KR102503157B1 - Multifunctional epoxy compound having alkoxysilyl group, preparing method thereof, composition, and use thereof - Google Patents

Abstract

According to the present invention, a multifunctional epoxy compound having an alkoxysilyl group having a controlled molecular weight and core structure, a method for preparing the same, a composition and a use thereof are provided. The multifunctional epoxy compound having an alkoxysilyl group of the present invention exhibits improved toughness (ie, reduced brittleness) and excellent thermal expansion characteristics (low CTE) of a cured product containing the same due to a specific molecular weight and core structure. In addition, by the method according to the present invention, a multifunctional epoxy compound having an alkoxysilyl group having a controlled molecular structure, that is, a core structure and molecular weight, can be easily and economically produced through a simple manufacturing process.

Description

Multifunctional epoxy compound having an alkoxysilyl group and its preparation method, composition and use

The present invention relates to a novel multifunctional epoxy compound having an alkoxysilyl group, a method for preparing the same, a composition including the same, uses, and a novel multifunctional epoxy compound. More specifically, it relates to a multifunctional epoxy compound having an alkoxysilyl group having a controlled molecular weight and core structure, a method for preparing the same, a composition, a use, and a novel multifunctional epoxy compound.

Epoxy material is a material with excellent mechanical properties, electrical insulation, heat resistance, water resistance and adhesiveness, and is widely used as paint, printed wiring board, IC encapsulant, electric and electronic parts, adhesives, and the like. Meanwhile, with the development of semiconductor packaging technology, the problem of warpage of packaging due to a difference in thermal expansion characteristics (CTE-mismatch) between component materials is becoming more serious. Therefore, in order to improve low CTE characteristics, a 'multifunctional epoxy resin having an alkoxysilyl group' has been developed, which exhibits very excellent Coefficient of Thermal Expansion (CTE) characteristics. However, the polyfunctional epoxy resin having an alkoxysilyl group also exhibits excellent thermal properties (eg, low thermal expansion characteristics) due to a high epoxide group concentration, like general multifunctional epoxy resins, but is still brittle due to high curing degree ( brittleness). In order to solve these problems, an epoxy material exhibiting excellent thermal expansion characteristics and improved brittleness is required.

On the other hand, the present applicant has been conducting research on multifunctional epoxy having an alkoxysilyl group, and in preparing multifunctional epoxy having an alkoxysilyl group, problems caused by the use of a strong base catalyst, etc., have been solved, and an epoxy compound having an alkoxysilyl group The manufacturing method was applied for patent application 2018-52731. Patent application 2018-52731 improved the problem caused by the use of a conventional strong base catalyst by using a phosphorus-based catalyst. However, the epoxy resin prepared by the method of the above application has the same core structure and the same repeating unit, and therefore, by the method of the above patent application, control of the molecular structure of the epoxy resin (i.e., control of molecular weight and core structure) and There is a limit to the improvement of toughness characteristics through this.

The present invention is to provide a multifunctional epoxy compound having a novel alkoxysilyl group having a controlled core structure and molecular weight.

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

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

In addition, it is to provide a novel multifunctional epoxy compound obtained as an intermediate product related to the production of the multifunctional epoxy compound according to the present invention.

According to the first aspect of the present invention, a multifunctional epoxy compound having an alkoxysilyl group represented by the following formula A is provided.

[Formula A]

(In Formula A, the unit (PF) is any one selected from the group consisting of the following Formulas (AF) to (GF);

(In the above formulas (AF) to (GF), two of M are bonds with the moiety indicated by ** of the linking group (L1) below, and the remaining M is a glycidyl group of the following formula (E).

(연결기 (L1)에서, *는 하기 화학식 (1C) 내지 (5C)로 구성되는 그룹으로부터 선택된 어느 하나의 * 로 나타낸 부분과의 결합이고, **는 상기 화학식 (AF) 내지 (GF)로 구성되는 그룹으로부터 선택된 어느 하나의 M으로 나타낸 부분과의 결합이고, 작용기 R은 하기 화학식 (R)로 나타내어진다.

(화학식 (R)에서, n은 3 내지 10의 정수이고, R_a 내지 R_c 중 적어도 하나는 탄소수 1 내지 5 알콕시기이고 나머지는 탄소수 1 내지 10 알킬기이며, 상기 알콕시기의 알킬부분 및 알킬기는 직선형 혹은 분지형이다.))

(In the linking group (L1), * is a bond with any one of the moieties represented by * selected from the group consisting of the following formulas (1C) to (5C), and ** is composed of the above formulas (AF) to (GF) It is a bond with a moiety represented by any one M selected from the group to be, and the functional group R is represented by the following formula (R).

(In Formula (R), n is an integer of 3 to 10, at least one of R _a to R _c is an alkoxy group having 1 to 5 carbon atoms and the rest is an alkyl group having 1 to 10 carbon atoms, and the alkyl part and the alkyl group of the alkoxy group are It is straight or branched.))

In Formula (EF), q is -CH ₂ - or a linkage;

In formula (FF), R' is hydrogen or a linear or branched C1-C10 alkyl group;

In formula (GF), R" is hydrogen, a hydroxyl group, a linear or branched C1-C10 alkyl group, or a C6 or C10 aromatic group.),

The unit (PFE) is any one selected from the group consisting of Formulas (AF) to (GF), and in this case, one of M in Formulas (AF) to (GF) is * of the linking group (L1). It is a bond to the moiety indicated by *, and the remaining M is a glycidyl group of the above formula (E);

the core unit (QF) is any one selected from the group consisting of the following formulas (1C) to (5C);

(In Formula (1C), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S- or -SO ₂ -, and in Formula (3C), Y is Each independently selected from the group consisting of H and a linear or branched C1-C5 alkyl group, and * in formulas (1C) to (5C) is a bond with * in the linking group (L1));

The functional group R is represented by the above formula (R),

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delete

m is an integer from 0 to 10.)

According to the second aspect of the present invention, in the presence of a phosphorus-based catalyst, a polyfunctional epoxy monomer selected from the group consisting of the following formulas (AS) to (GS) and from the group consisting of the following formulas (1) to (5) A first step of obtaining an intermediate product by reaction with a selected difunctional aromatic alcohol; and

A second step of obtaining a multifunctional epoxy compound having an alkoxysilyl group represented by the following formula A by reaction of the intermediate product with an isocyanate alkoxysilane of the following formula C,

In the first step, the content of the multifunctional epoxy monomer relative to 1 mole of the difunctional aromatic alcohol is 2.5 to 10 moles, and a method for preparing a multifunctional epoxy compound of Formula A is provided.

(In the formulas (AS) to (GS), all K are glycidyl groups of the following formula (E),

In Formula (ES), q is -CH ₂ - or a direct linkage;

In formula (FS), R' is hydrogen or a straight or branched C1-C10 alkyl group;

In formula (GS), R" is hydrogen, a hydroxyl group, a linear or branched C1-C10 alkyl group, or a C6 or C10 aromatic group.)

(In Formula (1), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S- or -SO ₂ -, and in Formula (3), Y are each independently selected from the group consisting of H and a linear or branched C1-C5 alkyl group.)

[Formula A]

(In Formula A, the unit (PF) is any one selected from the group consisting of the following Formulas (AF) to (GF);

(연결기 (L1)에서, *는 하기 화학식 (1C) 내지 (5C)로 구성되는 그룹으로부터 선택된 어느 하나의 * 로 나타낸 부분과의 결합이고, **는 상기 화학식 (AF) 내지 (GF)로 구성되는 그룹으로부터 선택된 어느 하나의 M으로 나타낸 부분과의 결합이고, 작용기 R은 하기 화학식 (R)로 나타내어진다.

(화학식 (R)에서, n은 3 내지 10의 정수이고, R_a 내지 R_c 중 적어도 하나는 탄소수 1 내지 5 알콕시기이고 나머지는 탄소수 1 내지 10 알킬기이며, 상기 알콕시기의 알킬부분 및 알킬기는 직선형 혹은 분지형이다.))

(In the linking group (L1), * is a bond with any one of the moieties represented by * selected from the group consisting of the following formulas (1C) to (5C), and ** is composed of the above formulas (AF) to (GF) It is a bond with a moiety represented by any one M selected from the group to be, and the functional group R is represented by the following formula (R).

(In Formula (R), n is an integer of 3 to 10, at least one of R _a to R _c is an alkoxy group having 1 to 5 carbon atoms and the rest is an alkyl group having 1 to 10 carbon atoms, and the alkyl part and the alkyl group of the alkoxy group are It is straight or branched.))

In Formula (EF), q is -CH ₂ - or a linkage;

In formula (FF), R' is hydrogen or a linear or branched C1-C10 alkyl group;

In formula (GF), R" is hydrogen, a hydroxyl group, a linear or branched C1-C10 alkyl group, or a C6 or C10 aromatic group.),

The unit (PFE) is any one selected from the group consisting of Formulas (AF) to (GF), and in this case, one of M in Formulas (AF) to (GF) is * of the linking group (L1). It is a bond to the moiety indicated by *, and the remaining M is a glycidyl group of the above formula (E);

the core unit (QF) is any one selected from the group consisting of the following formulas (1C) to (5C);

(In Formula (1C), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S- or -SO ₂ -, and in Formula (3C), Y is Each independently selected from the group consisting of H and a linear or branched C1-C5 alkyl group, and * in formulas (1C) to (5C) is a bond with * in the linking group (L1))

The functional group R is represented by the above formula (R),

m is an integer from 0 to 10.)

delete

delete

[Formula C]

OCN(CH ₂ ) _n SiR _a R _b R _c

(In Formula C, n is an integer from 3 to 10, at least one of R _a to R _c is a C1-C5 alkoxy group, and the rest is a C1-C10 alkyl group, and the alkyl part and the alkyl group of the alkoxy group are linear or branched)

According to the third aspect of the present invention, the reaction temperature of the first step is 80 ℃ to 200 ℃, the manufacturing method according to the second aspect is provided.

According to the fourth aspect of the present invention, the reaction time of the first step is 30 minutes to 1 hour, the manufacturing method according to the second aspect is provided.

According to a fifth aspect of the present invention, the phosphorus-based catalyst is selected from the group consisting of triphenylphosphine, diphenylpropylphosphine, and tricyclohexylphosphine, and a production method according to the second aspect is provided.

According to the sixth aspect of the present invention, 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 polyfunctional aromatic alcohol, the production method according to the second aspect is provided.

According to the seventh aspect of the present invention, an epoxy composition comprising a multifunctional epoxy compound having an alkoxysilyl group represented by Formula A of the first aspect, a curing agent and an inorganic filler is provided.

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

According to the ninth aspect of the present invention, an article comprising the cured product of the eighth aspect is provided.

According to the tenth aspect of the present invention, the article of the ninth aspect is at least one kind selected from the group consisting of semiconductor materials, semiconductor components, semiconductor devices, electrical and electronic materials, electrical and electronic components, and electrical and electronic devices. Provided.

According to the eleventh aspect of the present invention, a multifunctional epoxy compound represented by the following formula (B) is provided.

[Formula B]

(In the above formula B, the unit (PC) is any one selected from the group consisting of the following formulas (AC) to (GC);

(In the above formulas (AC) to (GC), two of L are bonds with the moiety indicated by ** of the linking group (L2) below, and the remaining L is a glycidyl group of the following formula (E).

(연결기 (L2)에서, *는 하기 화학식 (1C) 내지 (5C)로 구성되는 그룹으로부터 선택된 어느 하나의 *로 나타낸 부분과의 결합이고, **는 상기 화학식 (AC) 내지 (GC)로 구성되는 그룹으로부터 선택된 어느 하나의 L로 나타낸 부분과의 결합이다.)

(In the linking group (L2), * is a bond with any one of the moieties represented by * selected from the group consisting of the following formulas (1C) to (5C), and ** is composed of the above formulas (AC) to (GC) It is a bond with the part represented by any one L selected from the group that is.)

In Formula (EC), q is -CH ₂ - or a direct linkage;

In formula (FC), R' is hydrogen or a straight or branched C1-C10 alkyl group;

In formula (GC), R" is hydrogen, a hydroxyl group, a linear or branched C1-C10 alkyl group, or a C6 or C10 aromatic group)

The unit (PCE) is any one selected from the group consisting of the formulas (AC) to (GC), and in this case, one of L in the formulas (AC) to (GC) is * of the linking group (L2). It is a bond with the moiety indicated by *, and the remaining L is a glycidyl group of the above formula (E)),

the core unit (QC) is any one selected from the group consisting of the following formulas (1C) to (5C);

(In Formula (1C), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S- or -SO ₂ -, and in Formula (3C), Y is each independently selected from the group consisting of H and a linear or branched C1-C5 alkyl group, and in the formulas (1C) to (5C), * is a bond with the moiety indicated by * of the linking group (L2));

m is an integer ranging from 0 to 10.)

The novel polyfunctional epoxy compound having an alkoxysilyl group (hereinafter, also referred to as 'silylated multifunctional epoxy' or 'modified epoxy') has improved brittleness (ie, brittleness) by controlled molecular weight and core structure. decrease). That is, cured products (including composites) using the silylated multifunctional epoxy having a controlled core structure and molecular weight distribution of the present invention exhibit improved toughness (ie, reduced brittleness) and excellent thermal expansion characteristics (ie, low CTE).

Furthermore, the control of molecular weight and core structure of the present invention is achieved by the reaction of a multifunctional epoxy monomer as a starting material with a difunctional aromatic alcohol in the method for preparing a silylated multifunctional epoxy according to the present invention. That is, the core structure and molecular weight of the repeating unit constituting the silylated multifunctional epoxy can be easily controlled by the method of the present invention. Moreover, since no strong base and/or inorganic base catalyst affecting the alkoxysilylation reaction is used, alkoxysilylation is performed without a purification process (workup) after formation of an intermediate product having a controlled core structure (repeating unit of epoxy resin) and molecular weight. Since the steps can proceed continuously in-situ, the manufacturing process is simplified. Also, the formation of by-products is inhibited. In this way, according to the method of the present invention, a multifunctional epoxy compound having an alkoxysilyl group can be efficiently produced by a simple process, and thus can be economically mass-produced. The epoxy composition including the silylated multifunctional epoxy exhibiting improved brittleness and heat resistance of the present invention is suitable for use in applications requiring such physical properties. Furthermore, the non-silylated multifunctional epoxy compound obtained as an intermediate product in the silylated multifunctional epoxy production method of the present invention also exhibits improved brittleness and can be used in the field of epoxy resin applications.

1 is a graph showing the GPC results (molecular weight) of starting materials and reaction products in Synthesis Example 1.
2 is a SEM photograph showing a cured cross section of a cured epoxy material ((a) cured cross section of physical property example 1, (b) cured cross section of physical property example 2, (c) cured cross section of physical property example 3, (d) comparative physical property example Cured cross section of 1, (e) cured cross section of Comparative Physical Property Example 2)
3 is a graph showing the dimensional change according to the temperature change of the cured composites of Example 1 and Comparative Examples 1 and 2.

The present invention exhibits improved brittleness and heat resistance, and a multifunctional epoxy compound having an alkoxysilyl group whose molecular structure (ie, core structure and molecular weight) is controlled by insertion of an aromatic alcohol structure, a method for preparing the same, a composition, an article and an intermediate It relates to a multifunctional epoxy compound provided as a product, and each of these is described below.

go. Multifunctional epoxy compound having an alkoxysilyl group

According to one embodiment of the present invention, a multifunctional epoxy compound having an alkoxysilyl group represented by the following formula A is provided, which uses an intercalated aromatic alcohol structure (unit (QF) in formula A), a core structure (repeated unit) and molecular weight are controlled.

[Formula A]

In the formula (A), the unit (PF) is any one selected from the group consisting of the following formulas (AF) to (GF);

(In the above formulas (AF) to (GF), two of M are bonds with the moiety indicated by ** of the linking group (L1) below, and the remaining M is a glycidyl group of the following formula (E).

(연결기 (L1)에서, *는 하기 화학식 (1C) 내지 (5C)로 구성되는 그룹으로부터 선택된 어느 하나의 * 로 나타낸 부분과의 결합이고, **는 상기 화학식 (AF) 내지 (GF)로 구성되는 그룹으로부터 선택된 어느 하나의 M으로 나타낸 부분과의 결합이고, 작용기 R은 하기 화학식 (R)로 나타내어진다.

(화학식 (R)에서, n은 3 내지 10의 정수이고, R_a 내지 R_c 중 적어도 하나는 탄소수 1 내지 5 알콕시기이고 나머지는 탄소수 1 내지 10 알킬기이며, 상기 알콕시기의 알킬부분 및 알킬기는 직선형 혹은 분지형이다.))

(In the linking group (L1), * is a bond with any one of the moieties represented by * selected from the group consisting of the following formulas (1C) to (5C), and ** is composed of the above formulas (AF) to (GF) It is a bond with a moiety represented by any one M selected from the group to be, and the functional group R is represented by the following formula (R).

(In Formula (R), n is an integer of 3 to 10, at least one of R _a to R _c is an alkoxy group having 1 to 5 carbon atoms and the rest is an alkyl group having 1 to 10 carbon atoms, and the alkyl part and the alkyl group of the alkoxy group are It is straight or branched.))

In Formula (EF), q is -CH ₂ - or a linkage;

In formula (FF), R' is hydrogen or a linear or branched C1-C10 alkyl group;

In formula (GF), R" is hydrogen, a hydroxyl group, a linear or branched C1-C10 alkyl group, or a C6 or C10 aromatic group.),

The unit (PFE) is any one selected from the group consisting of Formulas (AF) to (GF), and in this case, one of M in Formulas (AF) to (GF) is * of the linking group (L1). It is a bond to the moiety indicated by *, and the remaining M is a glycidyl group of the above formula (E);

the core unit (QF) is any one selected from the group consisting of the following formulas (1C) to (5C);

(In Formula (1C), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S- or -SO ₂ -, and in Formula (3C), Y is are each independently selected from the group consisting of H and a linear or branched C1-C5 alkyl group, and in formulas (1C) to (5C), * is a bond with * of the linking group (L1))

The functional group R is represented by the following formula (R),

(Where n is an integer of 3 to 10, preferably 3 to 6, at least one of R _a to R _c is an alkoxy group having 1 to 5 carbon atoms and the others are an alkyl group having 1 to 10 carbon atoms, the alkyl moiety of the alkoxy group, and Alkyl group can be straight or branched),

m is an integer ranging from 0 to 10, preferably from 0 to 5.

As described above, units (PF) and (PFE) are selected from formulas (AF) to (GF) above, and units (QF) are selected from formulas (1C) to (5C) above. As such, in the silylated multifunctional epoxy of the present invention, core units (PF) and units (QF) of different structures alternate.

Furthermore, the molecular weight of the silylated multifunctional epoxy according to one embodiment of the present invention has a molecular weight in a range where m in Formula A corresponds to an integer ranging from 0 to 10, preferably from 0 to 5.

The molecular weight of the silylated multifunctional epoxy is preferably such that the repeating unit (m) is within the above range in terms of securing physical properties and/or fairness such as excellent toughness and heat resistance of the silylated multifunctional epoxy. If the molecular weight of the silylated multifunctional epoxy is less than the molecular weight corresponding to the repeating unit (m) of 0, the toughness is insufficient, and if the repeating unit (m) exceeds the molecular weight of 10, the thermal expansion characteristics and processability are deteriorated. It is not desirable in that respect.

The molecular weight of Chemical Formula A, even if the number of repeating units (m) is the same, depends on the specific structures of units (PF) and (QF), which are core structures. Therefore, the improved brittleness of the novel silylated multifunctional epoxy according to the present invention is partially due to molecular weight control, that is, molecular weight increase, but indirectly by defining the range of repeating units (m) rather than directly defining the molecular weight. defines the molecular weight range.

As described above, the silylated multifunctional epoxy compound according to the present invention not only exhibits improved brittleness due to a controlled core structure (repeating unit) and molecular weight, but also has physical properties required when applying an epoxy compound, such as excellent thermal expansion characteristics. do.

Meanwhile, in the present application, 'epoxy compound' and 'epoxy monomer' both have at least two epoxide groups and are epoxy resins. In addition, in the present application, 'epoxy compound' and 'epoxy resin' are briefly referred to as 'epoxy', and 'epoxy compound' and 'epoxy resin' are sometimes used interchangeably.

me. Method for producing a multifunctional epoxy compound having an alkoxysilyl group

According to another embodiment of the present invention, a method for preparing a silylated multifunctional epoxy compound having a controlled core structure (repeating unit of silylated multifunctional epoxy) and molecular weight by intercalation of aromatic alcohol is provided.

According to one embodiment of the present invention, the silylated multifunctional epoxy is a multifunctional epoxy compound having a controlled core structure (repeating unit of epoxy resin) and molecular weight by reacting a multifunctional epoxy monomer as a starting material with a difunctional aromatic alcohol (middle product) (first step, molecular structure adjustment step); and reacting the intermediate product of the first step with isocyanate alkoxysilane (second step, alkoxysilylation step). The mechanism of the method according to the present invention is as shown in Scheme 1 below. Molecular structure control is meant to include core structure and molecular weight control. The method for producing silylated multifunctional epoxy by the method according to the present invention is also referred to as 'modification reaction'.

[Scheme 1] Modification reaction of trifunctional epoxy resin through intercalation of bisphenol A

First, as shown in Scheme 1, in the first step, a multifunctional epoxy monomer (hereinafter also referred to as 'epoxy monomer') and a difunctional aromatic alcohol (hereinafter also referred to as 'aromatic alcohol') as starting materials are prepared. By reacting in the presence of a phosphorus-based catalyst and an optional solvent, an intermediate product, which is an epoxy compound having a controlled core structure (repeating unit) and molecular weight, is obtained.

The multifunctional epoxy monomer as the starting material may be any one selected from the group consisting of the following formulas (AS) to (GS).

In the formulas (AS) to (GS), all K are glycidyl groups of the above formula (E),

In Formula (ES), q is -CH ₂ - or a direct linkage;

In formula (FS), R' is hydrogen or a straight or branched C1-C10 alkyl group;

In formula (GS), R" is hydrogen, a hydroxyl group, a linear or branched C1-C10 alkyl group, or a C6 or C10 aromatic group.

The difunctional aromatic alcohol is selected from the group consisting of bisphenol A, naphthalene, biphenyl, benzene, or difunctional aromatic alcohol having two hydroxyl groups in the cardo core.

Difunctional aromatic alcohols, but are not limited thereto, may have a specific structure selected from the group consisting of the following formulas (1) to (5):

In formula (1), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S- or -SO ₂ -, and in formula (3), Y is H and a linear or branched C1-C5 alkyl group.

As can be seen from the structures of the starting materials, the polyfunctional epoxy monomers of Formulas (AS) to (GS) and the difunctional aromatic alcohols of Formulas (1) to (5), the core structures of the polyfunctional epoxy monomers and the difunctional aromatic alcohols is not the same Therefore, by selecting and reacting a polyfunctional epoxy monomer of any of the formulas (AS) to (GS) and a difunctional aromatic alcohol of any of the formulas (1) to (5) as starting materials, silylation having an alternating core structure is performed. Multifunctional epoxies can be prepared. That is, according to one embodiment of the present invention, the core structure of the silylated multifunctional epoxy is controlled.

The content of the multifunctional epoxy monomer is used at a higher concentration than that of the difunctional aromatic alcohol, thereby suppressing the formation of a high molecular weight modified epoxy compound having a repeating unit (m) of Formula A > 10.

Specifically, the polyfunctional epoxy monomer is reacted in an excess of 2.5 to 10 moles with respect to 1 mole of the difunctional aromatic alcohol. In this way, by using an excessive amount of epoxy monomer, the molecular weight of the silylated multifunctional epoxy can be adjusted to a molecular weight corresponding to 10 or less repeating units (m).

If the molar ratio of the epoxy monomer is less than 2.5, it is not preferable in that a polymer having a repeating unit m > 10 is produced, making it difficult to control the molecular weight of the silylated multifunctional epoxy, which is the final product. If the molar ratio exceeds 10, the final product It is undesirable in that the relative concentration of alkoxysilyl groups (molar concentration ratio of alkoxysilyl groups to epoxy groups) in the final reactant containing the phosphorus silylated multifunctional epoxy becomes too low. In addition, as described herein, as the first step reaction proceeds, an intermediate of a trimer structure having at least repeating unit (m) = 0 is produced. If m is less than 0, the reaction does not proceed.

In addition, by the first step reaction, a trimer (m = 0), a pentamer (m = 1), and/or an oligomer having a higher molecular weight are simultaneously produced, in a state in which they are mixed (ie, substances with different molecular weights) mixture) exists. In general, when sending an oligomerization reaction, it is theoretically impossible to make a resin having only one kind of molecular weight of a specific single resin, so it is generally known in the art that a mixture of materials having different molecular weights is obtained. and is not discussed 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 the silylated multifunctional epoxy is mixed, the [epoxy compound of the epoxy composition] Since the ratio (molar ratio) of the epoxide group]:[alkoxysilyl group] can be adjusted, it is not necessary to separate or remove it during the reaction.

The first-stage reaction is performed in the presence of a mild phosphorus-based catalyst. As the phosphorus catalyst, at least one 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 1 part by weight (i.e., 0.1 wt% to 2 wt% based on the weight of the aromatic alcohol, preferably 0.5 wt to 1 wt%). If the amount of the phosphorus-based catalyst is less than 0.1 parts by weight, the reaction rate is significantly slowed down, and the first stage reaction is poor, and even if it exceeds 2 parts by weight, no additional reaction rate improvement is observed. Therefore, it is not preferable to use more than 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 carried out at a temperature of, for example, 80 ° C to 200 ° C, more preferably 80 ° C to 150 ° C. can When the temperature is lowered to less than 80 ℃, the reaction rate can be significantly slowed down. In addition, when the temperature exceeds 200 ° C., it is preferable to react at the above temperature because it adversely affects molecular weight control.

The reaction time of the first step varies depending on the structure of the reactant, the degree of reaction, the solvent, and the amount of the catalyst, but may be 30 minutes to 1 hour. By reacting for 30 minutes to 1 hour, an intermediate product, which is a polyfunctional epoxy compound having a controlled core structure (repeating unit of epoxy resin) and molecular weight, is obtained by the reaction of the multifunctional epoxy monomer and the difunctional aromatic alcohol. If the reaction time is less than 30 minutes, the first-stage reaction does not sufficiently proceed, and if the reaction time is less than 1 hour, the first-stage reaction proceeds sufficiently, so it is not preferable to exceed 1 hour. In this way, in the method according to the present invention, an intermediate product having a controlled core structure and molecular weight is formed by reacting a polyfunctional epoxy monomer and a difunctional aromatic alcohol within a short time period of less than 1 hour.

In the first step reaction, the solvent may be optionally used as needed. For example, if the viscosity of the reactant at the reaction temperature is suitable for the reaction to proceed without a separate solvent in the first step reaction, the solvent may not be used. That is, when the viscosity of the reactants is low enough that mixing and stirring of the reactants can proceed smoothly without a solvent, no additional solvent is required, which can be easily determined by those skilled in the art. In the case of using a solvent, any organic solvent (aprotic solvent) can be used as a possible solvent as long as the reactant is dissolved and can be easily removed after the reaction without adversely affecting the reaction, but is not particularly limited thereto. For example, acetonitrile, MEK (methyl ethyl ketone), DMF (dimethyl formamide), DMSO (dimethyl sulfoxide), toluene, xylene, and the like may be used. If necessary, these solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, and may be used in an appropriate amount within a range in which the reactant is sufficiently dissolved and does not adversely affect the reaction, and a person skilled in the art may appropriately select it in consideration of this. Also, the first-stage reaction may be carried out without using a solvent (neat reaction).

In the first stage reaction, a polyfunctional epoxy monomer as a starting material is reacted with a difunctional aromatic alcohol to obtain an intermediate product having a controlled core structure (repeating unit of epoxy resin) and molecular weight. The novel epoxy compound obtained as an intermediate product does not have an alkoxysilyl group, but also has a controlled core structure (repeating unit of epoxy resin) and molecular weight, exhibits excellent toughness as an epoxy resin, and can be used as an epoxy resin in this technical field. can

Although not limited thereto, for example, an intermediate product obtained by the first step reaction may be represented by the following formula B.

[Formula B]

In the formula (B), the unit (PC) is any one selected from the group consisting of the following formulas (AC) to (GC);

(In the above formulas (AC) to (GC), two of the Ls are bonds with the moiety indicated by ** of the linking group (L2) below, and the remaining L is a glycidyl group of the above formula (E).

(연결기 (L2)에서, *는 하기 화학식 (1C) 내지 (5C)로 구성되는 그룹으로부터 선택된 어느 하나의 *로 나타낸 부분과의 결합이고, **는 상기 화학식 (AC) 내지 (GC)로 구성되는 그룹으로부터 선택된 어느 하나의 L로 나타낸 부분과의 결합이다.)

(In the linking group (L2), * is a bond with any one of the moieties represented by * selected from the group consisting of the following formulas (1C) to (5C), and ** is composed of the above formulas (AC) to (GC) It is a bond with the part represented by any one L selected from the group that is.)

In Formula (EC), q is -CH ₂ - or a linkage;

In formula (FC), R' is hydrogen or a straight or branched C1-C10 alkyl group;

In formula (GC), R" is hydrogen, a hydroxyl group, a linear or branched C1-C10 alkyl group, or a C6 or C10 aromatic group)

The unit (PCE) is any one selected from the group consisting of the formulas (AC) to (GC), and in this case, one of L in the formulas (AC) to (GC) is * of the linking group (L2). It is a bond with the moiety indicated by *, and the remaining L is a glycidyl group of the above formula (E)),

the core unit (QC) is any one selected from the group consisting of the following formulas (1C) to (5C);

(In Formula (1C), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -S- or -SO ₂ -, and in Formula (3C), Y is Each independently selected from the group consisting of H and a linear or branched C1-C5 alkyl group, and in formulas (1C) to (5C), * is a bond with the moiety indicated by * of the linking group (L2));

m is an integer ranging from 0 to 10, preferably from 0 to 5.

According to one embodiment of the present invention, a novel multifunctional epoxy compound of formula B obtained as an intermediate product in the method according to the present invention is also provided. As described above, the intermediate product of Formula B shows excellent toughness and can be used as an epoxy compound in the same application field.

In addition, the phosphorus-based catalyst used in the first step is oxidized and loses its reactivity when all of the aromatic alcohol is consumed. Therefore, since it does not affect the second-stage reaction like the strong base catalyst of the prior art, a separate purification process (eg, workup) is not required 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 that the second-stage reaction can proceed in situ.

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

In the second step, as shown in Scheme 1, the alkoxysilyl group is introduced into the secondary alcohol functional group (ie, hydroxyl group) of the intermediate product by the reaction of the intermediate product obtained in the first step with isocyanate alkoxysilane to obtain a core structure and A silylated multifunctional epoxy having a controlled molecular weight is prepared.

The isocyanate alkoxysilane used in the second step may be represented by Formula C below.

[Formula C]

OCN(CH ₂ ) _n SiR _a R _b R _c

In the above formula, n is an integer of 3 to 10, preferably an integer of 3 to 6, at least one of R _a to R _c is a C1-C5 alkoxy group, preferably a C1-C3 alkoxy group, and the others are It is a C1-C10 alkyl group, and the alkyl part and the alkyl group of the alkoxy group may be linear or branched.

Meanwhile, the alkoxysilylation reaction of the hydroxy group is carried out without a catalyst or in the presence of an arbitrary base catalyst to increase the reaction rate. Examples of usable base catalysts 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 cause side reactions with isocyanate alkoxysilanes and require workup purification after completion of the reaction. application is not desirable.

These base catalysts may be used alone or in combination of two or more. It is good in terms of reaction efficiency that the base catalyst is used in an amount of 0.1 equivalent to 1 equivalent, preferably 0.5 equivalent to 1 equivalent, based on 1 equivalent of the hydroxyl group of the intermediate product of the first step. If the amount of the base catalyst is less than 0.1 equivalent, the catalytic action for the reaction may be insufficient, and the intended catalytic action is exhibited by adding an amount of 1 equivalent, and further excess is unnecessary.

In the above reaction, since the intermediate product and the isocyanate alkoxysilane react in an equivalent ratio according to the stoichiometry between the hydroxyl group and the isocyanate group of the intermediate product, the hydroxyl group in the intermediate product is reacted in a suitable ratio according to the degree of alkoxysilylation, and the degree of alkoxysilylation can be adjusted. For example, 0.1 equivalent to 1.0 equivalent 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, the alkoxysilyl groups in the final product are insufficient. If it is 1.0 equivalent, it is sufficiently alkoxysilylated, and if it is used in excess of this amount, there is a high possibility that urea by-product is produced.

The reaction temperature and reaction time of the second step reaction vary depending on the reactant, but the reaction rate (reactivity) of the hydroxyl group of the intermediate product is slow at low temperatures, so the reaction temperature is preferably 60 ° C. or higher. In addition, when the reaction temperature exceeds 150° C., thermal stability of the reactant may deteriorate during the reaction time, which is not preferable. Therefore, the second step reaction is carried out at a temperature of 60 °C to 150 °C.

The second-stage reaction is reacted for 6 hours to 72 hours, preferably 12 hours to 24 hours. If the time is less than 6 hours, the alkoxysilylation of the hydroxy group is insufficient, and if the time exceeds 72 hours, further reaction does not proceed, which is not preferable. Therefore, by reacting for 6 hours to 72 hours, the hydroxy group is alkoxysilylated without unreacted hydroxy group or unnecessary continuation of the reaction.

In the reaction of the alkoxysilylation step, a solvent may be optionally used as needed. For example, in the reaction, if the viscosity of the reactants at the reaction temperature is suitable for the reaction to proceed without a separate solvent, the solvent may not be used. That is, when the viscosity of the reactants is low enough that mixing and stirring of the reactants can proceed smoothly without a solvent, no additional solvent is required, which can be easily determined by those skilled in the art. In the case of using a solvent, any aprotic solvent can be used as long as the reactants are dissolved and can be easily removed after the reaction without adversely affecting 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 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 used in an appropriate amount within a range in which the reactant is sufficiently dissolved and does not adversely affect the reaction, and those skilled in the art can appropriately select it in consideration of this.

The silylated multifunctional epoxy produced by the method of the present invention is not limited thereto, but the above a. It can be represented by Formula A, which describes silylating functional epoxies.

all. epoxy composition

According to another embodiment of the present invention, an epoxy composition including a silylated multifunctional epoxy according to an embodiment of the present invention, a curing agent, and an inorganic filler (filler) is provided. The above item a. All of the contents described in the silylated multifunctional epoxy apply.

In addition, the epoxy composition may further include, as an epoxy compound, not only the silylated multifunctional epoxy, but also any epoxy compound generally known in the art (hereinafter referred to as 'typical epoxy compound'). . Common epoxy compounds include, but are not limited to, for example, bisphenol, biphenyl, naphthalene, benzene, thiodiphenol, fluorene, anthracene, isocyanurate, triphenylmethane, 1,1,2,2 -Tetraphenylethane, tetraphenylmethane, 4,4'-diaminodiphenylmethane, aminophenol, alicyclic, aliphatic, or glycidyl ether type, glycidylamine type, or glycidyl having a novolak unit It may be an ester type epoxy resin. In the composition containing the 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. If the molar concentration ratio of the alkoxysilyl group is less than 0.1, it is not preferable in that the effect of improving physical properties due to the alkoxysilyl group is insignificant, and if the ratio of the alkoxysilyl group is greater than 1.0, the curing rate is reduced due to the introduction of the alkoxysilyl group. don't

As the inorganic filler, any inorganic filler generally used in this technical field can be used.

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

The inorganic filler has a particle size (cut-size) of 0.1 μm to 100 μm, preferably 1 μm to 70 μm, and more preferably 5 μm to 50 μm in terms of dispersibility, fairness and reliability. Preference is given to using spherical powders. At this time, if the particle size of the inorganic filler is less than 0.1 μm, it is not only expensive, but there may be a problem in dispersion, and if it exceeds 100 μm, pattern damage or cracking of the controller die and / or semiconductor chip due to the inorganic filler is a problem. It can be.

The inorganic filler is 30 wt% to 90 wt%, preferably 45 to 90 wt%, preferably 60 wt% to 90 wt%, based on the total weight of the solid content of the epoxy composition according to the present invention in terms of physical properties and / or processability. It may be included in 60wt% to 87wt%. If it is less than 30wt%, properties by the inorganic filler may not be sufficiently expressed, and if it exceeds 90wt%, process efficiency may be reduced.

The epoxy composition of the present invention also includes a curing agent. As the curing agent, any curing agent generally known as a curing agent for an epoxy resin may be used, and is not particularly limited thereto. These are thermal curing agents activated by heat, and the epoxy composition according to the present invention is thermally cured.

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

Examples of acid anhydride-based curing agents include, but are not limited to, aliphatic acid anhydrides such as dodecenyl succinic anhydride (DDSA), poly azelaic poly anhydride, and the like, hexahydrophthalic anhydride Alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA), methyl tetrahydrophthalic anhydride (MeTHPA), methylnadic anhydride (MNA), trimellitic anhydride and aromatic acid anhydrides such as anhydride (TMA), pyromellitic acid dianhydride (PMDA), and benzophenonetetracarboxylic dianhydride (BTDA).

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

In general, the content of the curing agent can be adjusted based on the concentration of the epoxide group of the epoxy compound (specifically, all epoxy compounds contained in the epoxy composition) according to the purpose. For example, the content of the curing agent may be appropriately selected and used according to an 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 (ie, the functional group reacting with the epoxide group) react in an equivalent ratio, the epoxide group equivalent of the epoxy compound: The ratio of the reactive functional group equivalent of the curing agent The content of the curing agent may be adjusted to be 1:0.5 to 2.0, preferably 1:0.8 to 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 as necessary to promote the curing reaction.

As the curing catalyst, any curing catalyst known to be generally used for curing of epoxy compositions in the art may be used, but is not limited thereto, for example, imidazole-based, tertiary amine-based, organic acid salts , a curing catalyst such as a phosphorus compound and a boron compound may be used.

More specifically, for example, dimethyl benzyl amine, 2-methylimidazole (2MZ), 2-undecylimidazole, 2-ethyl-4-methylimidazole (2E4M), 2-phenylimidazole imidazoles 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; diazabicycloundecene (DBU) or organic acid salts of DBU; phosphorus compounds such as triphenylphosphine and phosphoric acid esters; boron compounds such as BF ₃ -monoethyl amine (BF ₃ -MEA); and the like, but are not limited thereto. As these curing catalysts, those latent due to their microcapsule coating and complex salt formation may be used. These may be used alone or in combination of two or more depending on curing conditions.

The content of the curing catalyst is not particularly limited, and may be used in combination with an amount generally used in the art. For example, 0.1 to 10 phr (parts per hundred resin, parts by weight per 100 parts by weight of the epoxy resin) relative to the epoxy resin (that is, an epoxy resin mixture including an epoxy resin having an alkoxysilyl group and an alicyclic epoxy resin), e.g. For example, it may be 0.2 to 5 phr. The curing catalyst is preferably used in the above content in terms of curing reaction accelerating effect and curing reaction rate control. By using the curing catalyst in a compounding amount within the above range, curing is effectively promoted, and an improvement in work throughput can be expected.

The epoxy composition according to one embodiment of the present invention is a wax, a flame retardant, a plasticizer, an antibacterial agent, a leveling agent, and an antifoaming agent commonly formulated in epoxy compositions in the art to adjust the physical properties of the composition within the range of not damaging the physical properties of the composition. , colorants, stabilizers, coupling agents, viscosity modifiers, diluents, curing catalysts, carbon fibers, and other additives such as molding agents may also be incorporated as needed. In addition, the epoxy composition according to one embodiment of the present invention may be dispersed by using a solvent if necessary so that the compound can be easily dispersed before curing. The types, formulations, contents, etc. of these other additives and/or solvents are generally known to those skilled in the art and are not described in detail herein.

As described above, the epoxy composition of the present invention includes a silylated multifunctional epoxy compound, a curing agent, and an inorganic filler, and the balance may be an optional curing catalyst and other additives that may be mixed according to other needs. For convenience, it is the weight of the sum of the solid content of the remainder (hereinafter, referred to as 'residual weight'). The epoxy composition of the present invention is formulated so that the sum of the silylated multifunctional epoxy compound, the curing agent, the inorganic filler, and the components constituting the remaining weight (solid content, based on weight) is 100% by weight, the inorganic filler is the above Based on the total weight of the solid content of the epoxy composition, 30wt% to 95wt%, preferably 45 to 93wt%, preferably 60wt% to 90wt%, and the rest is a silylated multifunctional epoxy compound, a curing agent, and a curing catalyst and the remainder including other additives. More specifically, the silylated multifunctional epoxy compound, the curing agent, the inorganic filler, and the components constituting the remaining weight are formulated so that the total amount (solid content, based on weight) is 100% by weight, and the inorganic filler is the epoxy composition Based on the total weight of the solid content of, 30wt% to 95wt%, preferably 45 to 93wt%, preferably 60wt% to 90wt%, the epoxy resin and the modified phenolic curing agent [epoxide group of the epoxy compound Equivalent]: [The equivalent of the reactive functional group of the curing agent] may be formulated so that the ratio 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, parts by weight per 100 parts by weight of epoxy resin), for example, 0.2 to 5 phr, based on the total epoxy resin.

In the present application, 'total weight of the solid content of the epoxy composition' means, when a liquid component and/or a solvent that may be incidentally present in the epoxy composition is used, any liquid component such as the solvent used is removed and the solid content of the cured epoxy composition Means the total weight of the content.

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 cured product forming method and curing conditions are not particularly limited, and those skilled in the art can suitably select and apply from items generally known to those skilled in the art for curing of an epoxy composition, for example, thermal curing. It is not separately described in this specification.

Therefore, the epoxy composition and/or cured product according to the present invention is suitable for application to semiconductor and/or electrical and electronic materials, parts, and devices. Specifically, the epoxy composition of the present invention may be used as a sealing material for electrical and electronic components and/or semiconductor components, a sealing material, and a packaging material, such as EMC and/or electrical and electronic components. As used herein, 'packaging' is used to mean including sealing and encapsulation. Specifically, the cured product of the present invention is not limited thereto, but may be used for applications requiring high thermal expansion characteristics, such as, for example, semiconductor packaging systems, for example, EMC (Epoxy Molding Compound) underfill. Any epoxy composition having high thermal expansion properties of any embodiment of the present invention can be used in applications requiring improved flexural properties (e.g., EMC) to exhibit improved processability and/or reliability of the part. In addition, the cured product according to one embodiment of the present invention may be in the form of a film.

According to another embodiment of the present invention, an article comprising an epoxy composition and/or a cured product according to any embodiment of the present invention described above is provided. The article may be a semiconductor material, a semiconductor component, a semiconductor device, an electric/electronic material, an electric/electronic component, an electric/electronic device, and the like. The semiconductor device may include a semiconductor material and/or a semiconductor component, and the electrical/electronic device may include the electrical/electronic material and/or the electrical/electronic component. The electrical and electronic materials are not limited thereto, but for example, semiconductor substrates, for example, IC substrates or films, such as build-up substrates, prepregs, laminates in which metal layers are disposed on prepregs, encapsulating materials (packaging materials, sealing material), build-up film, etc., as well as electronic components such as printed wiring boards. In particular, as an encapsulation material, it is suitable for epoxy molding compound (EMC) for semiconductor packaging, EMC for large area, thin film packaging, wafer-level packaging (Wafer-level PKG), and panel-level packaging EMC. In addition, the epoxy composition of the present invention can be applied to various uses such as adhesives, paints and composite materials.

That is, when the epoxy composition of the present invention is applied to articles such as semiconductor parts, electric and electronic parts, reliability of the product is improved by combining excellent thermal expansion characteristics and toughness (ie, reduced brittleness).

[Example]

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

A. Synthesis example

(1) Synthesis Example 1:

40.5 g of triglycidyl-p-aminophenol and 10 g of bisphenol A were put in a flask and stirred at 130° C. for 10 minutes under nitrogen to sufficiently dissolve the reactants. After that, the reaction was started by adding 0.1 g of triphenylphosphine (TPP) to the reaction mixture. The reaction was reacted at 130 ° C. for 1 hour. After the reaction is complete, The temperature of the flask was lowered to 80° C., and 150 g of methyl ethyl ketone (MEK), 11.3 g of diisopropylethylamine (DIPEA), and 21.7 g of 3-triethoxysilylpropyl isocyanate were added and further reacted for 12 hours. After completion of the final reaction, the mixture was cooled to room temperature and the solvent and diisopropylethylamine were removed using an evaporator to obtain the final target product. [Epoxy group]:[Alkoxysilyl functional group] = 1.0: 0.27 (molar ratio), EEW=215 g/Eq.

(2) Synthesis Examples 2 to 9

Except for using the reactants and contents described in Tables 1 and 2 below, the reaction was performed in the same manner as in Synthesis Example 1 to obtain the final target product.

[Table 1] Starting materials used in the first step reaction

[Table 2] Starting materials used in the second stage reaction and final epoxy target products synthesized therefrom

(3) Comparative Synthesis Example 1

150.8 g of triglycidyl-p-aminophenol (EEW=92.44 g/Eq), 35.3 g of phenol, and 50 g of toluene were put in a flask and stirred at 100° C. under nitrogen to obtain a reactant. Thereafter, 1.5 g of triphenylphosphine was added to the reaction mixture and reacted at 110°C for 12 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the temperature of the flask was lowered to 80 ° C. Methyl ethyl ketone (MEK) 50g, 48.5 g of diisopropylethylamine and 92.8 g of 3-triethoxysilylpropyl isocyanate were added and further reacted for 12 hours. After the final reaction was completed, it was cooled to room temperature, and the solvent and diisopropylethylamine (DIPEA) were removed using an evaporator. [Epoxy group]: [alkoxysilyl functional group] = 1.0: 0.33 (molar ratio), EEW = 233 g / Eq The final target was obtained. (This comparative synthesis example is the alkoxysilylepoxy synthesis method of patent application 2018-52731)

B. Property evaluation:

1. Molecular weight distribution analysis:

The molecular weight change of the epoxy resin after the modification reaction was measured using gel permeation chromatography (GPC, Waters, 1525 HPLC pump, 2415 RIDetector). 1 shows the starting material epoxy monomer (triglycidyl-p-aminophenol) used in Synthesis Example 1 and the molecular weight of the silylated multifunctional epoxy product prepared using the same. It was confirmed from FIG. 1 that the molecular weight of the silylated multifunctional epoxy resin, which is a product, was increased by the intercalation reaction of aromatic alcohol.

2. Morphology analysis

2-1. Preparation of morphology analysis sample

In the composition shown in Table 3 below, the epoxy, curing agent, and acrylic binder for specimen molding were dissolved in methyl ethyl ketone to have a solid content of 60 wt%. After uniformly mixing this mixed solution for 2 hours in a magnetic stirrer, a curing catalyst was added and further mixed at 1500 rpm for 5 minutes. The mixture is cast on a release film to have a uniform thickness. The thus obtained film was placed in a convection oven heated to 70° C. to remove the solvent for 20 minutes, and then cured at 180° C. for 4 hours. Thereafter, the cured epoxy material was destroyed under liquid nitrogen conditions to prepare an SEM sample.

[Table 3] Morphological analysis sample composition

⁽¹⁾ PARACRON®, Negami Chem. Ind.

⁽²⁾ HF-1M®, Meiwa Plastic Industries

2-2. Electron microscope measurement

The cross section of the cured epoxy material was observed using SEM (scanning electron microscopy, SU-8000, HITACHI, Japan). The cross section of the analysis sample was pretreated with a thin platinum layer using an ion sputter coater (E-1045, HITACHI, Japan), and then measured at 5000x magnification.

As shown in FIG. 2, the cured products of the modified epoxy compound of the present invention, that is, (a) Physical Property Example 1 (FIG. 2 (a)) and (b) Physical Property Example 2 (FIG. 2 (b)) have increased toughness. Therefore, no brittle fracture surface was observed. In addition, the cured product of the multifunctional epoxy compound, which is an intermediate product obtained in the first stage reaction of Synthesis Example 1 (Physical Property Example 3, (FIG. 2(c))), also did not observe a brittle fracture surface. As such, a brittle fracture surface was not observed. It was confirmed that the toughness was improved from the fact that one fracture surface was not observed. In comparison, the cured product of the unmodified epoxy compound (Comparative Physical Property Example 1 ((FIG. 2(d))) and the conventional method (Patent Application 10-2018- 52731) (Comparative Physical Property Example 2 (Fig. 2(e))) showed a brittle fracture surface due to lack of toughness.

3. Thermal Expansion Characteristics

3-1. Preparation of epoxy filler composite (cured product)

With the composition shown in Table 4 below, a curing agent, silica (55 μm cut), and wax were dissolved in methyl ethyl ketone to have a solid content of 80 wt%. After mixing this liquid mixture at a speed of 1500 rpm for 20 minutes, an epoxy compound was added and further mixed for 10 minutes. A curing catalyst was added and mixed for 10 minutes to obtain a uniform solution. The mixture was placed in an aluminum dish. Put in a convection oven heated to 80 ℃ to remove the solvent for 15 minutes. After molding in a hot press preheated to 150 ° C, it was cured in an oven at 180 ° C for 4 hours to obtain an epoxy filler composite mold (8mmХ8mmХ3mm).

3-2. Evaluation of heat resistance properties

The dimensional change according to temperature of the cured product obtained with the composition of Table 4 below was evaluated using a thermo-mechanical analyzer, and CTE and Tg are shown as heat resistance characteristics in Table 4 below. 3 shows a graph of dimensional change according to temperature in Example 1 and Comparative Examples 1 and 2.

[Table 4] Heat resistance properties of filler composites

⁽¹⁾ PARACRON®, Negami Chem. Ind.

⁽²⁾ HF-1M®, Meiwa Plastic Industries

⁽³⁾ A mixture of WAX-E® and WaX-S®, manufactured by Clariant

⁽⁴⁾ FB-105FC® (Denka, 55㎛ cut)

* In the compositions of Examples 1 to 9 and Comparative Example 1, the molar ratio of [epoxy group]:[alkoxysilyl group] is 1:0.2.

As shown in FIG. 3, Example 1 (cured epoxy composite material of Synthesis Example 1) exhibited significantly less dimensional change with temperature change than Comparative Example 2 (cured composite material of unmodified epoxy). From this, it was confirmed that the cured product of the silylated multifunctional epoxy according to the present invention has improved heat resistance. On the other hand, Example 1 and Comparative Example 1 (cured composite of epoxy of Comparative Synthesis Example 1 prepared by the method of Patent Application No. 2018-52731) both exhibited excellent heat resistance properties.

In addition, as shown in Table 4, the cured composites of Examples 1 to 9 and Comparative Example 1 exhibited superior heat resistance properties (low CTE and high Tg) compared to Comparative Example 2.

Claims (11)

A multifunctional epoxy compound having an alkoxysilyl group represented by the following formula (A).
[Formula A]

(In Formula A, the unit (PF) is any one selected from the group consisting of the following Formulas (AF) to (GF);

(In the above formulas (AF) to (GF), two of M are bonds with the moiety indicated by ** of the linking group (L1) below, and the remaining M is a glycidyl group of the following formula (E).

(In the linking group (L1), * is a bond with any one of the moieties represented by * selected from the group consisting of the following formulas (1C) to (5C), and ** is composed of the above formulas (AF) to (GF) It is a bond with a moiety represented by any one M selected from the group to be, and the functional group R is represented by the following formula (R).

(In Formula (R), n is an integer of 3 to 10, at least one of R _a to R _c is an alkoxy group having 1 to 5 carbon atoms and the rest is an alkyl group having 1 to 10 carbon atoms, and the alkyl part and the alkyl group of the alkoxy group are It is straight or branched.))

In Formula (EF), q is -CH ₂ - or a linkage;
In formula (FF), R' is hydrogen,
In formula (GF), R" is a methyl group),
The unit (PFE) is any one selected from the group consisting of Formulas (AF) to (GF), and in this case, one of M in Formulas (AF) to (GF) is * of the linking group (L1). It is a bond to the moiety indicated by *, and the remaining M is a glycidyl group of the above formula (E);
the core unit (QF) is any one selected from the group consisting of the following formulas (1C) to (5C);

(In Formula (1C), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -SO ₂ -, and in Formula (3C), Y is H and linear or each independently selected from the group consisting of a branched C1-C5 alkyl group, and * in formulas (1C) to (5C) is a bond to the moiety indicated by * of the linking group (L1).),
The functional group R is represented by the above formula (R);
m is an integer from 0 to 10.) In the presence of a phosphorus-based catalyst, a reaction between a kind of polyfunctional epoxy monomer selected from the group consisting of the following formulas (AS) to (GS) and a kind of difunctional aromatic alcohol selected from the group consisting of the following formulas (1) to (5) A first step of obtaining an intermediate product; and
A second step of obtaining a multifunctional epoxy compound having an alkoxysilyl group represented by the following formula A by reaction of the intermediate product with an isocyanate alkoxysilane of the following formula C,
In the first step, the content of the polyfunctional epoxy monomer with respect to 1 mole of the difunctional aromatic alcohol is 2.5 to 10 moles, a method for producing a multifunctional epoxy compound of Formula A.

(In the formulas (AS) to (GS), all K are glycidyl groups of the following formula (E),
In Formula (ES), q is -CH ₂ - or a direct linkage;
In formula (FS), R' is hydrogen,
In formula (GS), R" is a methyl group.)

(In Formula (1), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -SO ₂ -, and in Formula (3), Y is H and are each independently selected from the group consisting of linear or branched C1-C5 alkyl groups.)
[Formula A]

(In Formula A, the unit (PF) is any one selected from the group consisting of the following Formulas (AF) to (GF);

(In the above formulas (AF) to (GF), two of M are bonds with the moiety indicated by ** of the linking group (L1) below, and the remaining M is a glycidyl group of the following formula (E).

(In the linking group (L1), * is a bond with any one of the moieties represented by * selected from the group consisting of the following formulas (1C) to (5C), and ** is composed of the above formulas (AF) to (GF) It is a bond with a moiety represented by any one M selected from the group to be, and the functional group R is represented by the following formula (R).

(In Formula (R), n is an integer of 3 to 10, at least one of R _a to R _c is an alkoxy group having 1 to 5 carbon atoms and the rest is an alkyl group having 1 to 10 carbon atoms, and the alkyl part and the alkyl group of the alkoxy group are It is straight or branched.))

In Formula (EF), q is -CH ₂ - or a linkage;
In formula (FF), R' is hydrogen,
In formula (GF), R" is a methyl group),
The unit (PFE) is any one selected from the group consisting of Formulas (AF) to (GF), and in this case, one of M in Formulas (AF) to (GF) is * of the linking group (L1). It is a bond to the moiety indicated by *, and the remaining M is a glycidyl group of the above formula (E);
the core unit (QF) is any one selected from the group consisting of the following formulas (1C) to (5C);

(In Formula (1C), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -SO ₂ -, and in Formula (3C), Y is H and linear or each independently selected from the group consisting of a branched C1-C5 alkyl group, and * in Formulas (1C) to (5C) is a bond with the * portion of the linking group (L1).)
The functional group R is represented by the above formula (R);
m is an integer from 0 to 10.)
[Formula C]
OCN(CH ₂ ) _n SiR _a R _b R _c
(In Formula C, n is an integer from 3 to 10, at least one of R _a to R _c is a C1-C5 alkoxy group, and the rest is a C1-C10 alkyl group, and the alkyl part and the alkyl group of the alkoxy group are linear or branched.) According to claim 2,
The reaction temperature of the first step is 80 ℃ to 200 ℃, manufacturing method. According to claim 2,
The reaction time of the first step is 30 minutes to 1 hour, manufacturing method. According to claim 2,
The phosphorus-based catalyst is selected from the group consisting of triphenylphosphine, diphenylpropylphosphine, and tricyclohexylphosphine. According to claim 2,
In the first step, the phosphorus catalyst is used in an amount of 0.1 to 2 parts by weight per 100 parts by weight of the polyfunctional aromatic alcohol. An epoxy composition comprising a multifunctional epoxy compound having an alkoxysilyl group represented by Formula A of claim 1, a curing agent, and an inorganic filler. A cured product of the epoxy composition of claim 7. An article comprising the cured product of claim 8. According to claim 9,
The article is at least one kind selected from the group consisting of semiconductor materials, semiconductor components, semiconductor devices, electrical and electronic materials, electrical and electronic components, and electrical and electronic devices. A multifunctional epoxy compound represented by the following formula (B).
[Formula B]

(In the above formula B, the unit (PC) is any one selected from the group consisting of the following formulas (AC) to (GC);

(In the above formulas (AC) to (GC), two of L are bonds with the moiety indicated by ** of the linking group (L2) below, and the remaining L is a glycidyl group of the following formula (E).

(In the linking group (L2), * is a bond with any one of the moieties represented by * selected from the group consisting of the following formulas (1C) to (5C), and ** is composed of the above formulas (AC) to (GC) It is a bond with the part represented by any one L selected from the group that is.)

In Formula (EC), q is -CH ₂ - or a direct linkage;
In formula (FC), R' is hydrogen;
In formula (GC), R" is a methyl group.)
The unit (PCE) is any one selected from the group consisting of the formulas (AC) to (GC), and in this case, one of L in the formulas (AC) to (GC) is * of the linking group (L2). It is a bond with the moiety indicated by *, and the remaining L is a glycidyl group of the above formula (E).),
the core unit (QC) is any one selected from the group consisting of the following formulas (1C) to (5C);

(In Formula (1C), X is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or -SO ₂ -, and in Formula (3C), Y is H and linear or a branched C1-C5 alkyl group, wherein in Formulas (1C) to (5C), * is a bond with the portion indicated by * of the linking group (L2));
m is an integer ranging from 0 to 10.)

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