KR101157567B1 - New Epoxy Resin and Thermosetting Polymer Composite Comprising the Same - Google Patents

Abstract

The present invention is a novel epoxy resin having excellent heat resistance comprising a naphthalene unit and a cardo unit in the main chain having excellent heat resistance; And a new epoxy resin and a filler having improved heat resistance. According to one aspect of the invention, a novel epoxy resin comprising a naphthalene unit and a cardo unit in the main chain; And a new epoxy resin and filler of the present invention are provided. The new epoxy resins comprising naphthalene-based and cardo-based units in the main chain exhibit improved heat resistance by the rigid cardo-based units included in the main chain. In other words, the glass transition temperature increases and the coefficient of thermal expansion decreases. In addition, since the heat resistance is increased even at low curing density due to the cardo-based unit and the linear epoxy structure, the increase in the OH group and the free volume accompanying the increase in the crosslinking density are not accompanied, so that the increase in the hygroscopicity and the dielectric constant, which are adverse effects, are suppressed. .

Description

New Epoxy Resin and Thermosetting Polymer Composite Comprising the Same}

The present invention relates to a novel epoxy resin having excellent heat resistance and a thermosetting polymer composite including the same. More specifically, the present invention relates to a novel epoxy resin having excellent heat resistance including a naphthalene-based unit and a cardo-based unit in a main chain, and a thermosetting polymer composite including the new epoxy resin and a filler.

Recently, it is required to increase heat resistance of materials used to secure processability and reliability of electronic components such as semiconductor substrates, packaging agents, and printed circuit boards (PCBs). For example, the use of high melting point lead-free materials to replace lead-containing solders has increased the reflow temperature of several hundreds of degrees compared to the conventional reflow temperatures of 260-275 ° C. Therefore, the development of a material having a high glass transition temperature is required to have a superior refluorination property at a higher temperature than existing materials.

In addition, it is required to increase the glass transition temperature of the material in order to secure thermal expansion characteristics at the processing temperature of the electronic component. When manufacturing an electronic component such as a semiconductor substrate, a polymer material, an inorganic (silicon) material, a metal material, and the like are used at the same time. In this case, since the CTE value of the polymer material is higher than that of other materials, the electronic part design is limited. Specifically, the coefficient of thermal expansion of the polymer material is approximately 50 to 80 ppm / ° C., and the coefficient of thermal expansion (CTE) of the ceramic material and the metal material, which are inorganic particles (eg, the coefficient of thermal expansion of silicon is 3 to 5 ppm / ° C., and copper The thermal expansion coefficient of is 17ppm / ℃), and the coefficient of thermal expansion (CTE) is very large, several to several tens of times. Thus, for example, when a polymer material is used simultaneously with an inorganic material or a metal material in a semiconductor or display field, the physical properties and processability of the polymer material are significantly limited due to the different coefficients of thermal expansion of the polymer material and the inorganic material or the metal material. do. In addition, for example, in the case of semiconductor packaging in which a silicon wafer and a polymer substrate are used adjacent to each other, or when an inorganic barrier film is coated on a polymer film to impart gas barrier properties, the composition may be changed during process and / or use temperature change. Due to the significant difference in coefficient of thermal expansion (CTE-mismatch), product defects such as crack generation of the inorganic layer, warpage of the substrate, peeling-off of the coating layer, and cracking of the substrate occur. As such, in the field of semiconductor and / or PCB, the design and processability of next-generation components requiring high integration, high micronization, flexibility, high performance, and / or the like due to polymer materials having a very high CTE compared to metal and / or ceramic materials. Or reliability is a problem.

On the other hand, as shown in Fig. 1, when the use temperature of the polymer material exceeds the glass transition temperature of the polymer material, the thermal expansion rate (dimensional change) of the polymer material rapidly rises. Therefore, in the case of the polymer resin having a low glass transition temperature (Tg), due to the rapid increase in the thermal expansion characteristics at a high temperature process temperature, not only defects occur during manufacturing of parts but also the process is limited. Therefore, in order to minimize the sudden volume change of the material under the process conditions (process temperature), it is also required to increase the glass transition temperature (increase of heat resistance) of the polymer resin.

Epoxy resins widely used in electronic parts such as semiconductors and PCBs are thermosetting resins mainly cured using amines, anhydrides, phenolic compounds, and imidazoles. As a method for increasing the heat resistance of the epoxy resin (increasing the glass transition temperature), a method of increasing the crosslinking density of the cured product by increasing the concentration of the epoxy functional group (reducing the epoxy equivalent) is generally used. However, when the crosslinking density of hardened | cured material becomes high, not only the density | concentration of the OH group produced | generated in a crosslinking point part increases, but the free volume of the hardened | cured material produced increases. Due to such an increase in OH groups and an increase in free volume, the inflow of water into the material is facilitated, thereby increasing the hygroscopicity and dielectric constant of the epoxy resin. As such, when the hygroscopicity of the material is increased, the processability of the material is greatly deteriorated due to the occurrence of cracks and defects due to the moisture absorbed during the part process, and when the dielectric constant of the material is increased, the high-speed signal of a high-performance electronic component using high frequency is used. The disadvantage is that transmission becomes difficult.

Therefore, rather than increasing the crosslinking density, it is required to develop an epoxy resin that exhibits excellent heat resistance even at low crosslinking density by increasing the rigidity of the epoxy resin core structure itself.

According to one embodiment of the present invention, an epoxy resin having a new core structure exhibiting improved heat resistance is provided.

According to another embodiment of the present invention, an epoxy resin is provided that exhibits improved heat resistance and is modified in the core structure as well as the side hydroxyl group of the epoxy resin.

According to another embodiment of the present invention, a thermosetting polymer composite including the new epoxy resin and the filler according to the present invention having improved heat resistance and thermal expansion characteristics is provided.

According to one aspect of the invention,

An epoxy resin comprising a naphthalene unit and a cardo unit is provided in the main chain.

According to another aspect of the present invention,

There is provided an epoxy resin comprising a naphthalene-based unit and a cardo-based unit in a main chain, and having at least one side modifier selected from the group consisting of an epoxy group, a (meth) acrylate group, a vinyl group, an allyl group, a carboxylic acid group, and an acid anhydride group. do.

According to another aspect of the present invention,

An epoxy resin comprising a naphthalene unit and a cardo unit in the main chain; And

Composed of inorganic particles and fibers There is provided a thermosetting resin composite comprising at least one filler selected from the group.

Furthermore, according to another aspect of the present invention,

An epoxy resin comprising a naphthalene-based unit and a cardo-based unit in the main chain, and having at least one side modifier selected from the group consisting of an epoxy group, a (meth) acrylate group, a vinyl group, an allyl group, a carboxylic acid group, and an acid anhydride group; And

There is provided a thermosetting resin composite comprising at least one filler selected from the group consisting of inorganic particles and fibers.

Modified epoxy resins comprising a naphthalene-based unit and a cardo unit in the main chain exhibit improved heat resistance by the rigid cardo-based units included in the main chain. In other words, the glass transition temperature is increased and the thermal expansion characteristics are improved. In addition, a cardo-based unit having an out-of-plane structure is introduced into the main chain to reduce the crystallinity of naphthalene, thereby improving the processability of the material. Furthermore, since the new epoxy resin including a naphthalene-based unit and a cardo unit in the main chain has increased heat resistance due to the improved rigidity of the main chain, the concentration of the epoxy functional group is increased in order to improve the heat resistance of the epoxy material as in the prior art. Reduction in epoxy equivalent weight) to increase the crosslinking density of the cured product. Therefore, the increase in the OH group and the increase in free volume are not accompanied by the increase in the crosslinking density, thereby increasing the hygroscopicity and dielectric constant, which are adverse effects.

In addition, an epoxy resin comprising a naphthalene-based unit and a cardo-based unit in the main chain and having at least one side modifier selected from the group consisting of an epoxy group, a (meth) acrylate group, a vinyl group, an allyl group, a carboxylic acid group, and an acid anhydride group In the case of compounding with the filler, the composite of the epoxy resin side modifier and the functional group of the filler is combined in the state of filling the filler firmly between the epoxy resins, and thus the composite can be manufactured with improved heat resistance. .

The composite of the novel epoxy resin and filler including naphthalene-based unit and cardo-based unit in the main chain has improved heat resistance at high temperatures, that is, glass transition temperature and mechanical strength at high temperature due to the high heat resistance of the epoxy resin itself.

In addition, the main chain provided by another embodiment of the present invention includes a naphthalene-based unit and a cardo-based unit, the composite of the new epoxy resin and filler having a side modifier is excellent heat resistance of the epoxy resin itself due to the new core structure of the epoxy resin In addition, since the epoxy resin and the filler are compounded in a solid chemically bonded state, they exhibit not only improved heat resistance but also significantly improve the coefficient of thermal expansion.

1 is a graph showing the relationship between the glass transition temperature and the coefficient of thermal expansion,
2 is a view showing that the hydroxyl group of the epoxy resin having a naphthalene-based unit and a cardo-based unit in the main chain is modified,
3 is a view showing a glass fiber having an amino functional group.

The present invention has been proposed to provide an epoxy resin and an epoxy resin composite having better heat resistance in response to changes in process conditions in which the epoxy resin is used as described above. According to the present invention, a new epoxy resin having improved heat resistance is provided. An epoxy resin for improving the thermal expansion properties of a composite, and a composite having improved heat resistance and thermal expansion properties including each of these epoxy resins and fillers is provided.

1. Epoxy Resin with Cardo Unit

Naphthalene epoxy resins are known as commercially available high heat resistant epoxy resins. Naphthalene-based epoxy resins have high glass transition temperature and low thermal expansion coefficient. However, as described above, development of an epoxy resin having better heat resistance is required as the process temperature increases. On the other hand, the epoxy resin as shown in the graph of the glass transition temperature and the thermal expansion (dimensional change) of the thermal transition (dimensional change) of Figure 1, at a temperature higher than the glass transition temperature, the degree of thermal expansion increase with the increase in temperature is significantly increased.

Therefore, in order to minimize the thermal expansion rate increase of the epoxy resin at a high process temperature, it is also required to increase the glass transition temperature of the epoxy resin, that is, to improve the heat resistance.

According to one embodiment of the present invention, an epoxy resin having improved heat resistance is provided with a new epoxy resin (hereinafter referred to as 'heat resistant epoxy resin' for convenience) including a naphthalene unit and a cardo unit as a main chain. do. However, the present invention is not limited thereto. However, as an example, a schematic structure of the heat resistant epoxy resin may be represented by Chemical Formulas 1 and 2 below. As shown in Formulas 1 and 2, in another aspect of the present invention, the naphthalene-based unit and the cardo-based unit may be alternately repeated. In the formulas (1) and (2) below, naphthalene-based units and cardo-based units positioned in the main chain in the repeating unit are alternately displayed for convenience, and one of the naphthalene-based units or the cardo-based units in the modified epoxy resin has a higher content than the other. It may be included continuously or irregularly.

 [Formula 1]

[Formula 2]

The naphthalene-based unit in the moiety represented by repeating units in Chemical Formulas 1 and 2 of the heat resistant epoxy resin may be a naphthalene-based unit in the naphthalene compound represented by the following Chemical Formula 1- (1).

[Formula 1- (1)]

The cardo-based unit in the moiety represented by repeating units in Chemical Formulas 1 and 2 of the heat resistant epoxy resin may be a cardo-based unit part in the cardo-based compound represented by Chemical Formula 1- (2).

[Formula 1- (2)]

The number of repeating units (n) in Chemical Formulas 1 and 2 of the heat resistant epoxy resin may be 0 to 100, preferably 0 to 20, and more preferably 0 to 10. In the epoxy resin according to the present invention represented by Chemical Formulas 1 and 2, even when the number of repeating units is zero (O), the -OH functional group at the terminal portion connected to the epoxy group may be modified with a reformer. When the epoxy molecular weight increases due to the increase in the number of repeating units, the viscosity of the resin increases, which makes it difficult to process the epoxy material. The number of repeating units may be 100 or less, preferably 20 or less, more preferably 10 or less in consideration of processability. .

The epoxy resin comprising a naphthalene-based unit and a cardo-based unit in the main chain is prepared by, for example, reacting a dihydroxy naphthalene compound with a diepoxy cardo compound or by reacting a diepoxy naphthalene compound with a dihydroxy cardo compound. Can be. It may also be prepared by reacting a dihydroxy naphthalene compound, a dihydroxy cardo compound and a diepoxy cardo compound or by reacting a dihydroxy naphthalene compound, a diepoxy naphthalene and a diepoxy cardo compound. In Formulas 1- (1) and 1- (2), dihydroxy naphthalene compounds and dihydroxy cardo compounds are shown as examples. The diepoxy naphthalene compound and the diepoxy cardo compound are those having an epoxy group instead of a hydroxy group in the chemical structures of Chemical Formulas 1- (1) and l- (2).

It is not limited to this, for example, the dihydroxy naphthalene compound may be used in the synthesis of heat-resistant epoxy resin by epoxidation as shown in Scheme 1 below.

[Reaction Scheme 1]

For example, the dihydroxy cardo compound may be used in the synthesis of a heat resistant epoxy resin by epoxidation as shown in Scheme 2 below.

Scheme 2

Although the present invention is not limited thereto, for example, a naphthalene unit of 2,6-dihydroxy naphthalene and a cardo unit of 9,9-bis (4-hydroxyphenyl) fluorene are alternately used in the naphthalene compound. Examples of the epoxy resin included in the main chain are shown in the following formulas (3) and (4).

(3)

[Formula 4]

The cardo compound refers to a compound having a structure having a cyclic side group in the molecular backbone. Cardo compounds have severe rotational hindrance of the main chain due to the structural characteristics of bulky lateral groups in the polymer backbone, resulting in very high heat resistance (high glass transition temperature). But also has excellent workability.

Thus, the heat resistance of the epoxy resin is increased by introducing a cardo-based unit having rigid and excellent heat resistance and workability into the main chain of the conventional epoxy resin. In addition, a cardo-based unit having an out-of-plane structure is introduced to reduce the crystallinity of the naphthalene-based unit, thereby improving the processability of the material, for example, solubility. In addition, since high heat resistance is achieved by copolymerization of the naphthalene compound and the cardo compound, there is no need to increase the degree of curing of the epoxy resin in order to achieve high heat resistance as in the prior art. Therefore, the crosslinking density of the epoxy cured product is lowered, thereby reducing the hygroscopicity.

2. Epoxy Resin with Side Modifier

As mentioned above, the new epoxy resin which contains a naphthalene unit and a cardo unit in the main chain by this invention shows the outstanding heat resistance. On the other hand, as can be seen in the graph of the glass transition temperature and thermal expansion characteristics of Figure 1, having a high glass transition temperature, the degree of dimensional change due to thermal expansion with the increase in temperature at the process temperature is reduced. In addition, the epoxy resin can be further improved to improve the thermal expansion properties of the composite in order to prevent product defects caused by the difference in thermal expansion between the polymer composite and the neighboring metal and / or ceramic material when applied to the product as a composite of epoxy resin and filler. Development of resin is required.

Thus, by another embodiment of the present invention, a new epoxy resin having a side modifier is also provided. In the epoxy resin having a side modifier according to the present invention, the side hydroxyl group of the epoxy resin having a cardo unit and a nattalene type unit in the main chain according to the present invention is modified with a specific side modifier. That is, the side hydroxyl group of the epoxy resin is modified with at least one side modifier selected from the group consisting of an epoxy group, a (meth) acrylate group, a vinyl group, an allyl group, a carboxylic acid group, and an acid anhydride group, and a naphthalene-based unit and a cardo ( Also provided are new epoxy resins (hereinafter referred to as 'modified epoxy resins' for convenience) containing cardo-based units.

Although not limited thereto, the structures of the epoxy resins having side modifiers are shown, for example, by the formulas (5) and (6) to aid in understanding the structure of the modified epoxy resins. As the modified epoxy resin is shown in the following Chemical Formulas 5 and 6, the naphthalene-based unit and the cardo-based unit may be alternately repeated. In the formulas 5 and 6, the naphthalene-based unit and the cardo-based unit, which are located in the main chain in the repeating unit for convenience, are alternately displayed for convenience, and in the modified epoxy resin, one of the naphthalene-based unit or the cardo-based unit is higher than the other. It may be included continuously or irregularly.

[Chemical Formula 5]

(Side modifier R is selected from the group consisting of an epoxy group, a (meth) acrylate group, a vinyl group, an allyl group, a carboxylic acid group, and an acid anhydride group, and 0 ≦ n ≦ 100.)

[Formula 6]

(Side modifier R is selected from the group consisting of an epoxy group, a (meth) acrylate group, a vinyl group, an allyl group, a carboxylic acid group, and an acid anhydride group, and 0 ≦ n ≦ 100.)

As in the heat resistant epoxy resin, the naphthalene-based unit in the moiety represented by the repeating unit in the formula 5 and 6 of the modified heat-resistant epoxy resin may be a naphthalene ring structure of the naphthalene-based compound represented by Formula 1- (1) The cardo-based unit may be a cardo-based unit of the cardo-based compound represented by Chemical Formula 1- (2).

The hydroxy side groups present in the main chain of the epoxy resin are specific side modifiers as shown in FIG. 2, specifically epoxy groups, (meth) acrylate groups, vinyl groups, allyl groups, carboxylic acid groups and acids. It may be modified with at least one type of reformer selected from the group consisting of anhydride groups. The epoxy resin having a side modifier may include 0 to 100 repeating units (n is 0 to 100), preferably 0 to 20, more preferably 0 to 10 repeating units. For example, the epoxy resin according to the present invention represented by Chemical Formulas 5 and 6 may be modified with a -OH functional group at the terminal portion connected to the epoxy group even when the number of repeating units is zero (O). When the epoxy molecular weight increases due to the increase in the number of repeating units, the viscosity of the resin increases, making it difficult to process the epoxy material. Therefore, the number of repeating units is 100 or less, preferably 20 or less, more preferably 10 or less in consideration of functionality. have.

As shown in FIG. 2, the modified heat resistant epoxy resin deprotonated the protons (H ⁺ ) in the hydroxyl group in the epoxy resin backbone using a base or the like, followed by epichlorohydrin (epichlohydrin), ( It can be prepared by reacting with a meta) acrylic halide, allyl halide and the like. In this case, K ₂ CO ₃ , KOH, NaOH, triethylamine, tetraethylammonium halide, triethylbenzylammonium halide and the like may be used as the base.

The epoxy resin having the side modifier is firmly complexed by forming a network by chemical bonding between the side modifier and the functional group in the filler, thereby forming a network.

Conventional epoxy resins do not contain functional groups capable of chemically bonding particles or fibers when forming a composite with a filler in the resin itself. Thus, upon temperature change, each independent behavior of the polymer chain and the filler is not efficiently limited. However, since the epoxy resin having the side modifier according to the present invention has a side modifier in addition to the terminal epoxy group which is a curable functional group, there is an additional chemical bond between the epoxy resin and the filler. Therefore, the mobility of the polymer backbone is limited by the additional bonding and the glass transition temperature of the epoxy resin is increased by about 10 ~ 50 ℃ by the compounding. That is, the glass transition temperature of the conventional epoxy resin does not rise by the compounding, but in the case of the epoxy resin having a side modifier, the glass transition temperature of the epoxy resin cured composite having no side modifier is about 200 ° C., but has a side modifier. In the composite containing the epoxy resin, the glass transition temperature is increased to 250 ° C.

On the other hand, the hydroxyl group (OH group) of the epoxy resin has a disadvantage of increasing the dielectric constant and moisture absorption of the resin. However, according to one embodiment of the present invention, since the concentration of OH groups in the epoxy resin is reduced by the reforming reaction, the dielectric constant and hygroscopicity of the epoxy resin are lowered. In addition, since the hydrogen bonds between the epoxy molecules are eliminated, the viscosity of the epoxy resin is lowered, thereby improving the blendability. Furthermore, since the inorganic particles chemically bonded to the main chain of the epoxy resin may act as a crosslinking point, the curing degree of the epoxy resin is increased as a whole, thereby improving heat resistance characteristics and physical properties of the composite such as modulus.

3. Composite containing new epoxy resin

In another embodiment of the present invention, (1) a thermosetting polymer composite including the heat resistant epoxy resin and a filler; And (2) there is provided a thermosetting polymer composite comprising an epoxy resin and a filler having the side modifier.

(1) The heat resistant epoxy resin and (2) the epoxy resin which has a side modifier which comprise the composite by this invention are the epoxy resin containing a cardo unit, and 2. the epoxy resin which has a side modifier with respect to the said epoxy resin. All of the above apply, and are not described separately in this section.

As the filler constituting the composite, at least one species selected from the group consisting of inorganic particles and fibers may be used.

As the inorganic particles and fibers, any inorganic particles and fibers known to be used for forming a complex with an organic resin may be used.

Inorganic particles include, but are not limited to, SiO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O _3, or mixed metal oxides (eg, silica-Zr oxides) and silsesquinoxanes containing them alone. Or a mixture of two or more kinds. The silsesquioxane (silsesquioxane) is a cage (cage), T-10 type, ladder (ladder) type, these can all be used in the present invention.

The fiber is not limited thereto, but any fiber generally used for improving physical properties of the conventional organic resin composite, specifically, an epoxy resin composite for use as a substrate, may be used. Specifically, glass fibers, organic fibers or mixtures thereof can be used. In addition, the term 'glass fiber' as used herein is used to mean not only glass fiber, but also glass fiber fabric, glass fiber nonwoven fabric, and the like. Although not limited to this, Glass fiber, such as E, T (S), NE, E, D, quartz, is mentioned as a glass fiber. Although it does not specifically limit as an organic fiber by this, Liquid crystalline polyester fiber, polyethylene terephthalate fiber, wholly aromatic fiber, polyoxybenzazole fiber, etc. can be used individually or in mixture of 2 or more.

The filler is generally not limited to this on the surface, but for example selected from the group consisting of epoxy groups, amino groups, (meth) acrylate groups, C ₂ -C ₆ alkylene groups, allyl groups, thiol groups and maleimide groups It may have at least one functional group (hereinafter referred to as 'reactive functional group'). The functional group of the filler is chemically bonded to the side modifier of the epoxy resin, so that the filler can be more firmly and bonded to the epoxy resin to form a composite having improved glass transition temperature and thus heat resistance.

Although not limited to this, Examples of the filler having the functional group include those shown in the following formula (7).

[Formula 7]

In which n is 0 to 10

Also, as an example, glass fibers having amino functional groups that can be used as filler in the composite according to the present invention are shown in FIG. 3.

Furthermore, the filler may further include functional groups (hereinafter referred to as 'compatibility functional groups') of aliphatic or aromatic molecules in addition to the reactive functional groups described above. The compatibility of the epoxy resin and the filler is improved by the compatible functional group. In the compatible functional groups are, but are not limited to, for example, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₈ aromatic, C ₃ -C ₈ aromatic alkyl, C ₃ - C ₈ aromatic alkoxy, C ₃ -C ₇ heteroaromatic alkoxy group (hetero element is at least one selected from the group consisting of O, N, S, P), C ₃ -C ₇ heteroaromatic alkyl (hetero element is O, At least one selected from the group consisting of N, S, and P).

The filler may also be used further comprising at least one or more of the above-mentioned compatible functional groups in consideration of reactivity and compatibility (mixability) with the modified epoxy resin. Furthermore, as the filler, those containing a reactive functional group and a compatible functional group may be used. Although not limited thereto, examples of the filler including the reactive functional group and the compatible functional group include the filler of Formula 8 below. More specifically, but not limited thereto, for example, a filler having 50 mol% of benzene groups and 50 mlo% epoxy functional groups can be used.

[Formula 8]

In which n is 0 to 10

The inorganic particles are not limited thereto, but inorganic particles having a particle size of 0.5 nm to several tens of μm may be used in consideration of the use of the composite, specifically, the dispersibility of the inorganic particles. Since the inorganic particles are dispersed in the epoxy resin, it is preferable to use the inorganic particles of the above size due to the difference in dispersibility according to the particle size. On the other hand, since the fiber is mainly compounded in a manner in which the epoxy resin is wetted with the fiber, the size of the fiber is not particularly limited, and any fiber generally used in this field may be used.

Among the composites according to the present invention, (1) the thermosetting polymer composite including the heat resistant epoxy resin and the filler may be applied to the heat resistant epoxy resin including the cardo unit, as described in the above section 1. Epoxy resin comprising a cardo unit. The rigid cardo-based unit is included to increase the glass transition temperature, thereby improving heat resistance and thermal expansion characteristics. In addition, a cardo-based unit having an out-of-plane structure is introduced into the main chain to reduce the crystallinity of naphthalene, thereby improving the processability of the material.

(2) The thermosetting polymer composite including the epoxy resin having the side modifier and the filler in the composite according to the present invention, as described in item 2. Epoxy resin having the side modifier, the reactivity of the side modifier and the filler of the epoxy resin Due to the chemical bonding of the functional groups, the epoxy resin and the filler are firmly bonded and complexed, and the mobility of the polymer backbone is limited by the filler. Therefore, the thermosetting polymer composite has a glass transition temperature which shows a thermal transition with a temperature rise. In addition, the thermal transition phenomenon is suppressed. Accordingly, the thermosetting polymer composite according to the present invention exhibits improved heat resistance. Furthermore, since the epoxy resin having a side modifier is used as the thermosetting polymer composite, the hydroxyl group (-OH group) concentration of the epoxy resin is reduced, and thus the dielectric constant and hygroscopicity of the composite are lowered. On the other hand, due to the filler chemically bonded to the main chain of the epoxy resin, the heat resistance and physical properties of the composite such as modulus are also improved.

Although not limited to this, the epoxy resin which has a side modifier, and the filler which has an amino group in the surface react, for example like following Reaction Formula 3, and a filler is chemically bonded to an epoxy resin.

Scheme 3

When inorganic particles are used as the filler in the composite according to the present invention, the inorganic particles may be blended in an amount of 5 to 95 phr (parts per hundred, parts by weight per 100 parts by weight) with respect to the epoxy resin. If the amount of the inorganic particles is less than 5 phr, it is not preferable in that the glass transition temperature rise and the heat resistance improvement of the composite are insufficient, and if it exceeds 95 phr, the viscosity of the composite is increased and the workability is greatly reduced.

When fiber is used as a filler in the composite according to the present invention, the content of the fiber may be 10% to 90% by weight based on the total weight of the composite. If the content of the glass fiber having a reactive functional group is less than 10% by weight, it is not preferable in that it is insufficient in improving the heat resistance of the composite, and in excess of 90% by weight, it is preferable in that the processing of the composite is difficult due to the insufficient amount of epoxy as a binder. Not. The total weight of the composite refers to the total composite weight, including the amount of the composite when the composite includes inorganic particles, a curing agent and / or a catalyst, and the like.

The fillers used in the composite according to the present invention, specifically inorganic particles and glass fibers, and methods for producing them are generally known in the art, and any of these known inorganic particles and glass fibers may be used in the composite of the present invention. . For example, a glass fiber having an amino functional group is obtained by adding 0.2-1.0 wt% of γ-aminopropyltriethoxysilane as a silane coupling agent to a mixed solvent of 95 wt% ethanol and 5 wt% distilled water. Thereafter, the solution can be modified with an amino functional group by impregnating glass fibers for 30 minutes, taking them out, reacting for 30 minutes in an oven at 110 ° C., and completely drying them at room temperature for one day.

Since the thermosetting polymer composite of the present invention forms a specific article by curing in the presence of a curing agent by applying heat, the curing agent may also include a curing agent. Furthermore, the thermosetting polymer composite of the present invention may further include any catalyst as necessary to improve the required physical properties. The blending ratio of these additional blending components is not particularly limited, and may be blended in an amount suitable for improving physical properties of the composite in a range known to be generally blendable in the art.

As the curing agent, any curing agent generally known as an epoxy resin curing agent may be used. Although it does not specifically limit by this, For example, an amine resin, a phenol resin, an anhydride type, etc. can be used. More specifically, as the amine curing agent, aliphatic amines, cycloaliphatic amines, aromatic amines, other amines and modified polyamines may be used, and amine compounds including two or more primary amine groups may be used. Specific examples of the amine curing agent include 4,4'-dimethylaniline (diamino diphenyl metone) (4,4'-Dimethylaniline (Diamino diphenyl methone, DAM or DDM), diamino diphenyl sulfone (DDS) , at least one aromatic amine selected from the group consisting of m-phenylene diamine, diethylene triamine (DETA), diethylene tetraamine, triethylenetetraamine (Triethylene Tetramine, TETA), m-xylene diamine (MXDA), methane diamine (MDA), N, N'-diethylenediamine, N, N'-DEDA ), Tetraethylenepentaamine (TEPA), and at least one aliphatic amine selected from the group consisting of hexamethylenediamine, isophorone diamine (IPDI), N-aminoethyl pyrrazine (N -Aminoethyl piperazine, AEP), Bis (4-A One or more alicyclic amines selected from the group consisting of no 3-methylcyclohexyl) methane (Bis (4-Amino 3-Methylcyclohexyl) Methane, Larominc 260), dicyandiamide (DICY), and other polyamides And modified amines such as epoxides.

The amine curing agent may adjust the degree of curing of the composite by reaction with an epoxy group, and may adjust the content of the amine curing agent based on the concentration of the epoxy group of the epoxy resin according to the desired degree of curing. In particular, in the equivalent reaction of the amine curing agent and the epoxy group, one amine group per two epoxy groups is a quantitative concentration, and in the equivalent reaction, the amine curing agent has a molar ratio of epoxy group / amine group [NH ₂ ] of 2/1. It can be used in the concentration ratio which becomes. Therefore, the content of the amine curing agent in the present invention is preferably 1.0 to 2.5 so that the molar ratio of the epoxy group [epoxy group] / amine group [NH ₂ ] to 0.5 to 3.0 based on the epoxy group of the epoxy resin. It is preferable to use it so that it can be adjusted. The molar concentration of the amine group in the molar ratio of the epoxy group / amine group does not include the amino group contained in the glass fiber. On the other hand, the epoxy group of the side epoxy group and the filler in an epoxy resin is contained in the said epoxy group molar concentration.

Although not limited to this, examples of the phenolic curing agent include phenol noblock, o-cresol novolac, phenol p- xylene resin, phenol 4,4'-dimethylbiphenylene resin, phenol dicyclopentadiene resin, and the like. have.

Examples of the anhydride-based curing agent include, but are not limited to, aliphatic anhydrides such as dodecenyl succinic anhydride (DDSA), POLY AZELAIC POLY ANHYDRIDE, and hexahydrophthalic anhydride. cycloaliphatic anhydrides such as (hexahydrophthalic anhydride (HHPA), methyl tetrahydrophthalic anhydride (MeTHPA), methylnadic anhydride (MNA), trimellitic anhydride Aromatic anhydrides such as anhydride (TMA), pyromellitic acid dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), tetrabromophthalic anhydride, TBPA ), Such as chlorendic anhydride (HET) And halogen-based anhydrides.

As the catalyst, any catalyst known in the art commonly used for epoxy resin composites may be used, but is not limited thereto. For example, dimethyl benzyl arnine (BDMA), 2,4 Tertiary amines such as 6-tris (dimethylaminomethyl) phenol (2,4,6-Tris (dimethylaminomethyl) phenol, DMP-30), 2-methylimidazole (2MZ), 2-ethyl-4-methyl -Imidazoles such as -imidazole (2E4M), 2-heptadecylimidazole (2HDI), and Lewis acids such as BF3-monoethyl amine (BF3-MEA) and the like.

(1) A thermosetting polymer composite comprising a heat resistant epoxy resin and a filler according to one embodiment of the present invention is cured by a curing reaction of an epoxy group and a curing agent in an epoxy resin. On the other hand, (2) the thermosetting polymer composite including an epoxy resin and a filler having a side modifier according to another embodiment of the present invention, the following two reactions proceed simultaneously. That is, (1) the curing reaction of the epoxy functional group of the epoxy resin end group and the curing agent and (2) the chemical reaction of the side modifier of the epoxy resin and the reactive functional group of the filler. The reaction between the epoxy resin and the hardener during the above two chemical reactions produces an epoxy polymer network and at the same time the filler forms a composite integrated with the epoxy polymer network, so that the heat resistance and glass transition properties of the composite do not have a conventional reforming group. It is remarkably improved compared to the composite including the epoxy resin and the filler. Furthermore, the compatible functional groups also participate in the curing reaction.

Hereinafter, the hardening reaction of an epoxy resin and a filler is demonstrated.

The curing reaction of the epoxy resin and the curing agent may be used under any reaction conditions generally known as the epoxy resin curing reaction, and the curing reaction conditions do not change due to the addition of the filler. Curing reaction conditions may vary depending on the structure of the epoxy used, the type of curing agent and whether the catalyst is used.

As described above, the curing reaction of the epoxy resin and the curing agent is common and is not limited thereto. For example, naphthalene units of 2,6-dihydroxy naphthalene and 9,9-bis (4-hydroxyphenyl) In the case of an epoxy resin containing alternating cardo-based units of fluorene in the main chain, 4,4'-dimethylaniline is reacted at 150 ° C for 2 hours when using a curing agent, and then further at 200 ° C for 5 hours. React. In the case of curing using a phenolic curing agent such as phenol noble resin as a curing agent, a triphenylphosphine (1 phr) catalyst is additionally used, and the epoxy group and the curing agent react by heating at 200 ° C. for 5 hours. The above reaction is intended to assist the understanding of the present invention and thus does not limit the present invention.

On the other hand, the reaction between the side modifier of the epoxy resin having the side modifier and the reactive functional group of the filler depends on the kind of functional group participating in the reaction. For example, as shown in Scheme 3, the side epoxy group, carboxylic acid group, and acid anhydride group in the epoxy resin may be chemically reacted with the amino group or epoxy group reactive functional group in the filler to be bonded. On the other hand, as in Scheme 4, in the epoxy resin modified with the meta (acrylate), vinyl group and / or allyl functional group, the meta (acrylate), vinyl group and / or allyl modified functional group is meta (acrylate) in the inorganic particles And chemically react with at least one reactive functional group selected from the group consisting of a vinyl group, a C ₂ -C ₆ alkylene group, an allyl group, a maleimide group, and a thiol group.

Scheme 4

The epoxy composite provided by one embodiment of the present invention is suitable for use in next generation semiconductor substrates, next generation PCBs, packaging, OTFTs, flexible display substrates, and the like.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to illustrate the present invention, which does not limit the present invention.

Example 1 Synthesis of Naphthalene-Cado-Naphthalene Trimer Epoxy Resin

In a 250 ml flask, 11.26 g of 9,9-bis (4-hydroxyphenyl) fluorene, 35 g of 1,6-diepoxy naphthalene, 0.88 g of tetraethylbenzylammonium chloride (TEBAC) and 70 ml of acetonitrile were added at 80 ° C. Stirred. 9,9-bis (4-hydroxyphenyl) fluorene and 1,6-diepoxy naphthalene were dissolved, and then the reaction proceeded at 80 ° C for 12 hours. After completion of the reaction, the solvent was removed by an evaporator and then dissolved in ethyl acetate and then worked up with H ₂ O. After separating the organic layer, ethyl acetate was removed by an evaporator to obtain an epoxy resin containing a naphthalene unit and a cardo unit in the main chain. Synthesis scheme of a new epoxy resin according to Example 1 is the same as in Scheme 5.

Scheme 5

Example 2 Synthesis of Cardo-Naphthalene-Cado Trimer Epoxy Resin

57.7 g of cardo-epoxymonomer and 0.85 g of Tri-ethyl Benzyl Ammonium Chloride were added to the flask, and the air in the reaction vessel was removed to obtain a vacuum. 300 ml of CH ₃ CN was added to the flask and stirred at room temperature for 5 minutes to form a uniform solution. To the solution was slowly added dropwise a naphthalene solution in which 5 g of dihydroxyl naphthalene was dissolved in 100 ml of CH ₃ CN, and then reacted at 80 ° C. for 24 hours. The solvent was removed by an evaporator and then dissolved in ethyl acetate and then worked up with H ₂ O. After separating the organic layer, ethyl acetate was removed by an evaporator to obtain an epoxy resin containing a naphthalene unit and a cardo unit in the main chain. Synthesis scheme of a new epoxy resin according to Example 2 is shown in Scheme 6 below.

[Reaction Scheme 6]

Example 3 Synthesis of Naphthalene-Cado-Naphthalene Trimer Epoxy Resin with Side Modifier

250ml at room temperature 5 g of the trimer synthesized in Example 1 was added to the flask and stirred in 60 ml of methylene chloride. 3 ml of triethylamine and 1.8 ml of acryloyl chloride were slowly added at 0 ° C. and reacted at 0 ° C. for 2 hours. After completion of the reaction, the organic layer was worked up with water after quenching with saturated NaHCO ₃ . After separating the organic layer, water remaining in the organic layer was removed with MgSO ₄ , filtered and the solvent was removed with an evaporator. Synthesis scheme of a new epoxy resin according to Example 3 is the same as in Scheme 7.

Scheme 7

Example 4 Curing of Naphthalene-Cado-Naphthalene Trimer Epoxy Resin

At room temperature, 1.6 g of naphthalene-cardo-naphthalene epoxy resin prepared in Example 1 and 0.189 g of 4,4'-diaminodiphenylmethane (DDM) were dissolved in 7 g of methylene chloride, and then uniformly mixed using a mixer. The prepared solution was placed in a vacuum oven preheated to 90 ° C., the solvent was removed, and then placed in a mold preheated to 90 ° C., and the reaction was carried out at 90 ° C. for 2 hours, at 150 ° C. for 2 hours, and at 200 ° C. for 2 hours. The reaction was further cured at 230 ℃ for 2hr.

Example 5 Curing of Cardo-Naphthalene-Cado Trimer Epoxy Resins

At room temperature, 2.5 g of cardo-naphthalene-cardo epoxy resin prepared in Example 2 and 0.87 g of DDM were dissolved in 7 g of methylene chloride, and then uniformly mixed using a mixer. The prepared solution was put in a vacuum oven preheated to 90 ° C., the solvent was removed, and then placed in a mold preheated to 90 ° C., and reacted at 90 ° C. for 2 hours, at 150 ° C. for 2 hours, and at 200 ° C. for 2 hours. The temperature was raised and further cured at 250 ° C. for 2 hours.

Example 6: Naphthalene-cardo-naphthalene trimer epoxy curing with side modifier

At room temperature, 1.75 g of naphthalene-cardo-naphthalene epoxy resin having a side acryl group prepared in Example 3 and 0.189 g of DDM are dissolved in 5 g of methylene chloride, and then uniformly mixed using a mixer. The prepared solution was placed in a vacuum oven preheated to 90 ° C., the solvent was removed, and then placed in a mold preheated to 90 ° C., and the reaction was carried out at 90 ° C. for 2 hours, at 150 ° C. for 2 hours, and at 200 ° C. for 2 hours. The mixture was further cured at 250 ° C. for 2hr.

Comparative Example 1: Curing of Naphthalene Epoxy Resin

After dissolving 2 g of 1,6-diepoxy naphthalene resin in an oven preheated to 120 ° C., 0.728 g of DDM is added and mixed for 2 to 3 minutes. The homogeneously mixed solution was placed in a mold preheated to 120 ° C., reacted at 120 ° C. for 2 hours, and at 150 ° C. for 2 hours, and then heated to an oven and further cured at 200 ° C. for 2 hours.

Example 7: Evaluation of the thermal properties of the cured product

Thermal properties of the cured products of Examples 4 to 6 and Comparative Example 1 were evaluated. Thermal properties were evaluated by using a thermo-mechanical analyzer (TMA) for the dimensional change with the temperature of the cured product. The cured product specimens were prepared in a width x length x thickness of 5 mm x 5 mm x 3 mm and measured in an expansion mode. The results are shown in Table 1 below.

Cured Product System CTE (ppm / ℃) Tg (℃)
(TMA) Epoxy resin Hardener α ₁ (T <Tg) Example 4 DDM 43 199 Example 5 DDM 40 225 Example 6 DDM 47 195 Comparative Example 1 DDM 55 175

As shown in Table 1, the cured product of the epoxy resin according to the present invention containing a cardo unit has a glass transition temperature of about 20 ~ 40 ℃ rise compared to the cured naphthalene epoxy of Comparative Example 1, the dimensions according to the temperature change It was confirmed that the dimensional change is reduced.

Example 8: Preparation of Resin Composite Using New Epoxy Resin

After mixing 1.6 g of the naphthalene-cardo-naphthalene epoxy resin synthesized in Example 1 at room temperature with 0.5 g of DDM and 7 g of MEK, the mixture was stirred to prepare a homogeneous solution, and the quartz glass fiber fabric having the amino group of FIG. 45 mm x 45 mm size), and then the solvent was dried for 10 minutes in a vacuum oven at 120 ℃. After drying, it was put in a hot press and cured to prepare a composite of an epoxy resin modified with an epoxy group and a glass fiber fabric. The curing conditions in the hot press were cured for 2 hours at 150 ° C, 200 ° C, 230 ° C and 250 ° C. Then, as a result of evaluating the thermal properties of the composite in the same manner as in Example 7, the CTE value was 12ppm / ℃ and the glass transition temperature was 200 ℃ showed very excellent thermal properties. The resin content in the epoxy polymer composite thus prepared is 50 wt%, and the thickness of the composite is 0.3 mm.

Example 9 Preparation of Resin Composite Using New Epoxy Resin

After mixing 1.6 g of the naphthalene-cardo-naphthalene epoxy resin synthesized in Example 1 at room temperature, 0.5 g of DDM, 0.5 g of amino particles having an amino group (average particle size of 1 μm), and 7 g of MEK (methyl ethyl ketone), followed by stirring To prepare a uniform solution and dried the solvent for 10 minutes in a vacuum oven at 120 ℃. After drying, the mixture was placed in a hot press and cured to prepare a composite of an epoxy resin and an inorganic particle modified with an epoxy group. The curing conditions in the hot press were cured for 2 hours at 150 ° C, 200 ° C, 230 ° C and 250 ° C. Then, as a result of evaluating the thermal properties of the composite in the same manner as in Example 7, the CTE value was 35ppm / ℃ and the glass transition temperature was 200 ℃ showed very excellent thermal properties.

Claims (15)

delete delete Epoxy resin of the following Chemical Formula 1 or 2 structure comprising a naphthalene-based unit and a cardo-based unit in the main chain.
[Formula 1]

(2)

In Chemical Formula 1 or 2, the naphthalene-based unit in the main chain is selected from the naphthalene-based units of the following Chemical Formula 1- (1),

[Formula 1- (1)]

In Chemical Formula 1 or 2, the cardo-based unit in the main chain is selected from the cardo-based unit of the following Chemical Formula 1- (2),

[Formula 1- (2)]

Number of repeat units (n) is 0 to 100.
According to claim 3, wherein the hydroxy group of Formula 1 and Formula 2 is at least one reactive side functional group selected from the group consisting of epoxy group, (meth) acrylate group, vinyl group, allyl group, carboxylic acid group and acid anhydride group Epoxy resin, characterized in that modified.
The epoxy resin of claim 3 or 4; And
A thermosetting resin composite comprising at least one filler selected from the group consisting of inorganic particles and fibers.
The method of claim 5, wherein the filler comprises at least one reactive functional group selected from the group consisting of an epoxy group, an amino group, a (meth) acrylate group, a C2-C6 alkylene group, an allyl group, a thiol group and a maleimide group Thermosetting resin composite.
The method of claim 5, wherein the inorganic particles are SiO ₂ , ZrO ₂ , TiO ₂ , BaTiO ₃ , Al ₂ O ₃ , mixtures thereof, T-10 type silsesquinoxane and ladder type silsesquinoxane alone or Thermosetting resin composite, characterized in that used as a mixture of two or more kinds.
6. The fiber according to claim 5, wherein the fiber is glass fiber or liquid crystal polyester fiber, polyethylene terephthalate fiber, wholly aromatic fiber, polyoxybene selected from the group consisting of E, T (S), NE, E, D and quartz. A thermosetting resin composite, characterized in that the organic fiber is selected from the group consisting of solazole fibers.
The method of claim 5, wherein the filler is C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₈ aromatic, C ₃ -C ₈ aromatic alkyl, C ₃ -C ₈ aromatic alkoxy, C _3- C ₇ heteroaromatic alkoxy group (hetero element is at least one selected from the group consisting of O, N, S, P), C ₃ -C ₇ heteroaromatic alkyl (hetero element is composed of O, N, S, P And at least one compatible functional group selected from the group consisting of: a minimum type selected from the group).
6. The thermosetting resin composite according to claim 5, wherein the inorganic particles are contained in 5 to 95 phr.
The thermosetting resin composite according to claim 5, wherein the fiber is included in an amount of 10% by weight to 90% by weight based on the total weight of the thermosetting polymer composite.
6. The thermosetting resin composite according to claim 5, wherein the resin composite further comprises at least one selected from the group consisting of a curing agent and a catalyst.
Packaging made of the thermosetting resin composite of claim 5.
A substrate made of the thermosetting resin composite of claim 5.
A transistor made of the thermosetting resin composite of claim 5.

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