KR101883642B1 - Surface treated filler, preparing method thereof, composition comprising the same and use thereof - Google Patents

Abstract

The present invention relates to a filler surface-treated with a curing agent having an alkoxysilyl group or an alkoxysilyl group exhibiting improved physical properties in a composite containing a filler, a method for producing the same, a composition comprising the same, and uses thereof. According to the present invention, a filler surface-treated with at least one surface treatment agent selected from the group consisting of an epoxy compound having at least one alkoxysilyl group and at least two epoxy groups, a curing agent having at least one alkoxysilyl group and a hydrolyzate thereof, Processes for their preparation, compositions comprising them and their uses. The composition containing the alkoxysilyl group-containing epoxy compound or the filler surface-treated with the curing agent of the present invention is not limited to the physical properties to be achieved by mixing the filler, but may be, for example, mechanical strength, heat resistance, thermal expansion characteristics, Physical properties such as heat radiation properties, electrical conductivity, and flame retardancy are improved.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a surface-modified filler, a method for producing the same, a composition comprising the same,

The present invention relates to a surface-treated filler, a method for producing the same, a composition comprising the same, and uses thereof. More particularly, the present invention relates to an epoxy compound having an alkoxysilyl group exhibiting improved physical properties in a composite containing a filler, a curing agent having an alkoxysilyl group, or a filler surface-treated with the hydrolyzate thereof, a method for producing the same, And its use.

A filler (filler) is ordinarily added to the organic compound and / or the polymer composition used for the electrical and / or electronic materials and / or semiconductor materials. Fillers are formulated to impart functionality that is not present in organic compounds and / or polymers, or to improve physical properties. For example, by mixing an inorganic filler, it is possible to improve the mechanical properties such as viscosity, fluidity adjustment, molding shrinkage and dimensional stability, modulus, tensile strength and toughness, thermal expansion characteristics (reduction in thermal expansion coefficient) , Imparting of functionality such as flame retardancy, and cost reduction.

On the other hand, as the technology of electric and electronic materials and / or semiconductor materials is improved, the particle size of the filler used in the composite is reduced and the filling ratio is increased to satisfy the required high performance physical properties. Therefore, the uniform dispersion of the filler in the organic compound and / or the polymer matrix is important. Therefore, in order to achieve the intended physical properties by improving the dispersion ratio of the filler particles and increasing the filler, the filler is subjected to surface treatment (surface modification). On the other hand, the physical properties of the composite are highly dependent on the characteristics of the surface treatment agent of the filler.

Conventionally, fillers have typically been surface treated with a silane coupling agent. Silane coupling agents used as surface treating agents for conventional fillers include vinyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-glycidoxypropyltrimethoxysilane, etc., in the Adhesion & Technical Association of Japan Society for Adhesion (vol 17, No. 3. 54 (1997), Nagata Gachuya) Gamma-methacryloxypropyltrimethoxysilane, and the like can be used. However, when a filler surface-treated with a conventional silane coupling agent is used in combination with a composition, desirable physical properties such as mechanical strength, moldability, and the like may not be sufficiently exhibited. Accordingly, there is a demand for a surface treating agent which is more effective in improving the processability and physical properties of the filler, and a surface-treated filler that effectively exhibits excellent dispersibility and intended physical properties when the filler is compounded. Such physical properties may be any physical properties which are not intended to be limited thereby but which are intended, for example, by the addition of fillers to conventional resin systems, such as mechanical properties, thermal conductivity, processability, strength, formability and adhesiveness.

It is an object of the present invention to provide a surface-treated filler exhibiting improved composite properties when blended with organic compounds and / or polymers. Another object of the present invention is to provide a method for producing the surface-treated filler. Another object of the present invention is to provide a resin composition comprising the surface-treated filler according to the present invention and its use.

According to the present invention, a filler surface-treated with at least one surface treatment agent selected from the group consisting of an epoxy compound having at least one alkoxysilyl group and at least two epoxy groups, a curing agent having at least one alkoxysilyl group, and a hydrolyzate thereof / RTI >

The epoxy compound having at least one alkoxysilyl group and at least two epoxy groups may be selected from the group consisting of the following formulas AI to MI.

(In the general formula AI to EI, substituent a and b is selected from the group consisting of the following formulas E1 to E4, wherein the at least one of a to c and f to a formula A1, the rest is hydrogen, - (CH _{2) Z- 2} CH = CH ₂ wherein z is an integer from 3 to 10, and E2,

In the general formula AI, Y is _{-CH 2 -, -C (CH 3} ) 2 -, -C (CF 3) 2 -, -S- or -SO ₂ - can be,

Formula FI to substituent g to j for at least two of the pieces of II is to a formula E2, and at least one of the following formulas A1 to A4, the rest is _{hydrogen, - (CH 2) Z-} 2 CH = CH 2 ( wherein z is Lt; / RTI > is an integer from 3 to 10,

In the formula (HI), r is hydrogen, a hydroxy group, an alkyl group (C1-C10)

In the formula (II), at the meta position of oxygen, hydrogen may be substituted with a linear or branched C1-C10 alkyl group,

At least two of the general formula JI to a number of the MI K dog is the formula E2, and at least one of the following formulas A1 to A4, the rest is _{hydrogen, - (CH 2) Z-} 2 CH = CH 2 ( wherein z is 3 To 10, and the formula (A5): < EMI ID =

(여기서 K는 상기 정의한 바와 같다)이며, In the above formula (JI), Z is

(Where K is as defined above)

이고, p는 1 또는 2의 정수이며, In the formula MI, x is

P is an integer of 1 or 2,

In the formulas JI to MI, n is an integer of 1 to 100.

[Chemical Formula (E1) to (E4)

(A1)

- (CH ₂ ) _z -SiY ₁ Y ₂ Y ₃

(A2)

-CONH (CH ₂ ) _z -SiY ₁ Y ₂ Y ₃

In the above formulas A1 and A2, Y ₁ to Y ₃ (Wherein R is an alkyl group having from 1 to 10 carbon atoms) and the remainder is an alkyl group having from 1 to 10 carbon atoms, the alkyl group and the alkoxy group are linear or branched, and z is an integer from 3 to 10 Lt; / RTI >

 (A3)

Wherein X1 is _{OR 4, OH, NR 4 R} 5, SR 4, or _{OCONH (CH 2) 3 SiY 1} Y 2 Y 3 and, X1 'is H or _{CONH (CH 2) 3 SiY 1} Y 2 Y 3. The above Y ₁ to Y ₃ Is an alkoxy group having 1 to 10 carbon atoms, and the remainder is an alkyl group having 1 to 10 carbon atoms. However, R ₄ Or R < ₅ > may be an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms and may include a hetero atom of N, O, P or S.

(A4)

Wherein X2 is _{OR 4, OH, NR 4 R} 5, SR 4, or _{O (CH 2) l CH 2} CH 2 SiY 1 Y 2 Y 3, ( where 1 is an integer of 1 to 8, Y ₁ to Y ₃ At least one of an alkoxy group having 1 to 10 carbon atoms, and the other is C 1 to 10 alkyl group), X2 'is H or _{(CH 2) l CH 2 CH} 2 SiY 1 Y 2 Y 3 ( wherein, 1 is an integer of 1 to 8, Y ₁ to Y ₃ Is an alkoxy group having 1 to 10 carbon atoms and the remainder is a C1-10 alkyl group), and R < ₄ > Or R < ₅ > may be an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms and may include a hetero atom of N, O, P or S.

(A5)

Wherein X is _{OR 4, OH, NR 4 R} 5 Or SR ₄ . However, R ₄ Or R < ₅ > may be an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms and may contain a hetero atom of N, O, P or S.

The curing agent having an alkoxysilyl group may be selected from the group consisting of the following formulas (I-1) to (I-4).

(I-1)

(In the formula (I-1), Z is one of the groups consisting of the following formulas (1A) to (1F).

)

)

[Formula I-2]

[Formula I-3]

; 및

; And

 [Formula I-4]

(In the formula (I-4), p is 1 or 2,

이며,

에서 R은 C1-C10의 직쇄 또는 측쇄상 알킬기이다.)
x is

Lt;

, R is a straight or branched alkyl group of C1-C10.)

(In the formulas (I-1) to (I-4)

At least one A of a plurality of A is represented by the following formula A6 or A7, and when at least one A is A6, the remaining A is represented by the following formula B2 or hydrogen, and when at least one A is A7, the remaining A is hydrogen And n is an integer of 1 or more, preferably an integer of 1 to 100.)

[Formula A6]

- (CH ₂ ) _m -SiY ₁ Y ₂ Y ₃

(A7)

-CONH (CH ₂ ) _m -SiY ₁ Y ₂ Y ₃

(In the above formula A6 and A7, Y ₁ to Y ₃ Is a straight or branched-chain alkoxy group having 1 to 10 carbon atoms and the remainder is a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, and m is an integer of 3 to 10.)

(B2)

- (CH ₂ ) ₁ -CH = CH ₂

(Wherein l is an integer of 1 to 8)

The filler may be selected from the group consisting of glass fiber, silica, alumina, boehmite, titania, zirconia, silicon nitride, aluminum nitride, clay, mica, kaolin, talc, wollastonite, montmorillonite, asbestos, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, Aluminum, copper, magnesium, lead, nickel, zinc, manganese, stainless steel, calcium carbonate, calcium carbonate, gold, silver, platinum, But may be selected from the group consisting of titanium, titanium, cerium, zinc, tin, indium, sulfur, cobalt, molybdenum, strontium, chromium and barium.

According to the present invention there is provided a process for the preparation of a coating composition comprising at least one alkoxysilyl group containing at least one alkoxysilyl group and at least two epoxy groups in a solvent and / or reacting the filler with a curing agent having at least one alkoxysilyl group, And a method for producing a filler surface-treated with an epoxy compound having at least two epoxy groups and / or a curing agent having at least one alkoxysilyl group.

According to the present invention, it is also possible to hydrolyze an epoxy compound having at least one alkoxysilyl group and at least two epoxy groups and / or a curing agent having at least one alkoxysilyl group among water, a solvent and an optional reaction catalyst, Forming a hydrolyzate of an epoxy compound having at least one silanol and at least two epoxy groups or a curing agent having at least one silanol; And

Reacting a filler with a hydrolyzate of an epoxy compound having at least one silanol and at least two epoxy groups and / or a curing agent having at least one silanol in the solvent in the presence of at least one silanol and at least two There is provided a process for producing a filler surface-treated with a hydrolyzate of an epoxy compound having at least one epoxy group and / or a curing agent having at least one silanol.

Wherein the filler is selected from the group consisting of glass fiber, silica, alumina, Boehmite, titania, zirconia, silicon nitride, aluminum nitride, clay, mica, kaolin, talc, wollastonite, montmorillonite, asbestos, aluminum hydroxide, Aluminum, copper, magnesium, lead, magnesium, magnesium, magnesium, magnesium, boron nitride, aluminum borate, barium titanate, calcium titanate, magnesium titanate, bismuth titanate, barium zirconate, calcium zirconate, May be selected from the group consisting of nickel, zinc, manganese, stainless steel, titanium, cerium, zinc, tin, indium, sulfur, cobalt, molybdenum, strontium, chromium and barium.

Further, according to the present invention, there is provided a composition comprising the surface-treated filler. Further, there is provided an electrical and electronic material, an adhesive, a paint, a coating agent, and a semiconductor material including the composition, and the electrical and / or electronic material may be a substrate, a film, a laminate, a prepreg, a printed wiring board, or a packaging material.

The composition containing the alkoxysilyl group-containing epoxy compound or the filler surface-treated with the curing agent of the present invention is not limited to the physical properties to be achieved by mixing the filler, but may be, for example, mechanical strength, heat resistance, thermal expansion characteristics, Physical properties such as heat radiation properties, electrical conductivity, and flame retardancy are improved.

1 shows a surface treatment of a filler by an epoxy compound having an alkoxysilyl group and an epoxy group.
Fig. 2 shows the surface treatment of the filler by the curing agent having an alkoxysilyl group.
Fig. 3 (a) is a photograph showing that the non-surface-treated silica was precipitated in water.
3 (b) is a photograph showing that the surface-treated silica of Example 2 is floated without being precipitated in water.
3 (c) is a photograph showing that the surface-treated commercial silica is precipitated in some water and partially floated.
4 (a) is a photograph showing that the surface-treated silica of Comparative Example 1 was precipitated in water.
4 (b) is a photograph showing that the surface-treated silica of Example 2 is floated without being precipitated in water.
5 (a) is a photograph of ZrO2 not subjected to surface treatment dispersed in methyl ethyl ketone.
5 (b) is a photograph of the surface-treated ZrO2 of Example 21 dispersed in methyl ethyl ketone.
Fig. 6 (a) is a photograph of TiO2 untreated and dispersed in toluene.
6 (b) is a photograph of the surface-treated TiO2 of Example 20 dispersed in toluene.

The present invention provides a method for improving physical properties to be achieved by combining a filler with a filler, a composition comprising a filler and an organic compound and / or a polymer matrix (hereinafter, also referred to as an 'organic matrix and / or a polymer matrix' , A surface-treated filler, a method for producing the same, a composition comprising the same, and uses thereof.

The filler is added for imparting or improving desired physical properties to the polymer matrix. The physical properties include, but are not limited to, mechanical strength, heat resistance, thermal expansion characteristics, high heat dissipation characteristics, electrical conductivity, .

As used herein, the term " complex " is used to mean a composition comprising a filler and an organic compound and / or polymer. The composite is used to mean both before and after curing. In the present invention, the term " composite " is used to mean a composition, a mixture, a blend, a cured product or the like containing a filler and an organic compound and / or a polymer blended therein.

1. Surface treated filler

According to the present invention, a filler surface-treated with at least one compound selected from the group consisting of an epoxy compound having at least one alkoxysilyl group and at least two epoxy groups, a curing agent having at least one alkoxysilyl group, Is provided.

In the present invention, an epoxy compound having at least one alkoxysilyl group and at least two epoxy groups (hereinafter referred to as a 'silyl epoxy compound') and a curing agent having at least one alkoxysilyl group (hereinafter referred to as a 'silyl curing agent' ) And a hydrolyzate thereof are used as a surface treating agent. These may be used singly or in combination of two or more as necessary.

In order to be used as a surface treating agent for a filler, a surface treating agent generally needs to have a unit having compatibility and / or reactivity with an organic compound and / or a polymer matrix to which a filler is compounded. The effect of the interfacial bond formation to control the physical properties of the composite, specifically, the effect of interfacial bond formation between the filler and the matrix (formation of bond between filler-surface treatment agent and matrix) through the surface treatment agent depends on the chemical structure of the surface treatment agent . Furthermore, it is also advantageous in terms of the chemical treatment of the filler that the surface treatment agent has a unit for reaction, hydrogen bonding and / or electrostatic interaction with the filler surface.

The present inventor has noted that the silyl epoxy compound and the silyl curing agent exhibit excellent physical properties as an epoxy compound and a curing agent in an epoxy composition but can be used as a surface treating agent for a filler. It has been noted that the silyl epoxy compound and the silyl curing agent have a silyl group capable of reacting with the filler, and an organic aromatic structure excellent in compatibility with the organic compound and / or the polymer matrix. That is, the silyl epoxy compound and the silyl curing agent have an aromatic core and a multifunctional epoxy group (in the case of silyl epoxy compounds) or a phenol group (in the case of silyl curing agents) as compared with conventional silyl coupling agents, The compatibility with the organic compound and / or the polymer matrix and the coating efficiency on the surface of the filler particles can be improved, so that the filler can be effectively treated with the silyl epoxy compound, the silyl curing agent and / or the hydrolyzate thereof However, it has been determined that the physical properties of the composite can be improved by using a silyl epoxy compound, a silyl curing agent and / or a filler surface-treated with the hydrolyzate thereof in the preparation of a composite, thereby completing the present invention.

The surface treatment in the surface-treated filler according to the present invention refers to any state in which the surface of the filler is coated with the surface treatment agent, irrespective of whether the filler and the surface treatment agent are bonded and / or reacted. That is, the surface treatment is used in a broad sense including, but not limited to, a state in which the surface of the filler is physically coated with the surface treatment agent, and a state in which the surface of the filler is bonded to the filler surface by chemical reaction of the filler and the surface treatment agent .

The surface-treated filler according to the present invention may be, for example, one wherein the surface of the filler is physically coated with a silyl epoxy compound, a silyl curing agent, or a hydrolyzate thereof. For example, the surface-treated filler according to the present invention may be chemically surface-treated with a filler having an OH group on the surface thereof and the silyl epoxy compound, the silyl curing agent, or the hydrolyzate thereof, have. Specifically, a bond is formed by the reaction between the silyl epoxy compound and the alkoxysilyl group of the silyl curing agent and the hydroxyl group on the surface of the filler.

The hydrolyzate of the silyl epoxy compound or silyl curing agent is obtained by converting an alkoxysilyl group or SiOR into a -Si-OH group (silanol group) by the reaction of the silyl epoxy compound and / or the silyl curing agent with water. The bond is formed by the reaction of the silyl epoxy group and the silanol group of the hydrolyzate of the silyl curing agent with the hydroxyl group on the surface of the filler.

For example, the schematic diagram (1) shown in FIG. 1 shows a state in which the surface of the filler is treated with the silyl epoxy compound, and the schematic diagram (2) shown in FIG. 2 shows the state in which the surface of the filler is treated with the silyl curing agent.

As shown in the schematic diagrams (1) and (2), the silyl epoxy compound and the silyl curing agent react with the surface functional group of the filler through the alkoxysilyl group, and the surface treatment of the filler proceeds. Further, in the case of the silyl epoxy compound and the silyl curing agent, the surface treatment efficiency (coating efficiency) of the filler is increased by forming a hydrogen bond between the epoxy group and the hydroxyl group on the surface of the filler or between the phenol group and the hydroxyl group on the surface of the filler.

The filler may be any filler conventionally known in the art to be used as a filler, for example, an inorganic filler and / or a metal filler. But are not limited to, inorganic fillers such as glass fibers, silica, alumina, Boehmite, titania, zirconia, graphite, carbon black silicon nitride, aluminum nitride, clay, mica, kaolin, talc, Calcium carbonate, magnesium carbonate, magnesium oxide, iron oxide (FeO, Fe ₂ O ₃ ), boron nitride, aluminum borate, barium titanate, calcium titanate, magnesium titanate, magnesium titanate, Bismuth titanate, barium zirconate, calcium zirconate, silsesquioxane, and the like. The inorganic filler may preferably be glass fiber, silica, alumina, Boehmite, talc, clay, mica, ascorbic acid, titania, zinc oxide, iron oxide (FeO, Fe ₂ O ₃ ).

But are not limited to metal fillers such as gold, silver, platinum, iron, aluminum, copper, magnesium, lead, nickel, zinc, manganese, stainless steel, titanium, cerium, zinc, tin, indium, Cobalt, molybdenum, strontium, chromium, barium and the like.

The inorganic filler and / or the metal filler may or may not have an OH group, but it is preferable that the inorganic filler and / or the metal filler have an OH group in terms of chemical bonding with the surface treatment agent.

The glass fiber is used not only for glass fiber but also for glass fiber cloth, glass fiber cloth and the like. Examples of the glass fiber include glass fibers such as E glass fiber, T glass fiber, S glass fiber, NE glass fiber, D glass fiber and quartz glass fiber, and examples thereof include E or T And glass fibers.

These fillers may be used singly or in combination of two or more thereof, if necessary.

The shape of the filler is not particularly limited, and either a fracture surface or a spherical shape can be used.

Although the filler is not limited thereto, a filler having a particle size of 0.5 nm to several tens of 탆 (for example, 50 탆 to 100 탆) may be used in consideration of the intended use of the composite, specifically, the dispersibility of the filler have. Since the filler is dispersed in the organic compound and / or polymer, it is preferable that fillers of various sizes are used together in the size range due to the difference in dispersibility depending on the particle size. In addition, in order to increase the amount of the filler to be blended, it is preferable to blend the filler with a wider particle distribution.

As the silyl epoxy compound, any epoxy compound having at least one alkoxysilyl group and at least two epoxy groups can be used. Examples of the silyl epoxy compounds that can be used in the surface treatment of the filler in the present invention include, but are not limited to, silyl epoxy compounds of the following formulas AI to MI.

In the general formula AI to EI, substituent a and b is selected from the group consisting of the following formulas E1 to E4, and the c to f at least one of the following formulas A1 of, and the other is _{hydrogen, - (CH 2) Z-} 2 CH = CH ₂ in the (wherein z is an integer of 3-10) alkenyl group, and the following may be independently selected from the general formula E2,

In the general formula AI, Y is _{-CH 2 -, -C (CH 3} ) 2 -, -C (CF 3) 2 -, -S- or -SO ₂ - can be,

Formula FI to substituent g to j for at least two of the pieces of II is to a formula E2, and at least one of the following formulas A1 to A4, the rest is _{hydrogen, - (CH 2) Z-} 2 CH = CH 2 ( wherein z is Lt; / RTI > is an integer from 3 to 10,

In the formula (HI), r is hydrogen, a hydroxy group, an alkyl group (C1-C10)

In the formula (II), at the meta position of oxygen, hydrogen may be substituted with a linear or branched C1-C10 alkyl group,

At least two of the general formula JI to a number of the MI K dog is the formula E2, and at least one of the following formulas A1 to A4, the rest is _{hydrogen, - (CH 2) Z-} 2 CH = CH 2 ( wherein z is 3 To 10, and the formula (A5): < EMI ID =

In the above formula (JI), Z is

(여기서, K는 상기 정의한 바와 같다.)이며,

(Where K is as defined above)

이고, p는 1 또는 2의 정수이며, In the formula MI, x is

P is an integer of 1 or 2,

In the formulas JI to MI, n is an integer of 1 or more, and preferably an integer of 1 to 100.

[Chemical Formula (E1) to (E4)

(A1)

- (CH ₂ ) _z -SiY ₁ Y ₂ Y ₃

(A2)

-CONH (CH ₂ ) _z -SiY ₁ Y ₂ Y ₃

In the above formulas A1 and A2, Y ₁ to Y ₃ Is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms, and the alkyl and alkoxy groups may be straight or branched chain alkyl groups having 1 to 10 carbon atoms, -OR (R is an alkyl group having 1 to 10 carbon atoms) Branched chain, and z is an integer from 3 to 10. [

 (A3)

Wherein X1 is _{OR 4, OH, NR 4 R} 5, SR 4, or _{OCONH (CH 2) 3 SiY 1} Y 2 Y 3 and, X1 'is H or _{CONH (CH 2) 3 SiY 1} Y 2 Y 3. The above Y ₁ to Y ₃ Is an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and the remainder is an alkyl group having 1 to 10 carbon atoms. However, R ₄ Or R < ₅ > may be an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms and may include a hetero atom of N, O, P or S.

(A4)

Wherein X2 is _{OR 4, OH, NR 4 R} 5, SR 4, or _{O (CH 2) l CH 2} CH 2 is _{SiY 1 Y 2 Y 3, X2} ' is H or _{(CH 2) l CH 2 CH} 2 SiY ₁ Y ₂ Y ₃ , wherein 1 is 1 to 8, Y ₁ to Y ₃ Is an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and the remainder is an alkyl group having 1 to 10 carbon atoms. However, R ₄ Or R < ₅ > may be an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms and may include a hetero atom of N, O, P or S.

(A5)

Wherein X is _{OR 4, OH, NR 4 R} 5 Or SR ₄ . However, R ₄ Or R < ₅ > may be an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms and may include a hetero atom of N, O, P or S.

For example, the epoxy compound having at least one alkoxysilyl group and at least two epoxy groups is disclosed in Applicants' patent applications Nos. 2012-93320, 2013-27308, 2013-0078347, 2014-0175937, 2013-111473, 2014-21884, and 2013-0035546, which are incorporated herein by reference.

The epoxy compound having at least one alkoxysilyl group of the above-mentioned Patent Application No. 2012-0093320 can be prepared by, for example, reacting a core selected from the group consisting of the following formulas A 'to K' An epoxy compound having an alkoxysilyl group containing an epoxy group of S2.

(In the formula D 'Y is _{-CH 2 -, -C (CH 3} ) 2 -, -C (CF 3) 2 -, -S- or -SO ₂ - a).

[Formula (S1)

-CR _b R _c -CHR _a -CH ₂ -SiR ₁ R ₂ R ₃

(In the formula (S1), the R_a,R_b And R_C Are each independently H or an alkyl group having 1 to 6 carbon atoms, R_One To R₃ Is an alkoxy group having 1 to 6 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkyl group and the alkoxy group may be linear or branched.

 ≪ RTI ID = 0.0 &

The epoxy compound having at least one alkoxysilyl group as described in Patent Application No. 2013-0027308 may be, for example, an epoxy compound having an alkoxy group silyl group selected from the group consisting of the following formulas AI to HI.

(A Formula AI or a substituent of the BI a to c 1 or 2, the formula S1 wherein one or two is a formula S2 or S3 to, and the other is hydrogen or _{- (CH 2) Z-2} CH = CH 2 ( Wherein z is an integer from 3 to 10,

1 to 3 of the substituents a to d of the above formulas CI to HI are represented by the following formula (S1), 1 to 3 are represented by the following formula (S2) or S3 and the remaining are hydrogen or - (CH ₂ ) _Z-2 CH═CH ₂ Is an integer of 3 to 10,

The formula BI may be substituted with a linear or branched C1-C10 alkyl group at the meta position of oxygen,

(Rb는 H 혹은 C1-C3 알킬기임)이며. In the formula CI, X is a single bond, -CH ₂ - or

(Rb is H or a C1-C3 alkyl group).

Y in formula (EI) is -CH ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -S- or -SO ₂ -

In formula (I), Ra is H or a C1-C3 alkyl group.)

[Formula (S1)

≪ RTI ID = 0.0 &

- (CH ₂ ) _z -SiR ₁ R ₂ R ₃

[Formula (S3)

-CONH (CH ₂ ) _z -SiR ₁ R ₂ R ₃

(In the above formulas (S2) and (S3), R ₁ to R ₃ Is an alkyl group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkyl group and the alkoxy group are linear or branched and z is an integer of 3 to 10.)

The epoxy compound having an alkoxysilyl group of the above-mentioned Patent Application No. 2013-0035546 may be an epoxy compound having an alkoxysilyl group of the following formula (1).

[Chemical Formula 1]

(Wherein, in the formula 1, the core unit C is independently selected from the structures of the following formulas (2-1) to (2-5), and the plurality of core units C in the formula (1) May be different,

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

In Formula (2-1), X is -CH ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -S- or -SO ₂ -

In Formula 2-3, Y is independently selected from the group consisting of H and C1 to C5 alkyl groups,

n is an integer of 1 to 10, and when n is 1, R is a structure of the following formula (3a) or (3b), and when n is 2 or more, at least one of the plurality of R is a structure And the remainder are hydrogen, the epoxy compound of formula (2-1) wherein X is -C (CH ₃ ) ₂ - and R is the following formula (3b) are all excluded in the epoxy compound of the above formula (1).

[Chemical Formula 3]

- (CH ₂ ) _m -SiR _a R _b R _c

(3b)

- CONH (CH ₂ ) _m --Si R _a R _b R _c

(In the above formulas (3a) and (3b), R _a to R _c Is an alkoxy group having 1 to 5 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group may be linear or branched, and m is an integer of 3 to 10)

The epoxy compound having an alkoxysilyl group in the above-mentioned Patent Application No. 2013-0078347 may be a novolak-based epoxy compound having at least one alkoxysilyl group selected from the group consisting of the following formulas (I-1) to (I-4).

(I-1)

(In the above formula I-1, Z is one of the groups consisting of the following formulas (1A) to (1F).

)

)

[Formula I-2]

[Formula I-3]

; 및

; And

 [Formula I-4]

이며,

에서 R은 C1-C10의 직쇄 또는 측쇄상 알킬기이다.)(Where x is

Lt;

, R is a straight or branched alkyl group of C1-C10.)

(In the formulas (I-1) to (I-4)

At least two of A's are of the structure of formula A2, at least one of which is A3 or A4 and at least one is A3, the remainder A is B3 or hydrogen and at least one is A4 , The remainder A is hydrogen,

In the above general formula (I-1), when Z is 1 to 1E, n is an integer of 2 or more,

When Z is 1F, n is an integer of 1 or more,

In Formulas (I-2) and (I-3), n is an integer of 1 or more,

인 경우에,In Formula (I-4), x is

in case of,

n is an integer of 2 or more,

인 경우에, n은 1이상의 정수이며, x is

, N is an integer of 1 or more,

In Formula (I-4), p is 1 or 2.

(A2)

 (A3)

- (CH ₂ ) _m -SiR ₁ R ₂ R ₃

(A4)

-CONH (CH ₂ ) _m -SiR ₁ R ₂ R ₃

(In the above formulas A3 and A4, R ₁ to R ₃ Is an alkoxy group having 1 to 5 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group are linear or branched and m is an integer of 3 to 10.)

(B3)

- (CH ₂ ) ₁ -CH = CH ₂

(Wherein l is an integer of 1 to 8)

The epoxy compound having an alkoxysilyl group of the above-mentioned Patent Application No. 2013-0111473 has a kind of core selected from the group consisting of the following formulas A 'to N'; (1) independently selected from the group consisting of the following formulas S11 to S16, (2) independently selected from the group consisting of the following formulas S21 to S26, or (3) , Or (4) at least one alkoxysilyl group independently selected from the group consisting of the following chemical formulas S21 to S26 and the following chemical formulas S31 to S38; And an epoxy compound having an alkoxysilyl group and having at least two epoxy groups independently selected from the group consisting of the following formulas (S51 to S58).

Or a direct bond (direct linkage), - (in formula A ', -q- is -CH ₂

In formula (D '), -r- is -C (CH ₃ ) ₂ -, -CH ₂ -, -C (CF ₃ ) ₂ -, -SO ₂ -

이며,In the formula K ', s is

Lt;

이며, In the formula N ', t is

Lt;

In the formulas K 'to N', n is an integer of 1 or more.

[Formula (S1)

(In the formulas S11 to S16, R ₁ to R ₃ Is an alkoxy group having 1 to 5 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group may be linear or branched.

≪ RTI ID = 0.0 &

(In the formulas S21 to S26, R ₁ to R ₃ Is an alkoxy group having 1 to 5 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group may be linear or branched.

[Formula (S3)

(In the formulas S31 to S38, R ₁ to R ₃ Is an alkoxy group having 1 to 5 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group may be linear or branched.

 [Chemical formula S5 (3)]

(Wherein, in formulas S56 to S58, R ₁ to R ₃ Is an alkoxy group having 1 to 5 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkoxy group and the alkyl group may be linear or branched.

The epoxy compound having an alkoxysilyl group of the above-mentioned Patent Application No. 2014-0021884 may be an epoxy compound having an alkoxysilyl group, represented by a compound selected from the group consisting of the following formulas AF to NF.

(In the formula DF, -p- is _{-C (CH 3) 2 -,} -CH 2 -, -C (CF 3) 2 -, -S-, -SO 2 -,

이며

And

In formula EF, -q- is -CH ₂ - or a direct bond (direct linkage),

In the formula HF, R is hydrogen, a hydroxy group, an alkyl group (C1-C10)

이며, In the formula KF, S is

Lt;

이며, In the formula NF, t is

Lt;

In the formulas KF to NF, n is an integer of 1 or more,

At least two of the plurality of M of the above formulas AF, BF, DF to IF, and KF to NF are epoxy groups selected from the group consisting of the following formulas S41 to S45, and at least one of them is a group Or an alkoxysilyl group that is an S2 substituent independently selected from the group consisting of the following formulas S21 to S25, and the balance of which is selected from the group consisting of hydrogen, or a group consisting of the following formulas S31 to S35: At least two of the plurality of M's of the formula CF and JF are epoxy groups of the following formula S42 and the other is an alkoxysilyl group of the formula S12 or S22.

[Formula (S1)

(Where, in the formula S11 to S15, wherein X1 is OR _4, OH, NR ₄ R _5, SR _4, or OCONH (CH _{2) 3,} and _{SiR 1 R 2 R 3, X1} ' is CONH (CH _{2) 3} SiR ₁ R ₂ R ₃ being Further, the R ₁ to R ₃ Is an alkoxy group having 1 to 5 carbon atoms, and the remainder is an alkyl group having 1 to 10 carbon atoms. However, R ₄ Or R < ₅ > may be an alkyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms and may include a hetero compound including N, O, P or S.

≪ RTI ID = 0.0 &

(Where, in the formula S21 to S25, the X2 is OR _4, OH, NR ₄ R _5, SR _4, or O (CH _{2) n} CH ₂ CH _2, and _{SiR 1 R 2 R 3, X2} ' is (CH ₂ ) _n CH ₂ CH ₂ SiR ₁ R ₂ R _{3 In} addition, the above R ₁ to R ₃ Is an alkoxy group having 1 to 5 carbon atoms, and the remainder is an alkyl group having 1 to 10 carbon atoms . However, R ₄ Or R < ₅ > may be an alkyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms and may include a hetero compound including N, O, P or S.

[Chemical formula S4 (3)]

(Wherein X3 is _{OR 4, OH, NR 4 R} 5, SR 4, OCONH (CH 2) 3 SiR 1 R 2 R 3 , or _{O (CH 2) n CH 2} CH 2 SiR 1 R 2 R 3 and, X3 ' is _{H, CONH (CH 2) 3} SiR 1 R 2 R 3 or _{(CH 2) n CH 2 CH} 2 SiR 1 R 2 R 3 being Further, the R ₁ to R ₃ Is an alkoxy group having 1 to 5 carbon atoms, and the remainder is an alkyl group having 1 to 10 carbon atoms. However, R ₄ Or R < ₅ > may be an alkyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms and may include a hetero compound including N, O, P or S.

[Formula (S3)

(Where, in the formula S31 to S35, wherein X is _{OR 4, OH, NR 4 R} 5 Or SR ₄ . However, R ₄ Or R < ₅ > may be an alkyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms and may include a hetero compound including N, O, P or S)

The epoxy compound having an alkoxysilyl group of the above-mentioned Patent Application No. 2014-0175937 is prepared by adding to the core i) at least two epoxy groups selected from epoxy groups of the following formulas E1 and E2; ii) at least one alkoxysilyl group selected from the group consisting of the following structural formulas A1 to A5; And iii) an epoxy compound having at least one non-reactive silyl group, alkenyl group, or combination thereof selected from the group consisting of the following formulas A6 to A10.

[E1]

[E2]

(A1)

-CR _b R _c -CHR _a -CH ₂ -SiR ₁ R ₂ R ₃

(A2)

-O- (CH ₂ ) _{m + 2} -SiR ₁ R ₂ R ₃

(A3)

-O-CONH (CH ₂ ) _m -SiR ₁ R ₂ R ₃

(A4)

- (CH ₂ ) _{m + 2} -SiR ₁ R ₂ R ₃

(A5)

-CONH (CH ₂ ) _m -SiR ₁ R ₂ R ₃

(Wherein R _{< a &} gt _{; and} R < _{b &} gt _; And R _C are each independently H or an alkyl group having 1 to 6 carbon atoms, and in the formulas (A1) to (A5), R ₁ to R ₃ Is an alkyl group having 1 to 6 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, and the alkyl group and the alkoxy group may be linear or branched and may be cyclic or acyclic, and N, O, S , Or a P hetero atom, and m is an integer of 1 to 10.)

[Formula A6]

-CR _b R _c -CHR _a -CH ₂ -SiR ₄ R ₅ R ₆

(A7)

-O- (CH ₂ ) _{m + 2} -SiR ₄ R ₅ R ₆

(A8)

-O-CONH (CH ₂ ) _m -SiR ₄ R ₅ R ₆

(A9)

- (CH ₂ ) _{m + 2} -SiR ₄ R ₅ R ₆

(A10)

-CONH (CH ₂ ) _m -SiR ₄ R ₅ R ₆

(Wherein R _a, R _b and R _c are each independently H or an alkyl group having 1 to 6 carbon atoms, and R ₄ to R ₆ in the formulas A ₆ to A 10 are aliphatic, alicyclic , Or an aromatic non-reactive group, which may be linear or branched, cyclic or acyclic, and may or may not have N, O, S, or P heteroatoms, and m is And is an integer of 1 to 10.)

Further, the epoxy compound having at least one alkoxysilyl group and at least two epoxy groups can be synthesized by a method known in the art, for example, in Patent Application No. 2012-93320, 2013-27308, 2013-0078347, 2014-0175937, 2013-111473, 2014-21884 and Patent Application No. 2013-0035546.

The silyl curing agent may be any curing agent having at least one alkoxysilyl group, and may be synthesized, for example, by the method disclosed in the applicant's patent application No. 2015-2675. The structure of such a curing agent having an alkoxysilyl group is as follows, for example.

(I-1)

(In the formula (I-1), Z is one of the groups consisting of the following formulas (1A) to (1F).

)

)

[Formula I-2]

[Formula I-3]

; 및

; And

 [Formula I-4]

(In the formula (I-4), p is 1 or 2,

이며,

에서 R은 C1-C10의 직쇄 또는 측쇄상 알킬기이다.)x is

Lt;

, R is a straight or branched alkyl group of C1-C10.)

(In the formulas (I-1) to (I-4)

At least one A among A plurality is represented by the following formula A6 or A7, and when at least one A is A6, the remaining A is represented by the following formula B2 or hydrogen, and when at least one A is A7, the remaining A is Hydrogen, and n is an integer of 1 or more, preferably an integer of 1 to 100.)

[Formula A6]

- (CH ₂ ) _m -SiY ₁ Y ₂ Y ₃

(A7)

-CONH (CH ₂ ) _m -SiY ₁ Y ₂ Y ₃

(In the above formula A6 and A7, Y ₁ to Y ₃ Is a straight or branched-chain alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and the remainder is a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, and m is an integer of 3 to 10.)

(B2)

- (CH ₂ ) ₁ -CH = CH ₂

(Wherein l is an integer of 1 to 8)

The hydrolyzate of the silyl epoxy compound or silyl curing agent is obtained by reacting the silyl epoxy compound and / or the silyl curing agent with water to convert the alkoxysilyl group -SiOR to the -Si-OH group.

The silyl epoxy compound and the silyl curing agent are surface treated on the surface of the filler through the alkoxysilyl group. Furthermore, the silyl epoxy compound and the silyl curing agent increase the surface treatment efficiency (coating efficiency) of the filler by forming a hydrogen bond between the epoxy group and the hydroxy group on the surface of the filler or between the phenol group and the hydroxy group on the surface of the filler.

Specifically, the use of silica treated with a silyl epoxy compound or a silyl curing agent in a composition described later improves the CTE of the epoxy cured product or improves the physical properties of the silica composite in the composition based on the thermoplastic polymer.

The thermal conductivity of the epoxy binder or other thermoplastic polymer can be improved by using alumina surface-treated with a silyl epoxy compound or silyl curing agent in a composition described later.

Zirconia or titania surface-treated with a silyl epoxy compound or a silyl curing agent has improved dispersibility in a composition to be described later, so that transparency in a light curing or thermosetting binder is improved.

2. Manufacturing method of surface-treated filler

The surface-treated filler can be produced by (1) a method of directly using a silyl epoxy compound and / or a silyl curing agent (Manufacturing Method 1: anhydrous condition) and (2) a method of using a silyl epoxy compound and / Method 2: Singlet conditions). In the production process, silyl epoxy compounds, silyl hardeners and fillers are those described in the above surface-treated filler item.

[Manufacturing Method 1] (anhydrous condition)

The filler surface may be coated (physically coated) with a silyl epoxy compound and / or a silyl curing agent by contacting (or reacting) the silyl epoxy compound or silyl curing agent with the filler as described below, or the hydroxyl group of the filler and the silyl epoxy compound and / The alkoxysilyl group of the silyl curing agent may be subjected to a reaction (surface treatment by chemical reaction) so that the filler may be surface-treated.

The case of surface treatment by chemical reaction is shown in Fig. 1 and Fig. FIG. 1 shows the reaction in which the filler is surface-treated with the silyl epoxy compound, and FIG. 2 shows the reaction in which the filler with the silyl curing agent is surface-treated. As shown in Figs. 1 and 2, the alkoxysilyl groups of the silyl epoxy compound and the silyl curing agent react with the OH on the surface of the filler, and the surface of the filler is surface-treated with a silyl epoxy compound or a silyl curing agent.

The surface treatment is carried out by placing the silyl epoxy compound or silyl curing agent in a filler dispersed in a solvent so that the alkoxy silyl group (Si-OR group) of the silyl epoxy compound and / or the silyl curing agent reacts with the hydroxy group on the surface of the filler, Silyl epoxy compound and / or silyl curing agent.

As the usable solvent, any aprotic solvent or protic solvent may be used as long as it can be easily removed after the reaction without any adverse effect on the reaction. Aprotic solvents include, but are not limited to, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), acetone, dimethyl formamide (DMF), dimethyl sulfoxide ), Methylene chloride (MC), and the like can be used. Protic solvents include, but are not limited to, methanol, ethanol, propanol, isopropanol, butanol, and the like. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be suitably used in an appropriate amount and / or concentration to the extent that the reactant is sufficiently dissolved and does not adversely affect the reaction, have. The reaction temperature and the reaction time in the surface treatment reaction vary depending on the reactants, but can be, for example, from 20 to 150 DEG C for 1 to 24 hours. By reacting at the reaction temperature and the reaction time, the desired reaction can be completed.

 [Manufacturing Method 2] (Conditions for hydrolysis)

The surface-treated filler of the present invention is prepared by bonding the -Si-OH group of the hydrolyzate of the silyl epoxy compound and / or the silyl curing agent with the hydroxy group of the filler surface. In other words, the silyl epoxy compound and / or the silyl curing agent is hydrolyzed to form a hydrolyzate, and then the hydrolyzate is used to treat the filler surface.

The silyl epoxy compound and / or silyl curing agent can be hydrolyzed in the presence of water, a solvent and optional reaction catalyst.

The blending amount of water used for hydrolysis is not particularly limited, but 0.01 to 100 equivalents of water may be used per 1 equivalent of the alkoxysilyl group in consideration of the efficiency of the hydrolysis reaction. The amount of water reacts with the alkoxy of the alkoxysilane according to the stoichiometry, so the lower the amount of water to be added, the slower the hydrolysis reaction. For this reason, water can be used in a suitable amount to the extent that the reactants are sufficiently dissolved and do not have an undesirable effect on the reaction, and those skilled in the art can select accordingly.

In the present invention, an acid or base reaction catalyst may be further included to facilitate the hydrolysis reaction of the alkoxysilane, if necessary. Alkoxysilane hydrolysis reaction catalysts include, but are not limited to, for example, at least one inorganic acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, acetic acid and phosphoric acid, alkylamines such as triethylamine, diisopropylethyl there may be mentioned amine, octyl amine, dodecyl amine and the like), pyridine, NH ₄ OH, such as tetraalkyl ammonium hydroxide. These may be used alone or in combination of two or more.

The amount of the alkoxysilane hydrolysis catalyst to be added is not particularly limited, but from the viewpoint of the reaction efficiency, it is preferable to use 0.01 to 1 equivalent of the catalyst per 1 equivalent of the alkoxysilane group from the viewpoint of the reaction efficiency.

Water may be both a reactant for the hydrolysis reaction and a solvent. In addition to water, further usable solvents include any aprotic solvent or protic solvent that can dissolve the reactants well and can be easily removed after the reaction without any adverse effect on the reaction. Can be used. Aprotic solvents include, but are not limited to, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), acetone, dimethyl formamide (DMF), dimethyl sulfoxide ), Methylene chloride (MC), and the like can be used. Protic solvents include, but are not limited to, methanol, ethanol, propanol, isopropanol, butanol, and the like. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited and may be suitably used in an appropriate amount and / or concentration to the extent that the reactant is sufficiently dissolved and does not adversely affect the reaction, have.

The reaction temperature and the reaction time in the hydrolysis reaction vary depending on the reactants, but can be, for example, from 20 ° C to 100 ° C for 30 minutes to 48 hours. By reacting at the reaction temperature and the reaction time, the desired reaction can be completed.

By the hydrolysis reaction, the alkoxysilyl groups (-SiOR) of the above formulas (A1) to (MI) and (I-1) to (I-4) become -Si-OH groups.

When the hydrolyzed silyl epoxy compound and / or silyl curing agent is put into a filler dispersed in a solvent, the Si-OH group of the hydrolyzate of the silyl epoxy compound and / or the silyl curing agent reacts with the hydroxyl group on the surface of the filler and the silyl epoxy Compound and / or a hydrolyzate of a silyl curing agent.

The reaction temperature and the reaction time of the solvent that can be used in the surface treatment reaction and the surface treatment reaction are the same as in the above-mentioned Production Method 1.

3. Composition comprising a surface-treated filler

According to another aspect of the present invention, there is provided a composition (composite) comprising the surface-treated filler of the present invention. The surface-treated fillers according to the present invention exhibit improved properties when forming composites.

The surface-treated filler of the present invention can be applied to the production of a composite comprising a filler and an organic compound and / or a polymer. That is, the surface-treated filler of the present invention can be equally applied to the case where fillers are conventionally used in the technical field, and does not particularly limit the composition (composite) to which the filler is applied. For example, the surface-treated filler of the present invention can be used as a filler in a composite comprising a thermosetting resin, a photo-curable resin and / or a thermoplastic resin containing an epoxy compound commonly used in the art as an organic compound and / or a polymer matrix .

In general, a composition (composite) comprising an organic compound and / or a polymer matrix and a filler includes a thermosetting resin, a photo-curing resin or a thermoplastic resin as an organic compound and / or a polymer matrix. The composition of the organic compound and / or the composition (composite) comprising the polymer matrix and the filler may vary depending on the kind of the polymer matrix, and their composition is generally known in the art.

Examples of the thermosetting resin include, but are not limited to, epoxy resin, vinyl resin, unsaturated polyester resin, polyurethane resin, epoxy ester resin, acrylic resin, polyimide resin, phenol resin, petroleum resin, A resin, a urea resin, a melamine resin, or a modified resin thereof may be used. These may be used alone or in combination of two or more.

Examples of the thermoplastic resin include, but are not limited to, polyethylene, polypropylene, polystyrene, polyvinyl alcohol, polyvinyl chloride, phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyether Sulfone resin, and polysulfone resin. These may be used alone or in combination of two or more. The composition comprising the thermoplastic resin as a matrix may include the surface treatment agent and the thermoplastic resin.

Examples of the photo-curing resin include, but are not limited to, unsaturated ester resins, (meth) acrylate resins, polyester acrylates, polyepoxyacrylates, polyurethane acrylates, polystyrenes, and polyvinyls . These may be used alone or in combination of two or more. Examples of the (meth) acrylate resin include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate, and bisphenol epoxy (meth) (Meth) acrylate, polyurethane (meth) acrylate, polybutadiene modified (meth) acrylate, benzyl methacrylate, Glycidyl Methacrylate, Dicyclopentanyl Methacrylate, and Methyl Methacrylate. The term " a " Further, in the present specification, (meth) acrylate is used to mean acrylate, methacrylate, and mixtures thereof.

Examples of the polyvinyl monomer include known ones such as styrene derivatives such as styrene, chlorostyrene, and? -Methylstyrene; Vinyl esters such as vinyl acetate, vinyl butyrate and vinyl benzoate; N-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether Vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; Acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide and N-butoxymethylacrylamide Meth) acrylamides; Allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; (Meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra Esters of (meth) acrylic acid such as acrylate; Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and pentaerythritol tri (meth) acrylate; Alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; Acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri , Alkylpolyol poly (meth) acrylates such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Polyoxyalkylene glycol poly (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane tri (meth) Meth) acrylates; Poly (meth) acrylates such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate; And isocyanurate type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate. These may be used singly or in combination of two or more kinds in accordance with required characteristics.

The composition comprising the photo-curing resin as a matrix may include a filler, a photo-curable resin and a photoinitiator treated with the surface treatment agent according to the present invention.

The composition of the complex depends on the type of polymer contained in the polymer matrix, and their composition is common in the art.

According to one embodiment of the present invention, there is provided a composition comprising an epoxy resin and the surface-treated filler as a polymer matrix (hereinafter referred to as an 'epoxy composition'). The epoxy compositions used in forming the epoxy composites are generally generally known to include epoxy resins, fillers, curing agents, and optional curing catalysts and the like. As described above, the surface-treated filler of the present invention can be used when a conventional filler is used, and it is preferable that the kind and mixing ratio of the epoxy resin, the curing agent, the curing accelerator (catalyst) It is not.

For example, the surface-treated filler can be used as a filler in a composition comprising an epoxy resin, a curing agent, an optional curing catalyst, and optional additives.

The epoxy resin may be any epoxy resin generally known in the art. Examples of the epoxy resin include, but are not limited to, at least one selected from the group consisting of glycidyl ether-based, glycidyl-based, glycidylamine-based, and glycidyl ester-based epoxy resins. For example, the epoxy resin may be at least one selected from the group consisting of bisphenol, biphenyl, naphthalene, benzene, thiophenol, fluorene, anthracene, isocyanurate, triphenylmethane, At least one selected from the group consisting of 2,2-tetraphenylethane based, tetraphenylmethane based, 4,4'-diaminodiphenylmethane based, aminophenol based, alicyclic based, aliphatic based and novolak based epoxy resins It can be all kinds of things. The epoxy resin may have at least one alkoxysilyl group or no alkoxysilyl group. Further, the epoxy resin having at least one alkoxysilyl group may be, for example, a bisphenol-based, biphenyl-based, naphthalene-based, benzene-based, thiodiphenol-based, fluorene-, anthracene-, isocyanurate-, A group composed of a methane-based, 1,1,2,2-tetraphenylethane based, tetraphenylmethane based, 4,4'-diaminodiphenylmethane based, aminophenol based, alicyclic based, aliphatic based, ≪ / RTI > More specifically, the epoxy resin having at least one alkoxysilyl group can be produced by a method described in, for example, Japanese Patent Application Nos. 2012-0093320, 2013-0027308, 2013-0035546, 2013-0078347, 2013-0111473, 2014-0021884, and / or 2014-0175937. It may also be an epoxy compound of the above formulas AI to MI.

As the epoxy resin, an epoxy resin (epoxy compound) having at least one alkoxysilyl group and an epoxy resin having no alkoxysilyl group may be used alone, or they may be used together.

As the curing agent, any curing agent generally known as a curing agent for an epoxy resin can be used. Although not particularly limited, for example, an amine, a phenol resin, a non-hydroxide and the like can be used.

More specifically, although not limited thereto, as the amine curing agent, aliphatic amines, alicyclic amines, aromatic amines, other amines and modified polyamines can be used, and amine compounds containing two or more primary amine groups can be used. Specific examples of the amine curing agent include 4,4'-dimethylaniline (diaminodiphenyl methane, DAM or DDM), diamino diphenyl sulfone (DDS) at least one aromatic amine selected from the group consisting of m-phenylene diamine, diethylene triamine (DETA), diethylene tetramine, triethylene tetramine (triethylene tetramine) tetramine, TETA), m-xylene diamine (MXDA), methane diamine (MDA), N, N'-diethylenediamine (N, N'-DEDA) At least one aliphatic amine selected from the group consisting of tetraethylenepentaamine (TEPA), and hexamethylenediamine, isophorone diamine (IPDI), N-aminoethylpyrazine (N- Aminoethyl piperazine, AEP), bis (4- One or more alicyclic amines selected from the group consisting of Bis (4-Amino 3-Methylcyclohexyl) methane, Larominc 260), other amines such as dicyandiamide (DICY) , Epoxides, and the like.

Although not limited thereto, examples of the phenol curing agent include phenol novolac resin, trifunctional phenol novolac resin, cresol novolak resin, bisphenol A novolac resin, xylene novolak resin, triphenyl novolac resin, novolac resins, phenol p- xylene resins, phenol-dimethyl-4,4'-biphenylene resin, dicyclopentadiene phenol novolak resin, dicyclopentadiene-phenol novolak (phenol DCPD-), xylene lock (xylok) (p-xylene-modified), biphenyl-based phenol resin, naphthalene-based phenol novolak resin, triazine-based compound, dihydroxynaphthalene, dihydroxybenzene and the like. The phenolic curing agent may have at least one alkoxysilyl group or no alkoxysilyl group.

As the phenol curing agent, a phenol curing agent having at least one alkoxysilyl group and a phenol curing agent having no alkoxysilyl group may be used alone, or they may be used together. The phenolic curing agent having at least one alkoxysilyl group may be, for example, those described in the aforementioned applicant's patent application No. 2015-0002675.

Examples of the non-hydroxide curing agent include, but are not limited to, aliphatic anhydrides such as dodecenyl succinic anhydride (DDSA), poly azelaic poly anhydride, etc., hexahydrophthalic anhydride alicyclic anhydrides such as hexahydrophthalic anhydride (HHPA), methyl tetrahydrophthalic anhydride (MeTHPA), methylnadic anhydride (MNA) and the like, trimellitic anhydride , Tetrabromophthalic anhydride (TBPA), tetrabromophthalic anhydride (TMA), pyromellitic acid dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA) , Chlorendic anhydride, and the like Gengye and the like anhydride.

Generally, the degree of curing of the epoxy composite can be controlled by the degree of reaction between the curing agent and the epoxy group, and the content of the curing agent can be controlled based on the concentration of the epoxy group of the epoxy resin according to the desired degree of curing. For example, when an amine curing agent is used, the equivalent ratio of the epoxy group to the amine group in the equivalent reaction between the amine curing agent and the epoxy group is set to 0.5 to 2.0, and the content of the curing agent is adjusted to be, for example, 0.8 to 1.5 It is preferable to use them in a controlled manner.

Although the amount of the curing agent is described taking the case of the amine curing agent as an example, any of the curing agents that can be used for curing the phenolic curing agent, the non-hydroxide curing agent, and the epoxy resin not separately described in this specification, Based on the total epoxy group concentration, can be suitably used in combination with a stoichiometric amount depending on the chemical reaction formula of the reactive functional group of the epoxy functional group and the curing agent, which is general in this technical field.

As the cationic photo-curing agent (which may be referred to as a photoinitiator), any photo-curing agent generally known in the art may be used, including, but not limited to, aromatic phosphonium salts, aromatic iodonium salts, and aromatic sulfonium salts, . Specific examples thereof include diphenyl iodonium tetrakis (pentafluorophenyl) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluoro Triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4'-bis [diphenylsulfonio] di Bis [di (? - hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate, 4,4'-bis [di (? -hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate, and the like. Although not limited thereto, for example, the photo-curing agent is generally used in an amount of 0.5 to 20 phr (parts per hundred, parts by weight per 100 parts by weight of epoxy resin), preferably 1 phr or more, and preferably 15 phr or less Can be used.

The epoxy composition may further include optional curing accelerators (curing catalysts) to facilitate the curing reaction. As the curing accelerator (curing catalyst), any catalyst known to be generally used in the art for curing the composition can be used, including, but not limited to, imidazole, tertiary amine, Quaternary ammonium-based, organic acid salt-based or phosphorus-based curing accelerators may be used.

More specifically, for example, there may be mentioned dimethylbenzylamine, 2-methylimidazole (2MZ), 2-undecylimidazole, 2-ethyl-4-methylimidazole (2E4M) Imidazole compounds such as 1- (2-cyanoethyl) -2-alkyl imidazole and 2-heptadecylimidazole (2HDI); Tertiary amine compounds such as benzyl dimethyl amine (BDMA), trisdimethylaminomethyl phenol (DMP-30) and triethylenediamine; Quaternary ammonium salts such as tetrabutylammonium bromide; Organic acid salts of diazabicyclo undecene (DBU) or DBU; Triphenylphosphine, a phosphoric acid ester of a phosphorus compound such as, BF ₃ - may be made of Lewis acid such as, such as monoethylamine (BF ₃ -MEA), thus not limited. These curing accelerators may be those which have been latent by their microcapsule coating and complex formation. These may be used alone depending on the curing conditions, or two or more kinds may be used in combination.

The blending amount of the curing catalyst is not particularly limited and may be used in an amount generally used in this technical field. For example, it may be 0.1 to 10 phr (parts per hundred resin, parts by weight per 100 parts by weight of epoxy resin), for example, 0.2 to 5 phr for the epoxy resin. The curing accelerator is preferably used in the above-mentioned contents in terms of the curing reaction promoting effect and the curing reaction rate control. By using the above curing accelerator in the above amount range, it is possible to accelerate curing and improve the throughput of the work.

The composition may contain various additives such as a release agent, a surface treatment agent, a flame retardant, a plasticizer, an antibacterial agent, a leveling agent, a defoaming agent, a colorant, a stabilizer, a coupling agent, , Rubber, thermoplastic resin and the like may also be blended if necessary.

The epoxy composition containing the above-mentioned components can be prepared, for example, as follows.

For example, (A) an epoxy resin (B) a curing agent, (C) a surface-treated filler of the present invention, (D) an optional curing catalyst, and (E) optional additives.

The composition is cured by reaction between the epoxy resin (A) and the curing agent (B), and the epoxy resin (A) and the curing agent (B) are cured by reacting the epoxy group of the epoxy resin with the curing reaction unit of the curing agent at an equivalent ratio. Therefore, in consideration of the degree of curing and the reactivity, in the composition, (B) the curing agent is preferably added such that the ratio of the equivalent of the curing reactor of the epoxy resin / the curing reactor equivalent of the curing agent is 0.5 to 2.0, May be included in the composition. The curing reactor of the curing agent may be a phenolic group in the case of a phenol curing agent, an amine group in the case of an amine curing agent, or an acid anhydride group in the case of an acid anhydride curing agent.

The surface-treated filler (C) may be used in an amount of 5 to 95 parts by weight, for example, 5 to 90 parts by weight, based on 100 parts by weight of the total solid content, based on the total solid content (including filler) For example, from 10 parts by weight to 90 parts by weight, for example, from 30 parts by weight to 95 parts by weight, for example, from 30 parts by weight to 90 parts by weight, for example, from 5 parts by weight to 85 parts by weight, For example, from 5 parts by weight to 70 parts by weight, for example, from 10 parts by weight to 80 parts by weight, for example, from 10 parts by weight to 50 parts by weight. That is, if the filler is 5 parts by weight based on 100 parts by weight of the total solid content, the content of the filler per 100 g of the solid content of the composition containing the filler is 5 g. The term " solids " in the composition refers to all components other than the solvent in the composition. For example, (A) to (E) correspond to a solid content.

That is, the filler (C) may be included in the above-described weight parts based on the total amount of (A), (B), and (C). When the filler (D) and / or the filler (E) is contained as an optional component, the filler (C) may contain the total amount of the components (A), (B), (C), (D) May be included as the above-mentioned weight parts by reference.

The filler may be compounded in an appropriate amount in the art depending on the physical properties required in the epoxy composition, the appropriate viscosity, and the application, and may be formulated in the above range in terms of the manifestation of the physical properties required in the composition.

For example, the composition may be prepared by mixing the components (A) to (E) in a solvent such that the solids content thereof is 1 wt% to 95 wt%, removing the solvent, and curing. The solids content in the solvent may be suitably adjusted by those skilled in the art depending on the final article required.

Any composition provided in any of the above embodiments of the present invention may be used for electronic materials. Although the electronic material is not limited to this, for example, a substrate for a semiconductor, a film, a prepreg, or a laminate in which a metal layer is disposed on a base layer made of the composition of the present invention, a sealing material (packaging material) ), As well as electronic parts such as printed wiring boards. It can also be applied to various applications such as adhesives, paints, coatings and composites. According to another embodiment of the present invention, there is provided an electronic material comprising or consisting of a composition comprising the surface-treated filler of the present invention. Furthermore, a semiconductor device comprising, consisting essentially of, or consisting of the electronic material is also provided. Specifically, the semiconductor device includes a semiconductor device including a printed wiring board (for example, mounting a semiconductor element), and / or a semiconductor package including a composition including the surface-treated filler of the present invention, And may be a semiconductor device including a material. Also provided are cured products, adhesives, paints, coatings or composites comprising, consisting essentially of, or consisting of any composition provided in any of the embodiments of the present invention. The composition comprising the surface-treated filler of the present invention may be, for example, an epoxy composition, a composition comprising a photocurable resin as a matrix, or a composition comprising a thermoplastic resin as a matrix.

end. Surface treatment of fillers

Example 1. Preparation of silica-coated particles using bisphenol A-based silyl epoxy compound as a surface treatment agent (hydrolysis conditions)
The surface-treated filler prepared by the method for manufacturing the surface-treated filler of claim 6

0.60 g of bisphenol-based silyl epoxy (the following structural formula 1), 1.20 g of H ₂ O, 0.18 g of 0.1M HNO ₃ and 25 g of isopropyl alcohol were added to a two-necked flask at room temperature, and the reaction temperature was raised to 60 ° C., The silane was hydrolyzed. Thereafter, 150 g of isopropyl alcohol and 60 g of silica were further added into the inside of the flask, and the mixture was heated and stirred for 16 hours. After the completion of the reaction, the solvent was removed and dried in an oven at 120 ° C for 2 hours to obtain silica particles coated with silyl epoxy.

[Structural formula 1]

Example 2: Preparation of silica-coated particles using a bisphenol A-based silyl epoxy compound as a surface treatment agent (anhydrous condition)

60 g of silica and 150 g of toluene were added to a two-necked flask at room temperature, and the mixture was stirred at room temperature for 2 hours. Thereafter, 0.60 g of bisphenol-based silyl epoxy (formula 1) was further added into the inside of the flask, and the reaction temperature was elevated to 100 ° C., and the mixture was heated and stirred for 16 hours. After the completion of the reaction, the solvent was removed and dried in an oven at 120 ° C for 2 hours to obtain silica particles coated with silyl epoxy.

Example 3 Preparation of silica-coated particles using biphenyl-based silyl epoxy compound as surface treatment agent (anhydrous condition)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural formula 2]

Example 4 Preparation of Silica Coated Particle Using Naphthalene Silyl Epoxy Compound as Surface Treatment Agent (Anhydrous Conditions)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 3]

Example 5: Preparation of silica-coated particles using a cadmium silyl epoxy compound as a surface treatment agent (anhydrous condition)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 4]

Example 6 Preparation of silica-coated particles using a phenyl-based silyl epoxy compound as a surface treatment agent (anhydrous condition)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 5]

Example 7 Preparation of silica-coated particles using a tetraphenylethane-based silyl epoxy compound as a surface treatment agent (anhydrous condition)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 6]

Example 8 Preparation of silica-coated particles using a bisnaphthalene-based silyl epoxy compound as a surface treatment agent (anhydrous condition)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 7]

Example 9 Preparation of silica-coated particles using a triphenylmethane-based silyl epoxy compound as a surface treating agent (anhydrous condition)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural formula 8]

Example 10 Preparation of Silica-Coated Particle Using Aminophenol Silyl Epoxy Compound as Surface Treatment Agent (Anhydrous Conditions)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 9]

Example 11 Preparation of silica-coated particles using phenol novolac silyl epoxy compound as a surface treatment agent (anhydrous condition)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 10]

(q is an integer of 1 to 100)

Example 12. Preparation of silica-coated particles using cresol novolac silyl epoxy compound as a surface treatment agent (anhydrous condition)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 11]

(n is an integer of 1 to 100)

Example 13. Preparation of silica-coated particles using bisphenol novolac silyl epoxy compound as a surface treatment agent (anhydrous condition)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 12]

(n is an integer of 1 to 100)

Example 14. Preparation of silica-coated particles using naphthalene novolac silyl epoxy compound as a surface treatment agent (anhydrous conditions)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 13]

(n is an integer of 1 to 100)

Example 15 Preparation of silica-coated particles using phenol novolac-based silyl hardener as surface treatment agent (hydrolysis conditions)

0.71 g of silylated novolak curing agent (following structural formula 14), 1.42 g of H ₂ O, 0.21 g of 0.1 M HNO ₃ and 25 g of isopropyl alcohol were added to a two-necked flask at room temperature, and the reaction temperature was raised to 60 ° C. and stirred for 2 hours To hydrolyze the alkoxysilane. Thereafter, 150 g of isopropyl alcohol and 71 g of silica were added to the inside of the flask, and the mixture was heated and stirred for 16 hours. After completion of the reaction, the solvent was removed and the mixture was dried in an oven at 120 ° C for 2 hours to obtain a composition coated with a novolac curing agent.

[Structural Formula 14]

Example 16 Preparation of silica-coated particles using phenol novolac-based silyl hardener as surface treatment agent (anhydrous condition)

60 g of silica and 150 g of toluene were added to a two-necked flask at room temperature, and the mixture was stirred at room temperature for 2 hours. Thereafter, 0.60 g of a phenol novolac-based silyl curing agent (the structural formula 14) was further added to the inside of the flask, and the reaction temperature was elevated to 100 ° C and the mixture was heated and stirred for 16 hours. After the completion of the reaction, the solvent was removed and dried in an oven at 120 ° C for 2 hours to obtain silica particles coated with a silyl curing agent.

Example 17. Preparation of silica-coated particles using cresol novolak silyl hardener as surface treatment agent (anhydrous condition)

The composition of the surface treating agent used was the same as in Example 16 except that the kind of the surface treating agent was different.

[Structural Formula 15]

(n is an integer of 1 to 100)

Example 18 Preparation of silica-coated particles using a bisphenol-novolac-based silyl curing agent as a surface treatment agent (anhydrous condition)

The composition of the surface treating agent used was the same as in Example 16 except that the kind of the surface treating agent was different.

[Structural Formula 16]

(n is an integer of 1 to 100)

Example 19 Preparation of Silica-Coated Particles Using a Naphthalene Novolac Silicone Hardener as Surface Treatment Agent (Anhydrous Conditions)

The composition of the surface treating agent used was the same as in Example 16 except that the kind of the surface treating agent was different.

[Structural Formula 17]

(n is an integer of 1 to 100)

Example 20: Preparation of TiO ₂ -containing particles using phenol novolac silyl hardener as a surface treatment agent (anhydrous condition)

60 g of TiO ₂ and 150 g of toluene were added to a two-necked flask at room temperature, and the mixture was stirred at room temperature for 2 hours. Thereafter, 0.60 g of a phenol novolac-based silyl curing agent (the structural formula 14) was further added to the inside of the flask, and the reaction temperature was elevated to 100 ° C and the mixture was heated and stirred for 16 hours. After the completion of the reaction, the solvent was removed, and the coating was dried in an oven at 120 ° C for 2 hours to obtain TiO ₂ particles coated with a silyl curing agent.

Example 21 Preparation of ZrO ₂ Coated Particles Using Bisphenol A Silyl Epoxy Compound as Surface Treatment Agent (Hydrolysis Conditions)

0.60 g of a bisphenol-based silyl epoxy compound (structural formula 1), 1.20 g of H ₂ O, 0.18 g of 0.1M HNO ₃ and 25 g of isopropyl alcohol were added to a two-necked flask at room temperature, and the reaction temperature was raised to 60 ° C and stirred for 2 hours The alkoxysilane was hydrolyzed. Thereafter, 150 g of isopropyl alcohol and 60 g of zirconia were further added into the inside of the flask, and the mixture was heated and stirred for 16 hours. After the completion of the reaction, the solvent was removed and dried in an oven at 120 ° C. for 2 hours to obtain ZrO ₂ particles coated with silyl epoxy.

Example 22 Preparation of Al ₂ O ₃ Coated Particles Using Phenol Novolac Silyl Hardener as Surface Treatment Agent (Anhydrous Conditions)

60 g of Al ₂ O ₃ and 150 g of toluene were added to a two-necked flask at room temperature, and the mixture was stirred at room temperature for 2 hours. Thereafter, 0.60 g of a phenol novolac-based silyl curing agent (the structural formula 14) was further added to the inside of the flask, and the reaction temperature was elevated to 100 ° C and the mixture was heated and stirred for 16 hours. After the completion of the reaction, the solvent was removed and dried in an oven at 120 ° C for 2 hours to obtain Al ₂ O ₃ particles coated with a silyl curing agent.

Example 23 Preparation of E-glass Glass Fiber Using Phenol Novolac Silyl Hardener as Surface Treatment Agent (Anhydrous Conditions)

In an 80-degree reactor, 1 g of a phenol novolac-based silyl curing agent (structural formula 14), 100 g of toluene and E-glass fiber glass were impregnated for 2 hours. Thereafter, the surface-treated glass fibers were washed with MEK to remove the unreacted phenol novolac silyl curing agent and dried in a 100 ° C oven for 2 hours to obtain an E-glass glass fiber coated with a silyl curing agent.

Example 24. Preparation of T-glass glass fiber using phenol novolac silyl hardener as surface treatment agent (anhydrous condition)

The synthesis was carried out in the same manner as in Example 23 except that the type of filler was changed from E-glass to T-glass.

Example 25. Preparation of boehmite using a phenol novolac silyl hardener as a surface treating agent (anhydrous condition)

The synthesis was carried out in the same manner as in Example 23 except that the type of filler was changed from E-glass to boehmite.

COMPARATIVE EXAMPLE 1 Preparation of Silica-Coated Particle Using (3-Glycidyloxypropyl) trimethoxysilane (GPTMS) as a Surface Treatment Agent (anhydrous condition)

The surface treatment agent was synthesized in the same manner as in Example 2 except that the surface treatment agent was different, and the structure of the surface treatment agent used was as follows.

[Structural Formula 18]

I. Property evaluation

1. Assessment of flooding on water

The untreated silica sinks directly into the water when placed in water. However, the silica surface-treated with the silyl epoxy compound, silyl curing agent and / or hydrolyzate thereof according to the present invention floats without submerging in water due to organic functional groups on the surface. Therefore, by examining the floating property against water, it was confirmed whether or not the silica surface was surface-treated with an organic functional group.

(1) surface-treated silica, (2) surface-treated silica of Example 2, and (3) surface-treated commercial silica product were added to water as shown in FIG. 3, And the precipitation was visually confirmed. The results are shown in the photographs of Figs. 3 (a) to 3 (c).

The untreated silica was submerged in water as it was in water as shown in Fig. 3 (a). The silica surface-treated in Example 2 did not sink into water as shown in Fig. 3 (b). As shown in the photograph of FIG. 3 (c), a commercially available surface treatment product (silica for EMC, surface functional group: alkylsilane) was observed to be partially submerged in water and partially floated on water immediately after it was immersed in water.

From this, it can be seen that the silica is effectively treated with the silyl epoxy compound, the silyl curing agent and / or the hydrolyzate thereof according to the present invention.

(2) Water of silica surface-treated with (3-glycidyloxypropyl) trimethoxysilane, which is a conventional silane coupling agent (Comparative Example 1), and silica treated with the silyl epoxy compound of Example 2 of the present invention Were compared.

As shown in FIG. 4, when the surface was treated under the same conditions, the surface-treated silica using the conventional silane coupling agent was mostly submerged in water as shown in the photograph of FIG. 4 (a). However, the silica of Example 2 using the surface treatment agent of the present invention was kept floating on water as shown in the photograph of Fig. 4 (b). From this, it can be seen that the surface treatment agent according to the present invention is superior to commercial products.

2. Evaluation of dispersibility in organic solvents

One of the purposes of surface treating the filler with a surface treatment agent is to ensure that the filler is well dispersed in the binder and / or organic dispersion solvent containing the filler. Therefore, the dispersibility of the unfaced filler and the filler surface-treated by the present invention in the solvent was evaluated.

When the ZrO2 particles and the TiO2 particles that have not been subjected to the surface treatment are dispersed in the organic solvent, they are not dispersed in the organic solvent as shown in Fig. 5 (a) and Fig. 6 (a), respectively. However, the surface-treated ZrO2 particles of Example 21 according to the present invention and the TiO2 particles of Example 20 were observed to be stably dispersed in an organic solvent as shown in the photographs of Figs. 5 (b) and 6 (b) . 5 (a) and 5 (b) were dispersed in methyl ethyl ketone (MEK), and in FIGS. 6 (a) and 6 (b), toluene was dispersed.

2. Manufacture of cured products and evaluation of heat resistance

(1) Production of epoxy filler composite (cured product)

The epoxy compound, the surface-treated silica and the wax were dissolved in methyl ethyl ketone so as to have a solid content of 70% by weight in the compositions shown in [Table 1-1] and [Table 1-2]. The mixture was mixed for 20 minutes, then the curing agent was added, and the mixture was further mixed for 10 minutes. The curing catalyst was added and further mixed for 10 minutes so as to become a homogeneous solution. The mixture was placed in a convection oven heated to 80 DEG C to remove the solvent and then cured at 120 DEG C for 2 hours, 180 DEG C for 2 hours, and> 200 DEG C for 2 hours in a hot press preheated to 120 DEG C to obtain an epoxy filler Particle) composite (5 mm x 5 mm x 3 mm).

(2) Production of epoxy glass fiber composite (cured product)

The resulting mixture was dissolved in an epoxy compound, a silica slurry (solid content 70 wt%, methyl ethyl ketone solvent, silica average size 1 mu m) and methyl ethyl ketone so as to have a solid content of 60 wt% in the composition shown in the following Table 2, Mix for 1 hour at speed. The curing agent was added to the mixed solution and further mixed for 30 minutes. Thereafter, the curing catalyst was added thereto and further mixed for 10 minutes to obtain a uniform epoxy mixture. Glass fiber (coated E-glass or T-glass) was immersed in the resulting mixture to prepare a glass fiber composite containing an epoxy compound. The composite was then placed in a convection oven heated to 80 DEG C to remove the solvent and then cured at 120 DEG C for 2 hours and at> 200 DEG C for 2 hours in a hot press preheated to 120 DEG C to obtain a glass fiber composite film 4 Mm x 6 mm x 0.1 mm). In preparing the composite film, the resin content of the composite film was controlled according to the pressure of the press and the viscosity of the resin, and the content of the resin in the composite film was as shown in Table 2 below. The resin content (resin content (R / C)) refers to the fraction of the total solids, excluding fibers.

(3) Evaluation of heat resistance characteristics

The dimensional changes according to the temperature of the cured product obtained in the physical properties examples of [Table 1-1], [Table 1-2] and [Table 2] were evaluated using a thermo-mechanical analyzer, Table 1-1], [Table 1-2], and [Table 2]. The epoxy filler composite specimen was 5 × 5 × 3 (㎣) and the glass fiber composite film specimen was 4 × 16 × 0.1 (㎣).

[Table 1-1] Heat resistance characteristics of the filler composite

[Table 1-2] Filler complex

(Units of wax and silica content in grams (gram, g) in Tables 1-1 and 1-2 above)

[Table 2] Glass fiber composite

(In Table 2, the unit of silica content is gram (gram, g)

3. Evaluation of thermal conductivity

(1) Production of epoxy alumina composite (cured product)

The epoxy compound and the filler (alumina (Al ₂ O ₃ ) or boehmite) were dissolved in methyl ethyl ketone so as to have a solid content of 60 wt% in the composition shown in Table 3 below. After the mixture was mixed for 30 minutes, the curing agent was added and the mixture was further mixed for 20 minutes. The curing catalyst was added and further mixed for 10 minutes so as to become a homogeneous solution. The mixture was placed in a convection oven heated to 80 DEG C to remove the solvent and then cured at 120 DEG C for 2 hours, 180 DEG C for 2 hours, and> 200 DEG C for 2 hours in a hot press preheated to 120 DEG C to obtain an epoxy filler Particle) composite (12 mm x 12 mm x 2 mm).

(2) Evaluation of thermal diffusivity

The thermal diffusivity of the cured product obtained in the physical properties example shown in Table 3 was evaluated using a laser flash analyzer (NETZSH) and is shown in Table 3 below. Specimens of heat - resisting epoxy filler composites were prepared with dimensions of 12 × 12 × 2 (.).

[Table 3] Heat-resistant epoxy composites

The physical properties Examples 22 and 23 including the surface-treated filler according to the present invention show excellent thermal diffusivity compared to Comparative Examples 4 and 5 including the surface-treated filler. Property Example 22 is compared with Comparative Example 4 and Property Example 23 is compared with Comparative Example 5. From this, it can be seen that alumina and boehmite are fillers generally incorporated into the composite for improved thermal conductivity. As can be seen from Table 3 above, by using the surface-treated filler according to the present invention, It can be seen that it is further improved.

Likewise, by using the surface-treated filler as in the present invention, the physical properties inherently required in the filler are further improved. This is considered to be due to the fact that the physical properties of the composite usually depend on the characteristics of the interface between the matrix resin, the filler and the matrix resin and the filler, and the physical properties and / or the interface properties of the filler are improved by the surface treatment of the filler.

Ltd.: The compounds used in Tables 1, 2 and 3 are as follows.

(1) BPA-based epoxy compound (EEW = 319)

(2) Novolac epoxy compound (EEW = 380)

(n is an integer of 1 to 100)

(3) YX4000H epoxy compound (EEW = 193)

(4) HF-1M: phenol novolac type curing agent (Meiwa Plastic Industries, HEW = 107)

(n is an integer of 1 to 100)

(5) MEH-7851SS Hardener (Meiwa Plastic Industries, HEW = 203)

(n is an integer of 1 to 100)

(6) 2PZ: 2-phenylimidazole curing accelerator (curing catalyst) (Aldrich)

Claims (18)

(i) reacting an epoxy compound having at least one alkoxysilyl group and at least two epoxy groups in a solvent or a curing agent having at least one alkoxysilyl group and the filler at 20 DEG C to 150 DEG C for 1 hour to 24 hours; or
(ii) water and an epoxy compound having at least one alkoxysilyl group and at least two epoxy groups in a solvent or a curing agent having at least one alkoxysilyl group is hydrolyzed at 20 DEG C to 100 DEG C for 30 minutes to 48 hours, Of silanol and an epoxy compound having at least two epoxy groups or at least one silanol, and then, in a solvent, an epoxy compound having at least one silanol and at least two epoxy groups, or Which is obtained by reacting a hydrolyzate of a curing agent having at least one silanol and a filler at 20 DEG C to 150 DEG C for 1 hour to 24 hours,
A filler surface-treated with at least one surface-treating agent selected from the group consisting of an epoxy compound having at least one alkoxysilyl group and at least two epoxy groups, a curing agent having at least one alkoxysilyl group, and a hydrolyzate thereof.
The method according to claim 1,
The epoxy compound having at least one alkoxysilyl group and at least two epoxy groups is selected from the group consisting of the following formulas AI to MI.

(In the general formula AI to EI, substituent a and b is selected from the group consisting of the following formulas E1 to E4, wherein the at least one of a to c and f to a formula A1, the rest is hydrogen, - (CH _{2) Z- 2} CH = CH ₂ wherein z is an integer from 3 to 10, and E2,
In Formula AI above, Y is -CH ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -S- or -SO ₂ -
Formula FI to substituent g to j for at least two of the pieces of II is to a formula E2, and at least one of the following formulas A1 to A4, the rest is _{hydrogen, - (CH 2) Z-} 2 CH = CH 2 ( wherein z is 3 to 10), or a compound represented by the following formula (A5)
In the formula (HI), r is hydrogen, a hydroxy group, an alkyl group (C1-C10)
The formula (II) may be substituted with a linear or branched C1-C10 alkyl group at the meta position of oxygen,
At least two of the general formula JI to a number of the MI K dog is the formula E2, and at least one of the following formulas A1 to A4, the rest is _{hydrogen, - (CH 2) Z-} 2 CH = CH 2 ( wherein z is 3 ≪ / RTI > to 10) and < RTI ID = 0.0 >
In the above formula (JI), Z is

(Where K is as defined above)
In the formula MI, x is

P is an integer of 1 or 2,
In the formulas JI to MI, n is an integer of 1 to 100.
[Chemical Formula (E1) to (E4)

(A1)
- (CH ₂ ) _z -SiY ₁ Y ₂ Y ₃

(A2)
-CONH (CH ₂ ) _z -SiY ₁ Y ₂ Y ₃
Wherein at least one of Y ₁ to Y ₃ is -OR (R is an alkyl group having 1 to 10 carbon atoms) which is an alkoxy group having 1 to 10 carbon atoms and the remainder is an alkyl group having 1 to 10 carbon atoms, the alkyl group and the alkoxy The group is straight-chain or branched, and z is an integer of 3 to 10.

(A3)

Wherein X1 is _{OR 4, OH, NR 4 R} 5, SR 4, or _{OCONH (CH 2) 3 SiY 1} Y 2 Y 3 and, X1 'is H or _{CONH (CH 2) 3 SiY 1} Y 2 Y 3. At least one of Y ₁ to Y ₃ is an alkoxy group having 1 to 10 carbon atoms, and the remainder is a C1 to C10 alkyl group. R ₄ or R ₅ is an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms, and may contain N, O, P, or S heteroatoms.

(A4)

Wherein X2 is _{OR 4, OH, NR 4 R} 5, SR 4, or _{O (CH 2) l CH 2} CH 2 is _{SiY 1 Y 2 Y 3, X2} ' is H or _{(CH 2) l CH 2 CH} 2 SiY ₁ Y ₂ Y ₃ wherein l is an integer of 1 to 8, at least one of Y ₁ to Y ₃ is an alkoxy group having 1 to 10 carbon atoms, and the remainder is an alkyl group having 1 to 10 carbon atoms. R ₄ or R ₅ is an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having from 1 to 20 carbon atoms, and may contain N, O, P, or S heteroatoms.

(A5)

Wherein X is OR ₄ , OH, NR ₄ R ₅ or SR ₄ . R ₄ or R ₅ is an alkyl group, an alkenyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms and may contain a hetero atom of N, O, P or S.
The method according to claim 1,
Wherein the curing agent having an alkoxysilyl group is selected from the group consisting of the following formulas (I-1) to (I-4).

(I-1)

(In the formula (I-1), Z is one of the groups consisting of the following formulas (1A) to (1F).

)

[Formula I-2]

[Formula I-3]

; And

[Formula I-4]

(In the formula (I-4), p is 1 or 2,
x is

Lt;

, R is a straight or branched alkyl group of C1-C10.)
(In the formulas (I-1) to (I-4)
At least one A of a plurality of A is represented by the following formula A6 or A7, and when at least one A is A6, the remaining A is represented by the following formula B2 or hydrogen, and when at least one A is A7, the remaining A is hydrogen And n is an integer of 1 to 100.)

[Formula A6]
- (CH ₂ ) _m -SiY ₁ Y ₂ Y ₃

(A7)
-CONH (CH ₂ ) _m -SiY ₁ Y ₂ Y ₃
At least one of Y ₁ to Y ₃ is a linear or branched alkoxy group having 1 to 10 carbon atoms and the remainder is a linear or branched alkyl group having 1 to 10 carbon atoms and m is 3 to 10 It is an integer.)

(B2)
- (CH ₂ ) ₁ -CH = CH ₂
(Wherein l is an integer of 1 to 8)
The method according to claim 1,
The filler may be selected from the group consisting of glass fiber, silica, alumina, boehmite, titania, zirconia, silicon nitride, aluminum nitride, clay, mica, kaolin, talc, wollastonite, montmorillonite, asbestos, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, Aluminum, copper, magnesium, lead, nickel, zinc, manganese, stainless steel, calcium carbonate, calcium carbonate, gold, silver, platinum, Wherein the surface-treated filler is selected from the group consisting of steel, titanium, cerium, zinc, tin, indium, sulfur, cobalt, molybdenum, strontium, chromium and barium.
Reacting an epoxy compound having at least one alkoxysilyl group and at least two epoxy groups of claim 2 in a solvent or a curing agent having at least one alkoxysilyl group of claim 3 with a filler at 20 DEG C to 150 DEG C for 1 hour to 24 hours And an epoxy compound having at least two epoxy groups or a curing agent having at least one alkoxysilyl group.
Water and a solvent, the epoxy compound having at least one alkoxysilyl group and at least two epoxy groups of claim 2 or the curing agent having at least one alkoxysilyl group of claim 3 is hydrolyzed at 20 ° C to 100 ° C for 30 minutes to 48 hours Forming a hydrolyzate of an epoxy compound having at least one silanol and at least two epoxy groups or a curing agent having at least one silanol; And
Reacting, in a solvent, the hydrolyzate of the epoxy compound having at least one silanol and at least two epoxy groups or the curing agent having at least one silanol and the filler at 20 ° C to 150 ° C for 1 to 24 hours , An epoxy compound having at least one silanol and at least two epoxy groups, or a curing agent having at least one silanol.
6. The method of claim 5,
The filler may be selected from the group consisting of glass fiber, silica, alumina, boehmite, titania, zirconia, silicon nitride, aluminum nitride, clay, mica, kaolin, talc, wollastonite, montmorillonite, asbestos, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, Gold, silver, platinum, iron, aluminum, copper, magnesium, lead, nickel, zinc, manganese, stainless steel, calcium carbonate, barium carbonate, barium carbonate, Wherein the surface of the filler is selected from the group consisting of titanium, cerium, zinc, tin, indium, sulfur, cobalt, molybdenum, strontium, chromium and barium.
A composition comprising the surface treated filler of any one of claims 1 to 3.
An electro-electronic material comprising the composition of claim 8.
10. The method of claim 9,
The electrical and / or electronic material may be a substrate, a film, a laminate, a prepreg, a printed wiring board, or a packaging material.
An adhesive comprising the composition of claim 8.
A paint comprising the composition of claim 8.
A coating comprising the composition of claim 8.
A semiconductor material comprising the composition of claim 8.









The method according to claim 6,
Wherein the step of forming the hydrolyzate is carried out in the presence of a reaction catalyst.
The method according to claim 6,
The filler may be selected from the group consisting of glass fiber, silica, alumina, boehmite, titania, zirconia, silicon nitride, aluminum nitride, clay, mica, kaolin, talc, wollastonite, montmorillonite, asbestos, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, Gold, silver, platinum, iron, aluminum, copper, magnesium, lead, nickel, zinc, manganese, stainless steel, calcium carbonate, barium carbonate, barium carbonate, Wherein the surface of the filler is selected from the group consisting of titanium, cerium, zinc, tin, indium, sulfur, cobalt, molybdenum, strontium, chromium and barium.
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