JPH02296832A - Silicone resin - Google Patents

Abstract

PURPOSE:To obtain a silicone resin having a high glass transition temperature and excellent adhesion to a substrate by using a siloxane segment as the principal component and introducing a polar group and/or a reactive group, and a urethane and/or a urea bond thereinto. CONSTITUTION:A silicone resin having a siloxane segment (e.g. a segment based on a polydimethylsiloxane having hydroxyls and/or aminos on both ends) and having a polar group and/or a reactive group (e.g. COOH, SO3H or OH), and a urethane bond or/and a urea bond introduced thereinto. This silicone resin has a high glass transition temperature and excellent adhesiveness to another polymeric compound and, when it is used as a coating agent or an additive for a resin coating film, it can improve the lubricity and water repellency of the surface and can give excellent retentivity of the properties.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to silicone resins, and more particularly to silicone resins that have a high glass transition temperature and excellent adhesiveness to other polymeric substances.

[Conventional technology]

Silicone compounds have excellent lubricity and water contact, and are widely used as coating agents and additives for resin products. However, since the glass transition temperature is low and it is generally liquid at room temperature, the coating strength is negligible.
, dissipated from resin moldings, etc. Improve this point
Silicone compounds into which polar groups or reactive groups have been introduced are also commercially available.

The silicone layer that adheres to the surface is thin, and even in this case, the film strength is 1! l is not as strong as it is on the left.

Therefore, with conventional silicone compounds, a
Sufficient sustainability of performance such as lubricity and water contact was not achieved.

[The point during which the invention attempts to solve the problem]

This invention solves the shortcomings of earthenware products, such as low swelling strength and poor adhesion.

The object of the present invention is to provide an NFC silicone compound with excellent lubricity and long-lasting water contact.

[Means to solve the problem]

In order to solve the above problem, we have carried out intensive research and have found no results.

]1! We discovered that it is effective to introduce a polyurethane urea bond into a silicone compound in order to impart film strength, and this led to the present invention.

9. It has a lower glass transition temperature than general silicone compounds @ 1. It is very effective to introduce a hard segment containing a urethane urea bond with a high glass transition temperature and to polymerize the silicone compound via this bond. It turned out to be true.

However, by introducing a urethane urea bond, the ratio alone cannot be achieved.

Although the mechanical strength of the coating film itself can be increased, the adhesion to the base is insufficient, and this peeling of the coating film occurs, making it difficult to maintain the initial properties over a long period of time. Therefore, if a polar group/reactive group is further introduced into the silicone compound by introducing a urethane urea bond, it is possible to obtain a silicone resin with improved adhesion to the lower pond and excellent long-lasting hydrophobicity and water repellency. .

It is preferable that the silicone segment content in the silicone resin of the present invention is 30% by weight or more; if it is less than that, the characteristics of the silicone compound will deteriorate. It is feminine to fully express sex and water contact.

The amount of urethane urea bonds introduced and the ratio of urethane bonds to urea bonds can be arbitrarily selected depending on the purpose within a range that satisfies the above silicone segment content. For example, as the amount of urea bond increases or the ratio of urea bond increases, the toughness of the obtained 9m fat increases. The solubility in subsequent drilling is reduced.

Polar groups/reactive groups introduced to increase adhesion include ri, carboxylic acid, sulfonic acid, phosphoric acid, and tertiary amines.
hydroxyl groups, salts thereof, epoxy groups, etc. can be used, and the amount introduced is o, o Os ~ 5 r
rmol/9 is preferred. Below that level, almost no improvement in adhesion is observed, and above that level, a decrease in lubricity and water contact is observed, resulting in 7tI.

The method for synthesizing the silicone-1 fat of the present invention is not particularly limited,
Any method may be used. An example of a synthesis method that can be used industrially is as follows.

(1) (a) Silicone with hydroxyl group or 7t at both ends is amino group (b) Organic diisocyanate (c) Polar group or chain extender with reactive group (d) Polar group or 7t is reactive group It is produced by reacting a chain extender that does not have a chain extender. The ratio of (e) and (d) is adjusted as necessary, and there is no groove even if (d) 1/i is not used.

Or +2) (a) Silicone with hydroxyl or amino groups at both ends (b) Polar group or high molecular weight polyol or polyamine having reactive groups (C) Organic diincyanate (d) Ilitg& agent reacted and manufacture it. (b) can be silicone compounds or other polyols or polyamines such as polyesters or polyethers. Not in k.

Commercially available silicones may be used as the silicone having both terminal hydroxyl groups or amine groups in (1) O and (2) (&). An example has the following structure.

The organic diisocyanates in (C) of O(b) and (2) include tolylene diinocyanate,
4.4'-diphenylmethane diisocyanate, hequinamethylene diisocyanate, and the like.

Examples of the chain extender having a polar group or a reactive group in (e) of (1) include 2,2-dimethylolpropionic acid, sodium bis(4-hydroxybutyl)-5-sulfoisophthalate, and β-glycerophosphoric acid. Sodium, N-
Examples include medeldiethanolamine. These can also be used in (2) (d).

As the chain extender in (d) of (1) and (2), ethylene glycol, 1,3-propanediol, 1
Examples include diols such as 4-butanediol and neopentyl glycol, cyamines such as ethylenediamine and tolylenecyamine, and water.

As the polyol or polyanne of (2) (b).

Diols or diamines shown in (e) of (11) above; ■ Diols or diamines shown in (d) of (1) and (2) above; and ■ dicarboxylic acids such as adipic acid, phthalic acid, and sebacic acid. ■■■Polyester diol obtained by Iia synthesis of 3 woodcutters or 7td boria-based dodian, (adjust the functional groups by changing the ratio of Shikupoly (C
-caprolactone), and polyether diols such as polyethylene glycol and polybutylene glycol. In addition, silicone diols or diamines obtained by condensation of the silicone shown in (l) and (2) with (&) and 5-σ sodium sulfoisophthalate, methyliinoniacetic acid, etc. can also be used. In addition to the above components, other components may be added as necessary. In other words, it is possible to adjust the @ property etc. by adding another polyol, a tethering agent, etc.

Alternatively, other substances may be reacted with 0 anticentricity 1 in the resin after resin synthesis. For example, it is possible to introduce polar groups, which are difficult to introduce directly, such as a reactive group, a crosslinking compound, a di-directly bonded dye, and a hexagonal stabilizer.

Crosslinking agent 1 color material, gold! 4 powder, IR fiber, etc. can be mixed as necessary. However, the silicone tree'J shield is 0.1
It is necessary to contain at least 0.1% by weight, and the effect of the silicone resin will be significantly reduced.

Since the silicone resin of the present invention has excellent specific lubricity and sustained water repellency, it can be used for various coatings. For example, rubber and glass.

It can be applied to coating molded products such as urethane foam, woodwork, metal products, leather products, and various building materials. It is particularly effective for parts subject to mechanical forces such as sliding. By adding colorants, metal powders, etc., it can be applied as a paint, such as a coloring agent, an IE magnetic wave absorbing material, and a 1M paint.

〔Example〕

Examples of the present invention will be described below.

Example 1 Polydimethylsiloxane with hydroxyl groups at both ends (manufactured by Tetsun Co., Ltd., Silagrain FM4411″Mn=9.l X l G
) 91 parts 4.4-diphenylmethane diisocyanate 0s 2.2-dimethylolgropion fJJ14.8 parts 1,
4-Butanediol 5.8 parts Tin octylate 0.05 parts Tetrahydrofuran 200 parts The above composition was heated at 80°C.
Stir and allow to react until the molecular weight increases sufficiently. After the reaction, the mixture was diluted to 301% by weight with tetrahydrofuran to obtain a silicone resin solution. The number average molecular weight of the obtained Jll fat was 3.8 x I in terms of polystyrene by GPC measurement.
Q' de atatsu 几.

This resin composition was applied to a 20 μm thick polyethylene terephthalate film clay and dried to obtain a film.

Example 2 Water at both ends of Example 1! In place of the polypolytylsiloxane group, polydimethylsilane r-xdPt with anno groups at both ends (
Manufactured by Chisso Corporation, tiraplane FM3311. Mn=s,
A silicone resin was synthesized in the same manner as in Example 1, except that 94 parts of 4xio) were used. Using this composition, a film was produced in the same manner as in Example 1.

Example 3 Silicone tree obtained in Example 2 100 parts Epoxy crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., TgTRAD-X
) 1. Part S: The above assemblage was thoroughly mixed, and after step 7, it was coated with a polyethylene terephthalate film of 20 μm thickness and dried to obtain a film.

Example 4 Silene resin obtained in Example 2 100 parts 7-Fe
! on particles 120 parts Tetrahydrofuran 150 parts The above composition was dispersed in a ball mill for 96 hours.

This molecule, kM, was applied to a thickness of 60 μm on a 20 μm thick polyethylene terephthalate film and dried to obtain a film.

Comparative example 1 Implementation? Silicone oil KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied on a polyethylene terephthalate film in place of the silicone resin, and the film was dried at 41E to obtain a film.

Comparison? ! 12 Same as Example 1 except for using 2,2-dimethylolpropionic acid in Example 1 and changing the amount of 1,4-butanediol from 5.8 parts to 9.0 parts. A silicone resin was obtained, and a film was produced using this resin composition in the same manner as in Example 1.

Lubricity of the films obtained in each of the above Examples and Comparative Examples.

We evaluated the durability of water contact and lubrication performance.

Lubricity was determined by cutting the sample film into 5mm width pieces and using a sliding tester to determine the dynamic MflA coefficient.

Water contact is determined by determining the contact angle of the sample film surface with water using the droplet method9. @The sustainability of the beak performance is determined by rubbing the above lubricity on the sample film surface 1000 times! After that, measure it.

〔Effect of the invention〕

As explained above, the main component is a siloxane segment, a polar group and/or a reactive group, and a urethane and/or
The coating is coated with silicone resin that also has urea bonds or resin j1! Lubricity of its surface by using it as an additive in the film.

It is clear that the water repellency is improved and the durability of the performance is much better.

Applicant: Hitachi Maxell, Ltd. Representative Atsushi Mizu

Claims (3)

[Claims] (1) A silicone resin characterized by having a siloxane segment as a main component and also having a polar group and/or a reactive group, and a urethane and/or urea bond. (2) The siloxane segment has hydroxyl groups and/or
Or polydimethylsiloxane with amino groups (
The silicone resin according to claim 1, which is a segment. (3) Claim (1) characterized in that the polar group and/or the reactive group is one or more of carboxylic acid, sulfonic acid, phosphoric acid, tertiary amine, hydroxyl group and salts thereof, or epoxy group. ) Silicone resin described.