JPS5936135A - Photo-curable polyorgano-siloxane - Google Patents

Abstract

PURPOSE:To provide titled polyorganosiloxane constituted by a specific recurring unit, capable of giving uniform cured coating film by coating on a substrate, drying followed by irradiating an ultraviolet on electron beam. CONSTITUTION:The objective polyorgnosiloxane having a recurring unit of formula I (R1 is an aromatic residue, or group having carbon-carbon double bond; R2, R3, R4, R5 and R6 are each lower aliphatic residue, aromatic residue, or group having carbon-carbon double bond; l is 1-100; m is an integer : 0-300) (e.g., a recurring unit of formula II), with an average molecular weight ranging from ca, 2,000 to 100,000. When dissolved in a diluent followed by coating the resultant solution on a substrate, drying, and irradiating an ultraviolet or electron beam, this polyorgano-siloxane will provide an uniform and adequately cured coating film.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photocurable polyorganosiloxane.

Various photopolymerizable polyorganosiloxanes have already been developed for use in semiconductor devices (diodes, etc.).

It is used in a variety of applications, such as coating agents for printed circuit boards (transistors, etc.), and plate-making in printing.

However, in conventional photocurable polyorganosiloxanes, most of the photosensitive groups are vinyl groups, so when irradiated with light, a radical reaction occurs and the polyorganosiloxane is cured. For this reason, the surface of the coating is affected by oxygen, resulting in insufficient curing or non-uniform curing of the coating.

It is an object of the present invention to provide a photocurable polyorganosiloxane which eliminates the drawbacks of the prior art described above, and which cures the coating surface well and uniformly.

The above object is achieved by using a photocurable silyl active species that is relatively long-lived and is not easily affected by oxygen.

That is, the present invention has a repeating unit represented by the general formula (1). (However, R1 is an aromatic residue, a group having a carbon-carbon double bond, , R,, R, is a lower aliphatic residue, an aromatic residue, a group having a carbon-carbon double bond, l is 1
~100,77L is an integer from 0 to 300. ) Achieved by a photocurable polyorganosiloxane having an average molecular weight of 2000 to 100,000.

Further, the present invention will be explained in detail. The present invention is based on the general formula (2
) and R2! R8 (However, R1 is an aromatic residue, a group having a carbon-carbon double bond, R2y R3J R4 is a lower aliphatic residue.

aromatic residue, a group having a carbon-carbon double bond, R6 , indicates a lower aliphatic residue, an aromatic residue, a group having a carbon-carbon double bond, X indicates a hydrolyzable group consisting of a halogen atom or an alkoxy group having 6 or less carbon atoms) Remove living organisms by washing with water, etc. Note that the above hydrolysis may be performed by adding a lower alcohol such as methanol as a hydrolysis auxiliary agent.

Next, the hydrolyzed product is diluted with an inert solvent such as toluene or xylene so that the hydrolyzed product concentration is 5 to 70% by weight, and a catalytic amount of a strong basic substance is added thereto as a dehydration condensation catalyst. Number 10 at room temperature (18°C) 170°0
The photocurable polyorganosiloxane represented by the general formula (11) is prepared by stirring for several minutes to several tens of hours to cause a dehydration condensation reaction.

This dehydration condensation reaction involves toluene coexisting in the reaction system,
If the process is carried out at a temperature at which an inert solvent such as xylene refluxes while removing the produced water conveniently from the system, the resulting photocurable polyorganosiloxane will not undergo gelation.

Thereafter, the dehydration condensation catalyst (strongly basic substance) is inactivated or removed, for example, by neutralizing it with acetic acid.

In this way, a photocurable polyorganosiloxane free of impurities is obtained.

Examples of the photocurable polyorganosiloxane of the present invention represented by the general formula (11) include those having the following repeating units.

Bs M ■ Ms C”E.

C1l.

CM -5t C' II CHa33 CH=CH2- (However, in the formula, l is 1-100, 771 is 0-600) The disilane compound represented by the general formula (2) used in the present invention is (α), for example, 1,1.1- IJ methyl-2
-Phenyldichlorodisilane, 1,1.1-triethyl-2-phenyldichlorodisilane, 1゜1.1-dumenalphenyl-2-phenyldichlorodisilane, 1,
At least one selected from the group consisting of 1,1-dimethylvinyl-2-phenyldichlorodisilane, 1,1,1-trimethyl-2-)'J-dichlorodisilane, and 1,1,1-trimethyl-2-vinyldichlorodisilane. one type of compound, (h) a small number of compounds selected from among the compounds in which one chlorine atom of the dichlorodisilane compound (α) is hydrolyzed and converted to OH-; (C) one type of compound as described above; (d) at least one compound selected from compounds in which all two chlorine atoms of the dichlorodisilane compound of (α) are hydrolyzed and converted to OR-; (d) of the dichlorodisilane compound of (α); One chlorine atom is hydrolyzed and converted to OH-, and the remaining chlorine atom is converted into methanol,
At least one compound selected from compounds alkoxylated with ethanol etc. (may be hydrolyzed after alkoxylation); (e) two chlorine atoms of the dichlorosifurane compound of (a) above; At least one compound selected from compounds entirely alkoxylated with methanol, ethanol, etc., (f) the above (a) to (
Mixtures of item e) may be mentioned.

Furthermore, the silane compound represented by the general formula (3) used in the present invention is ω), for example, dimethyldichlorosilane, diethyldichlorosilane, methylethyldichlorosilane,
At least one compound selected from methylvinyldichlorosilane, methylphenyldichlorosilane, vinylphenyldichlorosilane, diphenyldichlorosilane, and alkoxysilanes corresponding to these chlorosilanes; At least one compound selected from compounds in which one chlorine atom is hydrolyzed to OB-, (i) all two chlorine atoms of the dichlorodisilane compound of 0 above are hydrolyzed to OB-. - at least one compound selected from the compounds in which the dichlorodisilane compound of (!I) is hydrolyzed to convert one chlorine atom into OH-, and the remaining one chlorine atom A small number of compounds (at least one kind of compound, (k
) at least one compound selected from the compounds in which all two chlorine atoms of the dichlorodisilane compound of (!I) are alkoxylated, (1) the above (&) to (k);
A mixture of terms may be mentioned.

Further, the mixing ratio of the general formula (11) and the general formula (2) is not limited as long as it does not impair photocurability.

Examples of the dehydration condensation catalyst (strongly basic substance) used in the present invention include potassium hydroxide and sodium hydroxide.

Examples include alkali metal hydroxides such as cesium hydroxide, quaternary ammonium hydroxides such as tetramethylammonium hydroxide, benzyltrimethylammonium hydroxide, and quaternary phosphonium hydroxides such as tetrabutylphosphonium hydroxide. .

The diluent may be, for example, an inert solvent for the dehydration condensation reaction described below or a good solvent for photocurable polyorganosiloxane.

Examples of the inert solvent for the dehydration condensation reaction used in the present invention include toluene, xylene, and tetralin.

Examples include aromatic hydrocarbon solvents such as heratrol.

The photocurable polyorganosiloxane represented by the general formula (1) is dissolved in a diluent, and this solution is applied onto a support, dried, and then exposed to deep ultraviolet rays.

When irradiated with ultraviolet rays, soft X-rays, electron beams, etc., the surface of the coating is well cured, and the coating is uniformly cured.

Note that, depending on the application, the adhesion to the substrate may be improved by heating the above-mentioned deep ultraviolet rays, ultraviolet rays, soft X-rays, etc. together with exposure.

The substrate used in the present invention is made of, for example, metal such as copper or aluminum, Tie, SiO, Sin, Ta2O.
Examples include metal oxides such as , silicon nitride, synthetic resins such as polyimide, polyamide, and polyester.

In addition, the photocurable polyorganosiloxane of the present invention can be used as a coating agent for semiconductors, magnetic bubbles, printed circuit boards, etc.
It can also be applied to paints, etc.

The present invention will be explained below with reference to Examples.

Example 1 10 equipped with stirrer, cooler and dropping funnel
34+d(71)0.1A' in a 0- three-necked flask
A sodium hydroxide aqueous solution and 40-ether were added.

1,1.1-) I was dissolved in 10-1 dry ether from a dropping funnel while stirring vigorously while cooling with water.
J, 7' thyl-2-phenyldichlorofusi. run 5
f was added as quickly as possible. Immediately after the addition was completed, the ether layer was decomposed, the aqueous layer was extracted with ether, and both ether layers were combined and washed with water. This was dried over calcium carbonate, the ether was distilled off, and approximately 20-pentane was added to the remaining solution, followed by cooling. 2.5 t of product was obtained.

Next, put 1,1,1-)dimethyl-2-phenyldichlorodisilane 22 dissolved in 3 ml of toluene and 0.01 F of potassium hydroxide into a 30 ml two-bottle flask, and stir with a magnetic stirrer until the reflux temperature of toluene is reached. It was held for about 4 hours. At this time, the produced water is fractionally distilled, and toluene is further fractionated to about 2-140 to 150
The test was carried out for about 2 hours at a temperature of 0°C. The product was dissolved in 10-g of toluene and 10 g of methanol was added thereto to precipitate a photocurable polyorganosiloxane (hereinafter abbreviated as polymer). The precipitated polymer was washed with methanol, then water, and dried under reduced pressure. The yield of the polymer thus obtained was 84% (+, ar). Further, the number average molecular weight of this polymer was 2,500.

Add 0.5f of the polymer obtained above to 5rn! of toluene! .

The sample was prepared by dissolving it in Next, this was coated on a glass plate, dried at 100° for 30 minutes, and then irradiated with ultraviolet rays for 2 minutes from a 3A'F ultra-high pressure mercury lamp 30cn1 apart, and the surface of the coating was well cured.
Moreover, the coating was uniformly cured. It also had excellent chemical resistance.

Example 2 Disilane compounds shown in columns 1 to A6 of Table 1.

Six types of polymers were obtained in the same manner as in Example 1 using a silane compound, a solvent, and a catalyst. The number average molecular weights and yields of these polymers were as shown in Table 1. In addition, each of the six types of polymers obtained was applied onto a glass plate, dried,
When irradiated with ultraviolet rays, as shown in /I61-6 in Table 2, the surface of each coating was well cured, and the coating was uniformly cured. Furthermore, as shown in Table 2, the chemical resistance was also good.

Margins below Comparative Example 1 A sample was prepared by dissolving polydimethylsiloxane (number average molecular weight 2100) 1y having a terminal vinyl group in 10 - of toluene. Then, a photocured coating was obtained in the same manner as in Example 1. The surface of the coating was insufficiently cured, and the coating was non-uniformly cured.

As detailed above, according to the present invention, the following (1) to 6 are possible.
There are 10 effects.

(]) Synthesis of photocurable polyorganosiloxane is easy.

(11) Photocurable polyorganosiloxane has a coating surface that is sufficiently cured and a coating that is uniformly cured. It also has good chemical resistance.

(iiD Suitable as a coating agent.

Claims (1)

[Claims] General formula (where R is an aromatic residue, a group having a carbon-carbon double bond, R,, R,, R,, R,, R6 is a lower aliphatic residue, an aromatic group residue, group having a carbon-carbon double bond, l is 1
-1oo1m is an integer from o to 3oo) with an average molecular weight of about 2000 to 1oo, 0
00 photocurable polyorganosiloxane.