High Purity Alkyl Phenolic Novolac Resins, Their Continuous Manufacturing Processes and Components Containing Those

Abstract

The present invention relates to a continuous manufacturing method for obtaining high-purity alkylphenol novolac resins with high yield and without loss by using a Short Path Distillator (SPD), which is an advanced thin-film distiller with a built-in condenser, to feed general-purpose alkylphenol novolac resins as a feed liquid (raw material), thereby obtaining unreacted phenol monomers including alkylphenol monomers that are raw materials for these resins as distillation components, and simultaneously removing these phenol monomers as residual components to 0.1 weight% or less. The invention also relates to a composition containing the same. To this end, the present invention specifies in detail the form and structure of an advanced type of SPD facility, and in addition to general matters, specifies the form of the internal condenser, the form and material of the internal rotating body, and the input and output facilities for continuous production. In addition, SPD process conditions such as evaporator temperature, condenser temperature, vacuum level, feed rate, and internal rotor rotation speed were presented to maximize the yield and purity of high-purity alkylphenol novolak resin while avoiding thermal deformation and minimizing commercial losses due to excess conditions, and the characteristics of the high-purity alkylphenol novolak obtained through this were specified. In addition, the obtained high-purity alkylphenol novolak resin was applied to rubber and tire compositions and copper clad laminate compositions to demonstrate the improved properties of these compositions.

Description

Technology Field

[0001] The present invention relates to a method for continuously producing high-purity alkylphenol novolac resin by removing unreacted phenol monomers, such as phenol, bisphenol, para-tert-butylphenol (hereinafter PTBP), and para-tert-octylphenol (hereinafter PTOP), remaining in alkylphenol novolac resins, and a composition comprising the same. More specifically, the invention relates to a method for continuously producing high-purity alkylphenol novolac resin by removing unreacted phenol monomers remaining as SPD distillate, which is an advanced type of TFE (Thin Film Evaporator) equipped with a condenser, using a general-purpose alkylphenol novolac resin as a feed liquid (raw material), thereby removing the phenol monomers remaining as SPD distillate. The present invention relates to a continuous manufacturing method capable of obtaining high-purity alkylphenol novolak with a content of 0.1 weight% or less, and to rubber, tire, and copper clad laminate compositions containing the same. Background Technology

[0002] PTBP represented by [Chemical Formula 1], PTOP represented by [Chemical Formula 2], and Para Nonyl Phenol (hereinafter PNP) represented by [Chemical Formula 3] are representative alkylphenol compounds. Alkylphenol novolak resins produced using these as raw materials have excellent effects in improving the brittleness, which is a disadvantage of phenol resins based on a benzene structure, due to the flexibility of the alkyl groups possessed by each of them. As a result, they have been widely used for a long time as tackifiers to impart tackiness to tires and rubber compositions.

[0003]

[0004]

[0005]

[0006] However, starting with the European Union in 2003, PNP of [Chemical Formula 3] was designated as an endocrine disruptor and its use was regulated. Since 2006, Korea has also been fully regulating the manufacture, distribution, storage, and use of compounds containing 0.1% or more of PNP. However, there are currently no regulations regarding PNP novolak polymer materials manufactured using PNP as a raw material. Nevertheless, as no technical, realistic, or economic solution has been found to reduce the residual PNP monomer content in PNP novolak to 0.1% or less, PNP novolak has long since been withdrawn from the market.

[0007] Although there are no specific reports regarding the harmfulness to the human body and the environment of PTBP novolac of [Formula 4] or PTOP novolac of [Formula 5], or general-purpose alkylphenol novolacs having mixed and copolymer structures, which are polymeric materials having repeating units, the content of residual PTBP or PTOP alkylphenol monomers, typically at a level of 1 to 2 weight percent in these alkylphenol novolacs, has emerged as an important observation point, similar to the residual PNP in PNP novolacs. Consequently, research results reporting the harmfulness to the human body and the environment of these residual PTBP and PTOP monomers are being reported. As a result, these PTBP and PTOP monomers have already been designated as substances suspected of disturbing ecosystems and substances suspected of high risk. It is generally expected that specific usage restrictions or regulations will be imposed on PTBP and PTOP alkylphenol novolacs containing these residual alkylphenol monomers in the near future.

[0008] Accordingly, there is a very urgent need to develop a new type of tackifier to replace these alkylphenol novolacs, or to develop high-purity alkylphenol novolacs with reduced alkylphenol monomer content to a Monomer-Free level (in this invention, this expression is used to mean a residual phenol content of 0.1% by weight or less including alkylphenol monomer). Industrial and technical efforts to achieve this have been ongoing for a long time, but to date, no results of industrial significance have been produced.

[0009]

[0010]

[0011] Alkylphenol Monomer reduction technologies known to date include traditional phenolic resin-related literature such as ["Chemistry and application of phenolic resins", Polymer / properties and application, A. Knop and W. Scheibe, Springer-Verlag, 1979] and literature [J. Although some technologies have been introduced to minimize the content of unreacted alkylphenol monomers by changing the reaction molar ratio ((Form)aldehydes to (Alkyl) Phenols Molar Ratio, hereinafter referred to as "F / P") of aldehydes (typically formaldehyde) and alkylphenols, or by using an excess amount of catalyst, as described in Borrajo, MI Aranguren and RJJ Williams, Polymer, 1982, 23, 2, 263, and KR Published Patent 10-2006-0066134, these technologies have technical limitations. Not only is there a significant technical gap between the unreacted alkylphenol monomer content of 1 wt%—which corresponds to the PNP regulatory standard of less than 0.1 wt%—but these technologies are also very difficult to apply commercially to ensure economic feasibility. Fundamentally, this is because the unreacted residual alkylphenol monomers have a high boiling point and very low solubility in water. This is because, due to the characteristic of not forming an azeotrope with water, they cannot be separated or removed by temperature, pressure, vacuum control, or steam stripping in conventional alkylphenol novolac manufacturing facilities, or because it is impossible to separate and purify these alkylphenol novolac monomers by means of separation based on differences in solubility while ignoring yield.

[0012] In addition, although some technologies for reducing residual alkylphenol content have been disclosed through KR Public Patent 10-2023-0022064, they only specified a "high vacuum" state regarding the vacuum level, which is the most demanding condition, and did not specify specific manufacturing conditions. Furthermore, as these technologies are questionable in terms of economic feasibility and commercial utility as well as the limitations of batch processes rather than the continuous manufacturing conditions of the present invention, there is an urgent need to develop technologies that can overcome these problems. Prior art literature

[0013] [Reference 1] KR Published Patent 10-2006-0066134 [Reference 2] KR Published Patent 10-2023-0022064 [Reference 3] US 6,326,453 [Reference 4] EP 1,108,734 [Reference 5] JP 11-349,655

[0014] [Document 1] A. Knop, W. Scheibe, Chemistry["Chemistry and application of phenolic resins", Polymer / properties and application, Springer-Verlag, 1979[Document 2] A. Gardziella, LA Pilato, A. Knop, Phenolic Resins: Chemistry, Applications, Standardization, Safety and Ecology, 2nd edition, Springer, 2000 3] Wolfgang Hesse "Phenolic Resins" in Ullmann's Encyclopedia of Industrial Chemistry, 2002, Wiley-VCH, Weinheim. doi 10.1002 / 14356007.a19_371.[Reference 4] J. Borrajo, MI Aranguren, RJJ Williams, Polymer, 1982, 23, 2, 263 The problem to be solved

[0015] PTBP and PTOP alkylphenol novolaks are thermosetting resins having repeating units of phenol novolak structures obtained by the condensation reaction of alkylphenol and formaldehyde as shown in [Formulas 4 and 5]. Despite numerous studies and technological developments, the residual PTBP and PTOP monomer content of currently commercially used alkylphenol novolaks is at the level of 1 to 2 weight percent, which should be considered the limit of current technology.

[0016] PTBP and PTOP novolak resins serve as tackifiers in terms of the physical properties of rubber and tire compositions. However, residual PTBP and PTOP monomers, which are present in amounts of only 1 to 2 weight percent, cause significant loss in the physical properties of the rubber and tire compositions. This is because, as with other polymer materials, residual monomer components rather than polymers become impurities, and the degradation of physical properties caused by these monomers is unavoidable. In particular, although the application of alkylphenol novolak as an epoxy curing agent for copper clad laminates has been continuously considered due to its low dielectric properties, commercial application is currently impossible due to the decrease in heat resistance caused by the aforementioned residual unreacted monomers.

[0017] Accordingly, the present invention aims to provide a continuous manufacturing method for producing high-purity alkylphenol novolak resin with significantly reduced PTBP and PTOP monomer content using a residual component (a heavy component with a relatively high molecular weight and high boiling point) by using an advanced type of SPD with a built-in condenser to completely remove PTBP and PTOP monomer components from a distillation component (a light component with a relatively low molecular weight and low boiling point) by using a conventional alkylphenol novolak resin as a feed liquid (input raw material), and a composition including these components. means of solving the problem

[0018] The present invention provides an advanced type of TFE with a built-in condenser, professionally referred to as a molecular distiller or SPD, as a continuous manufacturing method capable of obtaining high-purity alkylphenol novolak resin in which PTBP and PTOP monomers are completely removed in a stable state.

[0019] Unlike conventional TFE, the SPD device minimizes pressure drop by having the condenser located inside the main body of the distiller, thereby minimizing the distance vaporized distillation components travel to the vapor state before condensing. Consequently, it forms a very low vacuum of 0.001 mbar, which is much lower than the mechanical limit of 2 mbar of conventional TFE, allowing for the separation and purification of PTBP and PTOP monomers—which have high boiling points and cannot be vaporized at atmospheric pressure or even at the vacuum level of TFE—through single distillation without thermal decomposition or thermal deformation. The present invention was completed by defining the detailed device conditions and simultaneously identifying the distillation conditions.

[0020] Generally, in simple distillation, vacuum and boiling point show a relationship in which the boiling point decreases rapidly as the vacuum decreases. As a prime example, in the case of Stearic Acid, the boiling point is 390°C at an atmospheric pressure of about 1,013 mbar, but drops to 190°C under a vacuum of 1 mbar and to 90°C under a vacuum of 0.001 mbar. It goes without saying that a low vacuum, based on this semi-logarithmic proportional relationship between vacuum and boiling point, is the most important process condition in the present invention.

[0021] The main body of the SPD used in the present invention comprises a cylindrical evaporator (or vaporizer) body and a condenser in the form of a coil or bundle that condenses vaporized components; it also comprises a winged rotating body that rotates between the evaporator and the condenser to form a thin film of the feed liquid on the inner wall of the cylindrical evaporator of the main body, thereby expanding the heat transfer surface area and facilitating evaporation and vaporization; and is characterized by having heating, cooling, and vacuum equipment on the outer surface of the main body, raw material input equipment on the upper side, and a heating jacket for distilled components and residual components and an outlet on the lower side. This describes a continuous manufacturing facility and manufacturing method.

[0022] In the above distillation process, it is preferable to obtain the monomer-free high-purity alkylphenol novolak resin, which is the object of the present invention, by continuously separating distillation components and residual components by feeding an alkylphenol novolak resin with an SP (Softening Point) of 150°C or lower as a feed liquid into an SPD maintained under conditions of vacuum level of 0.1~0.001 mbar, evaporator temperature of 190~290°C, condenser temperature of 100~180°C, and rotary speed of 50~400 rpm at a rate of 3~15 kg / hr per 0.1 m² of evaporator heat transfer area.

[0023] The distillation component obtained through this process may vary depending on the monomer composition (including alkylphenols) of the feed solution and manufacturing conditions, but it is a high-purity monomer (or mixture of monomers) with a phenol purity of 95.0 wt% or more based on GPC area analysis standards, and at the same time, the high-purity alkylphenol novolak obtained as a residual component has an unreacted monomer content of 0.1 wt% or less, and by removing these monomer components, it has an SP that is 10°C or higher than the SP of the feed solution, thereby providing a specialized application that compensates for the disadvantages in terms of brittleness, heat resistance, and adhesion of the conventional alkylphenol novolak resin (feed solution). Effects of the invention

[0024] The manufacturing method of the present invention is a simple single distillation method, yet it obtains a monomer with a purity of 95.0 mass% or higher as a distillation component and simultaneously obtains an alkylphenol novolak resin with a monomer content of 0.1 weight% or less as a residual component, thereby enabling the commercial use of both the distillation component and the residual component. It is an eco-friendly manufacturing method that does not generate waste or by-products during the manufacturing process and is characterized by being manufactured as a continuous process, which is very advantageous in terms of cost. Furthermore, once the stabilization process is reached after the operation of the SPD facility, it has the advantage of enabling continuous production in a semi-permanent state without the need for additional control or adjustment. Brief explanation of the drawing

[0025] [Fig. 1] is a schematic diagram of a typical TFE facility with an external condenser, and [Fig. 2] is a schematic diagram of an SPD facility having an internal condenser used in the present invention, and [Figure 3] shows the GPC analysis results of the general-purpose alkylphenol novolak of <Comparative Example 3> and the high-purity alkylphenol novolak obtained as a residual component in <Example 6>. Specific details for implementing the invention

[0026] In the specific details for implementing the present invention, when describing preferred embodiments of the present invention in detail, specific descriptions of related known functions or configurations are omitted to avoid obscuring the essence of the present invention. Furthermore, throughout this specification, when a part is described as "including or containing" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include or contain additional components. Additionally, terms of degree used in this specification, such as "approximately," "substantially," and "preferably," are used to mean at or near the stated value when inherent manufacturing and material tolerances are presented in the mentioned meaning, and are used to prevent unscrupulous infringers from unfairly exploiting the posted content in which precise or absolute values ​​are mentioned to aid in understanding the present invention.

[0027] The distillation component obtained in the present invention has a purity of phenol monomers containing [Chemical Formula 1] and [Chemical Formula 2] of 95.0 wt% or higher, preferably 97.0 wt% or higher, and most preferably 99.0 wt% or higher. The composition of these distillation components may vary depending on the phenol composition including alkylphenol used in the manufacturing process of the feed solution and the manufacturing process of the feed solution. The obtained distillation component can be reused in a recycled form in the alkylphenol novolac manufacturing process based on component analysis such as simple gas chromatography analysis without any problems.

[0028] At the same time, the monomer-free high-purity alkylphenol novolak resin obtained as a residual component has a Free-Phenol content, which means the content of unreacted residual phenols including alkylphenol, of 0.1% by weight or less, preferably 0.05% by weight or less, and more preferably 0.01% by weight or less.

[0029] These monomer-free high-purity alkylphenol novolak resins provide characteristics such as a weight-average molecular weight of 1,500–4,500 g / mol and a PDI of 1.5–6.0, depending on the feed solution, and a melting viscosity of 300–2,500 cps at 160°C and an SP of 85–150°C. By removing the alkylphenol monomer, they have an SP that is more than 10°C higher than the feed solution SP, and exhibit superior heat resistance, toughness, and adhesion properties compared to conventional alkylphenol novolak resins having the same SP.

[0030] The feed solution used in the present invention is a general-purpose, conventional alkylphenol novolak resin, which generally has a single structure of [Formula 4] or [Formula 5], or a mixed and copolymerized structure of these structures, and is often used together with other alkylphenols such as phenol, bisphenol, and CNSL (Cashew Nut Shell Liquid) as raw materials.

[0031] These conventional alkylphenol novolak resins can be obtained by condensing phenol monomers containing various types of alkylphenols and formaldehyde monomers under an acid catalyst. Generally, phenols and formaldehyde are added in the F / P range of 0.7 to 1.1. The catalyst used can be any acid catalyst that is generally usable for the synthesis of phenol novolak resins, such as oxalic acid, sulfuric acid, or hydrochloric acid, without any restrictions on use. However, an oxalic acid catalyst is most preferable as it does not require the addition of a basic neutralizing agent to terminate the reaction and thus does not generate neutralization salt. It is generally used in the range of 0.2 to 1.5 weight percent relative to the amount of phenol added, and the reaction can be carried out for 2 to 6 hours. After the reaction is finished, the temperature can be raised to 100 to 180°C under atmospheric pressure and vacuum conditions to remove condensed water, unreacted materials, etc., thereby producing a conventional alkylphenol novolak resin used as a feed solution in the present invention. Any method capable of synthesizing alkylphenol novolak resin can be used without limitation.

[0032] Commercialized alkyl phenol resins such as SI Group’s CRJ-418, 716, HRJ-10420, HRJ-10518, and HRJ-2118; Kolon Industries’ KPT-S1503, KPT-F1360, KNR-1200, KNR-1300, and KPA-1350K; and Kangnam Chemical’s R-3060, KC-7505, and KC-7800 can all be used as feed liquids, and a mixture of these resins may also be used as a feed liquid.

[0033] In the present invention, the alkylphenol novolak resin used as the feed solution is heated to a temperature 50 to 100°C higher than the SP of the feed solution to lower its viscosity and then fed into the SPD distillation apparatus so that it can be easily fed into the SPD. If the feed solution input temperature is too low, the viscosity increases, making transfer difficult and reducing the efficiency of the evaporator; if the input temperature is too high, thermal deformation including color deterioration and carbonization of the resin occurs. Therefore, a temperature 40 to 60°C higher than the SP of the feed solution is preferable.

[0034] When phenol is used together with alkylphenol as a raw material for the feed solution, unreacted alkylphenol monomer components remaining in the feed solution are mostly found along with unreacted phenol components called Free Phenol in an amount of less than 1.0 weight%, methylene phenol, methylol phenol, and low molecular weight impurity components. Since these impurity components cause rapid chromophore reactions under high-temperature atmospheric conditions, leading to rapid color deterioration and side reactions of alkylphenol novolak, it is desirable to block contact with oxygen and minimize exposure to high temperatures as much as possible during the SPD input stage of the alkylphenol novolak resin.

[0035] In addition, as these unreacted phenol components and components such as methylene phenol and methylol phenol are introduced into the SPD, they vaporize before the alkylphenol novolak components, increasing in volume by more than 1,000 times compared to the molten liquid state, making it difficult to lower the vacuum level of the SPD. Therefore, it is desirable to introduce these impurity components into the SPD after removing them in advance, which can be easily removed in a continuous manner using a general TFE or Degasser.

[0036] It is also possible to configure a process for separating alkylphenol monomers in a second step after removing unreacted phenol components and impurities such as methylene phenol and methylol phenol using the SPD provided in the present invention. Generally, under conditions where the content of unreacted phenol components, methylene phenol, and methylol phenol is 0.5 wt% or less, it is acceptable to simultaneously remove unreacted phenol, methylene phenol, methylol phenol, and alkylphenol monomer components by adding the SPD once without the aforementioned first impurity removal pretreatment. However, since this is a variable that is interconnected with whether the required vacuum level is reached, the feed liquid input speed, and the evaporator temperature, it is not possible to specify the impurity content requiring pretreatment.

[0037] The room temperature boiling point of the alkylphenol monomer component is 237°C or higher, which is higher than the thermal deformation and thermal decomposition temperature of the alkylphenol novolak resin. Since separation by distillation is impossible with conventional TFE [Fig. 1] having a vacuum of 2 mbar or higher, equipment and conditions different from these are required.

[0038] A method to achieve separation by distillation under conditions where thermal decomposition and thermal discoloration do not occur is to lower the distillation temperature by forming a low vacuum of 0.1 mbar or less, and the present invention provides a vertical SPD as shown in [Fig. 2].

[0039] [Fig. 1] and [Fig. 2] show schematic cross-sectional views of an example of a TFE and a vertical SPD related to the present invention to briefly compare and explain the differences between the two manufacturing equipment, but this is not limited to this example as long as it does not exceed the gist of the present invention.

[0040] Referring to [Fig. 2], the vertical SPD of the present invention comprises an evaporator housing, a rotor, a condenser, and a jacket. The vertical SPD of the present invention is a thin-film evaporator having a cylindrical housing, and the jacket is installed on the outer surface of the evaporator housing to maintain the inside of the evaporator at an appropriate temperature.

[0041] The above-mentioned rotating body is located inside the housing and rotates through a driving unit. The rotating body may be equipped with a plurality of wipers installed on the side rotating portion, and these wipers can rotate while maintaining a constant gap of about 0.1 to 2 mm with the inner wall of the cylindrical evaporator of the main body.

[0042] The feed liquid supplied from the top of the SPD by gravity, vacuum, or pump operation flows down along the inner wall of the main body evaporator due to the rotating wiper, forming a thin film. The feed liquid forming this film has specific components evaporated in the evaporator region by the heat of the heating jacket, and the evaporated components (alkylphenol monomer) are cooled and condensed in the condenser located inside the SPD and discharged to the outside through the distillation component outlet at the bottom of the SPD. At the same time, relatively high-boiling point high molecular weight components (alkylphenol novolak resin components) that cannot evaporate flow down along the evaporator wall and are discharged to the outside through the residual component outlet at the bottom of the SPD.

[0043] The feeding and discharging processes into and out of the SPD may be carried out by gravity or vacuum suction of the SPD body; however, to maintain a high vacuum in the SPD and improve operational stability, it is desirable to use a forced transfer device such as a gear pump. It is necessary to select appropriate equipment that matches the viscosity and characteristics of the feed liquid, evaporative components, and residual components. In some cases, smooth transfer and discharge can be achieved by increasing or decreasing the viscosity through preheating the feed liquid or changing the temperature of the discharge jacket.

[0044] In addition, alkylphenol monomer components such as PTBP and PTOP that are distilled are crystalline substances with a melting point, and there is a risk that they may solidify after condensation and clog pipes or gear pumps. Therefore, it is very important to manage the temperature of the condenser and the distillation component outlet to be higher than the melting point of alkylphenol monomer components such as PTBP and PTOP. Generally, the temperature of the distillation component outlet is maintained at 100 to 180°C, but a condition of 110 to 160°C is preferable, and a condition of 120 to 140°C is even more preferable.

[0045] In order to ensure smooth discharge of high-purity alkylphenol novolak discharged as a residual component, the temperature of the SPD residual component discharge port is preferably 50 to 70°C higher than the SP of the feed solution. This is a range about 10°C higher than the temperature control range of the feed solution, because the SP of the high-purity alkylphenol novolak obtained as a residual component rises about 10°C relative to the feed solution due to the removal of alkylphenol monomer components, which ultimately means that a temperature 40 to 60°C higher than the SP of the obtained high-purity alkylphenol novolak is desirable.

[0046] It is preferable that the wiper attached to the stirring blade of the internal rotating body of the SPD be equipped with a mist separator, as this can minimize the side effects caused by the sudden splashing or evaporation of feed components during the distillation process, which results in the mixing of evaporated components and residual components, thereby reducing the purity of both the alkylphenol monomer and the alkylphenol novolak resin and lowering the separation efficiency.

[0047] The wiper of the rotating body is preferably a brush-type wiper or a blade-type wiper with diagonal grooves such as a saw blade. Since it is necessary to press the wiper against the inner wall of the evaporator body to form a thin film, a spring-actuated type or a centrifugal operating method is more preferable than a fixed wiper. In addition, a blade-type wiper is preferred because there is a high risk that the brush function will deteriorate due to the generation of localized carbon deposits during prolonged use in the case of a brush-type wiper.

[0048] During the long-term rotation of the rotating body, the inner wall of the evaporator and the wiper come into contact, making it impossible to avoid damage caused by abrasion of the inner wall of the evaporator or the wiper. To minimize these adverse effects, it is desirable to use a material for the wiper that has lower strength than the general SUS 316 series inner wall material of the SPD evaporator. Representative materials include hybrid carbon, in which resin or metal is vacuum-pressurized to infiltrate carbon to improve mechanical strength, and fluorine-based materials that are resistant to corrosion. However, hybrid carbon material, which has a low risk of thermal deformation and excellent long-term shape stability, is even more desirable as a wiper material.

[0049] The gap between the inner wall of the evaporator and the wiper is a factor that significantly affects productivity, as it is linked to the supply speed of the feed liquid as well as the vacuum level, evaporator temperature, and the RPM of the rotating body. The most desirable condition is a gap that allows the distillation and residual components obtained to maintain high purity without generating droplets or splashes, and maximizes the flow rate of the feed liquid. Typically, for a facility with an evaporator heat transfer area of ​​0.1 m², a gap of 0.1 to 2.0 mm is desirable, a gap of 0.1 to 1.0 mm is more desirable, and a gap of 0.2 to 0.8 mm is most desirable.

[0050] Although operation is possible with a gap of 0.1 mm or less between the rotating body and the inner wall of the evaporator, if the set thickness becomes too thin, the lubricating function of the feed liquid itself decreases, leading to mechanical stress and the deterioration or carbonization of the feed liquid components at the bottom of the evaporator, which can cause problems that make continuous operation difficult. Furthermore, if this gap is too wide, it causes inefficiency in terms of evaporation, which is a phenomenon occurring on the surface. In accordance with the basic concept that the SPD is a device that achieves higher evaporation efficiency as the thin film is made in the form of a TFT, it is desirable to maintain a sufficiently narrow gap. While the gap should naturally vary depending on the evaporator capacity, this is a fact that is obvious even to those with ordinary technical skills.

[0051] The rotational speed of the rotating body is preferably at a level of 50 to 400 rpm, and at a level of 300 to 400 rpm is even more preferable. Although this varies depending on the capacity and diameter of the evaporator, it is desirable to maintain the same level in terms of line velocity rather than angle velocity, and it is desirable to maintain the thin film through operation at the highest possible rpm and to induce easier evaporation by adding physical shock, such as stirring, to the feed liquid.

[0052] It is desirable to maintain the evaporator temperature of the SPD at 190~290℃.

[0053] It is desirable for the temperature of the SPD evaporator to increase according to the SP of the feed liquid; generally, a condition of 190 to 290°C is suitable, 200 to 260°C is preferable, and 210 to 240°C is even more preferable. As long as sufficient vaporization of the alkylphenol monomer can be achieved at a given vacuum level, it is desirable for the evaporator temperature to be lower, taking into account energy efficiency, color deterioration, thermal decomposition, and the occurrence of side reactions. In particular, when operating the SPD for a long time under conditions where the evaporator temperature is 260°C or higher, the formation of carbides of the alkylphenol novolak resin on the inner wall of the evaporator and the SPD rotor increases rapidly; therefore, operation at the lowest possible temperature and vacuum level is desirable.

[0054] If the temperature or vacuum level in the SPD is insufficient and the alkylphenol monomer component is not sufficiently evaporated, the high-purity alkylphenol novolak resin cannot be properly produced and exhibits characteristics not significantly different from conventional alkylphenol novolak resin; therefore, setting the evaporator conditions to evaporate and separate 100% of the alkylphenol monomer component contained in the feed solution is of the utmost importance.

[0055] In practice, when the evaporator temperature is less than 200℃, the vaporization of alkylphenol monomer does not occur properly unless the vacuum is lowered to 0.01 mbar or less. When the vacuum is low and the evaporator temperature is high, such as when the vacuum is less than 0.005 mbar and the temperature is 260℃ or higher, not only is there a droplet phenomenon, but some of the n=1,2 oligomer components of alkylphenol novolak also evaporate and are mixed into the distillation components, which is undesirable in terms of yield and purity. When the vacuum exceeds 0.5 mbar, the evaporation of alkylphenol monomer does not occur properly, resulting in a problem of low separation and purification efficiency.

[0056] The condenser (or condenser tube) of the SPD functions to condense the alkylphenol monomer vaporized in the evaporator. Even if sufficient evaporation of the alkylphenol monomer component occurs due to sufficient temperature or vacuum, if it is not properly cooled and condensed in the internal condenser, the vacuum level increases, causing significant losses in terms of productivity, purity, and yield. Therefore, it is simultaneously necessary to set condenser conditions capable of condensing the vaporized alkylphenol monomer component by 100%.

[0057] In the above condenser, heat transfer fluid is supplied and discharged at a predetermined temperature and circulated. The temperature of the above condenser is generally maintained at 60 to 180°C, but a temperature of 80 to 160°C is preferable, and a temperature of 110 to 140°C is more preferable.

[0058] This temperature range is intended to prevent crystals from forming inside the condenser or at the outlet, as the condensing alkylphenol monomer has crystalline characteristics. However, if the condenser temperature is too high, the efficiency of liquefying (condensing) the vaporized component decreases, so a sufficiently low temperature is desirable so that the vaporized component can be condensed immediately. On the other hand, if the condenser temperature is too low, crystal precipitation of the condensate occurs, making it difficult to flow and discharge the condensate. Therefore, it is desirable to set the condenser temperature to the lowest temperature that does not cause problems with flow and discharge, which is typically at least 80°C lower than the evaporator temperature and higher than the melting point of the alkylphenol monomer.

[0059] Unlike the TFE of [Fig. 1], the implementation of low vacuum using an SPD facility with a built-in condenser is also a very important technological advancement. In the present invention, a vacuum level of 0.1 to 0.001 mbar is suitable, and as the vacuum level is lower, a vacuum level of 0.01 to 0.009 mbar is preferred, and a level of 0.001 to 0.009 mbar is even more preferred.

[0060] To achieve such a low vacuum level, a multi-stage vacuum pump with at least two stages equipped with a cold trap is required. Typically, it is preferable to use an oil diffusion pump and a rotary vane pump in series, and a watering pump may also be used as needed.

[0061] Controlling the feed rate is also very important. When the feed rate is less than 3 kg / hr based on an SPD with an evaporator heat transfer area of ​​0.1 m², productivity decreases and carbonization increases rapidly. Conversely, when the feed rate exceeds 15 kg / hr, yield and purity decrease due to splashing and droplet phenomena. However, if the evaporator temperature is lowered to eliminate this, the removal of alkylphenol monomer is insufficient, so this is also undesirable.

[0062] Therefore, the feed rate of the feed liquid introduced into the evaporator is preferably 3 to 15 kg / hr per 0.1 m² of the evaporator heat transfer area, and 5 to 10 kg / hr is more preferable. Although the feed rate is a variable directly related to the evaporator heat transfer area, it is desirable to set the overall operating conditions of the SPD in the order of optimizing the evaporator and condenser temperatures to ensure yield under the lowest vacuum conditions, and then increasing the feed rate to determine the maximum feed rate that reaches maximum yield and purity.

[0063] Representative distillation conditions for obtaining the monomer-free high-purity alkylphenol novolak resin of the present invention are an SPD vacuum of 0.005 mbar, an evaporator temperature of 240°C, a condenser temperature of 130°C, 400 rpm, and continuous supply of the feed liquid at a rate of 7.5 kg / hr per 0.1 m² of heat transfer area of ​​the evaporator.

[0064] Since the aforementioned variables such as temperature, vacuum level, and input speed are not independent but are interdependent process variables that influence one another, optimizing these process variables by comprehensively considering yield, purity, and operating costs is both difficult and critical. Furthermore, changes to these process variables are required depending on increases or decreases in the heat transfer area of ​​the SPD, but this falls within the realm of common sense for those familiar with the facts.

[0065] In addition, the Monomer-Free high-purity alkylphenol novolak manufacturing method of the present invention described above can be used economically and in an environmentally friendly manner in the simplest and most efficient way.

[0066] Monomer-free high-purity alkylphenol novolak resin, with significantly reduced alkylphenol monomer content, exhibits superior adhesion, toughness, and heat resistance compared to conventional alkylphenol novolak resin due to the removal of alkylphenol monomer, while also possessing low viscosity characteristics compared to conventional alkylphenol novolak with the same SP. As such, it can be used not only for tire and rubber compositions but also as an epoxy curing agent for CCLS (Copper Clad laminate Sheet) for printed circuit boards, as it has excellent dielectric properties absolutely necessary for 6G communication.

[0067] Specific parts of the present invention have been described in detail above, and will be explained in detail below according to the <Examples> and <Comparative Examples> of the present invention; however, the present invention is not limited thereto, and it will be apparent to those skilled in the art that such specific descriptions are merely preferred embodiments and do not limit the scope of the present invention. Accordingly, the actual scope of the present invention is defined by the appended claims and their equivalents.

[0069] <Comparative Example 1>

[0070] 2,553 g of PTBP and 471.7 g of 92% Para-Formaldehyde were added to a 5-liter 4-neck flask equipped with a reflux circuit to achieve a reaction Molar Ratio (reaction between Formaldehyde and Phenol-based raw materials) of 0.85 and mixed thoroughly. Then, 30.63 g of Oxalic Acid, a catalyst, was added at 40°C. The temperature was raised to the reflux temperature using heating from a mantle heater and the exothermic reaction of the reaction. After maintaining the reaction for 5 hours while continuing reflux at 102–110°C, the process was switched to a dehydration circuit to perform atmospheric dehydration up to 150°C. Subsequently, dehydration was continued up to 180°C under a vacuum of 5–20 mmHg to remove unreacted materials and condensed water, thereby synthesizing PTBP alkylphenol novolak resin. This is identical to the synthesis process of typical alkylphenol novolak resins produced at F / P = 0.60 to 1.10 levels, except for the reaction molar ratio of F / P = 0.85.

[0071] As a result of GPC (Gel Permeation Chromatography) measurement to determine the degree of polymerization of the PTBP alkylphenol novolak resin synthesized in this way, the weight-average molecular weight was 1,882 g / mol, the PDI was 1.79, the unreacted PTBP residual content was Free PTBP 1.77 wt%, and the SP was 138.7℃.

[0072] The softening point was measured using a METTLER TOLEDO FP90 instrument at a heating rate of 2°C / min, and the polystyrene equivalent weight-average molecular weight (Mw), number-average molecular weight (Mn), and residual phenol content were determined using a GPC (Waters 707 model). The sample to be measured was dissolved in tetrahydrofuran to a concentration of 4,000 ppm, and 100 µl was injected into the GPC. The mobile phase of the GPC was tetrahydrofuran injected at a flow rate of 1.0 mL / min, and the analysis was performed at 35°C. Four Waters HR-05, 1, 2, and 4E columns were connected in series. RI and PAD detectors were used as detectors, and the PDI was calculated by dividing the measured weight-average molecular weight by the number-average molecular weight.

[0074] <Comparative Example 2>

[0075] 3,095 g of PTOP and 416.1 g of 92% Para-Formaldehyde were added to a 5-liter 4-neck flask equipped with a reflux circuit to achieve a reaction Molar Ratio (reaction between Formaldehyde and Phenol raw materials) of 0.85, and then thoroughly mixed. Then, 37.14 g of Oxalic Acid, a catalyst, was added at 40°C, and the temperature was raised to the reflux temperature using heating with a mantle heater and the exothermic reaction. After maintaining the reaction for 5 hours while continuing reflux at 102–110°C, the process was switched to a dehydration circuit and dehydration was carried out at atmospheric pressure up to 150°C. Subsequently, dehydration was carried out at 180°C under a vacuum of 5–20 mmHg to remove unreacted materials and condensed water, thereby synthesizing PTOP alkylphenol novolak resin. This is identical to the synthesis process of typical alkylphenol novolak resins produced at F / P = 0.60 to 1.10 levels, except for the reaction molar ratio of F / P = 0.85.

[0076] As a result of GPC measurement to determine the degree of polymerization of the PTOP alkylphenol novolak resin synthesized in this way, the weight-average molecular weight was 1,706 g / mol, the PDI was 1.54, the unreacted PTOP residual content was Free PTOP 2.02 wt%, and the SP was 93.8℃.

[0078] <Comparative Example 3>

[0079] 1,591 g of PTBP and 874 g of PTOP were mixed in a 5-liter 4-neck flask equipped with a reflux circuit to achieve a reaction Molar Ratio (reaction Molar Ratio of Formaldehyde and Phenol-based raw materials) of 0.75, and 362.9 g of 92% Para-Formaldehyde was added and thoroughly mixed. Then, 29.58 g of Oxalic Acid, a catalyst, was added at 40°C, and the temperature was raised to the reflux temperature using heating with a mantle heater and the exothermic reaction. After maintaining the reaction for 5 hours while continuing reflux at 102–110°C, the process was switched to a dehydration circuit and dehydration was carried out at atmospheric pressure up to 150°C. Subsequently, dehydration was carried out at 180°C under a vacuum of 5–20 mmHg to remove unreacted materials and condensed water, thereby synthesizing a PTBP and PTOP copolymer alkylphenol novolak resin.

[0080] This is identical to the synthesis process of a typical copolymerized alkylphenol novolak resin produced at a level of F / P = 0.60 to 1.10, except for a reaction molar ratio of F / P = 0.75, and the compounding conditions of the phenols are not significantly different from the general raw material composition of alkylphenol novolak for conventional tire tackifiers, and in addition to PTBP and PTOP, phenol and Bisphenol-A as well as various other alkylphenols are used together.

[0081] As a result of GPC measurement to determine the degree of polymerization of the alkylphenol novolak resin synthesized in this way, the weight-average molecular weight was 2,325 g / mol, the PDI was 5.89, the residual content of unreacted phenols including alkylphenol monomer was 1.92 wt% Free Phenol, and the SP was 85.3℃.

[0082] <Example 1>

[0083] The PTBP alkylphenol novolak resin obtained in the above <Comparative Example 1> at SP 138.7℃ was preheated to 180.0℃ as a feed liquid, and the feed liquid was flowed for 1 hour at a constant rate of 1.0 Kg / hr through an SPD distillation apparatus set with an evaporator temperature of 280.0℃, a condenser temperature of 150.0℃, and a vacuum of 0.46 mbar, thereby obtaining distillation components and residual components in a weight ratio of 1.2:98.8.

[0084] The extracted distilled component had a PTBP purity of 98.6 wt%, a weight-average molecular weight of 158.3 g / mol, and a PDI of 1.03.

[0085] The residual component obtained simultaneously had an SP of 145.3℃, which was 6.6℃ higher than the feed solution, a weight-average molecular weight of 1,932 g / mol, a PDI of 1.66, and a residual Free PTBP content of 0.64 wt%.

[0086] In this case, in the following <Examples 1 to 8> that were empirically verified in the present invention, including <Example 1>, a carbon hybrid wiper with grooves on the blade was attached to an SPD with an evaporator heat transfer area of ​​0.045 m², and the device was operated at 380 rpm.

[0087] The above <Example 1> is a result of confirming that unreacted PTBP, which cannot be removed in a general alkylphenol novolak manufacturing facility, can be sufficiently removed using SPD. However, despite the high evaporator temperature approaching the thermal decomposition temperature of the alkylphenol novolak resin, the result is unsatisfactory as high-purity PTBP novolak with an ND (No Detect) level or the expected Monomer-Free condition of less than 0.1 wt% was not obtained due to the high vacuum.

[0089] <Example 2>

[0090] The PTOP alkylphenol novolak resin of SP 93.8℃ obtained in the above <Comparative Example 2> was preheated to 150.0℃ as a feed liquid, and the feed liquid was flowed for 1 hour at a constant rate of 1.0 Kg / hr through an SPD distillation apparatus set with an evaporator temperature of 250.0℃, a condenser temperature of 120.0℃, and a vacuum of 0.45 mbar, thereby obtaining distillation components and residual components in a weight ratio of 1.6 : 98.4.

[0091] The extracted distilled component had a PTOP purity of 99.0 wt%, a weight-average molecular weight of 228.3 g / mol, and a PDI of 1.02.

[0092] The residual component obtained simultaneously had an SP of 103.2℃, which was 9.4℃ higher than the feed solution, a weight-average molecular weight of 1,792 g / mol, a PDI of 1.48, and a residual Free PTBP content of 0.40 wt%.

[0093] The above <Example 2> also confirmed that unreacted PTOP, which cannot be removed in a general alkylphenol novolac manufacturing facility, can be sufficiently removed using SPD; however, despite the high evaporator temperature, the result was unsatisfactory as high-purity PTOP novolac with an ND (No Detect) level or the expected Monomer-Free condition of less than 0.1 wt% was not obtained due to the high vacuum.

[0095] <Example 3>

[0096] The PTBP and PTOP copolymer alkylphenol novolak resin obtained in the above <Comparative Example 3> at SP 85.3℃ was preheated to 130.0℃ as a feed liquid, and the feed liquid was flowed for 1 hour at a constant rate of 1.0 Kg / hr through an SPD distillation apparatus set with an evaporator temperature of 250.0℃, a condenser temperature of 120.0℃, and a vacuum of 0.45 mbar, thereby obtaining distilled components and residual components in a weight ratio of 1.50:98.50.

[0097] The extracted distilled component had an alkylphenol purity of 98.7 wt%, a weight-average molecular weight of 207.8 g / mol, and a PDI of 1.05, while the simultaneously obtained residual component had an SP of 95.7°C, which was 10.4°C higher than the feed liquid, a weight-average molecular weight of 2,502 g / mol, a PDI of 5.33, and a residual free phenol content including alkylphenol monomer of 0.49 wt%.

[0098] The above <Example 3> also confirmed that unreacted PTBP and PTOP monomers, which cannot be removed in a general alkylphenol novolac manufacturing facility, can be simultaneously removed using SPD. However, despite the high evaporator temperature, the high vacuum level resulted in an unsatisfactory outcome where high-purity PTBP-PTOP copolymer alkylphenol novolac with an ND (No Detect) level or the expected monomer-free condition of less than 0.1 wt% could not be obtained. Therefore, it was determined that a lower vacuum condition was necessary for more complete separation of the alkylphenol monomer contained in the feed liquid, which is common to the above <Examples 1-3>, and <Examples 4-8> were carried out under a lower vacuum condition of 0.01 to 0.009 mbar.

[0100] <Example 4>

[0101] As in <Example 3> above, the PTBP and PTOP copolymer alkylphenol novolak resin obtained in <Comparative Example 3> at SP 85.3℃ was preheated to 130.0℃ as a feed liquid, and the feed liquid was flowed for 1 hour at a constant rate of 1.0 Kg / hr through an SPD distillation apparatus set with an evaporator temperature of 230.0℃, a condenser temperature of 120.0℃, and a vacuum of 0.048 mbar, thereby obtaining distilled components and residual components in a weight ratio of 1.75:98.25.

[0102] The extracted distilled component had an alkylphenol purity of 98.5 wt%, a weight-average molecular weight of 208.2 g / mol, and a PDI of 1.05, while the simultaneously obtained residual component had an SP of 98.2°C, which was 12.9°C higher than the feed liquid, a weight-average molecular weight of 2,533 g / mol, a PDI of 5.20, and a residual free phenol content including alkylphenol monomer of 0.25 wt%.

[0103] This result confirms the importance of vacuum level in SPD, as the evaporator temperature was lowered by 20°C compared to <Example 3>, but more unreacted alkylphenol monomer was removed due to the lowered vacuum level.

[0105] <Example 5>

[0106] As in <Examples 3 and 4> above, the PTBP and PTOP copolymer alkylphenol novolak resin obtained in <Comparative Example 3> at SP 85.3℃ was preheated to 130.0℃ as a feed liquid, and the feed liquid was flowed for 1 hour at a constant rate of 1.0 Kg / hr through an SPD distillation apparatus set with an evaporator temperature of 230.0℃, a condenser temperature of 120.0℃, and a vacuum of 0.005 mbar, thereby obtaining distilled components and residual components in a weight ratio of 1.91:98.09.

[0107] The extracted distilled component had an alkylphenol purity of 98.7 wt%, a weight-average molecular weight of 208.9 g / mol, and a PDI of 1.05, while the simultaneously obtained residual component had an SP of 99.8°C, which was 14.5°C higher than the feed liquid, a weight-average molecular weight of 2,540 g / mol, a PDI of 5.23, and a residual free phenol content including alkylphenol monomer of 0.014 wt%.

[0108] This result shows that more unreacted alkylphenol monomer was removed with a lower vacuum level compared to <Example 4>, reaffirming the importance of vacuum level in SPD.

[0109] <Example 6>

[0110] As in <Examples 3 to 5> above, the PTBP and PTOP copolymer alkylphenol novolak resin obtained in <Comparative Example 3> at SP 85.3℃ was preheated to 150.0℃ as a feed liquid, and the feed liquid was flowed for 1 hour at a constant rate of 1.0 Kg / hr through an SPD distillation apparatus set with an evaporator temperature of 240.0℃, a condenser temperature of 120.0℃, and a vacuum of 0.002 mbar, thereby obtaining distilled components and residual components in a weight ratio of 1.87:98.13.

[0111] The extracted distilled component had an alkylphenol purity of 98.4 wt%, a weight-average molecular weight of 209.4 g / mol, and a PDI of 1.05. The residual component obtained at the same time had an SP of 101.5°C, which was 16.2°C higher than the feed liquid, a weight-average molecular weight of 2,561 g / mol, a PDI of 5.20, and a residual Free Phenol content including alkylphenol monomer of 0.008 wt%, which can be classified as a Trace or ND level.

[0112] This is the result of removing unreacted alkylphenol monomers to a perfect level due to the lowered vacuum level and increased evaporator temperature compared to <Example 5>. The GPC analysis results of the alkylphenol novolak resin of <Comparative Example 3> used as the feed solution and the high-purity alkylphenol novolak resin obtained as a distillation component in <Example 6> are shown together in [Fig. 3]. In the GPC results, the difference in the unreacted alkylphenol monomer peaks, which were lowered to a trace level while maintaining the molecular distribution of the alkylphenol novolak resin of the feed solution, can be clearly and visibly confirmed.

[0114] <Example 7>

[0115] As in <Examples 3 to 6> above, the PTBP and PTOP copolymer alkylphenol novolak resin obtained in <Comparative Example 3> at SP 85.3℃ was preheated to 130.0℃ as a feed liquid, and the feed liquid was flowed for 1 hour at a constant rate of 1.0 Kg / hr through an SPD distillation apparatus set with an evaporator temperature of 260.0℃, a condenser temperature of 120.0℃, and a vacuum of 0.002 mbar, thereby obtaining distilled components and residual components in a weight ratio of 1.95:98.05.

[0116] The extracted distilled component had an alkylphenol purity of 96.4 wt%, a weight-average molecular weight of 221.3 g / mol, and a PDI of 1.08. The residual component obtained at the same time had an SP of 101.8°C, which was 16.5°C higher than the feed liquid, a weight-average molecular weight of 2,566 g / mol, a PDI of 5.15, and a residual Free Phenol content including alkylphenol monomer of 0.007 wt%, which can be classified as a Trace or ND level.

[0117] This result confirms that an evaporator temperature of 240°C or higher is uneconomical under sufficient conditions, provided that the vacuum level is sufficiently low, such as 0.001 to 0.009 mbar, and that additional unreacted alkylphenol monomers were not removed despite the increase in evaporator temperature compared to Example 6, and instead some alkylphenol novolak components were transferred to distillation components due to the splash phenomenon.

[0119] <Example 8>

[0120] As in <Examples 3 to 7> above, the PTBP and PTOP copolymer alkylphenol novolak resin obtained in <Comparative Example 3> at SP 85.3℃ was preheated to 130.0℃ as a feed liquid, and the feed liquid supply rate was increased to twice the level of <Examples 3 to 7> and flowed for 1 hour at a constant rate of 2.0 Kg / hr through an SPD distillation apparatus set to an evaporator temperature of 260.0℃, a condenser temperature of 120.0℃, and a vacuum of 0.002 mbar, to obtain distillation components and residual components in a weight ratio of 1.85 : 98.15. The extracted distillation component had an alkylphenol purity of 98.3 wt%, a weight-average molecular weight of 209.1 g / mol, and a PDI of 1.05.

[0121] The residual components obtained simultaneously had an SP of 101.4℃, which was 16.1℃ higher than the feed solution, a weight-average molecular weight of 2,586 g / mol, a PDI of 5.22, and a residual free phenol content including alkylphenol monomer of 0.007 wt%, which can be classified as a trace or ND level.

[0122] This is the result of confirming that it is possible to manufacture high-purity alkylphenol novolak resin with improved economic efficiency by increasing the feed rate compared to <Example 7>.

[0124] The alkylphenol monomers of the distillation components obtained in <Examples 1 to 8> above were high-purity materials with a purity of 98% or higher that could be recycled and reintroduced into the production of conventional alkylphenol novolac. At the same time, through <Examples 1 to 8>, continuous high-purity alkylphenol novolac production conditions utilizing SPD were established to completely remove unreacted alkylphenol monomers that are highly harmful to the human body and the environment, and these conditions are summarized in below.

[0126] division SPD conditions Residual component separation rate (%) Purity of distilled components (%) Residue component (high-purity alkylphenol novolak) Evaporator temperature (°C) vacuum (mbar) Feed injection rate (Kg / hr) SP(℃) Molecular weight (g / mol) PDI Monomer content (%) Example 1 280 0.46 1.0 98.8 98.6 145.3 1,932 1.66 0.64 Example 2 250 0.45 1.0 98.4 99.0 103.2 1,792 1.48 0.40 Example 3 250 0.45 1.0 98.50 98.7 95.7 2,502 5.33 0.49 Example 4 230 0.048 1.0 98.25 98.5 98.2 2,533 5.20 0.25 Example 5 230 0.048 1.0 98.09 98.7 99.8 2,540 5.23 0.014 Example 6 240 0.005 1.0 98.13 98.4 101.5 2,561 5.20 0.008 Example 7 260 0.002 1.0 98.05 96.4 101.8 2,566 5.15 0.007 Example 8 260 0.002 2.0 98.15 98.3 101.4 2,586 5.22 0.007

[0128] <Comparative Example 4>

[0129] The characteristics of the high-purity alkylphenol novolak with an SP of 101.5°C obtained as a residual component in <Example 6> and the conventional alkylphenol novolak resin with an SP of 85.3°C prepared in <Comparative Example 3> were compared. These two types of resins have the same structure and molecular distribution, but can be considered as twin resins that differ only in the unreacted alkylphenol monomer content through the application of SPD. Using these two types of novolak resins, a rubber composition was prepared by blending and kneading in a Bambury Mixer with a mixing ratio of 5 parts by weight of alkylphenol novolak resin, 50 parts by weight of natural rubber, 50 parts by weight of butadiene rubber (BR-01), 45 parts by weight of carbon black (N330), 3.0 parts by weight of zinc oxide, 2.0 parts by weight of homogenizer (40MS), 2.0 parts by weight of stearic acid, 2 parts by weight of sulfur, and 1.5 parts by weight of vulcanization accelerator (TBBS).

[0130] After removing the above rubber composition from the Bambari Mixer, a rubber sheet was manufactured using the Roll Calendering method at 100°C, the rubber sheet was placed in a mold and vulcanized at 160°C for 20 minutes, and the specimen was prepared according to ASTM D2979 standards. Tensile strength, elongation, modulus, hardness, and abrasion resistance were measured using a Universal Testing Machine (UTM), and the results are shown in .

[0131] Mechanical properties using UTM were measured as initial adhesion and aging adhesion according to ASTM D2979 conditions, with aging measured after being left at 25°C for 5 days.

[0132] item Conventional alkylphenol novolak tackifier <Comparative Example 3> High-purity alkylphenol novolak tackifier <Example 6> Initial adhesion (gf) 308 381 Aging tackiness (gf) 272 325 Lecture intensity (Kgf / ㎠) 213 277 100% Modulus 35 42 300% Modulus 197 220 Wear resistance (wt%) 0.25 0.17 Growth rate (%) 355 363 Shore A hardness 66 69

[0133] As shown in above, even in rubber compounds containing 5% by weight of high-purity alkylphenol novolaks from which alkylphenol monomer components have been removed, mechanical properties improved by about 20-30% compared to conventional alkylphenol novolaks, which is because the adhesive strength of the alkylphenol novolak resin is improved by removing unreacted alkylphenol monomers.

[0134] As described above, another aspect of the present invention provides a rubber composition comprising the alkylphenol novolak resin. According to one embodiment, the rubber composition may comprise a rubber component comprising a rubber polymer, a synthetic rubber polymer, or any combination thereof; and the high-purity alkylphenol novolak resin, wherein the high-purity alkylphenol resin may be a tackifying resin.

[0135] Here, the rubber polymer may be a polymer synthesized from petroleum byproducts, and may include styrene-butadiene rubber, polybutadiene rubber, butyl halogenated rubber, butyl rubber, polyisoprene rubber, styrene-isoprene-butadiene rubber, or any combination thereof, and may also include natural rubber harvested from rubber trees in the form of latex, which includes isoprene polymers.

[0136] According to one embodiment, the content of the high-purity alkylphenol novolak resin in the rubber composition may be about 1 to 10 parts by weight per 100 parts by weight of the rubber component, and the rubber composition may be used to manufacture articles including tires, tire treads, tire shoulders, tire sidewalls, rubber belts, and rubber hoses.

[0138] <Comparative Example 5>

[0139] Copper Clad Laminate Sheets (CCLS) were prepared using two types of the same alkylphenol novolak resins used in <Comparative Example 4>, namely high-purity alkylphenol novolak with an SP of 101.5°C obtained as a residual component in <Example 6> and a conventional alkylphenol novolak resin with an SP of 85.3°C prepared in <Comparative Example 3> as curing agents for epoxy resins, and their characteristics were compared and analyzed.

[0140] An acetone solution varnish was prepared by mixing Kolon Industries' KEF-6087 epoxy resin, an MDI (Methyl Diisocyanate) modified epoxy resin, as the main component and alkylphenol novolak resin as the curing agent at an equivalent ratio of 1:1, followed by the addition and mixing of 2E4MZ (2-ethyl-4-methyl imidazole) as a curing accelerator at 0.035 wt% relative to the total solid weight. Subsequently, the prepared varnish was impregnated into glass fibers and dried at 140°C for 5 minutes to produce prepregs. Four sheets of these prepregs were laminated, copper foil was additionally laminated onto the top and bottom surfaces of the laminated prepregs, and a CCLS was manufactured by heat-pressurizing molding. The heat-pressurizing conditions were a temperature of 190°C and a pressure of 25 kgf / cm². 2 The plastic surgery took 2 hours.

[0141] The glass transition temperature (Tg) of the CCLS was measured by randomly taking 20 mg of solid samples from the fabricated CCLS and heating them to 250°C at a rate of 20°C / min using a differential scanning calorimeter (DSC, TA Instrument Q2000) under a nitrogen atmosphere. While conventional alkylphenol novolak showed a Tg of 133.4°C, when high-purity alkylphenol novolak was applied as a curing agent, it showed a Tg of 154.6°C, which is 21.2°C higher than that of conventional alkylphenol novolak. This is a very significant difference for CCLS applications where a difference in Tg of 2 to 3°C determines whether a product is accepted or rejected.

[0142] In addition, as a result of measuring dielectric constant and dielectric loss, which are the most important characteristics for 5G and 6G mobile communications, the high-purity alkylphenol novolak resin showed excellent characteristics compared to the conventional phenol novolak resin, which has a Dielectric Constant Dk of 2.8330 and a Dielectric Loss Df of 0.01370 due to the monomer removal effect, with Dk of 3.1~3.4 and Df of 0.02~0.03. Conventional alkylphenol novolak exhibits poor physical properties that make commercial application impossible in terms of heat resistance, such as solder dip and delamination, which are basic requirements for CCLS, due to the excessive content of alkylphenol monomer. However, the high-purity alkylphenol novolak has a monomer-free characteristic that compensates for these fatal shortcomings, confirming its potential as a next-generation CCLS curing agent. Including the above, the CCLS application results of the high-purity alkylphenol novolak are described in below, and the analysis and evaluation conditions followed the conventional CCLS evaluation conditions.

[0143] item Conventional alkylphenol novolak curing agent <Comparative Example 3> High-purity alkylphenol novolak curing agent <Example 6> note Tg (°C) 133.4 154.6 DSC Tg (°C) 151.7 176.2 DMA CTE α1 (ppm / ℃) 77.1 56.5 CTE α2 (ppm / ℃) 311.0 281.4 Inter-ply Adhesion (N / mm) 1.45 1.658 Delamination (°C) 276 358 TMA T-288 5 min or less 20 min or more Peel Strength (N / mm) 0.77 1.06 Absorption rate (%) 0.38 0.28 Permittivity linkage Solder Dip 3 seconds or less 20 seconds or more Psalms after PCT Flammability V-0 V-0 UL-94 Rating

[0144] In the CCLS application results of Comparative Example 5 above, in which high-purity alkylphenol novolak resin was applied as a curing agent for epoxy resin, the high-purity alkylphenol novolak resin showed superior characteristics compared to conventional alkylphenol novolak resin. As mentioned above, this overcomes the limitations of heat resistance and mechanical properties that are inevitable for alkylphenol monomer components that decompose easily at low temperatures, and at the same time, the removal effect of alkylphenol monomer components can be confirmed as a result associated with a uniform curing reaction due to monomer-free characteristics.

[0145] All simple variations or modifications of the present invention can be easily implemented by those skilled in the art, and all such variations or modifications are considered to be within the scope of the present invention.

Claims

Claim 1 A continuous manufacturing method for obtaining high-purity alkylphenol novolac resin with a significantly reduced alkylphenol monomer content as the distillate, wherein a general-purpose alkylphenol novolac resin is used as the feed liquid to remove unreacted alkylphenol monomers as the distillate and simultaneously, as the residue, a vertical short-path distillator (SPD) characterized by being an advanced type of thin-film evaporator in which a condenser is installed inside the evaporator body to minimize pressure drop and achieve a very low vacuum of 0.1 mbar or less, or at least 0.001 mbar, wherein the method comprises a condenser inside the evaporator, heating, cooling, and vacuum equipment outside the evaporator, a liquid supply port at the top, and outlets for distillate and residue at the bottom, and along the inner wall surface of the cylindrical evaporator body A method for producing high-purity alkylphenol novolak resin characterized by using a short-path distiller having a winged rotating body that rotates in the circumferential direction. Claim 2 A method for producing high-purity alkylphenol novolac resin in which unreacted alkylphenol monomers are removed as distillate and the alkylphenol monomer content is significantly reduced as residue. This is achieved by using an alkylphenol novolac resin with a softening point of 150°C or lower as a feed liquid in a short-path distiller maintained at a vacuum of 0.1 to 0.001 mbar, an evaporator temperature of 190 to 290°C, and a condenser temperature of 60 to 180°C, and continuously supplying the feed liquid at a flow rate of 3 to 15 kg / hr per 0.1 m² of the heat transfer area of ​​the short-path distiller. Claim 3 In claim 1 or 2, the high-purity alkylphenol novolak resin A method for manufacturing a high-purity alkylphenol novolak resin characterized by a phenol content including alkylphenols of 0.1 wt% or less, a softening point of 150°C or less, a weight-average molecular weight of 1,500 to 4,500 g / mol, and a polydispersity index of 1.5 to 6.

0. Claim 4 An alkylphenol novolak resin-containing rubber composition characterized by containing 1 to 10 parts by weight of the high-purity alkylphenol novolak resin of claim 3 per 100 parts by weight of the rubber composition, wherein the rubber composition is used in a tire, tire tread, tire shoulder, tire sidewall, rubber belt, or rubber hose. Claim 5 A copper clad laminate composition for a printed circuit board containing 10% by weight or more of the high-purity alkylphenol novolak resin of claim 3 among the total organic compound components, wherein the alkylphenol novolak resin is used as a curing agent for an epoxy resin.

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