KR102643390B1 - Epoxy compound having alkoxysilyl group, preparing method thereof, composition, and use thereof - Google Patents

Abstract

An epoxy compound having an alkoxysilyl group with controlled molecular weight and core structure, its preparation method, composition, and use are provided. The cured product containing an epoxy compound having an alkoxysilyl group with a controlled molecular structure of the present invention exhibits improved thermal expansion characteristics (low CTE) and also improves the resin evaporation problem of cycloaliphatic/aliphatic epoxy. Furthermore, by the method according to the present invention, an epoxy compound having an alkoxysilyl group with controlled molecular structure, that is, core structure and molecular weight, can be easily and economically produced through a simple manufacturing process.

Description

Epoxy compound having an alkoxysilyl group, manufacturing method, composition and use thereof {EPOXY COMPOUND HAVING ALKOXYSILYL GROUP, PREPARING METHOD THEREOF, COMPOSITION, AND USE THEREOF}

The present invention relates to a novel epoxy compound having an alkoxysilyl group, a method for producing the same, a composition containing the same, and its use. More specifically, it relates to an epoxy compound having an alkoxysilyl group with controlled molecular weight and core structure, its production method, composition, and use. Additionally, it relates to a novel epoxy compound obtained as an intermediate in the manufacturing method.

Epoxy materials have excellent mechanical properties, electrical insulation, heat resistance, water resistance, and adhesiveness, and are widely used in paints, printed wiring boards, IC encapsulation materials, electrical and electronic components, adhesives, etc. In addition, with the development of semiconductor packaging technology, the requirements for low thermal expansion characteristics for epoxy resins for packaging are increasing, and the filling ratio of fillers is increasing to satisfy these required properties.

Meanwhile, among epoxy resins, cycloaliphatic and/or aliphatic epoxy resins (hereinafter also referred to as 'cycloaliphatic/aliphatic epoxy' or 'non-aromatic epoxy') have lower viscosity than aromatic epoxy resins. Therefore, due to the low viscosity of cycloaliphatic/aliphatic epoxy, the use of cycloaliphatic/aliphatic epoxy has an advantage over the use of aromatic epoxy resin in controlling the increase in viscosity of the composite under high filler conditions, that is, ensuring fairness. However, cycloaliphatic/aliphatic epoxy does not have a sufficiently low CTE (Coefficient of Thermal Expansion) value, and also has a problem of resin evaporation during the molding process due to its low boiling point.

Meanwhile, the applicant of the present invention conducted research on epoxy modified with alkoxysilyl groups, and as a result developed an epoxy material with excellent thermal expansion characteristics. In addition, as a result of conducting research on epoxy modification, a method for producing an epoxy compound with an improved alkoxysilyl group was applied for in patent applications 2018-52731 and 2017-147526. However, the method of the prior art application is difficult to apply to cycloaliphatic and aliphatic epoxies, which are mostly bifunctional epoxies. Because the manufacturing method of the patent application uses the epoxide group of the starting epoxy resin in the alkoxysilylation reaction step, it is a method applicable only to multifunctional epoxy or noblock epoxy having at least 3 or more epoxide groups. am. In addition, patent applications 2018-52731 and 2017-147526 use a mono-functional aromatic alcohol as a ring-opening agent to prevent molecular weight increase during the reforming reaction. Therefore, it is generally unsuitable for improving the resin evaporation problem during the process of non-aromatic epoxy with a low boiling point.

The present invention was proposed to improve the problems of the conventional cycloaliphatic/aliphatic epoxy as described above, and improves the thermal expansion characteristics of the cycloaliphatic/aliphatic epoxy. The present invention also improves the problem of evaporation of cycloaliphatic/aliphatic epoxy resin during the process of cycloaliphatic/aliphatic epoxy. That is, according to the present invention, an epoxy compound having a novel alkoxysilyl group with controlled core structure and molecular weight is provided, thereby improving the problems of conventional cycloaliphatic/aliphatic epoxy.

The present invention also provides a method for producing an epoxy compound having a novel alkoxysilyl group with controlled core structure and molecular weight.

In addition, the present invention provides a novel epoxy compound with controlled core structure and molecular weight that is prepared as an intermediate product in the method for producing an epoxy compound having a novel alkoxysilyl group.

Furthermore, the present invention provides an epoxy composition containing an epoxy compound having an alkoxysilyl group with controlled core structure and molecular weight, a cured product thereof, and an article containing the same.

According to the first aspect, an epoxy compound having an alkoxysilyl group containing at least one structure selected from the group consisting of the following formulas A1 to A3 is provided.

[Formula A1]

[Formula A2]

[Formula A3]

(In the above formulas A1 to A3, the unit (QF) is each independently selected from the group consisting of the following formulas (1C) to (4C);

(In Formula (2C), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in Formula (4C), Z is each independently selected from the group consisting of H and a straight or branched C1-C5 alkyl group, and in formulas (1C) to (4C), * is a bond.);

The functional group R is Each independently represents the following formula (R) or hydrogen,

(Here, at least one of 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 alkyl portion and alkyl group of the alkoxy group are straight or branched.)

In formulas A1 and A3, m is an integer from 0 to 20;

In Formula A2, each X is independently H or a straight or branched C1-C5 alkyl group;

In Formula A3, the unit (P) is each independently selected from the group consisting of the following formulas (CF) to (HF).

(If the unit (P) is located at at least one terminal of the formula A3, one of the M in the formula (CF) to (HF) is a bond to the ** position of the linking group (L1) in the formula A3, The remaining M is a glycidyl group of the formula (E) below; If the unit (P) is not located at the terminal of the formula A3, two M of the M of the formulas (CF) to (HF) are adjacent to each of the linking groups below It is a bond to the ** position of (L1), and when the remaining M is present, the remaining M is a glycidyl group of the formula (E) below.

(R in L1 is the formula (R) above or hydrogen.)

In the above formula (CF), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S- or -SO ₂ -,

In the above formula (GF), n is an integer from 2 to 20.))

According to the second aspect, in the presence of a phosphorus-based catalyst, at least one epoxy monomer selected from the group consisting of the following formulas (AS) to (HS) and at least one type of transfer agent selected from the group consisting of the following formulas (1) to (4) A first step of obtaining an intermediate product by mixing and reacting functional aromatic alcohols; and

A second step of mixing and reacting the intermediate product with an isocyanate alkoxysilane of the formula C below to obtain an epoxy compound having at least an alkoxysilyl group selected from the group consisting of the formulas A1 to A3,

In the first step, a method for producing an epoxy compound having an alkoxysilyl group is provided, in which the mixing is performed with 2.0 to 10 moles of epoxy monomer per 1 mole of difunctional aromatic alcohol.

(In the above formula (BS), X is each independently H or a straight or branched C1 to C5 alkyl group,

In the formula (CS), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in the formula (GS), n is It is an integer from 2 to 20.)

(In the formula (2), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in formula (4), Z is each independently selected from the group consisting of H and a straight or branched C1 to C5 alkyl group.)

[Formula A1]

[Formula A2]

[Formula A3]

(In the above formulas A1 to A3, the unit (QF) is each independently selected from the group consisting of the following formulas (1C) to (4C);

(In Formula (2C), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in Formula (4C), Z is each independently selected from the group consisting of H and a straight or branched C1-C5 alkyl group, and in formulas (1C) to (4C), * is a bond.);

Each functional group R is independently of the following formula (R) or hydrogen,

(Here, at least one of 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 alkyl portion and alkyl group of the alkoxy group are straight or branched.)

In formulas A1 and A3, m is an integer from 0 to 20;

In formula A2, each X is independently H or a straight or branched C1 to C5 alkyl group;

In Formula A3, the unit (P) is each independently selected from the group consisting of the following formulas (CF) to (HF).

(If the unit (P) is located at at least one terminal of the formula A3, one of the M in the formula (CF) to (HF) is a bond to the ** position of the linking group (L1) in the formula A3, The remaining M is a glycidyl group of the formula (E) below; If the unit (P) is not located at the terminal of the formula A3, two M of the M of the formulas (CF) to (HF) are adjacent to each of the linking groups below It is a bond to the ** position of (L1), and when the remaining M is present, the remaining M is a glycidyl group of the formula (E) below.

(R in L1 is the formula (R) above or hydrogen.)

In the formula (CF), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in the formula (GF), n is It is an integer from 2 to 20.))

[Formula C]

OCN(CH ₂ ) ₃ SiR _a R _b R _c

(In the formula C, at least one of R _a to R _c is a C1-C5 alkoxy group, and the others are C1-C10 alkyl groups, and the alkyl portion and alkyl group of the alkoxy group are straight or branched.)

According to the third aspect, the production method of the second aspect is provided, wherein the reaction temperature in the first step is 80°C to 200°C.

According to the fourth aspect, the production method of the second aspect is provided, wherein the reaction time of the first step is 30 minutes to 3 hours.

According to the fifth aspect, the production method of the second aspect is provided, wherein the phosphorus-based catalyst is at least one selected from the group consisting of triphenylphosphine, diphenylpropylphosphine, and tricyclohexylphosphine.

According to the sixth aspect, a production method of the second aspect is provided, wherein in the first step, the phosphorus-based catalyst is used in an amount of 0.1 to 2 parts by weight per 100 parts by weight of the difunctional aromatic alcohol.

According to the seventh aspect, an epoxy composition containing at least one of the epoxy compounds having an alkoxysilyl group represented by the formulas A1 to A3 of the first aspect is provided.

According to the eighth aspect, a cured product of the epoxy composition of the seventh aspect is provided.

According to the ninth aspect, an article containing the hardened product of the eighth aspect is provided.

According to the tenth aspect, the article is at least one kind selected from the group consisting of semiconductor packaging materials, semiconductor components, semiconductor devices, electrical materials, electrical components, electrical devices, electronic materials, electronic components, and electronic devices. Goods are provided.

According to the eleventh aspect, an epoxy compound containing at least one structure selected from the group consisting of the following formulas B1 to B3 is provided.

[Formula B1]

[Formula B2]

[Formula B3]

(In the above formulas B1 to B3, the unit (QC) is each independently selected from the group consisting of the following formulas (1C) to (4C);

(In Formula (2C), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in Formula (4C), Z is each independently selected from the group consisting of H and a straight or branched C1-C5 alkyl group, and in formulas (1C) to (4C) * is a bond;

In Formula B3, the unit (PC) is each independently selected from the group consisting of the following formulas (CC) to (HC);

(When the unit (PC) is located at at least one terminal of the formula B3, one of the L in the formulas (CC) to (HC) is a bond to the ** position of the linking group (L2) in the formula B3, The remaining L is a glycidyl group of the formula (E) below; If the unit (PC) is not located at the terminal of the formula B3, two L among the Ls of the formulas (CC) to (HC) are adjacent to each of the linking groups below It is a bond to the ** position of (L2), and when the remaining L is present, the remaining L is a glycidyl group of the formula (E) below.

In the formula (CC), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in the formula (GC), n is It is an integer from 2 to 20.)

In the above formulas B1 and B3, m is an integer from 0 to 20,

In formula B2, each X is independently H or a linear or branched C1 to C5 alkyl group.)

The epoxy compound having a novel alkoxysilyl group of the present invention (hereinafter also referred to as ‘silylated epoxy,’ or ‘modified epoxy’) exhibits improved thermal expansion characteristics. That is, cured products (including composites) using the silylated epoxy having a controlled core structure and molecular weight distribution of the present invention exhibit improved thermal expansion characteristics (i.e., low CTE). In addition, the silylated epoxy of the present invention and the epoxy that is an intermediate obtained in the first step of the production method (hereinafter also referred to as 'non-silylated epoxy') improves the evaporation phenomenon of the resin during the process. That is, evaporation of the epoxy resin is reduced. Furthermore, the molecular weight and core structure of the silylated epoxy and non-silylated epoxy of the present invention are controlled by the reaction of the cycloaliphatic/aliphatic epoxy monomer, which is the starting material, and the difunctional aromatic alcohol in the silylated epoxy production method according to the present invention. achieved. That is, by the method of the present invention, the core structure and molecular weight of the repeating units constituting the silylated epoxy can be easily adjusted. Moreover, since strong bases and/or inorganic base catalysts that affect the alkoxysilylation reaction are not used, the core structure (repeating unit of epoxy resin) and molecular weight are controlled after the formation of intermediate products (intermediates) that undergo purification (e.g., Since the alkoxysilylation step can be performed continuously in-situ, without workup, the manufacturing process is simplified. Additionally, the formation of by-products is suppressed. In this way, by the method of the present invention, silylated epoxy can be efficiently manufactured through a simple process, and therefore can be mass-produced economically. The epoxy composition comprising the silylated epoxy exhibiting improved thermal expansion properties of the present invention is suitable for use in epoxy compound applications requiring such physical properties.

Figure 1a is a GPC graph showing the molecular weight of the modified epoxy and epoxy monomer starting materials of Synthesis Examples 1 to 3.
Figure 1b is a GPC graph showing the molecular weight of the modified epoxy and epoxy monomer starting materials of Synthesis Example 4.
Figure 1c is a GPC graph showing the molecular weight of the epoxy and epoxy monomer starting materials prepared in Synthesis Examples 11 to 13.
Figure 2a is a TGA graph showing the weight change of the modified epoxy and epoxy monomer starting materials of Synthesis Example 1.
Figure 2b is a TGA graph showing the weight change of the modified epoxy and epoxy monomer starting materials of Synthesis Example 4.
Figure 2c is a TGA graph showing the weight change of the epoxy and epoxy monomer starting materials prepared in Synthesis Examples 11 to 13.
Figure 3 is a graph showing the dimensional change of the composites of Example 1 and Comparative Example 1 according to temperature.

The present invention provides an epoxy compound having an alkoxysilyl group whose molecular structure (i.e., core structure and molecular weight) is controlled by insertion of an aromatic core structure, which exhibits improved thermal expansion characteristics, a method for producing the same, a composition, a cured product, an article, and the like. This relates to non-silylated epoxy compounds prepared as intermediates in the manufacturing method, and each of them is described below.

go. Epoxy compound having an alkoxysilyl group

According to one embodiment of the present invention, an epoxy compound having an alkoxysilyl group represented by the following formulas A1 to A3 is provided.

[Formula A1]

(In Formula A1, m is an integer from 0 to 20, preferably from 0 to 15.)

[Formula A2]

(In Formula A2, each X is independently H or a straight or branched C1 to C5 alkyl group.)

[Formula A3]

(In Formula A3, m is an integer from 0 to 20, preferably from 0 to 15.)

In the above formulas A1 to A3, the unit (QF) is each independently selected from the group consisting of the following formulas (1C) to (4C);

(In Formula (2C), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in Formula (4C), Z is each independently selected from the group consisting of H and a straight or branched C1-C5 alkyl group, and in formulas (1C) to (4C), * is a bond.);

Each functional group R is independently of the following formula (R) or hydrogen,

(Here, at least one of R _a to R _c is a C1-C5 alkoxy group, preferably a C1-C3 alkoxy group, and the remainder is an alkyl group with 1 to 10 carbon atoms, and the alkyl portion and alkyl group of the alkoxy group may be straight or branched. there is.).

In Formula A3, the unit (P) is each independently selected from the group consisting of the following formulas (CF) to (HF).

When the unit (P) is located at at least one terminal of the formula A3, one of the M in the formula (CF) to (HF) is a bond to the ** position of the linking group (L1) in the formula A3, and the remaining M is a glycidyl group of the formula (E) below; When the unit (P) is not located at the end of the formula A3, two M of the M in the formulas (CF) to (HF) are bonds to the ** positions of each adjacent linking group (L1) below, and the remaining M When present, the remaining M is a glycidyl group of the formula (E) below.

In the formula (CF), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in the formula (GF), n is It is an integer of 2 to 20, preferably an integer of 2 to 10.

As shown in the above formulas A1 to A3, the silylated epoxy compound according to the present invention not only has an alternating core structure with an aromatic core structure inserted, but also has a molecular weight compared to the cycloaliphatic/aliphatic epoxy monomer used as a starting material to be described later. It increases. Accordingly, the silylated epoxy compound of the present invention is prevented from evaporating in a high temperature process.

Meanwhile, in the present application, 'epoxy compound,' and 'epoxy monomer' are both epoxy resins having two or more epoxide groups. Additionally, in this application, 'epoxy compound' and 'epoxy resin' are sometimes simply referred to as 'epoxy', and 'epoxy compound' and 'epoxy resin' are sometimes used interchangeably.

me. Method for producing cycloaliphatic and aliphatic epoxy compounds having an alkoxysilyl group

According to another embodiment of the present invention, a method for producing silylated alicyclic and aliphatic epoxy compounds whose core structure and molecular weight is controlled by insertion reaction of aromatic alcohol is provided.

According to one embodiment of the present invention, the silylated epoxy compound is prepared by reacting a mixture of cycloaliphatic/aliphatic epoxy monomers as starting materials with a difunctional aromatic alcohol to produce an epoxy compound (repeating unit of epoxy resin) and molecular weight adjusted. Obtaining an intermediate product (first step, molecular structure adjustment step); and a step of reacting the intermediate product of the first step with an isocyanate alkoxysilane (second step, alkoxysilylation step). The mechanism of the method according to the present invention is shown in Scheme 1 below. Molecular structure control includes control of core structure and molecular weight. The method for producing silylated epoxy according to the method according to the present invention is also called 'reforming reaction'.

[Scheme 1] Modification reaction of cycloaliphatic epoxy resin through insertion reaction of bisphenol A

First, as shown in Scheme 1, in the first step, the starting materials, a cycloaliphatic/aliphatic epoxy monomer (hereinafter also referred to as 'epoxy monomer') and a difunctional aromatic alcohol (hereinafter also referred to as 'aromatic alcohol') ) is reacted in the presence of a phosphorus-based catalyst and an optional solvent to obtain an intermediate product, which is an epoxy compound with controlled core structure (repeating unit) and molecular weight.

The cycloaliphatic/aliphatic epoxy monomer as the starting material may be any one selected from the group consisting of the following formulas (AS) to (HS).

In the above formula (BS), each X is independently H or a straight or branched C1 to C5 alkyl group,

In the formula (CS), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in the formula (GS), n is It is an integer of 2 to 20, preferably 2 to 10.

The difunctional aromatic alcohol is selected from the group consisting of benzene, bisphenol, naphthalene, or a difunctional aromatic alcohol having two hydroxy groups in a biphenyl core. The difunctional aromatic alcohol is not limited thereto, but its specific structure may be any one selected from the group consisting of the following formulas (1) to (4):

In formula (2), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in formula (4), Z is H and a straight or branched C1-C5 alkyl group.

As can be seen from the structures of the starting materials, the cycloaliphatic/aliphatic epoxy monomers of formulas (AS) to (HS) and the difunctional aromatic alcohols of formulas (1) to (4), cycloaliphatic/aliphatic epoxy monomers and difunctional aromatic alcohols The core structures of alcohols are not identical. Therefore, by selecting and reacting cycloaliphatic/aliphatic epoxy monomers of any of the formulas (AS) to (HS) and difunctional aromatic alcohols of any of the formulas (1) to (4) as starting materials, an aromatic core structure is inserted. Silylated epoxies with controlled core structures can be prepared. That is, according to one embodiment of the present invention, the core structure of the silylated epoxy is controlled. Additionally, the molecular weight increases due to the reaction between the epoxy monomer and the difunctional aromatic alcohol.

Specifically, the cycloaliphatic/aliphatic epoxy monomer is reacted in an excess of 2.0 to 10 moles with respect to 1 mole of the difunctional aromatic alcohol. By using an excessive amount of epoxy monomer in this way, the increase in molecular weight of the silylated epoxy is controlled. If the molar ratio of the epoxy monomer is less than 2.0, an epoxy compound having a hydroxy group at the terminal may be generated, which is undesirable in that molecular weight control becomes difficult, and if the molar ratio of the epoxy monomer exceeds 10, the final product, silylated This is undesirable in that the relative concentration of alkoxysilyl groups (molar concentration ratio of alkoxysilyl groups to epoxy groups) in the final reactant containing epoxy is too low.

Meanwhile, through the first step reaction, trimers, pentamers, and/or oligomers with a higher molecular weight are simultaneously produced, and they exist in a mixed state (i.e., a mixture of substances with different molecular weights). In general, when conducting an oligomerization reaction, it is theoretically impossible to make a resin with only one type of molecular weight of a specific single resin, and it is generally known in the art that it is obtained in the form of a mixture of substances with different molecular weights. , and this is not mentioned in detail.

On the other hand, the residual epoxy monomer after the first step reaction not only does not participate in (1) the second step (alkoxysilylation step) reaction, but also (2) when mixing the silylated epoxy, the epoxy monomer of the epoxy composition [epoxy of the epoxy compound] Since it can be used to adjust the ratio (molar ratio) of [side group]:[alkoxysilyl group], there is no need to separate or remove it during the reaction.

The first step reaction is performed in the presence of a mild phosphorus-based catalyst. As the phosphorus-based catalyst, at least one type selected from the group consisting of triphenylphosphine (TPP), diphenylpropylphosphine, and tricyclohexylphosphine may be used.

The phosphorus-based catalyst is used in an amount of 0.1 to 2 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the difunctional aromatic alcohol as a starting material (i.e., 0.1 wt% to 2 wt%, preferably 0.5 parts by weight, based on the weight of the aromatic alcohol). wt to 2 wt%). If the amount of the phosphorus-based catalyst used is less than 0.1 parts by weight, the reaction rate is significantly slowed, resulting in a low first stage reaction, and even if it exceeds 2 parts by weight, no further improvement in the reaction rate is observed, so it is not desirable to use it in excess of 2 parts by weight. .

The reaction temperature and reaction time of the first step reaction vary depending on the type of reactant, but the first step is, for example, performed at a temperature of 80°C to 200°C, more preferably 80°C to 150°C. You can. If the temperature is lowered below 80°C, the reaction rate may slow down significantly. Additionally, if it exceeds 200°C, it has a negative effect on molecular weight control, so it is preferable to carry out the reaction at this temperature.

The reaction time of the first step varies depending on the structure of the reactant, degree of reaction, solvent, and amount of catalyst, but may be 30 minutes to 3 hours. By reacting for 30 minutes to 3 hours, an intermediate product, which is an epoxy compound with a controlled core structure (repeating unit of epoxy resin) and molecular weight, is obtained through the reaction of a cycloaliphatic/aliphatic epoxy monomer and a difunctional aromatic alcohol. If the reaction time is less than 30 minutes, the first step reaction does not proceed sufficiently, and if the reaction time is 3 hours, the first step reaction proceeds sufficiently, so it is not desirable to exceed 3 hours. As such, in the method according to the present invention, an intermediate product with a controlled core structure and molecular weight is formed through the reaction of a cycloaliphatic/aliphatic epoxy monomer and a difunctional aromatic alcohol within a short time of less than 3 hours.

In the first step reaction, the solvent may be used arbitrarily as needed. For example, in the first step reaction, if the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without a separate solvent, the solvent may not be used. That is, if the viscosity of the reactant is low enough that mixing and stirring of the reactant can proceed smoothly without a solvent, a separate solvent is not required, and this can be easily determined by a person skilled in the art. When using a solvent, any organic solvent (aprotic solvent) can be used as long as the reactant is dissolved and can be easily removed after the reaction without having any adverse effect on the reaction. The solvent may be used, but is not particularly limited, for example, acetonitrile, MEK (methyl ethyl ketone), DMF (dimethyl formamide), DMSO (dimethyl sulfoxide), toluene, xylene, etc. If necessary, these solvents can be used alone or in combination of two or more. The amount of solvent used is not particularly limited, and may be used in an appropriate amount as long as the reactant is sufficiently dissolved and does not have an undesirable effect on the reaction, and a person skilled in the art may consider this and select it appropriately. Additionally, the first step reaction may be performed without using a solvent (neat reaction).

In the first step reaction, an intermediate product with a controlled core structure (repeating unit of epoxy resin) and molecular weight is obtained through the reaction of the cycloaliphatic/aliphatic epoxy monomer of the starting material with a difunctional aromatic alcohol. For example, an intermediate product with a core structure (repeating unit of epoxy resin) and molecular weight controlled in which the core structure of the starting material, the cycloaliphatic/aliphatic epoxy monomer core structure, and the core structure of the difunctional aromatic alcohol alternate, is obtained. Although the new epoxy compound obtained as an intermediate product does not have an alkoxysilyl group, it can be used as an epoxy resin in this technical field. That is, the non-silylated epoxy obtained as an intermediate product has a controlled core structure (repeating unit of epoxy resin) and molecular weight, and shows improved evaporation of the epoxy resin. That is, evaporation of the epoxy resin is reduced.

Although not limited thereto, for example, the intermediate product obtained in the first step reaction may be represented by the following formulas B1 to B3.

[Formula B1]

(In Formula B1, m is an integer from 0 to 20, preferably from 0 to 15.)

[Formula B2]

(In Formula B2, each X is independently H or a linear or branched C1 to C5 alkyl group.)

[Formula B3]

(In Formula B3, m is an integer from 0 to 20, preferably from 0 to 15.)

In the above formulas B1 to B3, the unit (QC) is each independently selected from the group consisting of the following formulas (1C) to (4C);

In formula (2C), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in formula (4C), Z is each independently selected from the group consisting of H and a straight or branched C1-C5 alkyl group, and in formulas (1C) to (4C) * is a bond;

In Formula B3, the unit (PC) is each independently selected from the group consisting of the following formulas (CC) to (HC);

(When the unit (PC) is located at at least one terminal of the formula B3, one of the L in the formulas (CC) to (HC) is a bond to the ** position of the linking group (L2) in the formula B3, The remaining L is a glycidyl group of the formula (E) below; If the unit (PC) is not located at the terminal of the formula B3, two L among the Ls of the formulas (CC) to (HC) are adjacent to each of the linking groups below It is a bond to the ** position of (L2), and when the remaining L is present, the remaining L is a glycidyl group of the formula (E) below.

In the formula (CC), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in the formula (GC), n is It is an integer of 2 to 20, preferably 2 to 10.

In addition, the phosphorus-based catalyst used in the first step is oxidized and loses reactivity when all the aromatic alcohol is consumed. Therefore, unlike the strong base catalyst of the prior art, it does not affect the second-stage reaction, and therefore does not require a separate purification process (e.g., workup) after the first-stage reaction. In addition, there is no need to remove by-products, residual catalyst, and/or epoxy monomer after the reaction, so the second step reaction can be performed in-situ.

Afterwards, an epoxy compound having an alkoxysilyl functional group is obtained through a second step of reacting the intermediate product with the core structure and molecular weight controlled with an isocyanate alkoxysilane.

In the second step, as shown in Scheme 1, an alkoxysilyl group is introduced into the secondary alcohol functional group (i.e., hydroxy group) of the intermediate product by reaction between the intermediate product obtained in the first step and the isocyanate alkoxysilane, thereby forming the core structure and A silylated epoxy with controlled molecular weight is produced.

The isocyanate alkoxysilane used in the second step may be represented by the following formula C.

[Formula C]

OCN(CH ₂ ) ₃ SiR _a R _b R _c

In the above formula, at least one of R _a to R _c is a C1-C5 alkoxy group, preferably a C1-C3 alkoxy group, and the remainder is a C1-C10 alkyl group, and the alkyl portion and alkyl group of the alkoxy group may be linear or branched. You can.

Meanwhile, the alkoxysilylation reaction of the hydroxy group is performed without a catalyst or in the presence of an optional base catalyst to increase the reaction rate. Examples of base catalysts that can be used include, but are not limited to, those selected from the group consisting of triethylamine, diisopropylethylamine, and pyridine. Base catalysts such as NaOH, KOH, K ₂ CO ₃ , Na ₂ CO ₃ , KHCO ₃ , and NaHCO ₃ are used as catalysts because of the problem of side reactions with isocyanate alkoxysilanes and the need for a workup purification process after completion of the reaction. Application of is not desirable.

These base catalysts can be used alone or in combination of two or more. In terms of reaction efficiency, the base catalyst is preferably used in an amount of 0.1 to 1 equivalent, preferably 0.5 to 1 equivalent, per 1 equivalent of the hydroxyl group of the intermediate product of the first step. If the amount of base catalyst is less than 0.1 equivalent, the catalytic effect for the reaction may be insufficient. Adding it in an amount of 1 equivalent produces the intended catalytic effect, and any excess amount is unnecessary.

In the above reaction, the intermediate product and the isocyanate alkoxysilane react in an equivalent ratio according to the stoichiometry between the hydroxy group and the isocyanate group of the intermediate product, so the hydroxy group in the intermediate product is reacted at an appropriate ratio according to the degree to which alkoxysilylation is desired to obtain the degree of alkoxysilylation. can be adjusted. For example, 0.1 to 1.0 equivalents of isocyanate alkoxysilane may be reacted with respect to 1 equivalent of the hydroxyl group of the intermediate product. If the amount of isocyanate alkoxysilane is less than 0.1 equivalent, there are insufficient alkoxysilyl groups in the final product. At 1.0 equivalents, alkoxysilylation is sufficient, and if an amount exceeding this amount is used, there is a high possibility that urea by-products will be generated.

The reaction temperature and reaction time of the second step reaction vary depending on the reactants, but the hydroxyl group of the intermediate product has a slow reaction rate (reactivity) at low temperatures, so the reaction temperature is preferably 60°C or higher. Additionally, if the reaction temperature exceeds 150°C, it is undesirable because the thermal stability of the reactants may decrease during the reaction time. Therefore, the second step reaction is performed at a temperature of 60°C to 150°C.

The second step reaction is performed for 6 to 72 hours, preferably 12 to 24 hours. If it is less than 6 hours, alkoxysilylation of the hydroxy group is insufficient, and if it exceeds 72 hours, no further reaction will proceed, so it is not preferable. Therefore, by reacting for 6 to 72 hours, the hydroxy group is alkoxysilylated without unreaction of the hydroxy group or continuation of unnecessary reaction.

In the reaction of the alkoxysilylation step, a solvent may be used arbitrarily as needed. For example, in the above reaction, if the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without a separate solvent, a solvent may not be used. That is, if the viscosity of the reactant is low enough that mixing and stirring of the reactant can proceed smoothly without a solvent, a separate solvent is not required, and this can be easily determined by a person skilled in the art. When using a solvent, any aprotic solvent may be used as long as it dissolves the reactants and can be easily removed after the reaction without having any adverse effect on the reaction. Although not limited thereto, for example, toluene, xylene, acetonitrile, tetrahydrofuran (THF), methylethylketone (MEK), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), methylene chloride (MC), etc. may be used.

These solvents can be used alone or in combination of two or more. The amount of solvent used is not particularly limited, and can be used in an appropriate amount as long as the reactant is sufficiently dissolved and does not have an undesirable effect on the reaction. Those skilled in the art can take this into consideration and select the solvent appropriately.

The silylated cycloaliphatic/aliphatic epoxy produced by the method of the present invention is not limited thereto, but is as follows. It can be represented by formulas A1 to A3 described for silylated epoxies.

all. Epoxy composition

According to another embodiment of the present invention, an epoxy composition containing a silylated epoxy according to an embodiment of the present invention is provided. The silylated epoxy, which is a component of the epoxy composition of the present invention, includes the above items A. All descriptions for epoxy compounds having an alkoxysilyl group apply.

Additionally, the epoxy composition is an epoxy compound and may include at least one type of silylated epoxy. In addition, the epoxy composition may further include any epoxy compound generally known in the art (hereinafter referred to as 'common epoxy compound'). Common epoxy compounds include, but are not limited to, bisphenol, biphenyl, naphthalene, benzene, thiodiphenol, fluorene, anthracene, isocyanurate, triphenylmethane, 1,1,2,2 -tetraphenylethane, tetraphenylmethane, 4,4'-diaminodiphenylmethane, aminophenol, glycidyl ether type with cycloaliphatic, aliphatic, or novolac unit, glycidylamine type, or glycidyl It may be an ester-type epoxy resin. In addition, the epoxy composition of the present invention may further include a non-silylated epoxy obtained as an intermediate in the production method of the present invention described above. In a composition containing an epoxy compound having an alkoxysilyl group prepared by the method of the present invention, the molar concentration ratio of the epoxy group and the alkoxysilyl group is preferably [epoxy group]:[alkoxysilyl group]=1:0.1 to 1.0 ( When it includes common epoxy compounds and/or non-silylated epoxies that are intermediates, the epoxy groups of these epoxies are included.) If the molar concentration ratio of the alkoxysilyl group is less than 0.1, it is undesirable because the effect of improving physical properties due to the alkoxysilyl group is minimal, and if the ratio of the alkoxysilyl group is greater than 1.0, it is preferable because the curing speed decreases due to the introduction of the alkoxysilyl group. don't do it Furthermore, the epoxy composition according to one embodiment of the present invention may include an inorganic filler. As the inorganic filler, any inorganic filler commonly used in this technical field can be used.

Although not limited thereto, for example, any inorganic filler known to be used to reinforce the physical properties of conventional epoxy resins may be used as the inorganic filler. Specifically, but not limited thereto, inorganic fillers include, for example, silica (including, for example, fused silica and crystalline silica), metal oxides such as zirconia, titania, alumina, silicon nitride, aluminum nitride, silicon carbide, and At least one selected from the group consisting of silsesquioxane may be used. The inorganic filler may be used alone or in a mixture of two or more types.

In terms of dispersibility, fairness, and reliability, the inorganic filler has a particle size (cut-size) of 0.1㎛~100㎛, preferably 1㎛~70㎛, more preferably 5㎛~50㎛. It is preferable to use spherical powder. At this time, if the particle size of the inorganic filler is less than 0.1㎛, it is not only expensive, but there may be problems with dispersion, and if it exceeds 100㎛, there are problems such as pattern damage or cracks in the controller die and/or semiconductor chip due to the inorganic filler. It can be.

In terms of physical properties and/or processability, the inorganic filler is 30 wt% to 95 wt%, preferably 45 to 95 wt%, and more preferably 60 wt% to 93 wt%, based on the total weight of the solid content of the epoxy composition according to the present invention. may be included. If it is less than 30wt%, the properties of the inorganic filler may not be fully expressed, and if it exceeds 95wt%, process efficiency may be reduced.

The epoxy composition of the present invention may also include a curing agent. Any curing agent generally known as a curing agent for epoxy resin may be used as the curing agent, and is not particularly limited, but for example, phenol resin, acid anhydride, amine, etc. may be used. These are thermal curing agents that are activated by heat, and the epoxy composition according to the present invention is thermally cured.

More specifically, but not limited thereto, examples of phenolic resin curing agents include phenol novolak resin, trifunctional phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, xylene novolak resin, and triphenyl novolak. Resin, biphenyl-based novolak resin, dicyclopentadiene novolak resin, naphthalene-based novolak resin, phenol p-xylene resin, phenol 4,4'-dimethylbiphenylene resin, phenol dicyclopentadiene novolak resin. , dicyclopentadiene-phenol novolak (DCPD-phenol), xylok (p-xylene modification), triazine compounds, dihydroxy naphthalene, dihydroxy benzene, etc.

Although not limited thereto, examples of acid anhydride curing agents include aliphatic acid anhydrides such as dodecenyl succinic anhydride (DDSA), poly azelaic poly anhydride, and hexahydrophthalic anhydride. Alicyclic acid anhydrides such as (hexahydrophthalic anhydride, HHPA), methyl tetrahydrophthalic anhydride (MeTHPA), methylnadic anhydride (MNA), and trimellitic anhydride. , TMA), pyromellitic acid dianhydride (PMDA), and aromatic acid anhydride such as benzophenonetetracarboxylic dianhydride (BTDA).

Although not limited thereto, specific examples of amine curing agents include 4,4'-Dimethylaniline (diamino diphenyl methane, DAM or DDM), diamino diphenyl sulfone (diamino diphenyl methane), and diphenyl sulfone (DDS) and dicyandiamide (DICY).

In general, depending on the purpose, the content of the hardener can be adjusted based on the concentration of the epoxide group of the epoxy compound (specifically, all epoxy compounds contained in the epoxy composition). For example, the content of the hardener can be appropriately selected and used according to the amount generally used in this technical field, and is not particularly limited. For example, considering the curing reaction in which the epoxide group of the epoxy compound and the reactive functional group of the curing agent (i.e., the functional group that reacts with the epoxide group) react in an equivalent ratio, the ratio of the equivalent weight of the epoxide group of the epoxy compound to the reactive functional group of the curing agent is The content of the hardener can be adjusted to 1:0.5~2.0, preferably 1:0.8~1.5. If the curing agent content is less than 0.5, the curing reaction is insufficient, and even if it exceeds 2.0, there is no additional improvement in the curing reaction and it is inefficient.

The epoxy composition according to another embodiment of the present invention may optionally further include a curing catalyst to promote the curing reaction.

As a curing catalyst, any curing catalyst known to be generally used in the curing of epoxy compositions in this technical field may be used, but is not limited thereto, for example, imidazole-based, tertiary amine, organic acid salt, Curing catalysts such as phosphorus compounds and boron compounds can be used.

More specifically, for example, dimethyl benzyl amine, 2-methylimidazole (2MZ), 2-undecylimidazole, 2-ethyl-4-methylimidazole (2E4M), 2-phenylimidazole , 1-(2-cyanoethyl)-2-alkyl group imidazole, 2-heptadecylimidazole (heptadecylimidazole, 2HDI), etc.; Tertiary amine compounds such as benzyl dimethyl amine (BDMA), trisdimethylaminomethylphenol (DMP-30), and triethylenediamine; diazabicycloundecene (DBU) or organic acid salts of DBU; Phosphorus-based compounds such as triphenylphosphine and phosphoric acid esters, boron compounds such as BF ₃ -monoethyl amine (BF ₃ -MEA), etc. are included, but are not limited thereto. These curing catalysts can also be used as latent catalysts through microcapsule coating and complex salt formation. These may be used individually depending on the curing conditions, or two or more types may be used together.

The content of the curing catalyst is not particularly limited, and can be used by mixing it in an amount generally used in this technical field. For example, 0.1 to 10 phr (parts per hundred resin, parts by weight per 100 parts by weight of epoxy resin) relative to the epoxy resin (i.e., epoxy resin mixture including all epoxy contained in the epoxy composition), for example , may be 0.2 to 5 phr. The curing catalyst is preferably used in the above amount in terms of the effect of promoting the curing reaction and controlling the curing reaction rate. By using the curing catalyst in the above range, curing is effectively promoted and work throughput can be improved.

The epoxy composition according to one embodiment of the present invention includes wax, flame retardant, plasticizer, antibacterial agent, leveling agent, and antifoaming agent commonly mixed in epoxy compositions in this technical field to control the physical properties of the composition to the extent that the physical properties of the composition are not damaged. Other additives such as colorants, stabilizers, coupling agents, viscosity modifiers, diluents, carbon fibers, and molding agents can also be mixed as needed. Additionally, the epoxy composition according to one embodiment of the present invention may be dispersed using a solvent as needed so that the mixture can be easily dispersed before curing. The types, combinations, contents, etc. of these other additives and/or solvents are generally known to those skilled in the art and are not described in detail in this specification.

As noted above, the epoxy composition of the present invention includes a silylated epoxy compound, an optional conventional epoxy compound and/or a non-silylated epoxy, a curing agent, and an inorganic filler, with the balance being an optional curing catalyst and other ingredients as needed. There may be other additives that can be blended accordingly. For convenience, the weight is the sum of the solid content of the remaining portion (hereinafter referred to as 'remaining weight'). The epoxy composition of the present invention contains a silylated epoxy compound, an optional conventional epoxy compound and/or a non-silylated epoxy, a curing agent, an inorganic filler, and the remaining components (solid content, by weight) of 100 weight. %, the inorganic filler is 30 wt% to 95 wt%, preferably 45 to 95 wt%, preferably 60 wt% to 93 wt%, based on the total weight of the solid content of the epoxy composition, and the remainder is The content includes silylated epoxy compounds, curing agents, and the remainder including curing catalysts and other additives. In the above balance content, the epoxy resin and the modified phenol-based curing agent may be mixed so that the equivalent ratio of [epoxide group of the epoxy compound]:[curing agent] is 1:0.5 to 2.0, preferably 1:0.8 to 1.5. . As described above, the optional curing catalyst may be 0.1 to 10 phr (parts per hundred resin), for example, 0.2 to 5 phr, based on the total epoxy resin.

As used herein, 'the total weight of the solid content of the epoxy composition' means, when a solvent is used in the epoxy composition, the total weight of the solid content of the epoxy composition that is cured after the used solvent is removed.

According to another embodiment of the present invention, a cured product of the epoxy composition according to one embodiment of the present invention is provided, and the cured product includes a composite cured product. The method of forming the cured product and the curing conditions are not particularly limited, and can be appropriately selected and applied by those skilled in the art based on information generally known to those skilled in the art regarding curing of epoxy compositions, such as heat curing. It is not described separately in this specification.

Therefore, the epoxy composition and/or cured product according to the present invention is suitable for application to semiconductor, electrical, electronic materials, parts, devices, etc. Specifically, the epoxy composition of the present invention can be used in applications requiring high thermal expansion characteristics, such as sealants for electrical, electronic, and/or semiconductor components, underfill, IC substrates, adhesives, adhesive films, and copper clad laminate (CCL). . Any epoxy composition with high thermal expansion properties of any embodiment of the invention may be used in applications requiring improved flexural properties (e.g., EMC) to result in improved processability and/or reliability of the part. Additionally, the cured product according to one embodiment of the present invention may be in the form of a tablet, granule, or film.

According to another embodiment of the present invention, an article containing an epoxy composition and/or a cured product according to any of the above-described embodiments of the present invention is provided. The article may be a semiconductor material, semiconductor component, semiconductor device, electrical material, electronic material, electrical component, electronic component, electrical device, electronic device, etc. Additionally, the epoxy composition of the present invention can be applied to various applications such as adhesives, paints, and composite materials.

That is, when the epoxy composition of the present invention is applied to articles such as semiconductor components, electrical components, and electronic components, it exhibits excellent thermal expansion characteristics, thereby improving the reliability of the product. Additionally, the evaporation phenomenon of the epoxy resin during the process is improved.

[Example]

Hereinafter, the present invention will be described in detail through examples. The following examples illustrate the invention and are not intended to limit it.

A. Synthesis example

(1) Synthesis Example 1:

91.66 g of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and 10 g of 1,3-dihydroxy benzene were added to the flask and stirred at 130°C for 10 minutes under nitrogen. After the reactant was sufficiently melted, the reaction was started by adding 0.2 g of triphenylphosphine (TPP) to the reactant. The reaction was carried out at 130°C for 2 hours.

After completion of the reaction, the temperature of the flask was lowered to 80°C, 150 g of methyl ethyl ketone (MEK), 23.5 g of diisopropylethylamine (DIPEA), and 44.9 g of 3-triethoxysilylpropyl isocyanate were added and allowed to react for an additional 12 hours. . After completion of the final reaction, it was cooled to room temperature and the solvent and diisopropylethylamine were removed using an evaporator to obtain the final target product. [Epoxide group]:[Alkoxysilyl functional group] = 1.0: 0.28 (molar ratio), EEW=245 g/Eq.

(2) Synthesis Examples 2 to 13

The reaction was performed in the same manner as Synthesis Example 1, except that the reactants and contents described in Tables 1 and 2 below were used to obtain the final target product.

B. Physical property evaluation:

1. Molecular weight distribution analysis:

The change in molecular weight of the epoxy product after the modification reaction was measured using gel permeation chromatography (GPC, Waters, 1525 HPLC pump, 2415 RIDetector).

Figures 1a to 1c show the molecular weights of the silylated epoxy products prepared in Synthesis Examples 1 to 4 and Synthesis Examples 11 to 13. For comparison, the molecular weights of the epoxy starting materials used in Synthesis Examples 1 to 4 and Synthesis Examples 11 to 13 were measured and shown. From Figures 1a to 1c, it was confirmed that the molecular weight of the product, the silylated multifunctional epoxy resin (the epoxy resin obtained as an intermediate in Synthesis Example 11, in which only one step was performed) increased due to the insertion reaction of the difunctional aromatic alcohol. Additionally, from Figure 1a, a similar molecular weight increase effect was confirmed for all difunctional aromatic alcohols used. Moreover, from FIGS. 1A and 1C, compared to the reaction of the first step of Synthesis Example 1, if the amount of epoxy used relative to the aromatic alcohol is reduced as in the first step of Synthesis Examples 11 to 13, the resulting epoxy resin ( In Synthesis Example 11, it can be seen that the molecular weight of the intermediate epoxy resin increases. That is, the molecular weight of the intermediate and/or final silylated epoxy resin obtained can be adjusted by controlling the amount of epoxy used compared to aromatic alcohol.

2. Epoxy resin evaporation analysis

The evaporation characteristics of the epoxy resin were analyzed using a thermogravimetric analysis (TGA, TA Q500, TA Instruments). Before analysis, each sample was pretreated in a vacuum oven at 80°C for 1 hour to volatilize the solvent, and then the weight change of the silylated epoxy resin of the present invention (Synthesis Example 11 was an intermediate epoxy resin) and the starting epoxy monomer was measured using TGA. The analysis is shown in Figures 2A to 2C. As can be seen from FIGS. 2A to 2C, the weight reduction rate of the silylated epoxy resin of the present invention prepared in Synthesis Examples 1, 4, and 11 to 13 (Synthesis Example 11 is an epoxy resin as an intermediate) is significant compared to that of the epoxy monomer as the starting material. It was confirmed that it was very small. In addition, as shown in Figure 2c, it can be seen that when less epoxy is used compared to aromatic alcohol in the first step reaction and the molecular weight of the obtained epoxy further increases, evaporation of the epoxy resin is further reduced. In this way, the epoxy evaporation problem was improved by inserting an aromatic core structure and increasing the molecular weight. In addition, the tendency to improve the evaporation characteristics of the epoxy resin with increased molecular weight obtained by only the first stage reaction and the silylated epoxy resin is similar, and from this, the improvement of the evaporation characteristics of the epoxy resin is influenced by the molecular weight control of the first stage reaction. I could see how important this was.

3. Evaluation of thermal expansion characteristics

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

With the composition shown in Table 3 below, the hardener, silica (FB-105FC, silica 55㎛ cut) and wax are dissolved in methyl ethyl ketone so that the solid content is 80wt%. After mixing this mixture for 20 minutes at a speed of 1500 rpm, add the epoxy compound and mix for an additional 10 minutes. A curing catalyst was added and mixed for an additional 10 minutes to create a uniform solution. Place the mixture in an aluminum dish. The solvent was removed by placing it in a convection oven heated to 80°C for 15 minutes. After molding in a hot press preheated to 140~150℃, it was cured in an oven at 180℃ for 4 hours to obtain an epoxy filler composite mold (8mmХ8mmХ3mm).

(2) Evaluation of heat resistance properties

The dimensional change and heat resistance characteristics (thermal expansion coefficient) according to temperature of the cured product obtained with the composition shown in Table 3 below were evaluated using a thermo-mechanical analyzer and are shown in Figure 3 and Table 3 below.

Note: The compounds used in Table 3 above are as follows.

(1) 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate

(Sigmaaldrich, EEW=126g/Eq)

(2) Neopentyl glycol diglycidyl ether (Sigmaaldric, EEW=145g/Eq)

(3) Triglycidyl-p-aminophenol (Huntsman, My0510, EEW=92g/Eq)

(4) HF-1M® (Meiwa Plastic Industries, HEW=107)

(5) 2-phenylimidazole (Aldrich)

(6) WAX-E (Clariant)

(7) FB-105FC (Denka, 55㎛ cut)

As can be seen in Table 3, the composites of Examples 1 to 10 containing a modified epoxy compound having an alkoxysilyl group with a controlled molecular structure of the present invention are compared to the composites of Comparative Examples 1 to 3 containing an unmodified epoxy. showed a significantly lower CTE compared to From this, it was confirmed that the thermal expansion characteristics of the modified epoxy of the present invention were improved.

Claims (11)

Epoxy compounds having an alkoxysilyl group containing at least one structure selected from the group consisting of the following formulas A1 to A3:
[Formula A1]

[Formula A2]

[Formula A3]

(In the above formulas A1 to A3, the unit (QF) is each independently selected from the group consisting of the following formulas (1C) to (4C);

(In Formula (2C), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in Formula (4C), Z is each independently selected from the group consisting of H and a straight or branched C1-C5 alkyl group, and in formulas (1C) to (4C), * is a bond.);
The functional group R is Each independently represents the following formula (R) or hydrogen,

(Here, at least one of 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 alkyl portion and alkyl group of the alkoxy group are straight or branched.)
In formulas A1 and A3, m is an integer from 0 to 20;
In Formula A2, each X is independently H or a straight or branched C1-C5 alkyl group;
In Formula A3, the unit (P) is each independently selected from the group consisting of the following formulas (CF) to (HF).

(If the unit (P) is located at at least one terminal of the formula A3, one of the M in the formula (CF) to (HF) is a bond to the ** position of the linking group (L1) in the formula A3, The remaining M is a glycidyl group of the formula (E) below; If the unit (P) is not located at the terminal of the formula A3, two M of the M of the formulas (CF) to (HF) are adjacent to each of the linking groups below It is a bond to the ** position of (L1), and when the remaining M is present, the remaining M is a glycidyl group of the formula (E) below.

(R in L1 is the formula (R) above or hydrogen.)

In the above formula (CF), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S- or -SO ₂ -,
In the above formula (GF), n is an integer from 2 to 20.)) In the presence of a phosphorus-based catalyst, at least one type of epoxy monomer selected from the group consisting of the following formulas (AS) to (HS) and at least one type of difunctional aromatic alcohol selected from the group consisting of the following formulas (1) to (4) are mixed. A first step of reacting to obtain an intermediate product; and
A second step of mixing and reacting the intermediate product with an isocyanate alkoxysilane of the formula C below to obtain an epoxy compound having at least an alkoxysilyl group selected from the group consisting of the formulas A1 to A3,
In the first step, the mixing is performed with 2.0 to 10 moles of epoxy monomer per 1 mole of difunctional aromatic alcohol.

(In the above formula (BS), X is each independently H or a straight or branched C1 to C5 alkyl group,
In the formula (CS), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in the formula (GS), n is It is an integer from 2 to 20.)

(In the formula (2), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in formula (4), Z is each independently selected from the group consisting of H and a straight or branched C1 to C5 alkyl group.)
[Formula A1]

[Formula A2]

[Formula A3]

(In the above formulas A1 to A3, the unit (QF) is each independently selected from the group consisting of the following formulas (1C) to (4C);

(In Formula (2C), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in Formula (4C), Z is each independently selected from the group consisting of H and a straight or branched C1-C5 alkyl group, and in formulas (1C) to (4C), * is a bond.);
Each functional group R is independently of the following formula (R) or hydrogen,

(Here, at least one of 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 alkyl portion and alkyl group of the alkoxy group are straight or branched.)
In formulas A1 and A3, m is an integer from 0 to 20;
In formula A2, each X is independently H or a straight or branched C1 to C5 alkyl group;
In Formula A3, the unit (P) is each independently selected from the group consisting of the following formulas (CF) to (HF).

(If the unit (P) is located at at least one terminal of the formula A3, one of the M in the formula (CF) to (HF) is a bond to the ** position of the linking group (L1) in the formula A3, The remaining M is a glycidyl group of the formula (E) below; If the unit (P) is not located at the terminal of the formula A3, two M of the M of the formulas (CF) to (HF) are adjacent to each of the linking groups below It is a bond to the ** position of (L1), and when the remaining M is present, the remaining M is a glycidyl group of the formula (E) below.

(R in L1 is the formula (R) above or hydrogen.)

In the formula (CF), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in the formula (GF), n is It is an integer from 2 to 20.))
[Formula C]
OCN(CH ₂ ) ₃ SiR _a R _b R _c
(In the formula C, at least one of R _a to R _c is a C1-C5 alkoxy group, and the others are C1-C10 alkyl groups, and the alkyl portion and alkyl group of the alkoxy group are straight or branched.) According to paragraph 2,
The reaction temperature in the first step is 80°C to 200°C. According to paragraph 2,
The reaction time of the first step is 30 minutes to 3 hours. According to paragraph 2,
The production method wherein the phosphorus-based catalyst is at least one selected from the group consisting of triphenylphosphine, diphenylpropylphosphine, and tricyclohexylphosphine. According to paragraph 2,
In the first step, the phosphorus-based catalyst is used in an amount of 0.1 to 2 parts by weight per 100 parts by weight of the difunctional aromatic alcohol. An epoxy composition comprising at least one of the epoxy compounds having an alkoxysilyl group represented by the formulas A1 to A3 of claim 1. A cured product of the epoxy composition of claim 7. Goods containing the hardened cargo of paragraph 8. According to clause 9,
The article is at least one selected from the group consisting of semiconductor packaging material, semiconductor component, semiconductor device, electrical material, electrical component, electrical device, electronic material, electronic component, and electronic device. An epoxy compound comprising at least one structure selected from the group consisting of the following formulas B1 to B3.
[Formula B1]

[Formula B2]

[Formula B3]

(In the above formulas B1 to B3, the unit (QC) is each independently selected from the group consisting of the following formulas (1C) to (4C);

(In Formula (2C), Y' is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in Formula (4C), Z is each independently selected from the group consisting of H and a straight or branched C1-C5 alkyl group, and in formulas (1C) to (4C) * is a bond;
In Formula B3, the unit (PC) is each independently selected from the group consisting of the following formulas (CC) to (HC);

(When the unit (PC) is located at at least one terminal of the formula B3, one of the L in the formulas (CC) to (HC) is a bond to the ** position of the linking group (L2) in the formula B3, The remaining L is a glycidyl group of the formula (E) below; If the unit (PC) is not located at the terminal of the formula B3, two L among the Ls of the formulas (CC) to (HC) are adjacent to each of the linking groups below It is a bond to the ** position of (L2), and when the remaining L is present, the remaining L is a glycidyl group of the formula (E) below.


In the formula (CC), Y is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S-, or -SO ₂ -, and in the formula (GC), n is It is an integer from 2 to 20.)
In the above formulas B1 and B3, m is an integer from 0 to 20,
In Formula B2, each X is independently H or a linear or branched C1 to C5 alkyl group.)