JP2007142005A - Protective film and forming method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulator particulate in which an organic thin film having a reactive functional group is formed on the surface, and to provide a forming method of the protective film using the insulator particulate as the protective film where a base material is not limited and no vacuum chamber is required and as the forming method of the protective film. <P>SOLUTION: In the protective film, the insulator particulate having first reactivity and that having second reactivity are mixed, coated on the surface of the base material and cured. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a protective film (so-called passivation film) having a function of preventing leakage, waterproofing, moisture-proofing and scratch-proofing. More specifically, the present invention relates to a protective film using insulating fine particles having a surface provided with thermal reactivity or photoreactivity, radical reactivity or ionic reactivity.

  In the present invention, “insulator fine particles” mainly include silica, alumina, and zirconia.

  Conventionally, a sputtering method, a CVD method, or a sol-gel method has been used to form a highly durable protective film using an inorganic substance.

However, the sputtering method and the CVD method have a disadvantage that a special vacuum chamber is required and the manufacturing cost is increased. In addition, the sol-gel method has a disadvantage that the base material is limited to a heat-resistant one because a high temperature is required for the reaction.

  The present invention provides a protective film that does not require a vacuum chamber without limiting the base material, and a method for producing the same, and insulating fine particles formed with an organic thin film having a reactive functional group on the surface, and protection using the same It aims at providing a film | membrane and its manufacturing method.

  A first invention provided as means for solving the above-described problems is that an organic thin film containing insulating fine particles covered with an organic thin film containing a first reactive functional group and a second reactive functional group The protective film is characterized in that the insulating fine particles covered with (1) are mixed and coated on the surface of the substrate.

In the second invention, the surface of the substrate covered with an organic thin film containing a reactive functional group on the surface and the insulating fine particles covered with an organic thin film containing a functional group that reacts with the reactive functional group are respectively described above. The protective film is covalently bonded through an organic thin film and cured.
Here, when an epoxy group, an imino group, or a chalconyl group is included as a reactive functional group, a highly durable protective film can be advantageously provided.

  According to a third aspect of the present invention, there are provided a step of mixing the insulating fine particles having the first reactivity and the insulating fine particles having the second reactivity in an organic solvent to form a paste, and a step of applying to the substrate surface And a step of curing the protective film.

  At this time, an organic thin film having a functional group that reacts with the insulating fine particles having the first reactivity or the insulating fine particles having the second reactivity is formed in advance on the surface of the base material before coating. This is convenient because it can provide a protective film using fine particles having high peel resistance.

  As described above, according to the present invention, by covering the surface of the fine particles with a reactive organic thin film or monomolecular film, there is an effect that a protective film containing almost no binder component and having high film strength can be produced and provided. Further, by covering the substrate surface with a reactive organic thin film or a monomolecular film in advance, there is an effect that a protective film made of insulating fine particles having excellent peeling resistance can be produced and provided.

The present invention includes a step of mixing the insulating fine particles having the first reactivity and the insulating fine particles having the second reactivity in an organic solvent to form a paste, a step of applying to the substrate surface, And a step of curing to provide a protective film in which the insulating fine particles having the first reactivity and the insulating fine particles having the second reactivity are mixed and coated on the surface of the substrate. .

Further, an organic thin film having a functional group that reacts with the insulating fine particles having the first reactivity or the insulating fine particles having the second reactivity is formed in advance on the surface of the substrate before coating. Thus, the surface of the base material covered with an organic thin film containing a reactive functional group on the surface and the insulating fine particles covered with the organic thin film containing a functional group that reacts with the reactive functional group are formed into the respective organic thin films. A protective film that is covalently bonded through a film and cured and formed is provided.

Therefore, the present invention has the effect of providing and providing a protective film having almost no binder component and high coating strength. In addition, there is an effect that a protective film made of insulating fine particles having excellent peeling resistance can be produced and provided.

  Hereinafter, although the detail of this invention is demonstrated based on an Example, this invention is not limited at all by these Examples.

  Insulator fine particles related to the present invention include alumina, silica, zirconia, and the like. First, silica fine particles will be described as a representative example.

First, anhydrous silica fine particles 1 were prepared and well dried. Next, as a chemical adsorbent, a functional group having a reactive functional group such as an epoxy group or imino group and an alkoxysilyl group at the other end, such as a chemical represented by the following formula (Chemical Formula 1) or (Chemical Formula 2) 99% by weight of a silanol condensation catalyst, for example, dibutyltin diacetylacetonate or acetic acid as an organic acid is weighed to 1% by weight, and a solvent in which the same amount of silicone and dimethylformamide are mixed, for example, hexamethyl A chemical adsorption solution was prepared by dissolving in a solution of 50% disiloxane and 50% dimethylformamide to a concentration of about 1% by weight (preferably the concentration of the chemical adsorbent is about 0.5 to 3%).

The adsorbed liquid was mixed with anhydrous silica fine particles and stirred, and reacted in ordinary air (relative humidity 45%) for about 2 hours. At this time, since many hydroxyl groups 2 are bonded to the dangling bonds on the surface of the anhydrous silica fine particles (FIG. 1a), the -Si (OCH ₃ ) group of the chemical adsorbent and the hydroxyl group are a silanol condensation catalyst or an organic acid. In the presence, dealcoholization (in this case, de-CH ₃ OH) was reacted to form a bond as shown in the following formula (Chemical Formula 3) or (Chemical Formula 4), and chemically bonded to the surface over the entire surface of the silica fine particles. A chemisorption monomolecular film 3 containing an epoxy group or a chemisorption film 4 containing an amino group was formed with a film thickness of about 1 nanometer (FIGS. 1b and 2c).

Here, when an adsorbent containing an amino group is used, since a precipitate is generated with a tin-based catalyst, it is better to use an organic acid such as acetic acid. The amino group contains an imino group, but substances containing an imino group in addition to the amino group include pyrrole derivatives and imidazole derivatives. Furthermore, when a ketimine derivative was used, an amino group could be easily introduced by hydrolysis after film formation.
After that, chloroform, which is a chlorinated solvent, was added and washed with stirring. Silica fine particles covered with a chemisorbed monomolecular film having a reactive functional group such as an epoxy group or an amino group on the surface could be produced. .

Since the coating film was extremely thin with a film thickness of nanometer level, the particle diameter was not impaired.
Note that the reactivity does not substantially change when it is taken out into the air without washing, but the chemical adsorbent remaining on the particle surface reacts with the moisture in the air on the particle surface, and the chemical is adsorbed on the particle surface. Silica fine particles on which an extremely thin polymer film made of an adsorbent was formed were obtained.

  Since this method is a dealcoholization reaction, it is widely applicable.

Next, the same amount of silica fine particles 5 and 6 covered with the chemisorption monomolecular film having the epoxy group or amino group is taken out and mixed in isopropyl alcohol to form a paste, which is applied to the glass substrate 7 and applied. When heated to about -100 degrees, epoxy groups and amino groups are added by the reaction shown in the following formula (Chemical Formula 5), the silica fine particles are bonded and solidified, and a strong protective film 8 is formed without containing a binder. did it.

In Example 1, an organic thin film 9 having an epoxy or amino group as a reactive functional group is also formed on the surface of the glass substrate 7 in the same manner in advance, and then the same coating film is formed. The organic thin film on the surface of the silica fine particles reacted with the organic thin film on the surface of the substrate to produce a protective film 10 made of silica fine particles having high peel resistance. (Figure 2)

In addition, in the said Example 1, although the substance shown to Formula (Formula 1) or Formula (Formula 2) was used as a chemical adsorbent containing a reactive group, in addition to the above, the following (1) to ( The substances shown in 16) were available.
(1) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(2) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) ₃
(3) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₂ Si (OCH ₃ ) _{3
(4) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
_{(5) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OCH 3) 3
_{(6) (CH2OCH) CH 2} O (CH 2) 7 Si (OC 2 H 5) 3
(7) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OC ₂ H ₅ ) _{3
(8) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OC 2 H 5) 3
_{(9) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
(10) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₆ Si (OC ₂ H ₅ ) ₃
(11) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(12) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(13) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(14) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(15) H ₂ N (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(16) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

Here, the (CH ₂ OCH) — group represents a functional group represented by the following formula (Formula 6), and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group is represented by the following formula (Formula 7). Represents a functional group.

Furthermore, the substances shown in the following (21) to (26) can be used as chemical adsorbents containing energy beam reactive functional groups such as light or electron beams. In this case, it is not necessary to mix the two types of reactive fine particles, but only one type may be applied and cured by irradiation with an energy beam such as light or an electron beam.

(21) CH≡C—C≡C— (CH ₂ ) ₁₅ SiCl ₃
(22) CH≡C—C≡C— (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl ₃
(23) CH≡C—C≡C— (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl _{3
(24) (C 6 H 5} ) (CH) 2 CO (C 6 H 4) O (CH 2) 6 OSi (OCH 3) 3
_{(25) (C 6 H 5} ) (CH) 2 CO (C 6 H 4) O (CH 2) 6 OSi (OC 2 H 5) 3
_{(26) (C 6 H 5} ) CO (CH) 2 (C 6 H 4) O (CH 2) 6 OSi (OCH 3) 3
Here, (C ₆ H ₅ ) CO (CH) ₂ (C ₆ H ₄ ) represents a chalconyl group.

In Example 1, as the silanol condensation catalyst, carboxylic acid metal salt, carboxylic acid ester metal salt, carboxylic acid metal salt polymer, carboxylic acid metal salt chelate, titanate ester and titanate ester chelate can be used. It is. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyl Laurate, tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) dipropyl titanate could be used.

In addition, as a solvent for the film forming solution, the chemical adsorbent is an alkoxysilane-based solvent, a chlorosilane-based solvent, an organic chlorine-based solvent that does not contain water, a hydrocarbon-based solvent, a fluorocarbon-based solvent, a silicone-based solvent, Alternatively, it was possible to use a mixture thereof. In addition, when it is going to raise particle concentration by evaporating a solvent, without wash | cleaning, the boiling point of a solvent is good at about 50-250 degreeC.

Specifically usable are organic chlorinated solvents, non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone , Alkyl-modified silicone, polyether silicone, dimethylformamide and the like. Further, when the adsorbent is an alkoxysilane type and the organic film is formed by evaporating the solvent, an alcohol type solvent such as methanol, ethanol, propanol, or a mixture thereof can be used in addition to the solvent.

Fluorocarbon solvents include fluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Further, an organic chlorine solvent such as chloroform may be added.

On the other hand, when a ketimine compound or organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound is used instead of the above-mentioned silanol condensation catalyst, the treatment time is reduced to about half to 2/3 even at the same concentration. did it.

Furthermore, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound can be used in a range of 1: 9 to 9: 1. )), The processing time can be increased several times faster (up to about 30 minutes), and the film forming time can be reduced to a fraction of a minute.

For example, dibutyltin oxide, which is a silanol catalyst, was replaced with H3 from Japan Epoxy Resin, which is a ketimine compound, and the other conditions were the same, but the reaction time was reduced to about 1 hour. Results were obtained.

Furthermore, the silanol catalyst was replaced with a mixture of ketimine compound Japan Epoxy Resin H3 and silanol catalyst dibutyltin bisacetylacetonate (mixing ratio is 1: 1), and other conditions were the same. The same results were obtained except that the reaction time could be shortened to about 30 minutes.

Therefore, the above results revealed that ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are more active than silanol condensation catalysts.

Furthermore, it was confirmed that the activity is further increased when one of a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound is mixed with a silanol condensation catalyst.

Here, the ketimine compound that can be used is not particularly limited. For example, 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza-3 , 10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadeca Diene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza- 4,19-trieicosadiene and the like.

Further, the organic acid that can be used is not particularly limited, but there are, for example, formic acid, acetic acid, propionic acid, lactic acid, malonic acid, and the like, which have almost the same effects.

In the above two embodiments, silica fine particles have been described as an example. However, the present invention can be applied to any fine particles as long as they are insulator fine particles containing active hydrogen such as hydrogen of a hydroxyl group on the surface. is there. It can also be applied to organic insulator fine particles containing active hydrogen such as hydroxyl groups on the surface.
Furthermore, the present invention can be used for all applications using an inorganic protective film that has been conventionally produced using a sputtering method, a CVD method, or a sol-gel method.

Specific examples include a protective film on the surface of a semiconductor substrate, a protective film on the surface of a wiring board, a protective film on the surface of various metal products, a protective film on the surface of an eyeglass lens, a protective film on the surface of a building material, and a protective film on the surface of a coating film. .

It is the conceptual diagram which expanded the reaction of the insulator silica fine particle in the 1st Example of this invention to the molecular level, (a) is a figure of the silica fine particle surface before reaction, (b) is a single molecule containing an epoxy group. The figure after a film | membrane is formed, (c) shows the figure after the monomolecular film | membrane containing an amino group was formed. Moreover, (d) shows a cross-sectional conceptual diagram in a state in which fine particles are formed on the substrate surface as a protective film. FIG. 4 is a conceptual cross-sectional view of a state in which silica fine particles in a second embodiment of the present invention are bonded and formed on a substrate surface as a protective film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Silica fine particle 2 Hydroxyl group 3 Monomolecular film containing an epoxy group 4 Monomolecular film containing an amino group
Silica fine particles covered with monomolecular film containing 5 epoxy groups
Silica fine particles covered with monomolecular film containing 6 amino group 7 Glass substrate 8 Protective film 9 Monomolecular film containing epoxy group formed on substrate surface
10 Protective film bonded to substrate surface

Claims (5)

The insulating fine particles covered with the organic thin film containing the first reactive functional group and the insulating fine particles covered with the organic thin film containing the second reactive functional group are mixed on the surface of the substrate and coated and cured. A protective film characterized by The substrate surface covered with an organic thin film containing a reactive functional group on the surface and the insulating fine particles covered with the organic thin film containing a functional group that reacts with the reactive functional group are passed through the respective organic thin films. A protective film characterized by being covalently bonded and cured. The protective film according to claim 1 or 2, wherein the reactive functional group contains an epoxy group, an imino group, or a chalconyl group. A step of mixing the fine particles of the insulator having the first reactivity and the fine particles of the insulator having the second reactivity in an organic solvent to form a paste, a step of applying to the substrate surface, and a step of curing A manufacturing method of a protective film characterized by including. An organic thin film having a functional group that reacts with the insulating fine particles having the first reactivity or the insulating fine particles having the second reactivity is formed in advance on the surface of the base material before coating. The method for producing a protective film according to claim 4.

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