KR101742354B1 - Method of manufacturing coating composition including polysiloxane modified epoxy hybrid compound - Google Patents

Abstract

A method of making a coating composition is provided. In the above process, a polydialkylsiloxane-modified epoxy resin prepolymer is prepared by reacting a polydialkylsiloxane having an amine group, a hydroxyl group, or a thiol group at both terminals with an epoxy resin having at least one epoxy group in the molecule, Reacting the alkylsiloxane-modified epoxy resin prepolymer with a silane coupling agent to prepare a polydialkylsiloxane-modified epoxy hybrid compound, and mixing the polydialkylsiloxane-modified epoxy hybrid compound with an organic solvent. The coating composition of the present invention has the effect of enhancing the roughness of the substrate by including the polysiloxane-modified epoxy hybrid compound. In addition, it is possible to improve mechanical properties including flexibility and adhesive force of the substrate.

Description

[0001] The present invention relates to a method for preparing a coating composition comprising a polysiloxane-modified epoxy hybrid compound,

The present invention relates to a process for preparing a coating composition, and more particularly to a process for preparing a coating composition comprising an epoxy hybrid compound modified with a polydialkylsiloxane.

FCBGA, which acts as a medium between semiconductors and mainboards due to high speed, high capacity, and mobileization of semiconductors, is also gradually required to have a thin substrate and a high density circuit. Accordingly, substrate coating materials require corresponding mechanical and thermal properties, which necessitates optimization of the composition of the coating material.

Substrate coating materials are generally composed of various types of epoxy resins, various additives, solvents, inorganic fillers, and hardeners that cause curing reactions. The mechanical and thermal properties of the insulating material vary depending on the content of each composition. In particular, an insulation material having a modulus of some degree while maintaining proper elongation among mechanical properties is required.

Epoxy resins have epoxy groups that are highly reactive to the molecular structure and can be modified with various reactive compounds, so that they can be modified into a polymer having various properties. Moreover, it has a rigid structure and is excellent in high temperature characteristics and toughness. Also, since the hydrophilic hydroxyl group and the hydrophobic hydrocarbon are regularly distributed, the reactivity and adhesion are good, and the ether bond of the main chain can easily impart plasticity by free rotation. In addition, the epoxy resin has a low hardening shrinkage rate upon curing, and is excellent in chemical resistance, mechanical strength, and adhesion, and is used as an adhesive for displays and various electronic equipment parts. However, epoxy resins have limited flexibility and a decisive weakness that lacks toughness, limiting their use in many applications.

Accordingly, in the prior art, Korean Patent Laid-Open No. 2004-36219 discloses an epoxy / thermoplastic resin blend composition.

However, when the above epoxy / thermoplastic resin blend composition is applied to a substrate, if any one of mechanical properties, such as adhesion and flexibility, is adjusted to increase one of the two properties, There is a disadvantage that the improvement of the properties of the composition is limited. Further, the use of the additive and the reinforcing agent has a disadvantage in that the adhesion between the substrate and the substrate is lowered due to the limited roughness of the substrate itself.

Accordingly, it is an object of the present invention to provide a method for preparing a coating composition comprising a polysiloxane-modified epoxy hybrid compound capable of improving the roughness of a substrate.

Another object is to provide a method for producing a coating composition comprising a polysiloxane-modified epoxy hybrid compound having improved flexibility and adhesion of a substrate.

And a polysiloxane-modified epoxy hybrid compound. The production method includes the steps of reacting a polydialkylsiloxane having an amine group, a hydroxyl group, or a thiol group at both terminals with an epoxy resin having at least one epoxy group in the molecule to produce a polydialkylsiloxane-modified epoxy resin prepolymer, Reacting an alkylsiloxane-modified epoxy resin prepolymer with a silane coupling agent to prepare a polydialkylsiloxane-modified epoxy hybrid compound, and mixing the polydialkylsiloxane-modified epoxy hybrid compound with an organic solvent.

The polydialkylsiloxane having an amine group, a hydroxyl group, or a thiol group at both ends of the term is preferably an?,? -Aminoalkylpolydimethylsiloxane,?,? -Aminoalkylpolymethylethylsiloxane,?,? - hydroxyalkylpolydimethylsiloxane, may be at least one selected from the group consisting of α, ω-hydroxyalkylpolymethylethylsiloxane, α, ω-mercaptoalkylpolydimethylsiloxane, and α, ω-mercaptoalkylpolymethylethylsiloxane, Is at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, rubber modified epoxy resin and urethane modified epoxy resin have. In addition, the silane coupling agent may be an aminoalkylalkoxysilane compound having a secondary amine group (-NH 2).

 In the step of producing the polydialkylsiloxane-modified epoxy resin prepolymer, an epoxy resin having at least one epoxy group in the molecule relative to 100 parts by weight of the polydialkylsiloxane having an amine group, a hydroxyl group, To 35 parts by weight, and the step of preparing the polydialkylsiloxane-modified epoxy resin prepolymer is preferably performed at a temperature of 80 to 90 DEG C for 20 to 30 hours. In addition, the step of preparing the polydialkylsiloxane-modified epoxy hybrid compound is preferably performed at a temperature of 50 ° C to 60 ° C for 20 to 30 hours.

According to the present invention, a method for producing a coating composition comprising a polysiloxane-modified epoxy hybrid compound is effective in enhancing the roughness of a substrate. In addition, it is possible to improve mechanical properties including flexibility and adhesive force of the substrate.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing the sequence of a method for producing a coating composition according to the present invention.
2 is an FT-IR spectra of the preparation example of the present invention.
3 is a graph showing the results of ¹ H-NMR measurement in the production example of the present invention of the present invention.
4 is a graph showing the results of ²⁹ Si-NMR measurement of the polydimethylsiloxane-modified epoxy hybrid compound (EMPDMSH) in the production example of the present invention.
5 is a graph showing the thermal characteristics of the production example and the comparative example 1. Fig.
6 is an image showing the contact angles of the production example and the comparative example.
7 is a graph showing the adhesive strengths of the production example, the comparative example 1 and the comparative example 2. Fig.
8 is a graph showing the surface smoothness of the production examples and comparative examples.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Like reference numerals designate like elements throughout the specification.

A process for preparing a coating composition comprising a polysiloxane-modified epoxy hybrid compound is described. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing the sequence of a method for producing a coating composition according to the present invention. Referring to FIG. 1, the process comprises reacting a polydialkylsiloxane having an amine group, a hydroxyl group, or a thiol group at both ends with an epoxy resin having at least one epoxy group in the molecule to prepare a polydialkylsiloxane-modified epoxy resin prepolymer (S200) of reacting the polydialkylsiloxane-modified epoxy resin prepolymer with a silane coupling agent to prepare a polydialkylsiloxane-modified epoxy hybrid compound (S200), and a step (S200) of reacting the polydialkylsiloxane- And a step (S300) of mixing with a solvent.

First, a polydialkylsiloxane-modified epoxy resin prepolymer is prepared by reacting a polydialkylsiloxane having an amine group, a hydroxyl group, or a thiol group at its terminal end with an epoxy resin having at least one epoxy group in the molecule (S100).

The polydialkylsiloxane having an amine group, a hydroxyl group, or a thiol group at both ends of the end may be a polydialkylsiloxane represented by the following formula (1), but is not limited thereto.

[Chemical Formula 1]

_{R 1 -R 2 - (R 3} ) (R 4) Si-O - [(R 3) (R 4) Si-O-] n -Si (R 3) (R 4) -R 2 -R 1

(Wherein n is an integer of 2 to 200, R ₁ represents an amine group, a hydroxyl group, or a thiol group, R ₂ represents an alkyl group having 1 to 10 carbon atoms, and R ₃ and R ₄ represent hydrogen or a To 10 carbon atoms.)

At this time, the polydialkylsiloxane having an amine group, a hydroxyl group, or a thiol group at both ends of the term is preferably selected from the group consisting of?,? - aminoalkylpolydimethylsiloxane,?,? - aminoalkylpolymethylethylsiloxane,?,? - At least one selected from the group consisting of polydimethylsiloxane,?,? -Hydroxyalkylpolymethylethylsiloxane,?,? - mercaptoalkylpolydimethylsiloxane, and?,? - mercaptoalkylpolymethylethylsiloxane .

The epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, rubber modified epoxy resin and urethane modified epoxy resin Lt; / RTI >

In the step of producing the polydialkylsiloxane-modified epoxy resin prepolymer, an epoxy resin having at least one epoxy group in the molecule relative to 100 parts by weight of the polydialkylsiloxane having an amine group, a hydroxyl group, To 35 parts by weight. It is also preferable to carry out the reaction at a temperature of 80 to 90 DEG C for 20 to 30 hours. The most excellent reactivity can be exhibited when the reaction is carried out within the above-mentioned range.

For example, when an epoxy ring-opening reaction is carried out with an α, ω-aminopropylpolydimethylsiloxane and an epoxy resin as a material of a polydialkylsiloxane having an amine group, a hydroxyl group, or a thiol group at both ends thereof, a polydimethylsiloxane-modified epoxy resin prepolymer Can be produced. The mechanism for this can be expressed by the following reaction formula (1).

[Reaction Scheme 1]

Thereafter, a polydialkylsiloxane-modified epoxy resin prepolymer having an epoxy group resin at the terminal is reacted with a silane coupling agent to form an epoxy hybrid compound having a polydialkylsiloxane (S200).

The silane coupling agent is preferably an aminoalkylalkoxysilane compound having a secondary amine group (-NH 2).

For example, the aminoalkylalkoxysilane compound represented by Formula 2 below may be used, but is not limited thereto.

(2)

_{R 5 - (NH) -Y-} Si (OR 7) 3-m

(Wherein R ₅ represents an alkyl group having 1 to 10 carbon atoms or an alkyl ester and Y represents -CH ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ , - (CH ₂ ) (CH ₃ )) (CH ₂ ) -, or - (CH ₂ ) ₄ -, and R ₇ represents an alkyl group having 1 to 3 carbon atoms.

When a primary amine group (-NH ₂ ) is contained in the silane coupling agent, the curing reaction of the compound may occur and the flexibility of the substrate may be impaired. Therefore, a compound that is not cured can be obtained by having a secondary amine group (-NH 2), thereby improving the flexibility in coating a substrate.

 The step of preparing the polydialkylsiloxane-modified epoxy hybrid compound is preferably carried out at a temperature of 50 ° C to 60 ° C for 20 to 30 hours. The reactivity is most excellent when the reaction is carried out within the above-mentioned range.

For example, when a polydimethylsiloxane-modified epoxy resin prepolymer and an alkyl ester aminopropylalkoxysilane are reacted with the polydimethylsiloxane-modified epoxy resin prepolymer and the silane coupling agent as the material of the polydialkylsiloxane-modified epoxy resin prepolymer, an epoxy hybrid compound into which polydimethylsiloxane is introduced Can be manufactured. The mechanism for this can be expressed by the following reaction formula (2).

[Reaction Scheme 2]

Finally, the polydialkylsiloxane-modified epoxy hybrid compound is mixed with an organic solvent (S300).

The organic solvent may be at least one selected from the group consisting of acetone, methyl ethyl ketone, and methyl butyl ketone, but is not limited thereto.

In summary, the coating composition comprising the polysiloxane-modified epoxy hybrid compound according to the present invention can improve flexibility, durability, hydrophobicity and transparency to the coating film as the polysiloxane is included. Further, by reacting the silane coupling agent, the coating composition will contain a silane group. Accordingly, the surface of the coating film becomes hydrophobic during the formation of the coating film, so that the adhesive force with the substrate can be maximized.

Hereinafter, exemplary embodiments of the present invention will be described in order to facilitate understanding of the present invention. It should be understood, however, that the following examples are intended to aid in the understanding of the present invention and are not intended to limit the scope of the present invention.

<Production Example>

Preparation of polydialkylsiloxane-modified epoxy resin prepolymer

(Α, ω-aminopropylpolydimethylsiloxane, DMS-A12, Gelest Inc.) and epoxy resin (bisphenol-A type, YD-128, Kukdo Chemical Co.,

48 g of an epoxy resin (bisphenol-A type, YD-128, Kukdo Chemical Co., Ltd.) and 50 g of?,? - aminopropyldimethylsilane (manufactured by Kukdo Chemical Co., Ltd.) were added to a 500 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, 15 g of siloxane (α, ω-aminopropylpolydimethylsiloxane, DMS-A12, Gelest Inc.) and 20 ml of acetone were added, dissolved and reacted at 80 to 85 ° C. for 24 hours. Thereafter, the reaction product was dissolved in acetone (10 ml), and then 50 ml of methanol was added dropwise thereto to obtain a precipitated reaction product. The precipitated product was vacuum-dried at room temperature for 24 hours to obtain a viscous polydimethylsiloxane-modified epoxy resin (EMPDMS ) (Yield: 95%).

Preparation of Polydialkylsiloxane Modified Epoxy Hybrid Compounds

13 g of polydimethylsiloxane-modified epoxy resin (EMPDMS) prepared in the preparation of the polydialkylsiloxane-modified epoxy resin prepolymer and 30 ml of acetone were added and dissolved, followed by stirring at 50 to 55 ° C for 24 hours to obtain polydimethylsiloxane-modified To prepare an epoxy hybrid compound (EMPDMSH). The reaction product was dried under high vacuum for 12 hours to remove unreacted material.

Preparation of coating composition

The polydimethylsiloxane-modified epoxy hybrid compound (EMPDMSH) prepared in the preparation of the polydialkylsiloxane-modified epoxy hybrid compound was mixed with 23.6 ml of acetone to prepare a coating solution. The solid content of the coating solution was adjusted to 50%, and this was added to an epoxy / glass fiber composite film (I-component Co., Ltd.) using a spin process controller (SPIN-12000, MIDAS Co., Ltd) at 3000 rpm and then cured at room temperature for 6 hours to prepare specimens.

&Lt; Comparative Example 1 &

The epoxy resin was mixed with an acetone solution to prepare a coating solution. Thereafter, the composite film was coated with the coating solution.

&Lt; Comparative Example 2 &

The silicone-modified acrylate was mixed with an acetone solution to prepare a coating solution. Thereafter, the composite film was coated with the coating solution.

<Characteristic evaluation>

(1) Peak characteristics

2 is an FT-IR spectra of a polydimethylsiloxane-modified epoxy resin prepolymer (EMPDMS) and a polydimethylsiloxane-modified epoxy hybrid compound (EMPDMSH) in the production example of the present invention.

The infrared spectroscopic analysis was performed with FT-IR (Nicolet is 10) of Thermo Scientific Co., Ltd. Sample measurements were made using ATR.

Referring to FIG. 2 (a), the absorption peak of the epoxy group, which is the characteristic absorption of the epoxy resin, is shown at 915 cm ^-1 and the absorption peak of Si-O-Si appears at 1020 to 1100 cm ^-1 (b ) Shows that the absorption peak of the epoxy ring is weak, suggesting that EMPDMSH containing an alkoxy aminosilane compound introduced into EMPDMS was synthesized.

3 is a graph showing the results of ¹ H-NMR measurement of polydimethylsiloxane-modified epoxy resin prepolymer (EMPDMS) and polydimethylsiloxane-modified epoxy hybrid compound (EMPDMSH) in the production example of the present invention.

The NMR was measured using 400 MHz Zeol 400 from Zeol Co., Ltd. The sample was analyzed by ¹ H-NMR at room temperature using CDCl ₃ as a reference material.

Referring to FIG. 3, in (a), a methyl group bonded to the siloxane can be identified at 0.1 ppm, and a proton absorption peak originating from an epoxy group at 2.7 and 3.2 ppm, a photon absorption peak attributable to an aromatic ring at 6.8 to 7.1 ppm . In addition, in (b), it can be seen that the absorption peak attributable to the epoxy ring is weak.

4 is a graph showing the results of ²⁹ Si-NMR measurement of the polydimethylsiloxane-modified epoxy hybrid compound (EMPDMSH) in the production example of the present invention.

The NMR was measured using 400 MHz Zeol 400 from Zeol Co., Ltd. The sample was measured for ²⁹ Si-NMR at room temperature using CDCl ₃ as a reference material.

Referring to FIG. 4, it was confirmed that the absorption peak of Si attributable to siloxane at 21 ppm and the Si absorption peak bonded at the terminal methoxy silicon at 45 ppm were confirmed, and EMPDMSH was well synthesized.

(2) Thermal properties

5 is a graph showing the thermal characteristics of the production example and the comparative example 1. Fig.

The thermal properties were measured using a TG50 (Mettler Toledo Co., Ltd.) and the temperature was measured at a temperature of 25 to 800 ° C at a rate of 20 / min.

Referring to FIG. 5, Comparative Example 1 showed a decomposition temperature of 325 ° C, and in the case of Production Example, a decomposition temperature of 368 ° C.

It can be understood that PDMS having excellent heat resistance is introduced into an epoxy resin having high temperature characteristics and excellent high temperature characteristics are obtained by introducing a trimethoxysilyl group capable of causing a thermosetting reaction at the terminal.

As a result, it can be seen that the film coated with the coating composition according to one embodiment of the present invention has excellent high-temperature characteristics.

(3) Contact angle of the substrate with the coating liquid

6 is an image showing the contact angles of the production example and the comparative example. 6 (a) shows the contact angle of Comparative Example 1, and (b) shows the contact angle of the production example.

The contact angle was measured using a contact angle and surface tension analyzer (Phoenix 300, SEO Co., Ltd.).

Referring to FIG. 6, Comparative Example 1 had a contact angle of 41 °, and in the production example, it had a contact angle of 71 °.

Consequently, it can be seen that the coating composition according to an embodiment of the present invention has high adhesion.

(4) Surface adhesion

7 is a graph showing the adhesive strengths of the production example, the comparative example 1 and the comparative example 2. Fig.

Adhesion is And measured by a cross hatch cut test according to the method of ASTM D3359-02. The coated surface was cross-cut using a thin razor to form parallel lines of 6 lines each in 1 mm intervals in the horizontal and vertical directions, resulting in a total of 25 lattices. The tape is made by 3M's scotch magic tape cat. 810D was used to measure the cross-cut surface after all the surfaces were bonded with tape and the tape was peeled off with a certain force. The determination of adhesion was graded according to ASTM D3359-02 standard.

In order to increase the accuracy, the epoxy / glass fiber substrate used in the production examples and the comparative examples, as well as the epoxy substrate, were coated with the coating solution and further experiments were conducted.

7, Comparative Example 1 coated with an epoxy coating solution exhibited an adhesive strength value of 0B, Comparative Example 2 coated with a silicone-modified acrylate coating solution had an adhesive strength value of 4B, and a polysiloxane-modified epoxy In the case of the preparation example coated with the hybrid compound coating solution, it has an adhesive strength value of 5B and has the best adhesion.

As a result, it can be seen that the adhesive strength of the composite film coated with the coating composition according to one embodiment of the present invention is excellent.

(5) Surface smoothness

8 is a graph showing the surface smoothness of the production examples and comparative examples.

The surface smoothness of the coating liquid was measured by spin coating a coating liquid having a solid content of 50% at 3000 rpm using a D150 surface analyzer of Veeco Instrument Co., Ltd.

Referring to FIG. 8, when a glass fiber used for lowering the coefficient of thermal expansion (CTE) of an epoxy / glass fiber substrate (w / o coating) is used, the surface smoothness is increased to about 800 nm due to glass fiber. 687 nm in Comparative Example 1, 567 nm in Comparative Example 2, and 421 nm in the case of the production example. Thus, the smoothness of the composite film coated with the coating composition according to one embodiment of the present invention was greatly reduced. This is because the introduction of siloxane having a flexible chain on the surface improves the surface roughness.

As a result, in the case of the composite film coated with the coating composition according to an embodiment of the present invention, the roughness is improved and the contact force with the substrate can be further improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the present invention is not limited to the disclosed exemplary embodiments, and various changes and modifications may be made by those skilled in the art without departing from the scope and spirit of the invention. Change is possible.

Claims (7)

Preparing a polydialkylsiloxane-modified epoxy resin prepolymer by reacting a polydialkylsiloxane having an amine group, a hydroxyl group, or a thiol group at its terminal end with an epoxy resin having at least one epoxy group in the molecule;
Reacting the polydialkylsiloxane-modified epoxy resin prepolymer with a silane coupling agent to prepare a polydialkylsiloxane-modified epoxy hybrid compound; And
And mixing the polydialkylsiloxane-modified epoxy hybrid compound with an organic solvent,
Wherein the silane coupling agent is an aminoalkylalkoxysilane compound having a secondary amine group (-NH). The method according to claim 1,
The polydialkylsiloxane having an amine group, a hydroxyl group, or a thiol group at both ends of the term is preferably an?,? -Aminoalkylpolydimethylsiloxane,?,? -Aminoalkylpolymethylethylsiloxane,?,? - hydroxyalkylpolydimethylsiloxane, is at least one selected from the group consisting of?,? - hydroxyalkylpolymethylethylsiloxane,?,? - mercaptoalkylpolydimethylsiloxane, and?,? - mercaptoalkylpolymethylethylsiloxane. A process for preparing a coating composition comprising an alkylsiloxane-modified epoxy hybrid compound. The method according to claim 1,
The epoxy resin is at least one selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, rubber modified epoxy resin and urethane modified epoxy resin &Lt; RTI ID = 0.0 &gt; 1. &Lt; / RTI &gt; delete The method according to claim 1,
In the step of preparing the polydialkylsiloxane-modified epoxy resin prepolymer,
Wherein the epoxy resin having at least one epoxy group in the molecule is reacted in an amount of 25 to 35 parts by weight based on 100 parts by weight of the polydialkylsiloxane having an amine group, a hydroxyl group or a thiol group at both ends thereof . The method according to claim 1,
Wherein the step of preparing the polydialkylsiloxane-modified epoxy resin prepolymer is carried out at a temperature of 80 ° C to 90 ° C for 20 to 30 hours. The method according to claim 1,
Wherein the step of preparing the polydialkylsiloxane-modified epoxy hybrid compound is carried out at a temperature of 50 캜 to 60 캜 for 20 to 30 hours.

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