KR20130131870A - Phenol novolak resin and method for preparing the same - Google Patents

Abstract

The present invention relates to a phenol novolac resin and a production method of the same, more specifically a phenol novolac resin which can be used as a high thermal resistance and low viscosity hardener, and a production method of the same. The phenol novolac resin which can be used as a high thermal resistance and low viscosity hardener is simply produced by the present invention. The viscosity of the produced phenol novolac resin can be reduced without an addition of solvents, and the phenol novolac resin can be economically used in an environmentally friendly way.

Description

Phenol Novolak Resin and Method for Preparing the Same

The present invention relates to a phenol novolak resin and a method for producing the same, and more particularly, to a phenol novolak resin that can be used as a high heat resistant low viscosity curing agent and a method for producing the same.

Copper clad laminates (CCL) used in printed circuit boards and the like are laminated insulating plates composed of various insulating material base materials and bonding agents and copper foil is attached to one or both sides of the insulating material. There has been a growing demand for copper-clad laminates requiring insulating materials having a high glass transition temperature characteristic, and the demand for lead-free has increased.

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

However, the phenol novolak resin, which is conventionally applied as a curing agent, contains a large amount of oligomer products having low polymerization degree in the polymerization process. Particularly, the components in which the two monomers are polymerized have a small number of reactors and greatly lower the curing density of the final cured product. Also, due to the high reactivity, the curing is excessively promoted, so that the surface is cured before the solvent is sufficiently volatilized in the preparation process of the prepreg so that a large amount of solvent remains in the prepreg, and the separated curing density and residual solvent result in the final cured product The glass transition temperature is greatly lowered.

In addition, in order to obtain a high glass transition temperature, in the case of a phenol novolak resin having a high 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. As a result, the varnish production and prepreg impregnation process have a disadvantage in that the workability is lowered and the viscosity is decreased by adding a solvent. Furthermore, further use of the solvent is not preferable from the viewpoints of economic efficiency and environmental pollution.

Therefore, the development of a high heat resistance low viscosity curing agent that can solve these disadvantages.

The present invention is to provide a phenol novolak resin that can be used as a high heat resistance low viscosity curing agent and a method for producing the same.

The phenol novolak resin of the present invention is a phenol novolak resin comprising a compound represented by an integer of n = 0 to 5 in the formula (1), comprising 5 wt% or less of the compound of formula (1) n = 0, or In the absence of n = 0, the weight average molecular weight is characterized in that 500 ~ 10,000g / mol.

[Formula 1]

In Formula 1 n is an integer of 0 to 5, R is CH ₂ , CH ₃ -C-CH ₃ , C = O or O = S = O, X is H, para butyl phenol, chlorine, bromine or carbon number It is an alkyl group selected from the C1-C12 hydrogen group.

Herein, the phenol novolak resin of the present invention preferably contains a polydispersity index (PDI) of 1.1 to 6.0 with or without 5 wt% or less of a compound having n = 0 in Formula 1, and in particular, 160 It is preferable that melt viscosity in 80 degreeC is 80-12,000cps, and also it is more preferable that softening point is 80-150 degreeC.

In addition, in the phenol novolak resin of the present invention, in the general formula (1), R is CH ₂ , and X is H more preferably.

Method for producing a phenol novolak resin of the present invention is a synthetic step of condensation reaction of a phenolic monomer and formaldehyde-based monomer under an acid catalyst, to remove the condensation water to synthesize a phenol novolak resin; A heating step of heating and melting the phenol novolak resin obtained from the synthesis step above the softening point; And extracting the molten phenol novolak resin from the heating step into a high vacuum distillation apparatus to remove 5% by weight or less of the compound having n = 0 in Formula 1 or completely.

Here, in the extraction step, by setting the conditions of the wall temperature and pressure of the main body of the high vacuum distillation apparatus prepared in advance to any set conditions, to remove the compound of n = 0 in Formula 1 to 5% by weight or less, or completely removed It is preferable.

According to the present invention, a phenol novolak resin which can be used as a high heat resistance low viscosity curing agent can be easily produced by a simple method, and the prepared phenol novolak resin can reduce the viscosity without adding a solvent economically, Eco-friendly and useful.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted so as to avoid obscuring the subject matter of the present invention.

Throughout this specification, when an element is referred to as "containing or containing" an element, it is to be understood that the element does not exclude other elements, do.

The terms "about "," substantially ", etc. used to the extent that they are used herein are intended to be taken to mean an approximation of, or approximation to, the numerical values of manufacturing and material tolerances inherent in the meanings mentioned, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The present invention relates to a phenol novolak resin comprising a compound represented by an integer of n = 0 to 5 in the general formula (1), comprising 5 wt% or less of the compound having n = 0 in the general formula (1), or n = 0 in the general formula (1) Without containing a phosphorus compound, the weight average molecular weight is characterized in that 500 ~ 10,000g / mol.

[Formula 1]

In Formula 1 n is an integer of 0 to 5, R is CH ₂ , CH ₃ -C-CH ₃ , C = O or O = S = O, X is H, para butyl phenol, chlorine, bromine or carbon number It is an alkyl group selected from the C1-C12 hydrogen group.

That is, in the general phenol novolak resin represented by the general formula (1), the compound is synthesized by including about 10% by weight or more of the compound from n = 0 to n = 5, but in the present invention, only two monomers are polymerized n = 0 When the content of the phosphorus compound is 5 wt% or less, or is not included, the weight average molecular weight is 500 to 10,000 g / mol, and when compared to the conventional phenol novolak resin having the same weight average molecular weight, It is possible to greatly improve the curing density and the glass transition temperature of the cured product.

At this time, the phenol novolak resin of the present invention preferably contains or does not contain the content of the compound of n = 0 to 5% by weight or less and at the same time the polydispersity index (PDI) is 1.1 ~ 6.0 However, when PDI is 1.1-6.0, the compatibility of resin and the wettability with respect to glass fiber can be made excellent compared with the conventional phenol novolak resin which has the same PDI.

In addition, the lower the PDI is closer to 1, the better the compatibility of the resin and the wettability to the glass fiber.

According to the present invention, the content of n = 0 or less is contained in 5 wt% or less, thereby greatly improving the curing density of the final cured product, thereby satisfying the curing density and glass transition temperature required for the final cured product. While providing a phenol novolak resin, it is possible to provide a phenol novolak resin having a relatively low viscosity and softening point.

Herein, the phenol novolak resin of the present invention includes a content of a compound of n = 0 at 5 wt% or less, or does not contain a weight average molecular weight of 500 to 10,000 g / mol, and a PDI of 1.1 While the melt viscosity at 160 ° C is preferably 80 to 12,000 cps, the viscosity is 80 cps or more, whereby the resin impregnated or applied to the substrate can be prevented from flowing down, and the viscosity is 12,000 cps or less. By doing so, the substrate can be impregnated or applied without deterioration of workability due to high viscosity.

In addition, the phenol novolak resin of the present invention includes a weight average molecular weight of 500 to 10,000 g / mol with or without the content of the compound of n = 0 or less 5% by weight, PDI is 1.1 ~ At the same time as 6.0, the softening point of 80 ° C. or more 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 high heat resistance. When the temperature is 150 ° C. or lower, melting of the resin can be facilitated and workability can be improved.

Herein, in the phenol novolak resin of the present invention, in the general formula (1), R is CH ₂ , and X is more preferably H.

The method for producing a phenol novolak resin, comprising 5 wt% or less of the compound having n = 0 in the general formula (1) according to the present invention, or not including the compound having n = 0 in the general formula (1), is as follows.

The method for preparing a phenol novolak resin includes a synthesis step of condensing the phenol novolak resin with a phenol monomer and a formaldehyde monomer under an acid catalyst and obtaining a phenol novolak resin by removing the condensation water. The phenol novolak resin obtained through the synthesis step is heated to a softening point or more to a molten state, and the phenol novolak resin heated and melted above the softening point is put into a high vacuum distillation apparatus, and n An extraction step of separating the compound with = 0.

In the extraction step, the compound of n = 0 of Formula 1 is separated from the injected phenol novolak resin to completely remove the compound of n = 0, or high vacuum to include any set weight percentage of 5 wt% or less. By properly setting the wall temperature and the pressure of the main body of the distillation apparatus, the compound having n = 0 contained in the finally obtained phenol novolak resin may not be completely contained or may be included at an arbitrary set concentration.

The following describes examples and comparative examples of the present invention.

< Comparative Example  1-1>

3,200 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-neck flask, heated to 60 ° C, and stirred for 30 minutes to sufficiently mix. 11 g of oxalic acid was added as a catalyst to the mixed raw materials, and then heated to 100 ° C. and reacted for 3 hours. After the reaction was completed, a phenol novolak resin was synthesized by removing the condensed water at 760 mmHg.

< Comparative Example  1-2>

The phenol novolak resin obtained in Comparative Example 1-1 was heated to a molten state, and then a low molecular weight component was removed by feeding it into a high vacuum distillation apparatus having a wall temperature of 240 ° C. and a pressure of 0.7 mbar. To obtain a phenol novolak resin.

< Example  1-1> (Example when n = 0 4.5%)

The phenol novolak resin obtained in Comparative Example 1-1 was heated to a molten state, and then a low molecular weight component was removed by feeding it into a high vacuum distillation apparatus having a wall temperature of 235 ° C. and a pressure of 0.55 mbar. To obtain a phenol novolak resin.

< Example  1-2> (example where n = 0 is 2.3%)

The phenol novolak resin obtained in Comparative Example 1-1 was heated to a molten state, and then put into a high vacuum distillation apparatus in which the wall temperature of the high vacuum distillation apparatus was 240 ° C. and the pressure was set at 0.55 mbar to remove components of low molecular weight. To obtain a phenol novolak resin.

< Example  1-3> (Example when n = 0 is 0.7%)

The phenol novolak resin obtained in Comparative Example 1-1 was heated to a molten state, and then a low molecular weight component was removed by inputting it into a high vacuum distillation apparatus having a wall temperature of 240 ° C. and a pressure of 0.45 mbar. To obtain a phenol novolak resin.

< Example  1-4> (Example when n = 0 0.0%)

The phenol novolak resin obtained in Comparative Example 1-1 was heated to a molten state, and then the high-molecular distillation apparatus was put into a high vacuum distillation apparatus having a wall temperature of 240 ° C. and a pressure of 0.4 mbar to completely remove low molecular weight components. It removed and obtained the phenol novolak resin.

< Comparative Example  2-1>

3200 g of raw material phenol and 2000 g of formaldehyde contained in a concentration of 40 wt% 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 as a catalyst to the mixed raw materials, and then heated to 100 ° C. and reacted for 3 hours. After the reaction was completed, condensed water was removed at 760 mmHg to synthesize a phenol novolak resin.

< Comparative Example  2-2>

The phenol novolak resin obtained in Comparative Example 2-1 was heated to a molten state, and then a low molecular weight component was removed by feeding into a high vacuum distillation apparatus having a wall temperature of 230 ° C. and a pressure of 0.65 mbar. To obtain a phenol novolak resin.

< Example  2-1> (example where n = 0 is 4.1%)

The phenol novolak resin obtained in Comparative Example 2-1 was heated to a molten state, and then a low molecular weight component was removed by feeding it into a high vacuum distillation apparatus having a wall temperature of 230 ° C. and a pressure of 0.5 mbar. To obtain a phenol novolak resin.

< Example  2-2> (Example when n = 0 is 0.9%)

The phenol novolak resin obtained in Comparative Example 2-1 was heated to a molten state, and then a low molecular weight component was removed by feeding the high vacuum distillation apparatus having a wall temperature of 240 ° C. and a pressure of 0.5 mbar. To obtain a phenol novolak resin.

< Example  2-3> (Example when n = 0 0.0%)

The phenol novolak resin obtained in Comparative Example 2-1 was heated to a molten state, and then a low molecular weight component was removed by feeding it into a high vacuum distillation apparatus having a wall temperature of 240 ° C. and a pressure of 0.4 mbar. To obtain a phenol novolak resin.

< Comparative Example  3>

3,200 g of phenol as a raw material and 2,025 g of formaldehyde containing 40% by weight of water were added to a 5L four-neck flask, heated to 60 ° C, stirred for 30 minutes, and sufficiently mixed. After adding 18 g of oxalic acid as a catalyst to the mixed raw materials, the reaction mixture was heated at 100 ° C. for 3 hours, and after the reaction was completed, a phenol novolak resin was synthesized by removing the condensed water at 760 mmHg.

< Example  And Comparative example  Property Evaluation Method>

The physical properties of the phenol novolak resins prepared according to the Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

-Method of measuring the content of compound with n = 0

The gel permeation chromatography apparatus (manufactured by Waters) was used to calculate the integral value of the corresponding molecular weight band area in the resin and was calculated as the ratio of the relative molecular weight band to the relative area.

-Molecular weight measurement method

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using the Gel permeation chromatography apparatus (made by Waters).

-PDI measurement method

It was calculated by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured using a Gel permeation chromatography instrument (manufactured by Waters).

-Softening point measurement method

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

-Viscosity measurement method

The viscosity of the fully melted resin was measured at 160 ° C. using a Brookfield Viscometer (CAP 2000+).

-Measurement of physical properties after curing

Bisphenol A type epoxy resin having an epoxy equivalent weight (EEW) of 280 and a curing agent (phenolic novolac resins of Examples and Comparative Examples) were mixed in an equivalent ratio of 1: 1, and then 2E4MZ (2-ethyl-4-methyl-) as a curing accelerator. imidazole) was added and mixed with 0.035 wt% [epoxy (solid content) + phenol novolak resin (solid content): 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 were made (press conditions: temperature 190 ° C., pressure 25 kgf / cm ² , process time 2 hours).

The glass transition temperature of the prepared copper clad laminate was measured using a differential scanning calorimeter (DSC, Q2000 manufactured by TA Instrument) (measurement part: center part, 20 mg. Measurement conditions: nitrogen atmosphere, temperature rising rate of 20 ° C./min. To 250 ° C.). Elevated temperature).

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

division
n = 0 Content Weight% Evaluation Property Molecular Weight PDI Viscosity cps Softening point ℃ Gel time Tg after curing Comparative Example 1-1 22 1034 1.42 68 78 234 s 128.1 ℃ Comparative Example 1-2 7.1 1106 1.36 132 89 241 s 136.3 ℃ Example 1-1 4.5 1135 1.33 189 98.2 258 s 148.2 ℃ Examples 1-2 2.3 1149 1.31 246 99.1 262 s 151.2 ℃ Example 1-3 0.7 1162 1.29 287 101 267 s 154.3 ℃ Example 1-4 0.0 1172 1.26 291 101.5 266 s 155.7 ℃ Comparative Example 2-1 12.9 1848 2.03 390 101 212 s 153.1 ℃ Comparative Example 2-2 9.9 1915 1.96 784 109 219 s 155.2 ℃ Example 2-1 4.1 2059 1.83 1610 117 234 s 163.3 ℃ Example 2-2 0.9 2110 1.7 2171 120.1 239 s 164.1 ℃ Example 2-3 0 2150 1.64 2190 121.1 243 s 165.5 ℃ Comparative Example 3 9.2 4342 3.57 2876 119 219 s 162 ℃

Having described specific portions of the invention in detail, those skilled in the art will appreciate that these specific embodiments are merely preferred embodiments and that the scope of the invention is not limited thereby will be. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (7)

A phenol novolak resin comprising a compound represented by an integer of n = 0 to 5 in Formula 1, comprising 5 wt% or less of a compound having n = 0 in Formula 1, or a compound having n = 0 in Formula 1 Phenol novolac resin, characterized in that the weight average molecular weight of 500 ~ 10,000g / mol without including:
[Chemical Formula 1]

Wherein n is an integer from 0 to 5, R is CH ₂ , CH ₃ -C-CH ₃ , C = O or O = S = O, X is H, para butyl phenol, chlorine, bromine or 1 to C It is an alkyl group selected from the hydrogen group of 12.
The phenol novolak resin according to claim 1, wherein the phenol novolak resin has a PDI of 1.1 to 6.0.
The phenol novolak resin according to claim 1, wherein the phenol novolak resin has a melt viscosity of 80 to 12,000 cps at 160 ° C.
The phenol novolak resin according to claim 1, wherein the phenol novolak resin has a softening point of 80 to 150 ° C.
The phenol novolak resin according to claim 1, wherein in Formula 1, R is CH ₂ and X is H.
(a) a condensation reaction of a phenolic monomer with a formaldehyde monomer under an acid catalyst, and a condensation water to be removed to synthesize a phenol novolak resin;
(b) a heating step of heating and melting the phenol novolak resin obtained from the synthesis step above the softening point; And
(c) a phenol novolak resin comprising an extraction step of removing the molten phenol novolak resin from the heating step into a high vacuum distillation apparatus to remove 5% by weight or less of the compound having n = 0 in Formula 1; Manufacturing method.
The method of claim 6, wherein in the extraction step of (c), by setting the conditions of the wall temperature and the pressure of the main body of the high vacuum distillation apparatus prepared in advance to any set conditions, 5% by weight of the compound of n = 0 in the formula (1) A method for producing a phenol novolak resin, which is removed below or completely removed.