KR20130142361A - Novolac resin and method for manufacturing the same - Google Patents

Abstract

A disclosed novolak resin is represented by a chemical formula 1 and has the weight average molecular weight of 500-30,000. <chemical formula 1> In the chemical formula 1, n is a positive integer. R1, R2 and R3 independently represent a hydrogen atom, a hydroxyl group or an alkyl group of C1-C10. And R4 represents or.

Description

NOVOLAC RESIN AND MANUFACTURING METHOD THEREOF {NOVOLAC RESIN AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a novolak resin and a method for producing the same, and more particularly, to a novolak resin that can be used in the synthesis of epoxy resin and a method for producing the same.

Epoxy resins can be cured by reacting with a curing agent, and excellent in mechanical properties, water resistance, chemical resistance, electrical properties, adhesiveness, and the like, and are widely used as adhesives, paints, laminates, various molding materials, and binders.

For example, according to the manufacturing process of a general semiconductor package, first, a plurality of semiconductor chips manufactured at the wafer level are separated into individual semiconductor chips through a sawing process, and then each of the semiconductor chips is placed on a printed circuit board. Attached. Then, the bonding pads of the semiconductor chips and the bond fingers of the printed circuit boards are electrically bonded by metal wires. Subsequently, in order to protect the semiconductor chip from an external impact, an upper surface of the printed circuit board including the wire bonded with the semiconductor chip in a molding process is sealed, and then an external connection terminal is provided on the lower surface of the printed circuit board. Is attached to complete the semiconductor package, epoxy resin composition is widely used as a molding material used in the molding process.

The flame retardant method of the epoxy resin is known as an epoxide of tetrabromobisphenol A, but the compound containing bromine is excellent in flame retardancy, but generates a substance that causes environmental pollution during disposal and incineration. Is getting.

Therefore, many halogen flame retardant technologies of epoxy resins have been studied. Phosphorous compounds may be considered as flame retardants, but there are limitations in use such as hygroscopicity and hydrolysis.

Therefore, there is a need for a novel epoxy resin having excellent flame retardancy.

The present invention is to solve the problems of the existing epoxy resin as described above, and to provide a novolak resin having a flame retardancy as a starting material of the epoxy resin synthesis.

Another object of the present invention is to provide a method for producing the novolak resin.

The novolac resin according to one embodiment of the present invention is represented by the following Chemical Formula 1, and has a weight average molecular weight of 500 to 30,000.

&Lt; Formula 1 >

또는

를 나타낸다.In Formula 1, n is a positive integer, R1, R2 and R3 each independently represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, R4 is

or

Indicates.

In one embodiment, the number average molecular weight of the novolak resin is 400 to 10,000.

In one embodiment, the softening point of the novolak resin is 70 ℃ to 130 ℃.

According to the method for producing a novolak resin according to an embodiment of the present invention, 4-phenylbenzaldehyde and a phenolic compound are stirred. The mixture of 4-phenylbenzaldehyde and the phenolic compound is heated and firstly reacted in a reaction vessel. The aralkyl compound is added to the reaction vessel to carry out the second reaction. The product obtained by the above reaction is dehydrated to obtain a novolak resin represented by Chemical Formula 1, having a weight average molecular weight of 500 to 30,000.

In one embodiment, the phenolic compound is phenol, bisphenol-A, bisphenol-F, m-cresol, p-cresol, xyleneol, resorcinol, biphenol, parabutylbutylphenol (PTBP), paraoctylphenol (POP) or paranonylphenol (PNP).

In one embodiment, the polymerization of the 4-phenylbenzaldehyde and the phenolic compound is carried out in the presence of a hydroxyl catalyst.

In one embodiment, the aralkyl compound includes 4,4-bis (methoxymethyl) biphenyl or p-xyleneglycol dimethylether.

In one embodiment, the product obtained by the reaction is washed with ion exchange water.

The novolak resin according to the present invention is improved in flame retardancy with the introduction of a biphenyl structure, and consequently can be used in the production of an epoxy resin having excellent flame retardancy.

1 is a graph showing NMR data of a novolak resin obtained in Example 1. FIG.
2 is a graph showing NMR data of a novolak resin obtained in Example 2. FIG.

Hereinafter, a novolak resin and a manufacturing method of the novolak resin according to an embodiment of the present invention will be described in detail.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Novolac resin

The novolak resin according to one embodiment of the present invention is represented by the following Chemical Formula 1, and has a weight average molecular weight of about 500 to 30,000.

&Lt; Formula 1 >

또는

를 나타낸다. 예를 들어, 상기 탄소수 1 내지 10의 알킬기는 메틸기, 에틸기, 프로필기, 부틸기, 이소프로필기, 펜틸기, 이소부틸기, 헥실기, 헵틸기, 옥틸기, 노닐기, 데실기 등을 포함할 수 있다.In Formula 1, n is a positive integer, R1, R2 and R3 each independently represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, R4 is

or

Indicates. For example, the alkyl group having 1 to 10 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, isopropyl group, pentyl group, isobutyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. can do.

For example, the novolak resin may be represented by the following Chemical Formula 2 or Chemical Formula 3.

(2)

<Formula 3>

Preferably, the number average molecular weight of the novolak resin may be about 400 to 10,000. In addition, the molecular weight of the novolak resin may be measured by gel permeation chromatography (GPC).

The softening point of the novolak resin may be about 70 ℃ to 130 ℃.

The novolak resin may be obtained by reacting 4-phenylbenzaldehyde (4-PBA), a phenol compound, and an aralkyl compound, which is a biphenyl derivative.

For example, the phenolic compounds may be phenol, bisphenol-A, bisphenol-F, m-cresol, p-cresol, o-cresol, 2,4-xylenol, 2,5-xylenol, resorcinol , Biphenol, parabutylbutylphenol (PTBP), paraoctylphenol (POP), or paranonylphenol (PNP) can be used. These may each be used alone or in combination.

For example, the aralkyl compound may include 4,4-bis (methoxymethyl) biphenyl, p-xyleneglycol dimethylether, and the like. have.

The novolak resin, for example, may be used as an epoxy resin for semiconductor packaging by reacting with epochlohydrin and epoxidizing and having a self-extinguishing property by introduction of a biphenyl structure. In addition, the novolak resin may be dissolved in a solvent such as ketones and liquefied to be used as a curing agent for an epoxy resin for a printed circuit board.

Hereinafter, a method of manufacturing a novolac resin according to an embodiment of the present invention will be described.

Process for producing novolac resin

According to the method for producing a novolak resin according to an embodiment of the present invention, first, 4-phenylbenzaldehyde and a phenolic compound are stirred. The phenolic compound may be phenol, bisphenol-A, bisphenol-F, m-cresol, p-cresol, xenol, resorcinol, biphenol, parabutylbutylphenol (PTBP), paraoctylphenol (POP), Or paranonylphenol (PNP) may be used. These may each be used alone or in combination.

Next, the mixture of 4-phenylbenzaldehyde and the phenolic compound is heated to react in a reaction vessel.

Next, the aralkyl compound is added to the reaction vessel, followed by further reaction. The aralkyl compound may include 4,4-bis (methoxymethyl) biphenyl, p-xyleneglycol dimethylether, and the like.

The obtained reaction product is dehydrated and the unreacted substance is removed to obtain a novolak resin represented by the following formula (1) having a weight average molecular weight of about 500 to 30,000.

&Lt; Formula 1 >

또는

를 나타낸다. 예를 들어, 상기 탄소수 1 내지 10의 알킬기는 메틸기, 에틸기, 프로필기, 부틸기, 이소프로필기, 펜틸기, 이소부틸기, 헥실기, 헵틸기, 옥틸기, 노닐기, 데실기 등을 포함할 수 있다.In Formula 1, n is a positive integer, R1, R2 and R3 each independently represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, R4 is

or

Indicates. For example, the alkyl group having 1 to 10 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, isopropyl group, pentyl group, isobutyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. can do.

When the aralkyl compound is 4,4-bis (methoxymethyl) biphenyl, a novolak resin of Formula 2 below may be obtained, and the aralkyl compound is p- In the case of xylene glycol dimethyl ether, it is possible to obtain a novolak resin of the formula (3) below.

(2)

<Formula 3>

The softening point of the novolak resin may be about 70 ℃ to 130 ℃.

In this embodiment, the reaction of the 4-phenylbenzaldehyde and the phenolic compound proceeds prior to the addition of the aralkyl compound, which takes into account that the reactivity of 4-phenylbenzaldehyde is relatively slow.

For example, the 4-phenylbenzaldehyde and the phenol-based compound may be stirred at about 50 ° C. to 70 ° C. This can facilitate the stirring of the phenolic compound having a solid phase at room temperature.

Preferably, a catalyst for facilitating the reaction is used in the reaction of the 4-phenylbenzaldehyde and the phenolic compound. The catalyst may include organic acids such as hydroxyl (oxalic acid), succinic acid, formic acid, maleic acid, paratoluene sulfonic acid, methane sulfonic acid, phenol sulfonic acid or the like or inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc., each alone or in combination Can be used.

For example, the catalyst may be used in an amount of about 0.3 parts by weight to about 1.5 parts by weight based on 100 parts by weight of the phenolic compound.

Stirring and / or reaction of the 4-phenylbenzaldehyde and the phenolic compound may be performed without the presence of a solvent. Thereby, generation | occurrence | production of a side product by use of a solvent, etc. can be prevented.

Since the reaction of the 4-phenylbenzaldehyde, the phenol compound and the aralkyl compound is a condensation reaction, water is generated as a result of the reaction. Preferred reaction temperatures are about 100 ° C. to 150 ° C., and reaction times are about 30 minutes to 10 hours.

After the reaction is completed, water, catalyst, unreacted 4-phenylbenzaldehyde, phenolic compound, aralkyl compound, and the like produced by the reaction are removed by vacuum suction, heating, or the like. In addition, in order to remove impurities, ion-exchanged water may be added to proceed with a washing process.

The amount of the ion exchanged water may be about 10% to 100% by weight of the total reaction product weight, preferably about 30% to 60% by weight. The washing step by adding ion-exchanged water may be performed once or several times.

In addition, the reaction product can be dehydrated at atmospheric pressure or reduced pressure of about 100 to 400mmHg. The dehydration may be performed in the range of about 150 ° C. to 230 ° C., and additionally, a steam blow distillation process may be performed.

According to one embodiment of the present invention, it is possible to effectively obtain a novolak resin having improved flame retardancy by introducing a biphenyl structure.

Hereinafter, a novolak resin and a manufacturing method thereof according to an embodiment of the present invention will be described with reference to specific examples and production examples.

Example 1

Nitrogen gas purge was carried out to a flask equipped with a thermometer, a cooling tube, and a stirrer, and about 55 g of phenylbenzaldehyde and about 80 g of phenol were added thereto, and the mixture was heated to about 60 ° C. in a dehydration circuit to be dissolved. Then, about 0.3 g of oxalic acid was added and the temperature was raised to about 130 ° C. while stirring, followed by reaction for about 30 minutes. Then, about 25 g of 4,4-bis (methoxymethyl) biphenyl was reacted six times at about 5 minute intervals for about 30 minutes. It was divided and added. The reaction proceeded for about 3 hours while maintaining the temperature of about 130 ℃.

After the reaction was completed, the mixture was cooled to about 110 ° C, about 100 g of ion-exchanged water was added, stirred for about 30 minutes, and the resin layer and the supernatant were separated. After the separation was completed, the supernatant was removed by vacuum suction, and then heated to atmospheric pressure in a dehydration circuit to proceed to dehydration up to 190 ° C. Thereafter, vacuum dehydration was carried out at a vacuum degree of about 700 mmHg for 1 hour to remove unreacted material, and steam was added for 1 hour at the same temperature and vacuum condition to further remove residual unreacted material, thereby obtaining about 95 g of novolak resin. . The softening point of the obtained novolak resin was about 86 degreeC, and melt viscosity in 150 degreeC was 260 mPa * s. As a result of measuring the molecular weight by GPC, the weight average molecular weight was 925 and the unreacted phenol content by gas chromatography (hereinafter GC) was 0.1%.

Example 2

About 50 g of the following phenylbenzaldehyde and about 80 g of phenol were added to the flask equipped with a thermometer, a cooling tube, and a stirrer, and it heated up to about 60 degreeC in the dehydration circuit, and was dissolved. Subsequently, about 0.3 g of oxalic acid was added thereto, the reaction mixture was heated to about 130 ° C. with stirring, and reacted for about 30 minutes. Then, about 30 g of p-xylene glycol dimethyl ether was divided into six portions at about 5 minute intervals for about 30 minutes. The reaction proceeded for about 3 hours while maintaining the temperature of about 130 ℃.

After the reaction was completed, the mixture was cooled to about 110 ° C, about 100 g of ion-exchanged water was added, stirred for about 30 minutes, and the resin layer and the supernatant were separated. After the separation was completed, the supernatant was removed by vacuum suction, and then heated to atmospheric pressure in a dehydration circuit to proceed to dehydration up to 190 ° C. Thereafter, vacuum dehydration was carried out at a vacuum degree of about 700 mmHg for 1 hour to remove unreacted material, and steam was added for 1 hour at the same temperature and vacuum condition to further remove residual unreacted material, thereby obtaining about 90 g of novolak resin. . The softening point of the obtained novolak resin was about 83 ° C, and the melt viscosity at 150 ° C was 230 mPa · s. As a result of measuring the molecular weight by GPC, the weight average molecular weight was 27,641 and the number average molecular weight was 7,369. In addition, the unreacted phenol content by gas chromatography (hereinafter GC) was 0.07%.

1 is a graph showing NMR data of a novolak resin obtained in Example 1, and FIG. 2 is a graph showing NMR data of a novolak resin obtained in Example 2. FIG.

1 and 2, it can be seen that Example 1 and Example 2 obtained the novolak resin represented by the formula (1).

The novolak resins according to the invention can be used for the production of flame retardant epoxy resins.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims. It can be understood that it is possible.

Claims (10)

The novolak resin represented by the following Chemical Formula 1 and having a weight average molecular weight of 500 to 30,000.
&Lt; Formula 1 >

(In Formula 1, n is a positive integer, R1, R2 and R3 each independently represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, R4 is

or

Indicates.) The novolak resin according to claim 1, wherein the number average molecular weight is 400 to 10,000. The novolak resin according to claim 1, wherein the softening point is 70 ° C to 130 ° C. Stirring 4-phenylbenzaldehyde and the phenolic compound;
Firstly heating the mixture of 4-phenylbenzaldehyde and the phenolic compound in a reaction vessel;
Adding an aralkyl compound to the reaction vessel to perform a second reaction; And
Dehydrating the product obtained by the reaction, represented by the formula (1) below, obtaining a novolak resin having a weight average molecular weight of 500 to 30,000.
&Lt; Formula 1 >

(In Formula 1, n is a positive integer, R1, R2 and R3 each independently represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, R4 is

or

Indicates.) The phenolic compound according to claim 4, wherein the phenolic compound is phenol, bisphenol-A, bisphenol-F, m-cresol, p-cresol, xyleneol, resorcinol, biphenol, parabutylbutylphenol (PTBP), paraoctyl Method for producing a novolak resin, characterized in that it comprises at least one selected from the group consisting of phenol (POP) and paranonylphenol (PNP). The method for producing a novolac resin according to claim 4, wherein the polymerization reaction of the 4-phenylbenzaldehyde and the phenolic compound is carried out in the presence of a hydroxyl catalyst. The novolak of claim 4, wherein the aralkyl compound comprises 4,4-bis (methoxymethyl) biphenyl or p-xylene glycol dimethyl ether. Method for producing a resin. The method for producing a novolac resin according to claim 4, further comprising washing the product obtained by the reaction with ion-exchanged water. The method of claim 4, wherein the novolak resin has a number average molecular weight of 400 to 10,000. The method for producing a novolac resin according to claim 4, wherein the softening point of the novolac resin is 70 ° C to 130 ° C.

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