (2), and (A-3) a compound represented by the following formula (3) The interlayer insulation film for liquid crystal display elements obtained by heating the hydrolysis-condensation product formed by hydrolyzing and condensing a compound more than 1 type in the presence of a catalyst.

<Formula 1>

R _a Si (OR ¹ ) _4-a

<Formula 2>

Si (OR ² ) ₄

<Formula 3>

R ³ _b (R ⁴ O) _3-b Si- (R ⁷ ) _d -Si (OR ⁵ ) _3-c R ⁶ _c

In the formula,

R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, a is an integer of 1 to 2, R ² represents a monovalent organic group, R ³ to R ⁶ are the same or Or different and each monovalent organic group, b to c are the same or different and are an integer from 0 to 2, R ⁷ is an oxygen atom, a phenylene group or a group represented by-(CH ₂ ) _n- n is an integer from 1 to 6), and d represents 0 or 1.

Liquid crystal display element, interlayer insulation film, TFT array substrate, opposing substrate, low dielectric constant, hydrolysis, condensation

Description

Insulating interlayers for liquid crystal display elements and liquid crystal display elements using the same

1 is a cross-sectional conceptual view of a TFT array substrate in Embodiment 7 of the present invention.

2 is a cross-sectional conceptual view of an opposing substrate in a seventh embodiment of the present invention.

3 is a schematic cross-sectional view of the LCD of Embodiment 7 of the present invention.

<Explanation of symbols for main parts of the drawings>

1: glass substrate 2: underlayer film

3: amorphous silicon layer 4: gate electrode

5: semiconductor film 5 ': n + layer

6: insulating film 7: source wiring

8: drain wiring 8 ': pixel electrode

10: TFT array substrate 11: glass substrate

12: transparent counter electrode 20: counter substrate

22: liquid crystal aligning film 23: TN liquid crystal

24: polarizing plate 30: liquid crystal cell

31: LCD

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interlayer insulating film for a liquid crystal display device, and more particularly, to form a low temperature as an interlayer insulating film material used for a thin film transistor (TFT) for driving a liquid crystal display device (LCD), and exhibit a low dielectric constant. In addition, the present invention relates to an LCD interlayer insulating film having excellent heat resistance of a coating film and an LCD using the same.

Conventionally, silica (SiO ₂ ) films formed by vacuum processes such as the CVD method have been widely used as the interlayer insulating films for LCDs. However, as the precision of LCD pixels increases, the flicker of LCDs due to the height of the dielectric constant (4.1) of the SiO ₂ film used for the LCD interlayer insulating film becomes a problem. In order to eliminate this flicker, an LCD interlayer insulating film having a relative dielectric constant of 3 or less is required.

On the other hand, coating type interlayer insulating films mainly composed of hydrolyzed products of tetraalkoxysilanes called organic interlayer insulating films made of acrylic resins and SOG (Spin on Glass) films have been studied as LCD interlayer insulating films. In the organic interlayer insulating film formed, heat resistance to the heat treatment step (350 ° C.) required for TFT formation is inferior, and in the interlayer insulating film made of SOG, a dielectric constant of 3 or less cannot be achieved under a firing condition of 350 ° C.

The present invention relates to an LCD interlayer insulating film for solving the above problems, and more particularly, to a low temperature as a TFT for driving an LCD, and having a low relative dielectric constant, and at the same time excellent in heat resistance of the coating film, It is an object to provide an LCD using the same.

The present invention

(A) (A-1) at least one compound selected from the group of compounds represented by formula (1), (A-2) compounds represented by formula (2), and (A-3) compounds represented by formula (3) The interlayer insulation film for LCD obtained by heating the hydrolysis condensate formed by hydrolytic condensation in presence of a catalyst is provided.

R _a Si (OR ¹ ) _4-a

Si (OR ² ) ₄

R ³ _b (R ⁴ O) _3-b Si- (R ⁷ ) _d -Si (OR ⁵ ) _3-c R ⁶ _c

In the formula,                     

R is a hydrogen atom, a fluorine atom or a monovalent organic group,

R ¹ is a monovalent organic group,

a represents an integer of 1 to 2,

R ² represents a monovalent organic group,

R ³ to R ⁶ are the same or different and are each monovalent organic group,

b to c are the same or different and are an integer from 0 to 2,

R ⁷ is an oxygen atom, a phenylene group or a group represented by-(CH ₂ ) _n- , where n is an integer from 1 to 6,

d represents 0 or 1.

Next, the present invention relates to an LCD having an interlayer insulating film for LCD.

In the present invention, the (A) hydrolysis condensate is a hydrolysis condensate of at least one silane compound selected from the group of compounds (1) to (3).

In the hydrolysis in the component (A), the R ¹ O-group, R ² O-group, R ⁴ O-group, and R ⁵ contained in the compounds (1) to (3) constituting the component (A). It is not necessary that all of the O-groups be hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or a mixture thereof.

The condensation in the component (A) means that the silanol groups of the hydrolyzates of the compounds (1) to (3) constituting the component (A) condense to form a Si-0-Si bond. It is not necessary that all of the silanol groups be condensed, and the concept includes a mixture of some condensed silanol groups, a mixture of different degrees of condensation.

(A) hydrolysis condensate

(A) The hydrolysis condensate can be obtained by hydrolyzing and condensing at least one silane compound selected from the group of the compounds (1) to (3) in the presence of a catalyst.

Compound (1);

In the above formula (1), examples of the monovalent organic groups of R and R ¹ include alkyl groups, aryl groups, allyl groups, glycidyl groups, and the like. In formula (1), R is preferably a monovalent organic group, particularly an alkyl group or a phenyl group.

Here, the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, or the like, and preferably has 1 to 5 carbon atoms. The alkyl group may be linear or branched, and the hydrogen atom may be further substituted. It may be.

In Formula (1), a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group etc. are mentioned.

Specific examples of the compound represented by the formula (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane, tri-sec-butoxy Silane, tri-tert-butoxysilane, triphenoxysilane, fluoro trimethoxysilane, fluoro triethoxysilane, fluoro tri-n-propoxysilane, fluoro tri-iso-propoxysilane, fluoro Low tri-n-butoxysilane, fluoro tri-sec-butoxysilane, fluoro tri-tert-butoxysilane, fluoro triphenoxysilane and the like;

Methyl trimethoxysilane, methyl triethoxysilane, methyl tri-n-propoxysilane, methyl tri-iso-propoxysilane, methyl tri-n-butoxysilane, methyl tri-sec-butoxysilane, methyl tri -tert-butoxysilane, methyl triphenoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, ethyl tri-n-propoxysilane, ethyl tri-iso-propoxysilane, ethyl tri-n-butoxy Silane, ethyl tri-sec-butoxysilane, ethyl tri-tert-butoxysilane, ethyl triphenoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri-n-propoxysilane, vinyl tri- iso-propoxysilane, vinyl tri-n-butoxysilane, vinyl tri-sec-butoxysilane, vinyl tri-tert-butoxysilane, vinyl triphenoxysilane, n-propyl trimethoxysilane, n-propyl Triethoxysilane, n-propyl tri-n-propoxysilane, n-propyl tri-iso-propoxysilane, n-propyl tri-n-butoxysilane, n- Lofil tri-sec-butoxysilane, n-propyl tri-tert-butoxysilane, n-propyl triphenoxysilane, i-propyl trimethoxysilane, i-propyl triethoxysilane, i-propyl tri-n -Propoxysilane, i-propyl tri-iso-propoxysilane, i-propyl tri-n-butoxysilane, i-propyl tri-sec-butoxysilane, i-propyl tri-tert-butoxysilane, i -Propyl triphenoxysilane, n-butyl trimethoxysilane, n-butyl triethoxysilane, n-butyl tri-n-propoxysilane, n-butyl tri-iso-propoxysilane, n-butyl tri- n-butoxysilane, n-butyl tri-sec-butoxysilane, n-butyl tri-tert-butoxysilane, n-butyl triphenoxysilane, sec-butyl trimethoxysilane, sec-butyl triethoxy Silane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysil Column, t-butyl trimethoxysilane, t-butyl triethoxysilane, t-butyl tri-n-propoxysilane, t-butyl tri-iso-propoxysilane, t-butyl tri-n-butoxysilane , t-butyl tri-sec-butoxysilane, t-butyl tri-tert-butoxysilane, t-butyl triphenoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, phenyl tri-n-propoxy Silane, phenyl tri-iso-propoxysilane, phenyl tri-n-butoxysilane, phenyl tri-sec-butoxysilane, phenyl tri-tert-butoxysilane, phenyl triphenoxysilane, vinyl trimethoxysilane, Vinyl triethoxysilane, γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-triflo Ropropyl trimethoxysilane, γ-trifluoropropyl triethoxysilane, and the like;

Dimethyl dimethoxysilane, dimethyl diethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec-butoxysilane, Dimethyl-di-tert-butoxysilane, dimethyl diphenoxysilane, diethyl dimethoxysilane, diethyl diethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, Diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-tert-butoxysilane, diethyl diphenoxysilane, di-n-propyl dimethoxysilane, di -n-propyl diethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-n-propyl-di-n-butoxysilane, Di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propyl-di-phenoxysilane, di-iso-propyl dimethoxysilane, di -iso-propyl diethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso-propyl-di-iso -Propoxysilane, di-iso-propyl-di-n-butoxysilane, di-iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysilane, di-iso -Propyl-di-phenoxysilane, di-n-butyl dimethoxysilane, di-n-butyl diethoxysilane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di-iso -Propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di-tert-butoxysilane, di-n -Butyl-di-phenoxysilane, di-sec-butyl dimethoxysilane, di-sec-butyl diethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl-di-iso -Propoxysilane, di-sec-butyl-di-n-butoxysilane, di-sec-butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-butoxysilane, di-sec -Butyl-di-phenoxysilane, di-tert-butyl dimethoxysilane, di-tert-butyl diethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso -Propoxysilane, di-tert-butyl-di-n-butoxysilane, di-tert-part Tyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane, diphenyl dimethoxysilane, diphenyl-di-ethoxysilane , Diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-butoxysilane, diphenyl-di- tert-butoxysilane, diphenyl diphenoxysilane, divinyl trimethoxysilane, etc. are mentioned.

Preferred compounds as compound (1) include methyl trimethoxysilane, methyl triethoxysilane, methyl tri-n-propoxysilane, methyl tri-iso-propoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, Vinyl trimethoxysilane, vinyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, dimethyl dimethoxysilane, dimethyl diethoxysilane, diethyl dimethoxysilane, diethyl diethoxysilane, diphenyl dimethoxy Silane, diphenyl diethoxysilane and the like.

These can also use 1 type (s) or 2 or more types simultaneously.                     

Compound (2);

In the above formula (2), examples of the monovalent organic group represented by R ² include the same organic groups as those of the above formula (1).

Specific examples of the compound represented by the formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane , Tetra-tert-butoxysilane, tetraphenoxysilane, and the like.

Compound (3);

In the above formula (3), examples of the monovalent organic group represented by R ³ to R ⁶ include the same organic groups as those of the above formula (1).

In the formula (3), examples of the compound in which R ⁷ is an oxygen atom include hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3-methyldisiloxane, 1, 1,1,3,, 3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-methyldisiloxane, 1,1,1,3,3-penta Methoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaethoxy-3-ethyldisiloxane, 1,1,1,3,3-pentaphenoxy-3-ethyldisiloxane, 1 , 1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyldisiloxane, 1,1,1,3,3-penta Phenoxy-3-phenyldisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1 , 1,3,3-tetraphenoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diethyldisiloxane, 1,1,3,3-tetrae Oxy-1,3-diethyldisiloxane, 1,1,3,3-tetraphenoxy-1,3-diethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyl Disiloxane, 1,1,3,3-tetraethoxy-1,3-dipe Disiloxane, 1,1,3,3-tetraphenoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane, 1,1,3- Triethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triphenoxy-1,3,3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3,3- Triethyldisiloxane, 1,1,3-triethoxy-1,3,3-triethyldisiloxane, 1,1,3-triphenoxy-1,3,3-triethyldisiloxane, 1,1 , 3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,1,3-triphenoxy-1 , 3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraethyldisiloxane, 1,3-diethoxy-1, 1,3,3-tetraethyldisiloxane, 1,3-diphenoxy-1,1,3,3-tetraethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldi Siloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-dipe When 1,1,3,3 and the like tetraphenyl-disiloxane.

Among them, hexamethoxy disiloxane, hexaethoxy disiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3- Dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-die Oxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3- Tetraphenyldisiloxane etc. are mentioned as a preferable example.

In addition, in the formula (3), as the compound whose d is 0, hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1 , 1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-penta Methoxy-2-ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1 , 1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-penta Phenoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1 , 1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetrae Methoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyl Disilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2-diphenyl Silane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy C-1,2,2-trimethyldisilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-tri Ethyldisilane, 1,1,2-triphenoxy-1,2,2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1, 2-triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2 , 2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-diphenoxy-1,1,2,2-tetramethyldisilane, 1 , 2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1 , 2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane, etc. are mentioned.

Among them, hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2- Dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-die Oxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2- Tetraphenyldisilane etc. are mentioned as a preferable example.

In addition, in the formula (3), examples of the compound of the group in which R ⁷ is represented by-(CH ₂ ) _n -include bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane and bis (tri-n-pro Foxysilyl) methane, bis (tri-i-propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-t-butoxysilyl Methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri-n-propoxysilyl) ethane, 1,2-bis (Tri-i-propoxysilyl) ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane, 1,2-bis (tri -t-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- ( Di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-i-propoxymethylsilyl) -1- (tri-i-propoxysilyl) methane, 1 -(Di-n-butoxymethylsilyl) -1 -(Tri-n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-t-butoxymethylsilyl) -1- (tri-t-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) Ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-i-propoxymethylsilyl) -2- (tri-i-propoxy Silyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec-butoxymethylsilyl) -2- (tri-sec- Butoxysilyl) ethane, 1- (di-t-butoxymethylsilyl) -2- (tri-t-butoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, Bis (di-n-propoxymethyl silyl) methane, bis (di-i-propoxymethylsilyl) methane, bis (di-n-butoxymethylsilyl) methane, bis (di-sec-butoxymethylsilyl) Methane, bis (di-t-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) Ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-i-propoxymethylsilyl) ethane, 1 , 2-bis (di-n-butoxymethylsilyl) ethane, 1,2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-t-butoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri- i-propoxysilyl) benzene, 1,2-bis (tri-n-butoxysilyl) benzene, 1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-t- Butoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n-propoxysilyl) benzene, 1, 3-bis (tri-i-propoxysilyl) benzene, 1,3-bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene, 1,3- Bis (tri-t-butoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4- Bis (tri-n-propoxysilyl) benzene, 1,4-bis (tri-i-propoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis ( Tri-sec-butoxysilyl) benzene, 1,4-bis (tri-t-butoxysilyl) benzene, and the like.

Among them, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- ( Dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxy Silyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethyl Silyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (tri Methoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, and the like are preferable examples. Can be.

In the present invention, the compounds (1) to (3) may be used alone or in combination of two or more.

In addition, when hydrolyzing and condensing at least one silane compound selected from the group of the compounds (1) to (3), more than 0.5 moles and no more than 150 moles of water per mole of the compounds (1) to (3) Preference is given to adding more than 0.5 moles to 130 moles of water.

In preparing the hydrolysis-condensation product of the present invention (A), it is characterized by using a catalyst when hydrolyzing and combining at least one silane compound selected from the group of compounds (1) to (3).

As a catalyst which can be used at this time, an alkali catalyst is preferable.

As such an alkali catalyst, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl Diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Ammonia, methylamine, ethylamine, propylamine, butylamine, pentyl amine, hexylamine, pentylamine, octylamine, nonylamine, decylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, trimethylimidine, 1-amino-3-methylbutane, dimethylglycine, 3 -Amino- 3-methylamine etc. are mentioned, Organic amine is more preferable, Ammonia, alkylamine, and tetraalkylammonium hydroxide are especially preferable at the point of adhesiveness with respect to the board | substrate of a coating film.

These alkali catalysts can also use 1 type (s) or 2 or more types simultaneously.

It is also possible to use other catalysts or blend the hydrolytic condensates obtained with other catalysts within the scope of not impairing the effects of the present invention.

Examples of such other catalysts include metal chelate compounds and acid catalysts.

Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, and tri-i-propoxy mono (acetylacetonato). Titanium, tri-n-butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium , Diethoxy bis (acetylacetonato) titanium, di-n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-part Toxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonato) titanium, di-t-butoxy bis (acetylacetonato) titanium, monoethoxy tris (acetyl Acetonitrile) titanium, mono-n-propoxy tris (acetylacetonato) titanium, mono-i-propoxy tris (acetylacetonato) tea Mono-n-butoxy tris (acetylacetonato) titanium, mono-sec-butoxy tris (acetylacetonato) titanium, mono-t-butoxy tris (acetylacetonato) titanium, Tetrakis (acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) Titanium, tri-n-butoxy mono (ethylacetoacetate) titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy Bis (ethylacetoacetate) titanium, di-n-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-n-butoxy bis (ethylacetoacetate Titanium, di-sec-butoxy bis (ethylacetoacetate) Titanium, di-t-butoxy ratio (Ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i-propoxy tris (ethylacetoacetate) titanium, mono -n-butoxy tris (ethylacetoacetate) titanium, mono-sec-butoxy tris (ethylacetoacetate) titanium, mono-t-butoxy tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate Titanium, titanium, such as mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium Chelate compounds;

Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-part Toxy mono (acetylacetonato) zirconium, tri-sec-butoxy mono (acetyl acetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxy bis (acetylaceto Neato) zirconium, di-n-propoxy bis (acetylacetonato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) ) Zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono- n-propoxy tris (acetylacetonato) zirconium, mono-i-propoxy tris ( Cetylacetonato) zirconium, mono-n-butoxytris (acetylacetonato) zirconium, mono-sec-butoxytris (acetylacetonato) zirconium, mono-t-butoxytris (acetylaceto Neito) zirconium, tetrakis (acetylacetonato) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy mono (Ethylacetoacetate) zirconium, tri-n-butoxy mono (ethylacetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) zirconium, tri-t-butoxy mono (ethylacetoacetate Earth) zirconium, diethoxy bis (ethylacetoacetate) zirconium, di-n-propoxy bis (ethylacetoacetate) zirconium, di-i-propoxy bis (ethylacetoacetate) zirconium, di-n-part Toxy bis (ethyl acetate Acetate) zirconium, di-sec-butoxybis (ethylacetoacetate) zirconium, di-t-butoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium, mono-n- Propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxy tris (ethylacetoacetate) zirconium, mono-sec-butoxy tris ( Ethylacetoacetate) zirconium, mono-t-butoxytris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate Zirconium chelates such as earth) bis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium, etc. .;

Aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum; and the like, and preferably chelate compounds of titanium or aluminum, and particularly preferably chelate compounds of titanium.

These metal chelate compounds may be used alone or in combination of two or more.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, and oxalic acid;

Acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, melitric acid, arachidonic acid , Shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid Hydrolyzate of trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid, maleic anhydride And organic acids such as hydrolyzates of phthalic anhydride are mentioned, and organic acids are mentioned as more preferable examples.

These acid catalysts can also use 1 type (s) or 2 or more types simultaneously.

The amount of the catalyst used is usually 0.00001 to 10 with respect to 1 mol of the total amount of the groups represented by the R ¹ O-groups, R ² O-groups, R ⁴ O-groups, and R ⁵ O-groups in the compounds (1) to (3). Moles, preferably 0.00005 to 5 moles. When the usage-amount of a catalyst is in the said range, there exists little possibility of polymer precipitation and gelation during reaction. In addition, in this invention, the temperature at the time of hydrolyzing (A) component is 0-100 degreeC normally, Preferably it is 15-80 degreeC.

Further, in the component (A), when each component is converted into a fully hydrolyzed condensate, the compound (2) is 5 to 75% by weight, preferably 10 to 70% by weight in the total amount of the compounds (1) to (3). %, More preferably 15 to 70% by weight. Further, compounds (1) and / or (3) are 95 to 25% by weight, preferably 90 to 30% by weight, more preferably 85 to 30% by weight, based on the total amount of compounds (1) to (3). . The elasticity modulus of the coating film obtained that compound (2) is 5-75 weight% in the total amount of compounds (1)-(3) is high, and at the same time, it is especially excellent in low dielectric constant.

Here, the complete hydrolysis condensate in the present invention means that the R ¹ O-group, R ² O-group, R ⁴ O-group, and R ⁵ O-group in the compounds (1) to (3) are 100% hydrolyzed. To become an SiOH group, and more completely condensed to form a siloxane structure.

Moreover, as (A) component, since the storage stability of the composition obtained is more excellent, the hydrolysis-condensation product of compound (1) and compound (2) is preferable.

The interlayer insulation film for LCDs of this invention can be obtained by heating the solution containing (A) component and a solvent.

Examples of the solvent that can be used at this time include one or more selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents, and aprotic solvents.

Here, as the alcohol solvent, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octane Ol, 2-ethylcyclohexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, mono alcohol solvents such as sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2 Polyhydric alcohol solvents such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, And polyhydric alcohol partial ether solvents such as propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

These alcohol solvents may be used alone or in combination of two or more.

As a ketone solvent, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl acetylacetone in addition to -n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, phencone, etc. , 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptane (Beta) -diketones, such as dione, etc. are mentioned.

These ketone solvents can also use 1 type (s) or 2 or more types simultaneously.

As the amide solvent, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethyl Acetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrroli And N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like.

These amide solvents may be used alone or in combination of two or more.                     

Examples of the ester solvent include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate and n-butyl acetate , I-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate , Methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetic acid, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, acetate diethylene glycol monoethyl ether, acetic acid Diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetate glycol, methoxytriglycol acetate, ethyl propionate, N-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. Can be mentioned.

These ester solvents may be used alone or in combination of two or more.

Examples of aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethyl phosphate triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole and N -Methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methyl imidazole, N-methyl-4-piperidone, N-methyl-2 Piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, and the like.

These solvents can also use 1 type (s) or 2 or more types simultaneously.

The hydrolysis-condensation product used by this invention is manufactured by melt | dissolving (A) component in a solvent, for example, and hydrolyzing by adding a catalyst and water.

When hydrolyzing and condensing the said (A) component, it is preferable to use 0.8-20 mol of water with respect to 1 mol of alkoxyl groups in (A) component, and it is especially preferable to add 0.8-15 mol of water. If the amount of water to be added is less than 0.8 mol, the crack resistance of the coating film is inferior, and if it exceeds 20 mol, the coating uniformity of the coating film may be inferior.

In this invention, the temperature at the time of hydrolyzing (A) component and (B) component is 0-100 degreeC normally, Preferably it is 15-80 degreeC.

The total solid concentration of the hydrolyzed condensate used in the present invention is preferably 2 to 30% by weight, and is appropriately adjusted according to the purpose of use. When the total solid concentration of the composition is 2 to 30% by weight, the film thickness of the coating film is in a suitable range, and the storage stability is also excellent.

The hydrolysis-condensation product used by this invention may also contain the following components.

OTHER ADDITIVES

The hydrolytic condensates used in the present invention include components such as colloidal silica, colloidal alumina, organic polymers, surfactants, silane coupling agents, triazane compounds, radical generators, reactive double bond-containing compounds, reactive triple bond-containing compounds, and the like. It is also possible to add more.

Colloidal silica is, for example, a dispersion in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle diameter of 5 to 30 µm, preferably 10 to 20 µm, and a solid concentration of about 10 to 40 wt%. will be. Examples of such colloidal silica include methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industries, Ltd .; Oskal from Shokubai Kagaku Kogyo Co., Ltd. may be mentioned.

Examples of the colloidal alumina include alumina sol 520, 100, 200 manufactured by Nissan Chemical Industries, Ltd .; The alumina clear sol, the alumina sol 10, 132, etc. made by Kawaken Fine Chemical Co., Ltd. are mentioned.

Examples of the organic polymer include a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, a polyquinoxaline, and a polyoxa The compound which has a diazole, a fluorine-type polymer, a polyalkylene oxide structure, etc. are mentioned.

As a compound which has a polyalkylene oxide structure, a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, a polybutylene oxide structure, etc. are mentioned.

Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivatives, ethylene oxide derivatives of alkylphenol formalin condensation, polyoxyethylene polyoxypropylene block Ether type compounds, such as a copolymer and polyoxyethylene polyoxypropylene alkyl ether, ether, such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyoxyethylene fatty acid alkanolamide sulfate Ester compound, polyethylene glycol fatty acid ester, ethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose And the like ether ester type compounds such as esters.

As a polyoxyethylene polyoxypropylene block copolymer, the compound which has the following block structure is mentioned.

-(A) j- (B) k-

-(A) j- (B) k- (A) l-

Wherein, A is -CH ₂ CH ₂ group represented by O-, B represents a group represented by _{-CH 2 CH (CH 3) O-} , j is 1 to 90, k is 10 to 99, l is 0 To 90.

Among these, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, etc. Ether type compounds are mentioned as a more preferable example.                     

These can also use 1 type (s) or 2 or more types simultaneously.

As surfactant, a nonionic surfactant, anionic surfactant, cationic surfactant, an amphoteric surfactant, etc. are mentioned, for example, A fluorine-type surfactant, silicone type surfactant, polyalkylene oxide type surfactant, poly ( (Meth) acrylate type surfactant etc. are mentioned, Preferably, a fluorine type surfactant and silicone type surfactant are mentioned.

Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1, 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, perfluorododecylsulfonic acid sodium, 1,1,2 , 2,8,8,9,9,10,10-decaplododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctanesulfonamide) Propyl] -N, N'-dimethyl-N-carboxymethylene ammonium betaine, perfluoroalkylsulfonamide propyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bisphosphate bis (N-perfluorojade Terminal, main and branched chains, such as methylsulfonyl-N-ethylaminoethyl) and monoperfluoroalkyl ethylphosphate esters Alkyl or fluoroheteroborate to at least any one region may include a fluorine-based surface active agent comprising a compound having an alkylene group.

In addition, as a commercial item, Mega Pack F142D, F172, F173, F183 (above, Dai Nippon Ink Chemical Co., Ltd. product), F-Top EF301, 303, 352 (made by Shin-Kazada Kasei Co., Ltd.), Florid FC-430 FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Supron S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Asahi Gara) Fluorine-type surfactant marketed by names, such as the Corporation | KK Corporation ", BM-1000, BM-1100 (made by Yusho Corporation), NBX-15 (NEOS Corporation), etc. are mentioned. Among these, the said mega pack F172, BM-1000, BM-1100, and NBX-15 are especially preferable.

As a silicone type surfactant, SH7PA, SH21PA, SH30PA, ST94PA (all are manufactured by Toray Dow Corning Silicone Co., Ltd., etc. can be used, for example).

The use amount of surfactant is 0.0001-10 weight part normally with respect to 100 weight part (complete hydrolysis condensate) of the total amount of (A) component and (B) component.

These can also use 1 type (s) or 2 or more types simultaneously.

Examples of the silane coupling agent include 3-glycidyloxypropyl trimethoxysilane, 3-aminoglycidyloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-glycidyloxy. Propylmethyl dimethoxysilane, 1-methacryloxypropylmethyl dimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl trie Methoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl dimethoxysilane, 3-ureidopropyl trimethoxysilane, 3 -Ureidopropyl triethoxysilane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyl triethoxysilane, N-triethoxysilylpropyl triethylene Triamine, N-triethoxysilylpropyl triethylenetriamine, 10-tri Methoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-tri azadecane, 9-trimethoxysilyl-3,6-diazanyl acetate, 9-trie Oxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane , N-phenyl-3-aminopropyl triethoxysilane, N-bis (oxyethylene) -3-aminopropyl trimethoxysilane, N-bis (oxyethylene) -3-aminopropyl triethoxysilane, etc. are mentioned. Can be.

These can also use 1 type (s) or 2 or more types simultaneously.

As a triazene compound, a 1, 2-bis (3, 3- dimethyl triazenyl) benzene, a 1, 3-bis (3, 3- dimethyl triazenyl) benzene, a 1, 4-bis (3, 3-, Dimethyltriazenyl) benzene, bis (3,3-dimethyltriazenylphenyl) ether, bis (3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, bis (3,3 -Dimethyltriazenylphenyl) sulfide, 2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2, 2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] propane, 1,3,5-tris (3,3-dimethyltriazenyl) benzene, 2,7-bis (3,3-dimethyl Triazenyl) -9,9-bis [4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-methyl -4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-phenyl-4- (3,3-dimethyl Triazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9 , 9-bis [3-propenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-fluoro Rho-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3,5-difluoro-4- ( 3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-trifluoromethyl-4- (3,3-dimethyltri Azenyl) phenyl] fluorene, etc. are mentioned.

These can also use 1 type (s) or 2 or more types simultaneously.

Examples of the radical generator include isobutyryl peroxide, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxy neodecanoate, di-n-propylperoxydicarbonate, di Isopropyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxy neo Decanoate, di-2-ethoxyethylperoxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxy neodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl- 3-methoxybutylperoxy) dicarbonate, t-butylperoxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 3,5, 5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3- Tramethylbutylperoxy 2-ethylhexanoate, succinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2 -Ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m-toluoyl and benzoyl peroxide, benzoyl peroxide, t-butylperoxy isobutyl Late, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy ) Cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4, 4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butyl Peroxy-3,3,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluo Peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy ) Hexane, t-butylperoxy acetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate , Di-t-butylperoxy isophthalate, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-di (t-butylper Oxy) hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, p-mentane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3, diiso Propylbenzenehydroperoxide, t-butyltrimethylsilylperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, t-hexylhydroperoxide, t-butylhydroperoxide, di Benzyl, 2,3-dimethyl-2,3-diphenylbutane, α, α'-dimethoxy-α, α'-diphenyl ratio Vaginal, α, α'-diphenyl-α-methoxybibenzyl, α, α'-diphenyl-α, α'-dimethoxybibenzyl, α, α'-dimethoxy-α, α'-dimethylbibenzyl , α, α'-dimethoxybibenzyl, 3,4-dimethyl-3,4-diphenyl-n-hexane, 2,2,3,3-tetraphenylsuccinate nitrile and the like.

These can also use 1 type (s) or 2 or more types simultaneously.

Examples of the reactive double bond-containing compound include allylbenzene, diallylbenzene, triallylbenzene, allyloxybenzene, diallyloxybenzene, triallyloxybenzene, α, ω-diallyloxyalkane, α, ω-di Allyl alkenes, α, ω- diallyl alkenes, allylamine, diallylamine, triallylamine, N-allylphthalimide, N-allyl pyromellilimide, N, N'- diallylurea, triallyl Allyl compounds, such as isocyanurate and 2,2'-diallylbisphenol A;                     

Styrene, divinylbenzene, trivinylbenzene, stilbene, propenylbenzene, dipropenylbenzene, tripropenylbenzene, phenyl vinyl ketone, methyl styryl ketone, α, ω-divinyl alkanes, α, ω-di Vinyl alkenes, α, ω-divinyl alkynes, α, ω-divinyloxy alkanes, α, ω-divinyl alkenes, α, ω-divinyl alkynes, α, ω-diacryloxyalkanes , α, ω-diacrylic alkenes, α, ω-diacrylic alkenes, α, ω-dimethacryloxyalkanes, α, ω-dimethacrylic alkenes, α, ω-dimethacrylic alkenes, Vinyl compounds such as bisacryloxybenzene, trisacryloxybenzene, bismethacryloxybenzene, trismethacryloxybenzene, N-vinylphthalimide, and N-vinyl pyromellitimide;

The polyarylene ether containing 2,2'- diallyl-4, 4'- biphenol, the polyarylene containing 2,2'- diallyl-4, 4'- biphenol, etc. are mentioned.

These can also use 1 type (s) or 2 or more types simultaneously.

Examples of the reactive triple bond-containing compound include ethynylbenzene, dietynylbenzene, triethynylbenzene, transtrimethylsilylethynylbenzene, trimethylsilylethynylbenzene, bis (trimethylsilylethynyl) benzene, and tris (trimethylsilylethynyl ) Benzene, phenylethynylbenzene, bis (phenylethynyl) benzene, tris (phenylethynyl) benzene, bis (ethynylphenyl) ether, bis (trimethylsilylethynylphenyl) ether, bis (phenylethynylphenyl) ether Etc. can be mentioned.

These can also use 1 type (s) or 2 or more types simultaneously.

In the present invention, the content of alcohol having a boiling point of 100 ° C. or lower in the film-forming composition is preferably 20% by weight or less, particularly 5% by weight or less. Alcohols having a boiling point of 100 ° C. or less may occur at the time of hydrolysis and / or condensation of the component (A), and are removed by distillation or the like so that the content thereof is 20% by weight or less, preferably 5% by weight or less. It is desirable to.

When applying the hydrolysis-condensation product used by this invention to base materials, such as a gate insulating film, a gate oxide film, and a gate electrode of TFT, coating means, such as a spin coating method, an immersion method, a roll coating method, and a spray method, is used.

The film thickness at this time can form a coating film with a thickness of about 0.05 to 2 m in one coating and a thickness of about 0.1 to 4 m in two coatings as a dry film thickness. Thereafter, the insulating film of glassy or macromolecular polymer may be formed by drying at room temperature or by heating at a temperature of about 80 to 350 ° C. for about 2 to 240 minutes.

At this time, a hot plate, an oven, a furnace, etc. can be used as a heating method, As a heating atmosphere, it can carry out in air | atmosphere, nitrogen atmosphere, argon atmosphere, under vacuum, under reduced pressure which adjusted oxygen concentration.

Moreover, a coating film can also be formed by irradiating an electron beam and an ultraviolet-ray.

The interlayer insulating film for LCD thus obtained can be formed at low temperature, exhibits low relative dielectric constant, and is excellent in heat resistance of the coating film.

<Example>

Hereinafter, the embodiment of the present invention will be described in more detail. However, the following description shows the example of this invention generally, and there is no special reason, and this invention is not limited by this description.                     

In addition, "part" and "%" in an Example and a comparative example represent "weight part" and "weight%", respectively, unless there is particular notice.

In addition, each evaluation was performed as follows.

Weight average molecular weight (Mw)

It measured by the gel permeation chromatography (GPC) method by the following conditions.

Sample: Prepared by using tetrahydrofuran as a solvent and dissolving 1 g of hydrolysis condensate in 100 cc of tetrahydrofuran.

Standard polystyrene: Standard polystyrene manufactured by Pressure Chemical, USA was used.

Apparatus: high temperature high speed gel permeation chromatogram (Model 150-C ALC / GPC), manufactured by Waters, USA

Column: Showa Denko Corporation SHODEX A-80M (50 cm long)

Measuring temperature: 40 ℃

Flow rate: 1 cc / min

Relative dielectric constant

A sample of the composition was applied using an spin coating method on an 8 inch (20.32 cm) silicon wafer, and the substrate was dried at 90 ° C. for 3 minutes on a hot plate and at 200 ° C. for 3 minutes on a hot plate. The substrate was further baked for 10 minutes in the plate. An aluminum electrode pattern was formed with respect to the obtained film by the vapor deposition method, and the sample for specific dielectric constant measurement was produced. The dielectric constant of this coating film was measured by CV method using the HP16451B electrode of the Yokogawa Hewlett-Packard Co., Ltd. product, and the HP4284A Precision LCR meter at the frequency of 100 kHz of this sample.

Heat resistance

A composition sample was applied using an spin coating method on an 8 inch (20.32 cm) silicon wafer, dried on a hot plate for 3 minutes at 90 ° C., at 200 ° C. for 3 minutes, and at 350 ° C. for a nitrogen atmosphere hot plate. The substrate was further baked for 10 minutes at. The obtained film | membrane was cut out from the wafer, and thermogravimetric weight loss was measured on condition of the temperature increase rate of 10 degree-C / min in nitrogen atmosphere, and the following references | standards evaluated.

○: 1% or less in weight loss at 400 ℃

X: weight loss in 400 degreeC exceeds 1%

Synthesis Example 1

In a quartz separable flask, 276.01 g of methyltrimethoxysilane, 86.14 g of tetramethoxysilane and 0.0092 g of tetrakis (acetylacetonato) titanium were dissolved in 101 g of propylene glycol monoethyl ether, followed by stirring with a three-one motor. The solution temperature was stabilized at 55 ° C. Then, a mixed solution of 225.52 g of ion-exchanged water and 263.00 g of propylene glycol monoethyl ether was added to the solution over 1 hour. Then, after reacting at 55 degreeC for 4 hours, 48.12 g of acetylacetone were added, it was made to react for 30 more minutes, and the reaction liquid was cooled to room temperature. The solution containing methanol and water was removed from the reaction liquid at 50 degreeC by the 227g evaporative dehydration method, and reaction liquid (1) was obtained.                     

Thus, the weight average molecular weights of condensates, etc. obtained were 1,230.

Synthesis Example 2

In a quartz separable flask, 205.50 g of methyltrimethoxysilane and 85.51 g of tetramethoxysilane were dissolved in 426 g of propylene glycol monoethyl ether, and then stirred with a three-one motor to stabilize the solution temperature at 50 ° C. Next, 182 g of ion-exchanged water in which 0.63 g of succinic acid was dissolved was added to the solution over 1 hour. Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. The solution containing methanol was removed from the reaction liquid at 50 degreeC by the 360-g evaporation dehydration method, and reaction liquid (2) was obtained.

Thus, the weight average molecular weights, such as the condensate obtained, were 1,400.

Synthesis Example 3

370 g of distilled ethanol, 200 g of distilled propylene glycol monopropyl ether, 160 g of ion-exchanged water and 90 g of a 10% aqueous methylamine solution were added to a quartz separable flask and stirred uniformly. To this solution was added a mixture of 136 g of methyltrimethoxysilane and 209 g of tetraethoxysilane. The reaction was carried out for 2 hours while maintaining the solution at 52 ° C. 300 g of propylene glycol monopropyl ether was added to this solution, and the solution was then concentrated using an evaporator at 50 ° C until it became 10% (in terms of complete hydrolysis condensate), and then 10% propylene glycol mono of acetic acid. 10 g of propyl ether solution was added to obtain a reaction solution (3).

Thus, the weight average molecular weights of the condensate etc. which were obtained were 904,000.

Synthesis Example 4                     

428 g of distilled ethanol, 215 g of ion-exchanged water, and 15.6 g of 25% tetramethylammonium hydroxide aqueous solution were added to a quartz separable flask, and the mixture was stirred uniformly. To this solution was added a mixture of 40.8 g of methyltrimethoxysilane and 61.4 g of tetraethoxysilane. The reaction was carried out for 2 hours while maintaining the solution at 57 ° C. 300 g of propylene glycol monopropyl ether was added to this solution, and the solution was then concentrated using an evaporator at 50 ° C until it became 10% (complete hydrolysis condensate), and then 10% propylene glycol of maleic acid. 20 g of monopropyl ether solution was added to obtain a reaction solution ④.

Thus, the weight average molecular weights of condensates, etc. obtained were 1,600,000.

Comparative Synthesis Example 1

After dissolving 85.51 g of tetramethoxysilane in 426 g of propylene glycol monoethyl ether in the separable flask made of quartz, the solution temperature was stabilized at 50 degreeC by stirring with a three-one motor. Next, 182 g of ion-exchanged water in which 0.63 g of succinic acid was dissolved was added to the solution over 1 hour. Then, after making it react at 50 degreeC for 3 hours, the reaction liquid was cooled to room temperature. The solution containing methanol was removed from the reaction liquid at 50 degreeC by the 360-g evaporation dehydration method, and reaction liquid (5) was obtained.

Thus, the weight average molecular weights of condensates, etc. obtained were 2,400.

<Example 1>

The reaction solution 3 obtained in Synthesis Example 3 was filtered with a teflon filter having a 0.2 μm pore diameter to obtain a film-forming composition of the present invention.

The obtained composition was applied onto a silicon wafer by spin coating.                     

The relative dielectric constant of the coating film was 2.57, indicating a low relative dielectric constant value. Moreover, when the heat resistance of the coating film was evaluated, the weight loss was 1% or less.

<Examples 2 to 6>

In Example 1, it evaluated like Example 1 except having used the reaction liquid shown in Table 1. The evaluation results are shown in Table 1 together.

Example (A) component Relative dielectric constant Heat resistance One Reaction solution ③ 2.57 O 2 Reaction liquid ④ 2.34 O 3 Reaction liquid ③ 30 g + reaction liquid ① 10 g 2.65 O 4 Reaction liquid ③ 30 g + reaction liquid ② 10 g 2.69 O 5 Reaction solution ④ 30 g + reaction solution ① 20 g 2.78 O 6 Reaction solution ④ 30 g + reaction solution ① 20 g 2.82 O

<Example 7>

Two sheets of transparent glass plates (7059 manufactured by Corning Incorporated) consisting of boron silicate glass are prepared.

Subsequently, the TFT array substrate 10 as shown in FIG. 1 was produced by the method known in this one sheet.

1 is a cross-sectional conceptual view of a TFT array substrate in which one TFT portion is described as an example for convenience of drawing production. In Fig. 1, reference numeral 1 denotes a glass substrate, 2 denotes an underlayer film having a thickness of 400 nm formed on the substrate, 3 denotes a gate electrode, 4 denotes a gate insulating film, and 5 denotes amorphous silicon. The semiconductor film (may be a polysilicon film), (5 ') is an n + layer in which n-type impurities are diffused, (6) is an insulating film used in Example 1, (7) is source wiring, and (8) is drain wiring (8 ') is a pixel electrode, and (8') is connected with an electric drain wiring.

The other glass plate was made into the board | substrate of the back surface which opposes the said board | substrate 10, and the transparent counter electrode 11 which consists of indium tin oxide was formed on this glass plate 11 by a well-known method. In this way, the counter substrate 20 shown in FIG. 2 was produced.

Then, the liquid crystal aligning film 22 was formed in the surface of the said TFT array substrate 10, and the surface of the opposing board | substrate 20, respectively. Subsequently, four empty cells for the liquid crystal display device were fabricated, in which two substrates were laminated so that the liquid crystal alignment film 22 · 22 was inward, and at the same time maintained a gap of 5 μm so that the periphery of the four divided regions could be bonded. It was.

Thereafter, a twisted nematic (TN) type liquid crystal 23 (ZLI-4792; manufactured by Melk Co., Ltd.) was injected into the empty cell in a vacuum to seal the cell, and then the liquid crystal cell 30 was formed. The polarizing plate 24 was stuck to and the LCD 31 shown in FIG. 3 was produced.

An AC pulse wave of 60 µsec, 30 Hz, 2.6 V and a bias voltage of 2 V were applied to this LCD for 30 hours. After that, when the 2V bias voltage was removed, the change over time of the flicker on the LCD was measured optically. Flicker cleared 2.1 seconds after bias voltage removal, indicating good flicker resistance.

<Example 8>

In Example 7, the flicker of the LCD was measured in the same manner as in Example 7, except that the insulating film used in Example 2 was used as the insulating film. Flicker was erased 1.7 seconds after bias voltage removal, indicating good flicker resistance.                     

Example 9

In Example 7, the flicker of the LCD was measured in the same manner as in Example 7, except that the insulating film used in Example 3 was used as the insulating film. Flicker cleared 2.1 seconds after bias voltage removal, indicating good flicker resistance.

<Example 10>

In Example 7, the flicker of the LCD was measured in the same manner as in Example 7, except that the insulating film used in Example 4 was used as the insulating film. Flicker cleared 2.2 seconds after bias voltage removal, indicating good flicker resistance.

<Example 11>

In Example 7, the flicker of the LCD was measured in the same manner as in Example 7, except that the insulating film used in Example 5 was used as the insulating film. Flicker was erased 2.3 seconds after bias voltage removal, indicating good flicker resistance.

<Example 12>

In Example 7, the flicker of the LCD was measured in the same manner as in Example 7, except that the insulating film used in Example 6 was used as the insulating film. Flicker was erased 2.4 seconds after bias voltage removal, indicating good flicker resistance.

Comparative Example 1

Except having used reaction liquid (5) obtained by the comparative synthesis example 1, it carried out similarly to Example 1, and evaluated the coating film.

The relative dielectric constant of the coating film was 3.68 and the relative dielectric constant exceeded 3. Moreover, when the heat resistance of the coating film was evaluated, the weight loss in 400 degreeC fell to 1.3%.

Comparative Example 2

In Example 7, the flicker of the LCD was measured in the same manner as in Example 7, except that the insulating film used in Comparative Example 1 was used as the insulating film. Flicker was erased 15.3 seconds after bias voltage removal, resulting in poor flicker tolerance.

Comparative Example 3

In Example 7, the flicker of the LCD was measured in the same manner as in Example 7, except that a SiO ₂ film produced by a chemical vapor deposition method was used as the insulating film. Flicker was erased 120 seconds after bias voltage removal, resulting in poor flicker tolerance.

According to the present invention, an interlayer insulating film for LCD can be provided by heating a specific alkoxysilane hydrolyzable polymer, which can form a low temperature, exhibits a low dielectric constant, and is excellent in heat resistance of a coating film.

Claims (5)

(A) (A-1) at least one compound selected from the group of compounds represented by formula (1), (A-2) compounds represented by formula (2), and (A-3) compounds represented by formula (3) The interlayer insulation film for liquid crystal display elements obtained by heating the hydrolysis condensate formed by hydrolytic condensation in the presence of a catalyst. <Formula 1> R _a Si (OR ¹ ) _4-a <Formula 2> Si (OR ² ) ₄ <Formula 3> R ³ _b (R ⁴ O) _3-b Si- (R ⁷ ) _d -Si (OR ⁵ ) _3-c R ⁶ _c In the formula, R is a hydrogen atom, a fluorine atom or a monovalent organic group, R ¹ is a monovalent organic group, a represents an integer of 1 to 2, R ² represents a monovalent organic group, R ³ to R ⁶ are the same or different and are each monovalent organic group, b to c are the same or different and are an integer from 0 to 2, R ⁷ is an oxygen atom, a phenylene group or a group represented by-(CH ₂ ) _n- , where n is an integer from 1 to 6, d represents 0 or 1. The heating temperature of a hydrolysis-condensation product is 350 degrees C or less, The insulating film for liquid crystal display elements of Claim 1 characterized by the above-mentioned. The interlayer insulating film for liquid crystal display elements according to claim 1 or 2, wherein the relative dielectric constant is 3 or less. The interlayer insulating film for liquid crystal display device according to claim 1 or 2, wherein the catalyst is an alkali catalyst. The liquid crystal display element which has the interlayer insulation film for liquid crystal display elements of Claim 1 or 2.

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