WO2015076626A1 - Novolac resin, curing agent containing same, and epoxy resin composition, and novolac epoxy resin, preparation method therefor, and epoxy resin composition containing novolac epoxy resin - Google Patents

Abstract

The present invention relates to a novolac resin, a curing agent containing the same, and an epoxy resin composition, and more specifically, to: a novolac resin of which the degree of polymerization and the molecular weight are controlled to be in specific ranges in order to remarkably improve high thermal stability at a high temperature and moisture resistance while having low viscosity; a novolac curing agent containing the same; and an epoxy resin composition. In addition, the present invention relates to a novolac epoxy resin, a preparation method therefor, and an epoxy resin composition containing the novolac epoxy resin, and more specifically, provides: a novolac epoxy resin of which the degree of polymerization and the molecular weight are controlled to be in specific ranges in order to remarkably improve high thermal stability at a high temperature and moisture resistance while having low viscosity; a preparation method therefor; and an epoxy resin composition containing the novolac epoxy resin.

Description

Novolak resin, a curing agent and epoxy resin composition comprising the same, and a novolak epoxy resin, a method of manufacturing the same and an epoxy resin composition comprising a novolak epoxy resin

The present invention relates to a novolak resin, a curing agent and an epoxy resin composition comprising the same, and more particularly, a novolak resin having a low viscosity while having excellent hygroscopic resistance and high thermal stability at high temperature, a novolak curing agent comprising the same And an epoxy resin composition.

In addition, the present invention relates to a novolak epoxy resin, a method for producing the same and an epoxy resin composition comprising a novolak epoxy resin, and more particularly, a furnace having a low viscosity and a high thermal stability and high moisture absorption resistance at high temperatures. The present invention relates to a epoxy resin composition comprising a novolak epoxy resin, a method for producing the same, and the novolak epoxy resin.

Copper clad laminates (CCL) used for printed circuit boards are made by attaching copper foil to one or both sides of laminated insulating plates composed of various insulating materials and binders. As a result, requirements such as lead-free have been increased, and accordingly, the demand for copper-clad laminates requiring an insulating material having high glass transition temperature characteristics has recently increased considerably.

In addition, the application of a polyfunctional novolak curing agent and a novolak epoxy curing agent to replace the amine-based curing agent conventionally applied to manufacture such a copper clad laminate is attracting attention. When the novolak resin and the novolak epoxy curing agent which are polyfunctional resins are used as a hardening | curing agent, high glass transition temperature can be obtained with high hardening density.

However, the novolak resin, which is conventionally applied as a curing agent, contains a large amount of oligomer product having low polymerization degree in the polymerization process. In particular, the component in which two monomers were polymerized has few reactors, and it reduces the hardening density of a final hardened | cured material significantly. In addition, due to the high reactivity, the curing is excessively accelerated, the surface is hardened before the solvent is sufficiently volatilized in the prepreg manufacturing process, so that a large amount of the solvent remains in the prepreg. The glass transition temperature is greatly reduced.

In addition, in order to obtain a high glass transition temperature, in the case of a novolak resin having an increased molecular weight and a softening point, compatibility with a solvent may be lowered due to the characteristics of a component having a high molecular weight, and the viscosity may be increased. This has the disadvantage that the varnish manufacturing and prepreg impregnation process has a lower workability and the need to add a solvent to reduce the viscosity, furthermore, the further use of the solvent is undesirable in terms of economics and environmental pollution.

Accordingly, the present inventors have proposed a novolak resin having high heat resistance and low viscosity by removing low molecular weight (n = 0) of the novolak resin to 5 wt% or less in the application number 2012-0055777, but n = 0 Since 2.1% or more of the component is included, thermal stability is insignificant at a high temperature of 280 ° C. or higher, and moisture absorption resistance, which is an important physical property in manufacturing copper clad laminate (CCL), has not been significantly improved.

Therefore, there is a need for the development of a novolak resin that can improve these points.

The main object of the present invention is to provide a novolak resin having low viscosity and remarkably improved high thermal stability and hygroscopic resistance at a high temperature of 280 ° C. or higher, and a method for producing the same.

The present invention also provides a novolak curing agent comprising a low viscosity novolak resin having excellent hygroscopic resistance and high thermal stability at high temperatures.

The present invention also provides an epoxy resin composition and a cured product of the epoxy resin composition capable of simultaneously improving hygroscopic resistance and thermal stability at high temperature by including the novolak resin as a curing agent.

In addition, the main object of the present invention is to provide a novolak epoxy resin and a method for producing the same, which has a low viscosity and remarkably improved high thermal stability and hygroscopicity at a high temperature of 280 ° C or higher.

The present invention also provides an epoxy resin composition comprising a novolak epoxy resin having low viscosity while having excellent hygroscopic resistance and high thermal stability at high temperature, and a cured product of the epoxy resin composition.

In order to achieve the above object, one embodiment of the present invention is a novolak resin comprising a compound represented by an integer of n = 0 to 5 in formula 1, 2.8% by weight of a compound of the formula n = 0 It contains below, or without containing a compound of n = 0 in the formula (1), the weight average molecular weight is 500 to 5,500g / mol, polydispersity index is 1.0 to 3.0, melt viscosity at 180 ℃ 100 to 3,000 cps and a softening point of 80 to 160 ° C. to provide a novolak resin.

[Formula 1]

In Formula 1 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -C ₁₀ H _12- , -O = S = 0- or -CH (C ₆ H ₄ OH)-, X is -H, -Br, -C (CH ₃ ) ₂ C ₆ H ₄ OH or an alkyl group having 1 to 12 carbon atoms.

In a preferred embodiment of the present invention, in formula 1, R is -CH _2- , X may be characterized in that -C (CH ₃ ) ₂ C ₆ H ₄ OH or -CH ₃ .

Another embodiment of the present invention, (a) a condensation reaction between the phenolic monomer and the formaldehyde-based monomer under an acid catalyst, the condensation water is removed to a furnace comprising a compound represented by an integer of n = 0 to 5 in the formula Synthesizing a volac resin; (b) a heating step of heating and melting a novolak resin obtained from the synthesis step, wherein the novolak resin including a compound represented by an integer of n = 0 to 5 in Formula 1 above a softening point; And (c) a novolak resin comprising a compound represented by an integer of n = 0 to 5 in the following Chemical Formula 1, melted from the heating step, into a high vacuum distillation apparatus to obtain a compound having n = 0 in Chemical Formula 1 of 2.8. It provides a method for producing a novolak resin comprising an extraction step of removing by weight or less, or completely removed.

[Formula 1]

In Formula 1 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -C ₁₀ H _12- , -O = S = 0- or -CH (C ₆ H ₄ OH)-, X is -H, -Br, -C (CH ₃ ) ₂ C ₆ H ₄ OH or an alkyl group having 1 to 12 carbon atoms.

In another preferred embodiment of the present invention, the high vacuum distillation apparatus in step (c) may be characterized in that it is set to 200 to 280 ℃ under a pressure of 0.001 to 1.5 mbar.

Another embodiment of the present invention provides a novolak curing agent comprising the novolak resin.

Another embodiment of the invention, the epoxy resin; And it provides the epoxy resin composition and the cured product of the epoxy resin composition comprising the novolac curing agent.

In addition, an embodiment of the present invention, in the novolak epoxy resin comprising a compound represented by an integer of n = 0 to 5 in the formula (2), or less than 2.8% by weight of the compound of the formula (n = 0), or It provides a novolak epoxy resin, characterized in that the weight average molecular weight of 700 to 5,000 g / mol without including a compound of n = 0 in the formula (2).

[Formula 2]

In Formula 2 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -O = S = 0- or

X is -H, -Br, -CF ₃ , an alkyl group having 1 to 12 carbon atoms or

to be.

In a preferred embodiment of the present invention, in formula 2, R is -CH _2- , X is -H,

Or -CH ₃ .

In a preferred embodiment of the present invention, the novolak epoxy resin may be characterized in that the PDI is 1.0 to 3.0.

In a preferred embodiment of the present invention, the novolak epoxy resin may be characterized in that the melt viscosity at 160 ℃ 30 to 3,000cps.

In a preferred embodiment of the present invention, the novolak epoxy resin may be characterized in that the softening point is 40 to 130 ℃.

Another embodiment of the present invention is (a) poly / condensation reaction of the novolak-based polymer and epiclohydrin monomer under a basic catalyst, the condensation water and the resulting salt is removed by the integer of n = 0 to 5 in the formula Synthesis step of synthesizing a novolac epoxy resin comprising a compound represented by; (b) a heating step of heating and melting a novolak epoxy resin obtained from the synthesis step, the compound represented by an integer of n = 0 to 5 in Formula 2, above a softening point; And (c) a novolak epoxy resin comprising a compound represented by an integer of n = 0 to 5 in Chemical Formula 2, melted from the heating step, into a high vacuum distillation apparatus to give 2.8 weight of a compound having n = 0 in Chemical Formula 2. It provides a method for producing a novolak epoxy resin comprising an extraction step of removing to less than or completely removed.

[Formula 2]

In Formula 2 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -O = S = 0- or

X is -H, -Br, -CF ₃ , an alkyl group having 1 to 12 carbon atoms or

to be.

In another preferred embodiment of the present invention, the high vacuum distillation apparatus in the step (c) may be characterized in that it is set to 200 to 280 ℃ under a pressure of 0.001 to 0.5 mbar.

Another embodiment of the present invention provides an epoxy resin composition comprising the novolac epoxy resin and a cured product of the epoxy resin composition.

According to the present invention, a novolak resin and a novolak epoxy resin having low viscosity and high thermal stability and high hygroscopicity at high temperatures (above 280 ° C.) can be easily produced by a simple method, and novolak resin can be used without additional solvent. And it is possible to reduce the viscosity of the novolac epoxy resin can be useful economically, environmentally friendly.

1 is a GPC graph of a bisphenol novolak resin obtained in Comparative Example 1-1 and a bisphenol novolak resin obtained in Example 1-1.

2 is a GPC graph of a bisphenol novolac epoxy resin obtained in Comparative Example 6-1 of the present invention.

3 is a GPC graph of a bisphenol novolac epoxy resin obtained in Example 4-1 of the present invention.

4 is a GPC graph of a phenol novolac epoxy resin obtained in Example 6-1 of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are intended to aid the understanding of the invention. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

In one aspect, the present invention provides a novolak resin comprising a compound represented by an integer of n = 0 to 5 in formula (1), comprising: 2.8 wt% or less of the compound having n = 0 in formula (1), or Without including a compound having n = 0, the weight average molecular weight is 500 to 5,500 g / mol, the polydispersity index is 1.0 to 3.0, the melt viscosity at 180 ° C. is 100 to 3,000 cps, and the softening point is 80 to 160 It is related with the novolak resin characterized by the above-mentioned.

[Formula 1]

In Formula 1 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -C ₁₀ H _12- , -O = S = 0- or -CH (C ₆ H ₄ OH)-, X is -H, -Br, -C (CH ₃ ) ₂ C ₆ H ₄ OH or an alkyl group having 1 to 12 carbon atoms.

The novolak resin of the present invention, in formula 1, R is -CH _2- , X is -C (CH ₃ ) ₂ C ₆ H ₄ OH or -CH ₃ It is in terms of hygroscopicity and heat resistance and workability desirable.

Recently, researches to meet the technical requirements corresponding to the thin and thin sections of copper-clad laminates according to the trend of miniaturization and high functionalization of electronic devices have been actively conducted, but technology development has been delayed due to problems such as moisture absorption, thermal expansion, and high temperature stability. Thus, in the present invention, when the polymerization degree and molecular weight of the prepared novolak resin is adjusted to a specific range, it has been confirmed that it can significantly improve the hygroscopic resistance and thermal stability at high temperature (280 ℃ or more) while having a low viscosity, The invention was completed.

More specifically, in the process of synthesizing the novolak resin represented by Formula 1, it is common to include about 10% by weight or more of the compound from n = 0 to n = 5, but in the present invention, n = 0 in which only two monomers are polymerized When compared to the conventional novolak resin having the same weight average molecular weight, by adjusting the content of the phosphorus compound to 2.8% by weight or less, or not included, by controlling the weight average molecular weight to 500 to 5,500 g / mol It is possible to greatly improve hygroscopicity, thermal stability and curing density.

In particular, when compared to a conventional novolak resin having the same PDI (monodispersity index), in the present invention, the reaction with the epoxy resin is carried out by including or not containing 2.8% by weight or less of the compound of n = 0. When completed to form a non-reversible network structure, relatively unreacted hydroxyl group is generated relatively, the curing density is improved, the free volume is reduced, and the compatibility with the curing agent is improved to form the micro-void Can be suppressed.

In addition, the novolak resin of the present invention can achieve the improvement of the average number of functional groups in the molecule for improving the curing density required in the final cured product, and high heat resistance without including the polymer region, thereby copper clad laminate (Copper Clad It is possible to suppress the generation of micro-void generated during the manufacture of laminate (CCL) and to exhibit excellent hygroscopic resistance and high thermal stability at high temperature (above 280 ° C).

At this time, the novolak resin of the present invention preferably contains or does not contain the content of the compound of n = 0 to 2.8% by weight or less and at the same time the polydispersity index (PDI) is 1.0 to 3.0 When the PDI is 1.0 to 3.0, the compatibility of the resin and the wettability to the glass fiber can be improved. The lower the PDI is to a level close to 1, the more excellent the compatibility of the resin and the wettability to the glass fiber.

In addition, the novolak resin of the present invention contains a content of the compound of n = 0 to 2.8% by weight or less, with or without a weight average molecular weight of 500 to 5,500g / mol, PDI is 1.0 to 3.0 At the same time, the melt viscosity at 180 ° C is preferably 100 to 3,000 cps. By setting the viscosity to 100 cps or more, the resin impregnated or applied to the substrate can be prevented from flowing down, and the viscosity is set to 3,000 cps or less. It is possible to impregnate or apply the substrate without deteriorating workability due to high viscosity.

In addition, the novolak resin of the present invention is a weight average molecular weight of 500 to 5,500 g / mol with or without the content of the compound of n = 0 to 2.8% by weight or less, PDI is 1.0 to At the same time as 3.0, the softening point of 80 ° C or higher prevents the blocking of the resin, that is, the phenomenon of agglomeration in an environment with high temperature to high humidity, such as in summer, and excellent hygroscopicity and high temperature. High thermal stability can be ensured, and by making it 160 degrees C or less, melting of resin can be made easy and workability can be improved.

In another aspect of the present invention, (a) a novolac comprising a compound represented by an integer of n = 0 to 5 in the following Chemical Formula 1 by condensation reaction between a phenolic monomer and a formaldehyde monomer under an acid catalyst, and removal of the condensed water. Synthesis step of synthesizing a resin; (b) a heating step of heating and melting a novolak resin obtained from the synthesis step, wherein the novolak resin including a compound represented by an integer of n = 0 to 5 in Formula 1 above a softening point; And (c) a novolak resin comprising a compound represented by an integer of n = 0 to 5 in the following Chemical Formula 1, melted from the heating step, into a high vacuum distillation apparatus to obtain a compound having n = 0 in Chemical Formula 1 of 2.8. It relates to a method for producing a novolak resin comprising an extraction step of removing by weight or less, or completely removed.

[Formula 1]

In Formula 1 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -C ₁₀ H _12- , -O = S = 0- or -CH (C ₆ H ₄ OH)-, X is -H, -Br, -C (CH ₃ ) ₂ C ₆ H ₄ OH or an alkyl group having 1 to 12 carbon atoms.

Method for producing a novolak resin, characterized in that it contains 2.8 wt% or less of the compound of n = 0 in the formula (1) according to the present invention, or does not contain a compound of n = 0 in formula (1), as follows.

The method for producing a novolak resin according to the present invention synthesizes a novolak resin of a repeating unit represented by Chemical Formula 1 by condensation reaction between a phenolic monomer and a formaldehyde monomer under an acid catalyst and removal of the condensation water.

In the present invention, the synthesis of the novolak resin can be used without limitation, as long as it is a method capable of synthesizing the novolak resin, wherein the acid catalyst is generally not limited to use as long as it is a catalyst that can be used for the synthesis of novolak resin, The reaction time can be carried out for 2 to 6 hours.

As such, the novolak resin of the repeating unit represented by the formula (1) is softened to separate the compound having n = 0 in 2.8 wt% or less of the novolak resin of the repeating unit represented by the formula (1) obtained in the synthesis step. It is heated and melted above, and the molten compound is put into a high vacuum distillation apparatus set to a specific condition, and the extraction step of separating the compound of n = 0 in the formula (1) to 2.8% by weight or less. Softening point above or below was measured at the temperature increase rate of 2 degree-C / min. Using the FP90 apparatus of METTLER TOLEDO.

In the extraction step, a high vacuum distillation is performed to separate the n = 0 compound of Formula 1 from the introduced novolak resin to completely remove the n = 0 compound, or to include any set weight% of 2.8 wt% or less. By appropriately setting the temperature and pressure of the main body of the apparatus, the compound having n = 0 contained in the finally obtained novolak resin may not be completely contained or may be included at any set concentration.

At this time, the temperature and pressure of the high vacuum distillation apparatus are 200 to 280 ° C. and 0.001 to 1.5 mbar, respectively. When the temperature of the high vacuum distillation unit is less than 200 ° C., only novolac resin of the appropriate molecular weight cannot be efficiently extracted, and the temperature is 280 ° C. If exceeded, it may cause thermal deformation or deterioration of the novolak resin due to high temperature.

In addition, when the pressure of the high vacuum distillation apparatus is less than 0.001 mbar, the resin of the polymer region may also be separated together, and only novolac resins having an appropriate molecular weight may be taken out. Since only the resin having a molecular weight cannot be efficiently extracted, there is a problem in that separation efficiency is lowered.

Such a method for producing a novolak resin according to the present invention can be easily and conveniently produced through the polymerization degree and molecular weight control of the resin, while having excellent hygroscopic resistance and thermal stability, can be used as a low viscosity curing agent.

In still another aspect, the present invention relates to a novolak curing agent containing the novolak resin.

Novolak resins prepared as described above may be particularly useful as novolak curing agents. When used as a novolac curing agent, it may be used alone or in combination with other curing agents. One example of another curing agent is preferably a curing agent, and novolak, cresol novolak, and the like may also be possible. It is preferable to use at least 5% by weight or more of the total curing agent in combination with other curing agents in view of excellent hygroscopic resistance and thermal stability at high temperatures.

In another aspect, the present invention, the epoxy resin; And an epoxy resin composition comprising the novolac curing agent and a cured product of the epoxy resin composition.

Epoxy resin composition according to the present invention by containing a novolak of the polymerization degree and molecular weight of the resin as a curing agent, while having a good solvent solubility compared to the conventional epoxy temporary composition, it is possible to balance the excellent hygroscopic resistance and thermal stability at high temperatures have. In this case, the epoxy resin may be applied as long as it is a common epoxy resin, preferably an epoxy resin having two or more glycidyl groups and having an epoxy equivalent (EEW) of 150 to 300 g / eq.

The epoxy resin composition according to the present invention may include a novolak curing agent in an amount of 5 to 95 wt% based on the total weight of the composition in consideration of hygroscopic resistance, thermal stability, viscosity, and the like. If the novolac curing agent is added in an amount of less than 5% by weight based on the total weight of the composition, the effect is insignificant, and when added in excess of 95% by weight, the degree of curing may decrease.

The epoxy resin composition according to the present invention satisfies dimensional stability at high temperature, heat resistance, hygroscopicity, and the like, and is excellent in compatibility with other resins, and is used for sealing materials and moldings used for copper-clad laminates and electronic components used in printed circuit boards. It is possible to provide a cured product that can implement a balanced property suitable for the material, molding materials, adhesives, materials for electrical insulating paint, and the like.

In addition, the present invention, in one aspect, in the novolak epoxy resin comprising a compound represented by an integer of n = 0 to 5 in the formula (2), in the formula (2) comprises 2.8% by weight or less, or The present invention relates to a novolac epoxy resin, wherein the weight average molecular weight is 700 to 5,000 g / mol without including a compound having n = 0 in the formula (2).

[Formula 2]

In Formula 2 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -O = S = 0- or

X is -H, -Br, -CF ₃ , an alkyl group having 1 to 12 carbon atoms or

to be.

Novolak epoxy resin of the present invention in the formula 2 R is -CH _2- , X is

Or -CH ₃ bisphenol novolac epoxy resin, which is preferable in view of workability and thermal properties in the production of copper-clad laminates.

Recently, researches to meet the technical requirements corresponding to the thin and thin sections of copper-clad laminates according to the trend of miniaturization and high functionalization of electronic devices have been actively conducted, but technology development has been delayed due to problems such as moisture absorption, thermal expansion, and high temperature stability. Thus, in the present invention, when the polymerization degree and molecular weight of the prepared novolak epoxy resin is adjusted to a specific range, it has been confirmed that it can significantly improve the hygroscopicity and thermal stability at high temperatures (above 280 ℃) while having a low viscosity, The present invention has been completed.

More specifically, in the process of synthesizing the novolac epoxy resin represented by Formula 2, it is common to include about 9% by weight or more of the compound from n = 0 to n = 5, but in the present invention, n = Compared to the conventional novolak epoxy resin having the same weight average molecular weight, by including the content of the compound of 0 to 2.8% by weight or less, or with no weight average molecular weight of 700 to 5,000 g / mol, It is possible to greatly improve the hygroscopic resistance, thermal stability and curing density.

As described above, the present invention includes a non-reversible network by completing the reaction with an epoxy curing agent such as novolac, imidazole, amine, or the like with or without the content of a compound having n = 0 to 2.8% by weight or less. When the structure is formed, relatively unreacted hydroxyl groups are generated and the curing density is improved, thereby reducing the free volume and improving compatibility with the curing agent, thereby suppressing microvoid production. .

In addition, the novolac epoxy resin of the present invention can achieve the improvement of the average number of functional groups in the molecule for improving the curing density required in the final cured product and high heat resistance without including the polymer region, thereby copper foil laminated plate (Copper) It is possible to suppress the generation of micro-void generated during the production of clad laminate (CCL), and to exhibit excellent hygroscopic resistance and high thermal stability at high temperature (above 280 ° C).

At this time, the novolak epoxy resin of the present invention preferably contains or does not contain the content of the compound of n = 0 to 2.8% by weight or less and at the same time polydispersity index (PDI) of 1.0 to 3.0 is preferred When PDI is 1.0 to 3.0, the compatibility and wettability with respect to the glass fiber can be improved at the time of varnish blending of the resin. The lower the PDI is to a level close to 1, the more excellent the compatibility of the resin and the wettability to the glass fiber.

In addition, the novolak epoxy resin of the present invention is a weight average molecular weight of 700 to 5,000 g / mol with or without the content of the compound of n = 0 or less 2.8% by weight, PDI is 1.0 It is preferable that the melt viscosity at 160 ° C is 30 to 3,000 cps and the viscosity is 30 cps or more, and the resin impregnated or applied to the substrate can be prevented from flowing down, and the viscosity is 3,000 cps or less. By doing so, the substrate can be impregnated or applied without deterioration of workability due to high viscosity.

In addition, the novolak epoxy resin of the present invention is a weight average molecular weight of 700 to 5,000 g / mol with or without the content of the compound of n = 0 to 2.8% by weight or less, PDI 1.0 to At the same time, the softening point of 40 ° C or higher prevents the blocking of the resin, that is, the phenomenon of agglomeration in a high temperature to high humidity environment such as in summer, and ensures high heat resistance. By setting it as 130 degrees C or less, melting of resin is easy and workability can be improved.

In another aspect of the present invention, (a) a novolak-based polymer and epiclohydrin monomers under a basic catalyst in a poly / condensation reaction, and remove the condensation water and the salt formed by the integer of n = 0 to 5 in the formula Synthesis step of synthesizing a novolac epoxy resin comprising a compound represented by; (b) a heating step of heating and melting a novolak epoxy resin obtained from the synthesis step, the compound represented by an integer of n = 0 to 5 in Formula 2, above a softening point; And (c) a novolak epoxy resin comprising a compound represented by an integer of n = 0 to 5 in Chemical Formula 2, melted from the heating step, into a high vacuum distillation apparatus to give 2.8 weight of a compound having n = 0 in Chemical Formula 2. It relates to a method for producing a novolak epoxy resin comprising an extraction step to remove to less than or completely removed.

[Formula 2]

In Formula 2 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -O = S = 0- or

X is -H, -Br, -CF ₃ , an alkyl group having 1 to 12 carbon atoms or

to be.

Method of producing a novolak epoxy resin, characterized in that containing less than 2.8% by weight of the compound of n = 0 in the formula (2), or does not contain a compound of n = 0 in the formula (2) is as follows.

The method for producing an epoxy resin according to the present invention includes a compound of a repeating unit represented by the formula (2) by performing a poly / condensation reaction of a phenol novolak-based polymer and an epichlorohydrin monomer under a basic catalyst and removing the condensation water produced therein. An epoxy resin is synthesized.

In this way, in order to separate the compound of the repeating unit represented by the formula (2) obtained in the synthesis step to include less than 2.8% by weight of the compound of n = 0, an epoxy resin containing the compound of the repeating unit represented by the formula (2) It is heated to a softening point or more, and the molten compound is put into a high vacuum distillation apparatus set to a specific condition, and the extraction step of separating the compound of n = 0 in the formula (2) to 2.8% by weight or less.

In the present invention, the step of synthesizing the epoxy resin can be used without limitation as long as it is a method capable of synthesizing the epoxy resin, and preferably, by the poly / condensation reaction of the phenol novolak-based polymer and the epichlorohydrin monomer under a basic catalyst. Can be done. At this time, the polycondensation reaction time may be performed for 2 to 6 hours.

Sodium hydroxide (NaOH) may be preferably used as the basic catalyst, and sodium hydroxide used as the catalyst is suitable for discoloration, minimization of by-product generation, and reaction rate of a resin prepared at a concentration of 30 to 60 wt%, and a phenol furnace. It is preferable to use the rockac polymer, the epichlorohydrin monomer and the basic catalyst in a molar ratio of 1: 3.5 to 5.5 mol: 0.9 to 1.5 mol.

After the synthesis is completed, the synthesized epoxy resin is heated and melted above the softening point so as to be easily introduced into a high vacuum distillation apparatus. At this time, the softening point of the phenol epoxy resin is different depending on the epoxy resin, but is generally 40 to 80 ℃. Softening points above or below were measured at a temperature rise rate of 2 / min. Using a FP90 instrument from METTLER TOLEDO.

As such, the epoxy resin containing the molten repeating compound represented by the formula (2) is introduced into a high vacuum distillation apparatus, and the compound of n = 0 is separated from the epoxy resin containing the compound of the repeating unit represented by the formula (2). The temperature and pressure of the main body of the high vacuum distillation apparatus can be set appropriately. At this time, the temperature and pressure of the high vacuum distillation apparatus is 200 to 280 ℃ and 0.001 to 0.5 mbar, respectively, when the temperature of the high vacuum distillation apparatus is less than 200 ℃, there is a problem that the separation efficiency of n = 0 epoxy resin is lowered, 280 If it exceeds C, there is a problem due to thermal deformation or deterioration of the epoxy resin due to high temperature, if less than 0.001 mbar, there is a problem that n = 1 or more polymer regions are separated together, if n = more than 0.5 mbar 0 There is a problem that the separation efficiency of the epoxy resin is lowered.

Such a method for producing a novolac epoxy resin according to the present invention can be easily and simply produced through the polymerization degree and molecular weight control of the produced resin, a low viscosity, excellent thermal stability and high moisture resistance at high temperatures.

This invention relates to the epoxy resin composition containing the said novolak epoxy resin, and the hardened | cured material of the said epoxy resin composition from another viewpoint.

The epoxy resin composition according to the present invention includes a novolak epoxy resin having a controlled degree of polymerization and a molecular weight, thereby achieving a good solvent solubility compared to conventional epoxy temporary compositions, and achieving improved thermal stability and hygroscopic resistance at a higher temperature. .

The epoxy resin composition according to the present invention may include 5 to 95% by weight of novolak epoxy resin, based on the total weight of the composition in consideration of thermal stability, hygroscopicity, viscosity, and the like. If the novolac epoxy resin is added in an amount of less than 5% by weight based on the total weight of the composition, the effect is insignificant, and when it is added in excess of 95% by weight, adhesion characteristics may be lowered.

The epoxy resin composition according to the present invention satisfies dimensional stability at high temperature, heat resistance, hygroscopicity, and the like, and has excellent flowability of resin, sealing materials, molding materials, and molds used for copper-clad laminates and electronic components used in printed circuit boards. It is possible to provide a cured product capable of achieving a balance of properties suitable for materials, adhesives, materials for electrical insulating coating, and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by these Examples.

1. Manufacture of novolac resin

<Comparative Example 1-1: Bisphenol Novolak Resin Manufacture (n = 0 is 20.23 wt%)>

3,200 g of the raw material bisphenol-A monomer and 1,600 g of formaldehyde contained in a 40 wt% concentration in water were added to a 5 L four-neck flask, heated to 60 ° C., stirred for 30 minutes, and mixed well. 11 g of oxalic acid was added to the mixed raw materials as a catalyst, and then heated to 100 ° C. and reacted for 3 hours. After completion of the reaction, the condensed water was removed at 760 mmHg, whereby bisphenol A novolac resin (In Formula 1, R is -CH ₂ -and X is -C (CH ₃ ) ₂ C ₆ H ₄ OH).

<Comparative Example 1-2: Preparation of Bisphenol Novolak Resin (n = 0 is 13.08 wt%)>

The bisphenol A novolac resin obtained in Comparative Example 1-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 200 ° C. and a pressure of 1.7 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac resin.

Comparative Example 1-3: Preparation of Bisphenol Novolac Resin (n = 0 is 8.13% by Weight)>

The bisphenol A novolak resin obtained in Comparative Example 1-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 245 ° C. and a pressure of 1.7 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac resin.

<Comparative Example 1-4: Preparation of bisphenol novolak resin (n = 0 is 2.89 wt%)>

The bisphenol A novolak resin obtained in Comparative Example 1-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 245 ° C. and a pressure of 1.7 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac resin.

<Example 1-1: Preparation of bisphenol novolak resin (n = 0 is 2.80 wt%)>

The bisphenol A novolac resin obtained in Comparative Example 1-1 was heated to 180 ° C. to be in a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 1.25 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac resin.

<Example 1-2: Preparation of Bisphenol Novolak Resin (n = 0 is 0.51 wt%)>

The bisphenol A novolac resin obtained in Comparative Example 1-1 was heated to 180 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 260 ° C. and a pressure of 1.20 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac resin.

<Comparative Example 2-1: Preparation of phenol novolak resin (n = 0 is 22% by weight)>

3200 g of raw material phenol and 1600 g of formaldehyde contained in a concentration of 40% by weight in water were added to a 5L four-necked flask, heated to 60 ° C, stirred for 30 minutes, and thoroughly mixed. 11 g of oxalic acid was used as a catalyst in the mixed raw materials. After the addition, the reaction mixture was heated at 100 ° C. for 3 hours, and after the reaction was completed, phenol novolak resin (in Formula 1, R is —CH ₂ — and X is —H) by removing condensed water at 760 mmHg. Prepared.

<Comparative Example 2-2: Preparation of phenol novolak resin (n = 0 is 7.1 wt%)>

The phenol novolak resin obtained in Comparative Example 2-1 was heated to 160 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 240 ° C. and a pressure of 1.7 mbar, and then operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.

<Comparative Example 2-3: Preparation of phenol novolak resin (n = 0 is 4.5 wt%)>

The phenol novolak resin obtained in Comparative Example 2-1 was heated to 160 ° C. to be in a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 235 ° C. and a pressure of 1.55 mbar, and operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.

<Example 2-1: Preparation of phenol novolak resin (n = 0 is 2.3% by weight)>

The phenol novolak resin obtained in Comparative Example 2-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 240 ° C. and a pressure of 1.50 mbar, and then operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.

<Example 2-2: Preparation of phenol novolak resin (n = 0 is 0.7% by weight)>

The phenol novolak resin obtained in Comparative Example 2-1 was heated to 170 ° C. to be in a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 240 ° C. and a pressure of 1.45 mbar, and operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.

<Example 2-3: Preparation of phenol novolak resin (n = 0 is 0.1% by weight)>

The phenol novolak resin obtained in Comparative Example 2-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 240 ° C. and a pressure of 1.40 mbar, and then operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.

<Comparative Example 3-1: Preparation of phenol novolak resin (n = 0 is 12.7 wt%)>

3200 g of raw material phenol and 1800 g of formaldehyde contained in a concentration of 40% by weight in water were added to a 5L four-necked flask, heated to 60 ° C, stirred for 30 minutes, and thoroughly mixed. 11 g of oxalic acid was used as a catalyst in the mixed raw materials. After the addition, the reaction mixture was heated at 100 ° C. for 3 hours, and after the reaction was completed, phenol novolak resin (in Formula 1, R is —CH ₂ — and X is —H) by removing condensed water at 760 mmHg. Synthesized.

Comparative Example 3-2: Phenol Novolak Resin Preparation (n = 0 is 9.9 wt%)>

The phenol novolak resin obtained in Comparative Example 3-1 was heated to 170 ° C. to be in a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 245 ° C. and a pressure of 1.70 mbar, and then operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.

<Comparative Example 3-3: Preparation of phenol novolak resin (n = 0 is 4.1 wt%)>

Phenolic obtained in Comparative Example 3-1 The novolak resin was heated to 170 ° C. to make it molten, and then put into a high vacuum distillation apparatus (VTA, Germany) at a temperature of 240 ° C. and a pressure of 1.60 mbar, and operated for 60 minutes. The phenol novolak resin was prepared by removing the molecular weight component.

Example 3-1: Phenol Novolak Resin Preparation (n = 0 is 0.9 wt%)>

The phenol novolak resin obtained in Comparative Example 3-1 was heated to 180 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 250 ° C. and a pressure of 0.25 mbar, and then operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.

<Example 3-2: Preparation of phenol novolak resin (n = 0 is 0.1% by weight)>

The novolak resin obtained in Comparative Example 3-1 was heated to 180 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 250 ° C. and a pressure of 0.15 mbar, and operated for 60 minutes. Next, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.

<Comparative Example 4-1: Preparation of bisphenol novolak resin (n = 0 is 15.44 wt%)>

3200 g of raw material bisphenol-A monomer and 1800 g of formaldehyde contained in a 40 wt% concentration in water were added to a 5 L four-neck flask, heated to 60 ° C., stirred for 30 minutes, and sufficiently mixed. 11 g of oxalic acid was added and reacted for 3 hours by raising the temperature to 100 ° C., and after the reaction was completed, the condensed water was removed at 760 mmHg (In formula 1, R is -CH ₂ -and X is -C. (CH ₃ ) ₂ C ₆ H ₄ OH).

<Comparative Example 5-1: Preparation of phenol novolak resin (n = 0 is 5.53 wt%)>

1200 g of formaldehyde containing 3200 g of phenol as a raw material and 40% by weight of water was added to a 5L four-necked flask, heated to 60 ° C, stirred for 30 minutes, sufficiently mixed, and then 11 g of oxalic acid as a catalyst to the mixed raw material. After the reaction was heated to 100 ℃ and reacted for 3 hours, after completion of the reaction by removing the condensed water at 760mmHg phenol novolak resin (In Formula 1, R is -CH _2- , X is -H) Was prepared.

2. Manufacture of novolac epoxy resin

<Comparative Example 6-1> Preparation of bisphenol novolac epoxy resin (n = 0 is 18.56 wt%)

1000 g of bisphenol A monomer and 230 g of formalin (40% aqueous solution) were added to 3.5 g of oxalic acid, and the mixture was refluxed for 3 hours. The temperature was raised to 150 ° C. to degas the water, and vacuum degassing was carried out to 30 Torr or less. Phosphorus bisphenol A resin was obtained. 500 g of the obtained bisphenol A resin and 1600 g of epichlorohydrin were added to a 5 L four-necked flask, and the mixture was sufficiently mixed. Then, 360 g of NaOH (concentration of 40% by weight) was added dropwise at 80 ° C. for 2 hours, and then unreacted epichloro high The derin was completely removed by vacuum degassing and diluted with MIBK. After completion of the reaction, a bisphenol A novolac epoxy resin (wherein R is -CH ₂ -and X is

Lim) was synthesized.

Gel permeation chromatography (GPC) was measured to measure the degree of polymerization of the bisphenol A novolac epoxy resin thus synthesized (FIG. 2).

Comparative Example 6-2 Bisphenol Novolac Epoxy Resin Manufacture (n = 0 is 8.7 wt%)

The bisphenol A novolac epoxy resin obtained in Comparative Example 6-1 was heated to 160 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 215 ° C. and a pressure of 1.51 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.

<Comparative Example 6-3> Preparation of bisphenol novolac epoxy resin (n = 0 is 6.8 wt%)

The bisphenol A novolac epoxy resin obtained in Comparative Example 6-1 was heated to 160 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 195 ° C. and a pressure of 0.51 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.

Example 4-1 Preparation of Bisphenol Novolac Epoxy Resin (n = 0 is 2.8 wt%)

The bisphenol A novolac epoxy resin obtained in Comparative Example 6-1 was heated to 160 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.50 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.

Gel permeation chromatography (GPC) was measured to measure the polymerization degree of the bisphenol A novolac epoxy resin thus synthesized (FIG. 3).

Example 4-2 Preparation of Bisphenol Novolac Epoxy Resin (n = 0 is 1.3 wt%)

The bisphenol A novolac epoxy resin obtained in Comparative Example 6-1 was heated to 160 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.15 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.

Comparative Example 7-1 Bisphenol Novolac Epoxy Resin Manufacture (n = 0 is 13.5 wt%)

1000 g of bisphenol A monomer and 250 g of formalin (40% aqueous solution) were added to 3.5 g of oxalic acid, and the mixture was refluxed for 3 hours. The temperature was raised to 150 ° C. to degas the water, and vacuum degassing was carried out to 30 Torr or less. Phosphorus bisphenol A resin was obtained. 500 g of the obtained bisphenol A resin and 1600 g of epichlorohydrin were added to a 5 L four-necked flask, and the mixture was sufficiently mixed, and 360 g of NaOH (concentration: 40 wt%) was uniformly added dropwise at 80 ° C. for 2 hours, followed by unreacted epichlorohi The derin was completely removed by vacuum degassing and diluted with MIBK. After completion of the reaction, a bisphenol A novolac epoxy resin (wherein R is -CH ₂ -and X is

Lim) was synthesized.

<Example 5-1> Bisphenol novolac epoxy resin preparation (n = 0 being 2.6 weight)

The bisphenol A novolac epoxy resin obtained in Comparative Example 7-1 was heated to 160 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 250 ° C. and a pressure of 0.40 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.

Example 5-2 Preparation of Bisphenol Novolac Epoxy Resin (n = 0 is 1.1 wt%)

The bisphenol A novolac epoxy resin obtained in Comparative Example 7-1 was heated to 170 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 250 ° C. and a pressure of 0.30 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.

Example 5-3 Preparation of Bisphenol Novolac Epoxy Resin (n = 0 at 0.5 wt%)

The bisphenol A novolac epoxy resin obtained in Comparative Example 7-1 was heated to 170 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.15 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.

<Comparative Example 8-1> Preparation of phenol novolac epoxy resin (n = 0 is 23.07 wt%)

500 g of phenol novolak resin (KOLON INDUSTRIAL Co., Ltd., KPE-F2000, softening point 78) and 1600 g of epichlorohydrin were added to a 5 L four-necked flask, and the mixture was sufficiently mixed, and 360 g of NaOH was uniformly added dropwise at 80 ° C. for 2 hours. Unreacted epiclohydrin was completely removed by vacuum degassing and diluted with MIBK. After completion of the reaction, a phenol novolak epoxy resin (in Formula 2, R is -CH ₂ -and X is -H) was synthesized through a MIBK degassing step.

<Comparative Example 8-2> Preparation of phenol novolac epoxy resin (n = 0 is 9.39% by weight)

The phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 150 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 190 ° C. and a pressure of 1.65 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.

<Comparative Example 8-3> Preparation of phenol novolac epoxy resin (n = 0 is 3.01% by weight)

The phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 150 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 240 ° C. and a pressure of 1.75 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.

<Example 6-1> Preparation of phenol novolac epoxy resin (n = 0 is 2.8 wt%)

The phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 150 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 250 ° C. and a pressure of 0.5 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.

Gel permeation chromatography (GPC) was measured to measure the degree of polymerization of the phenol novolac epoxy resin thus synthesized (FIG. 4).

<Example 6-2> Preparation of phenol novolac epoxy resin (n = 0 is 2.3% by weight)

The phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 160 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.45 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.

<Example 6-3> Preparation of phenol novolac epoxy resin (n = 0 is 1.10 wt%)

The phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 160 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 260 ° C. and a pressure of 0.3 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.

<Example 6-4> Preparation of phenol novolac epoxy resin (n = 0 is 0.01% by weight)

The phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 160 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 270 ° C. and a pressure of 0.15 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.

Comparative Example 9-1 Cresol Novolac Epoxy Resin Preparation (n = 0 is 8.3 wt%)

500 g of cresol novolac resin (KOLON INDUSTRIAL Co., Ltd., KCE-F3113, softening point 113 ° C) and 1600 g of epichlorohydrin were added to a 5 L four-necked flask, and the mixture was sufficiently mixed, and 360 g of NaOH was added dropwise at 80 ° C. for 2 hours. Unreacted epichlorohydrin was completely removed by vacuum degassing and diluted with MIBK. After completion of the reaction, a cresol novolac epoxy resin (in Formula 2, R is -CH ₂ -and X is -CH ₃ ) was synthesized through a MIBK degassing process.

Comparative Example 9-2 Cresol Novolac Epoxy Resin Manufacture (n = 0 is 6.6 wt%)

The novolac epoxy resin obtained in Comparative Example 9-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 1.75 mbar, followed by 60 minutes. After operation, a low molecular weight component contained in the resin was removed to prepare a cresol novolac epoxy resin.

<Comparative Example 9-3> Manufacture of cresol novolac epoxy resin (n = 0 is 4.3% by weight)

The novolac epoxy resin obtained in Comparative Example 9-1 was heated to 170 ° C. to be in a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 195 ° C. and a pressure of 0.55 mbar, for 60 minutes. After operation, a low molecular weight component contained in the resin was removed to prepare a cresol novolac epoxy resin.

<Comparative Example 9-4> Cresol novolac epoxy resin (n = 0 is 3.2% by weight)

The novolak epoxy resin obtained in Comparative Example 9-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.51 mbar, followed by 60 minutes. After operation, a low molecular weight component contained in the resin was removed to prepare a cresol novolac epoxy resin.

Example 7-1 Cresol Novolac Epoxy Resin Preparation (n = 0 is 2.8 wt%)

The novolak epoxy resin obtained in Comparative Example 9-1 was heated to 170 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.31 mbar, for 60 minutes. After operation, a low molecular weight component contained in the resin was removed to prepare a cresol novolac epoxy resin.

Example 7-2 Cresol Novolac Epoxy Resin Preparation (n = 0 is 0.10% by Weight)

The novolak epoxy resin obtained in Comparative Example 9-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 260 ° C. and a pressure of 0.15 mbar for 60 minutes. After operation, a low molecular weight component contained in the resin was removed to prepare a cresol novolac epoxy resin.

<Characteristic evaluation method>

(1) Molecular weight (g / mol) measurement

Polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) (Waters: Waters707). The polymer to be measured was dissolved in tetrahydrofuran to a concentration of 4000 ppm, and 100 was injected into GPC. The mobile phase of GPC used tetrahydrofuran and was introduced at a flow rate of 1.0 mL / min, and the analysis was performed at 35 ° C. The column connected four Waters HR-05,1,2,4E in series. The detector was measured at 35 ° C using RI and PAD Detecter. At this time, PDI (polydispersity index) was calculated by dividing the measured weight average molecular weight by the number average molecular weight.

(2) Determination of the content of the compound of n = 0

Gel permeation chromatography (GPC) (Waters: Waters707) was used to calculate the integral value of the corresponding molecular weight band area in the resin and calculated the ratio of the relative molecular weight band to the relative area.

(3) softening point measurement

Using a FP90 / FP83HT instrument manufactured by Mettler Toledo Co., Ltd. was measured at a temperature increase rate of 2 ℃ / min.

(4) viscosity measurement method

The viscosity of the fully melted resin at 180 ° C. was measured using a Brookfield Viscometer (CAP 2000+).

(5) Copper Clad Laminate Manufacturing and Gel Time Measurement

(5-1) Novolak Resin Application

Bisphenol A type Epoxy resin (KOLON INDUSTRY, KES-9361A75) having an epoxy equivalent weight (EEW) of 187 and a curing agent (the novolak resins of the Examples and Comparative Examples) were mixed in an equivalent ratio of 1: 1, and then used as a curing accelerator. 2E4MZ (2-ethyl-4-methyl-imidazole) was mixed with 0.035 wt% [epoxy (solid) + novolak resin (solid): curing accelerator = 99.965: 0.035) based on the total solid weight to prepare a varnish. . Thereafter, the prepared varnish was impregnated with glass fibers, and then dried at 140 ° C. for 5 minutes to form a prepreg. Four prepregs thus prepared were laminated, and the copper foil was laminated on the upper and lower surfaces of the laminated prepreg, followed by pressing to obtain copper foil. Laminates (400 mm x 400 mm x 0.75 mm) were made (press conditions: temperature 190 ° C., pressure 25 kgf / cm ² , process time 2 hours). The varnish and prepreg (the semi-cured varnish in the prepreg) were shaken off. Gel time of making powder) was measured on a hot plate heated to 171 ℃ (use amount, varnish: 0.2cc, prepreg: 20mg).

(5-2) Novolak epoxy resin application

After mixing a novolak resin (Kolon Industries, KPH-F2004M62) with an active hydrogen equivalent weight (AHEW) of 106 g / eq and a novolak-based epoxy resin (the novolak epoxy resins of the Examples and Comparative Examples) in an equivalent ratio of 1: 1, 2E4MZ (2-ethyl-4-methyl-imidazole) was added as a curing accelerator by adding 0.035 wt% [epoxy (solid) + novolac epoxy resin (solid): curing accelerator = 99.965: 0.035) to the total solid weight. Varnishes were prepared. Thereafter, the prepared varnish was impregnated with glass fibers, and then dried at 140 ° C. for 5 minutes to make a prepreg. Four prepregs thus prepared were laminated, and the copper foil was laminated on the upper and lower surfaces of the laminated prepreg, and then pressed to obtain a copper foil. Laminates were made (press conditions: temperature 190 ° C., pressure 25 kgf / cm ² , process time 2 hours).

The gel time of the varnish and the prepreg (to shake off the semi-hardened varnish from the prepreg to make powder) was measured on a hot plate heated to 171 ℃ (usage, varnish: 0.2cc, prepreg: 20 mg).

(6) glass transition temperature measurement

20 mg of a solid sample was randomly taken out of the copper-clad laminate obtained in (5), and then measured by a differential scanning calorimeter (DSC, Q2000 manufactured by TA Instrument). (Measurement site: center part, 20 mg.Measurement condition: nitrogen atmosphere, 20 / temperature to 250 ° C. at a rate of min.

(7) Z-axis coefficient of thermal expansion (CET)

The copper-clad laminate obtained in (5) was cut to 6.35 mm × 6.35 mm × 0.75 mm (thickness), and the specimens were cut and dried in an oven at 105 ° C. for 2 hours to remove pollutants such as moisture, and then the Z-axis thermal expansion coefficient was measured by a thermal analyzer. (Measurement area: 6.35mm × 6.35mm × 0.75mm (thickness)) (TMA, TA Instrument Co., Q400) Measurement conditions: nitrogen atmosphere, temperature increase rate of 10 / min. To 40 ~ 260 ℃ Elevated temperature).

(8) absorption rate measurement

The copper-clad laminate obtained in (5) was cut into 50 mm × 05 mm × 0.75 mm (thickness) to obtain five specimens, which were then etched (etched) with FeCl ₃ to completely peel the copper foil, followed by etching solution and residual water. Water was completely removed and dried in an oven at 105 ° C. for 2 hours to completely remove residual material. After removing the remaining material, put the specimens into a Pressure Cooker Test (PCT) chamber set at 121 ° C and 0.22 MPa, and hold them for 90 minutes. Then, the moisture on the specimens is removed, and the mass change rate before and after moisture absorption is calculated by the following equation. Calculated from 1.

[Equation 1]

Absorption rate (%) = (Wet specimen weight-specimen weight before experiment) / specimen weight before experiment

(9) Heat stability measurement

The copper-clad laminate obtained in (5) was cut to 6.35 mm × 6.35 mm × 0/75 mm (thickness), and the specimens were cut and dried in an oven at 105 ° C. for 2 hours to remove pollutants such as moisture, and then a thermal analyzer (TMA, TA Instrument Q400) was used. In the measurement, the temperature was raised from 40 ° C. to 288 ° C. at 0 ° C./min, and then the time taken for specimen peeling while maintaining isothermal at 288 ° C. was measured. In this case, 'peeling' means not reversibly returning to its original size after rapid volume expansion, and if the measured value is 10 minutes or more, it is 'good', if it is within 5 minutes, 'normal', and if it is 1 minute or less, Marked as bad.

Table 1

		Property evaluation
	n = 0 content (% by weight)	Mw (g / mol)	PDI	Melt viscosity (cps)	Softening point (℃)	Gel time (sec.)	Tg after curing (℃)	CTE (%)	Absorption rate (wt%)	Heat-resistant stability
Comparative Example 1-1	20.23	2353	2.05	2090	113	138	215	2.58	0.36	Bad
Comparative Example 1-2	13.08	2456	1.90	2120	128	136	218	2.57	0.37	usually
Comparative Example 1-3	8.13	2488	1.85	2271	132	130	220	2.60	0.35	usually
Comparative Example 1-4	2.89	2498	1.89	2280	143	129	250	2.67	0.33	usually
Example 1-1	2.80	2502	1.86	2390	145	128	256	2.28	0.25	Good
Example 1-2	0.51	2553	1.79	2450	148	127	262	2.23	0.24	Good
Comparative Example 2-1	22	1034	1.42	1580	78	234	128.1	2.46	0.37	Bad
Comparative Example 2-2	7.1	1106	1.36	1620	89	241	136.3	2.48	0.36	usually
Comparative Example 2-3	4.5	1135	1.33	1650	98.2	258	148.2	2.49	0.35	usually
Example 2-1	2.3	1149	1.31	1750	99.1	262	151.2	2.25	0.24	Good
Example 2-2	0.7	1162	1.29	1760	101	267	154.3	2.24	0.25	Good
Example 2-3	0.1	1172	1.26	1780	101.5	266	155.7	2.24	0.24	Good
Comparative Example 3-1	12.7	1848	2.03	2120	101	212	153.1	2.49	0.35	Bad
Comparative Example 3-2	9.9	1915	1.96	2201	109	219	155.2	2.50	0.24	usually
Comparative Example 3-3	4.1	2059	1.83	2256	117	234	163.3	2.48	0.25	usually
Example 3-1	0.9	2110	1.7	2356	120.1	239	164.1	2.24	0.24	Good
Example 3-2	0.1	2150	1.64	2405	121.1	243	165.5	2.13	0.24	Good
Comparative Example 4-1	15.44	2847	3.12	3120	127	128	236	2.68	0.34	usually
Comparative Example 5-1	5.53	12308	7.16	4420	139.8	256	159.2	2.49	0.35	usually

As shown in Table 1, the novolak resin of the embodiment according to the present invention has a low viscosity characteristic compared to the novolak resin of the comparative example, and thermal stability such as low thermal expansion, high glass transition temperature, heat resistance at high temperature and the like. It was confirmed that the hygroscopicity was significantly increased. In addition, the bisphenol novolak resins from which the low molecular weights of Examples 1-1 and 1-2 were removed were compared with the phenol novolak resins (Examples 2-1 to 2-3) in measuring glass transition temperature and gel time after curing. It was confirmed that the improvement.

TABLE 2

	n = 0 content (% by weight)	Mw (g / mol)	PDI	Melt viscosity (cps)	Softening Point (℃)	Gel time (sec.)	Tg after curing (℃)	Thermal stability (T288)	CTE (%)	Absorption rate (wt%)
Comparative Example 6-1	18.56	2300	2.88	1678	65	126	225	Bad	2.58	0.35
Comparative Example 6-2	8.7	2990	2.72	1876	80	118	232	usually	2.57	0.33
Comparative Example 6-3	6.8	3010	2.68	2135	83	121	237	usually	2.58	0.32
Example 4-1	2.8	2945	2.32	2235	95	118	268	Good	2.23	0.23
Example 4-2	1.3	3068	2.28	2356	95	118	272	Good	2.22	0.21
Comparative Example 7-1	13.5	4163	4.04	2376	80.3	116	247	usually	2.76	0.34
Example 5-1	2.6	4732	2.93	2622	102	121	292	Good	2.21	0.22
Example 5-2	1.1	4757	2.87	2888	105	121	292	Good	2.20	0.22
Example 5-3	0.5	4814	2.76	2970	110	120	297	Good	2.20	0.21
Comparative Example 8-1	23.07	1231	1.95	28	46	240	196.3	Bad	2.68	0.35
Comparative Example 8-2	9.39	1423	1.78	187	55.6	225	203.5	usually	2.63	0.34
Comparative Example 8-3	3.01	1487	1.70	350	57.1	218	202.5	usually	2.64	0.33
Example 6-1	2.8	1539	1.66	376	59.1	216	214.5	Good	2.21	0.24
Example 6-2	2.3	1567	1.58	450	62.1	210	216.4	Good	2.22	0.23
Example 6-3	1.01	1589	1.58	455	62.1	210	218.4	Good	2.21	0.22
Example 6-4	0.01	1593	1.56	607	63.1	208	218.7	Good	2.18	0.20
Comparative Example 9-1	8.35	1758	1.90	1876	65	256	225	Bad	2.57	0.35
Comparative Example 9-2	6.60	1837	1.98	2135	60	255	228	usually	2.54	0.34
Comparative Example 9-3	4.30	1992	1.93	2245	63	242	232	usually	2.54	0.33
Comparative Example 9-4	3.20	1998	1.91	2367	65	238	234	usually	2.52	0.31
Example 7-1	2.8	2010	1.81	2569	72	235	257	Good	2.21	0.23
Example 7-2	0.1	2028	1.81	2658	72	235	259	Good	2.20	0.22

In addition, as shown in Table 2, the novolac epoxy resin of the embodiment has a low viscosity characteristics compared to the epoxy resin of the comparative example, thermal stability such as low thermal expansion, high glass transition temperature, heat resistance at high temperature and moisture absorption resistance This markedly increased. In addition, the bisphenol A novolac epoxy resin from which the low molecular weights of Examples 4-1 to 5-3 were removed was added to the phenol novolac epoxy resin (Examples 6-1 to 6-4) and cresol novolac epoxy resin (Example 7). It was confirmed that the glass transition temperature and the gel time measurement after curing were improved from -1 and 7-2).

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

The present invention can easily produce a novolak resin and a novolak epoxy resin having a low viscosity and high thermal stability at high temperature (above 280 ° C.) and excellent hygroscopicity by a simple method, and can be produced without using a solvent. Since the viscosity of the volac epoxy resin can be reduced, it can be economically and environmentally friendly.

Claims (16)

1. A novolak resin comprising a compound represented by an integer of n = 0 to 5 in Formula 1, comprising 2.8% by weight or less of a compound having n = 0 in Formula 1, or a compound having n = 0 in Formula 1 Weight average molecular weight of 500 to 5,500 g / mol, polydispersity index of 1.0 to 3.0, melt viscosity at 180 ° C of 100 to 3,000 cps, and softening point of 80 to 160 ° C. Volac Resin:

   [Formula 1]

   

   In Formula 1 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -C ₁₀ H _12- , -O = S = 0- or -CH (C ₆ H ₄ OH)-, X is -H, -Br, -C (CH ₃ ) ₂ C ₆ H ₄ OH or an alkyl group having 1 to 12 carbon atoms.
2. The method of claim 1, wherein in Formula 1, n is an integer of 0 to 5, R is -CH _2- , X is -C (CH ₃ ) ₂ C ₆ H ₄ OH or -CH ₃ characterized in that Novolak resin.
3. (a) a condensation reaction of a phenol-based monomer with a formaldehyde-based monomer under an acid catalyst to remove a condensed water to synthesize a novolak resin including a compound represented by an integer of n = 0 to 5 in Formula 1 below;

   (b) a heating step of heating and melting a novolak resin obtained from the synthesis step, wherein the novolak resin including a compound represented by an integer of n = 0 to 5 in Formula 1 above a softening point; And

   (c) 2.8 weight of a compound having n = 0 in Chemical Formula 1 by injecting a novolak resin containing a compound represented by an integer of n = 0 to 5 in Chemical Formula 1 melted from the heating step into a high vacuum distillation apparatus; Method for producing a novolak resin comprising an extraction step of removing to less than or completely removed:

   [Formula 1]

   

   In Formula 1 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -C ₁₀ H _12- , -O = S = 0- or -CH (C ₆ H ₄ OH)-, X is -H, -Br, -C (CH ₃ ) ₂ C ₆ H ₄ OH or an alkyl group having 1 to 12 carbon atoms.
4. The method of claim 3, wherein in the step (c), the high vacuum distillation apparatus is set at 200 to 280 ° C under a pressure of 0.001 to 1.5 mbar.
5. The novolak hardener containing the novolak resin of any one of Claims 1-2.
6. Epoxy resins; And

   An epoxy resin composition comprising the novolac curing agent of claim 8.
7. Hardened | cured material of the epoxy resin composition of Claim 6.
8. In the novolak epoxy resin comprising a compound represented by an integer of n = 0 to 5 in the formula (2), in the formula (2) comprising 2.8% by weight or less of the compound or n = 0 in the formula (2) Novolac epoxy resin, characterized in that the weight average molecular weight of 700 ~ 5,000g / mol without including:

   [Formula 2]

   

   In Formula 2 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -O = S = 0- or

   

   X is -H, -Br, -CF ₃ , an alkyl group having 1 to 12 carbon atoms or

   

   being.
9. According to claim 8, In Formula 2, R is -CH _2- , X is -H,

   

   Or -CH ₃ .
10. The novolac epoxy resin according to claim 8, wherein the novolac epoxy resin has a PDI of 1.0 to 3.0.
11. The novolac epoxy resin according to claim 8, wherein the novolac epoxy resin has a melt viscosity of 30 to 3,000 cps at 160 ° C.
12. The novolac epoxy resin of claim 8, wherein the novolac epoxy resin has a softening point of 40 to 130 ° C. 10.
13. (a) containing a compound represented by an integer of n = 0 to 5 in the following Chemical Formula 1 by performing a poly / condensation reaction of a novolak-based polymer and an epiclohydrin monomer under a basic catalyst, and removing the condensed water and the resulting salt. Synthesizing a novolac epoxy resin;

    (b) a heating step of heating and melting a novolak epoxy resin comprising a compound represented by an integer of n = 0 to 5 in Formula 1 obtained from the synthesis step above a softening point; And

    (c) 2.8 weight of a compound having n = 0 in Chemical Formula 1 by adding a novolak epoxy resin, which is melted from the heating step, to a high vacuum distillation apparatus including a novolak epoxy resin containing a compound represented by an integer of n = 0 to 5 in Chemical Formula 1; Method for producing a novolac epoxy resin comprising an extraction step of removing to less than or completely removed:

    [Formula 2]

    

    In Formula 2 n is an integer of 0 to 5, R is -CH _2- , -C (CH ₃ ) _2- , -C = O-, -O = S = 0- or

    

    X is -H, -Br, -CF ₃ , an alkyl group having 1 to 12 carbon atoms or

    

    being.
14. The method of claim 13, wherein the high vacuum distillation apparatus in the step (c) is set to 200 to 280 ℃ under a pressure of 0.001 to 0.5 mbar.
15. The epoxy resin composition containing the novolak epoxy resin of any one of Claims 8-12.
16. Hardened | cured material of the epoxy resin composition of Claim 15.

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