JPS5832622A - Novolak type phenol resin having wide molecular weight distribution and its preparation - Google Patents

Abstract

PURPOSE:The titled novel resin to be melted and to be dissolved, having a high average molecular weight, by condensing a phenol with a carbonyl compound in a specific equivalent ratio at a middle temperature in a short time, subjecting it to a high polymer reaction under specific conditions. CONSTITUTION:A mixture of (A) a phenol and (B) a carbonyl compound satisfying respectively the equation shown by the formulaI(fP and fF are the average functionality of the component A and the component B respectively), having an equivalent ratio of the component A to component B satisfying the equation shown by the formula II is first condensed at a middle temperature in a short time, and the condensate is subjected to high polymer reaction at high temperature for a long time until the viscosity of the system is extremely increased while volatile components are removed under neutral or weakly acidic conditions, to give the desired resin having the unreacted component A as less as possible, having a number-average molecular weight MN calculated by removing the unreacted component A, and a ratio of a weight-average molecular weight MW to MN of >=4 calculated by removing the unreacted component A. EFFECT:The resin having improved physical and chemical properties is obtained economically in high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel novolak type phenolic resin having a large average molecular weight and an extremely wide distribution, and a method for producing the same.

Conventionally, novolak, a type of phenolic resin, has a low molecular weight or
Alternatively, only a product with a narrow molecular weight distribution could be obtained.

(1) Ordinary novolaks are mainly trifunctional phenols, and are condensates of sulfenols (P) and formaldehyde (P) reacted under acidic conditions. When converted to a molar ratio, P/IF = 1.5/1 (molar ratio), it gels at a reaction rate of about 67% and becomes a macromolecule with a tertiary corpse network structure, becoming insoluble and infusible. It is known. Practical KFiP/7 (molar ratio) is 0. It is common practice to react by selecting a blending ratio of % to prevent gelation from occurring around V1. Therefore, the number average molecular weight (Ml) of the obtained novolac is usually 500 to 80011 degrees, and it is said to be extremely difficult to obtain a MNt of 1.000 or more without gelation. I came.

For conventional uses of phenolic resins, a product with a molecular weight as low as this is not enough to be used. Moreover, as for the width of the molecular weight distribution, the ratio of weighted average molecular weight (Mw) to log average molecular weight O (Mw/'*) was as small as 1.4 to 2.0. Even a special product that was heated at high temperatures for a long time until it almost gelled did not exceed 4.0.

(2) On the other hand, basic research has been carried out to determine the molecular weight distribution by fractionating the different molecular weights using a normal fractional precipitation method using a solvent, targeting ordinary novolacs with a weight of less than 1,000 for rice. According to Gyoda, the highest molecular weight class is 20.000 (Synthetic Resin, 25. A3, 13 (1979)). However, in this case, since it is a fractionated product, the molecular weight distribution is extremely narrow and the MW/M
It is N÷1.

0) On the other hand, in the novolak production reaction between difunctional P and 1, the system theoretically does not gel.
In the case of the above reaction between trifunctional P and r), it is also possible to further polymerize the produced novolak.

For example, according to Burke et al., P-chlorophenol, 0
- By reacting chlorophenol or P-cresol with P-)luenesulfonic acid t-catalyst and using bis(2-ethoxyethyl) ether as a solvent, a maximum of 4,260 'lF has been obtained. . (W @ J,
Burks, 5ta14, T, POlym,
Bcl,,.

20, 75 (1956): 1 bid, 32.
221 (1958) 11bid, 41t 49
(1960)). However, there is a report by Rame Imoto that an additional attempt was made against such data, but that the increase in mustard size was not achieved to such an extent (M. Komoto, et&13
Bull, (:h@m, 80c, Japan,
30. '5gO (1963)). In addition, Tarusaki gave Arnoji ``phenol and rose formaldehyde t-P''.
-) Using luenesulfonic acid as a catalyst and toluene as a solvent, a 'C reaction is carried out, and the yield is lower than the starting point due to the by-product of kanacine solubles, but the maximum yield is 4 and a novolac of 4.560 is obtained. ing. (Tarusaki: Ouka, Tsuchi, 392 (
1963)). In summary, there are 30,000 cases of polymerization of novolak.
Of course, there have not been sufficient reports on the use of P and/or 1 with higher functionality or higher functionality, and even on the use of bifunctional P and 1, there is no practical technical knowledge. It was missing.

In other words, it is generally accepted that when the molecular weight of novolac increases beyond a certain level, it becomes difficult to convert it into a polymer due to factors such as (1) addition reaction, which lowers the K, and (1) decomposition. It's from a friend. The production limit for the town is approximately 2,000 and the MWZ
It has been said that the MN ratio is usually 7.0 (44.0 in terms of percentage).

On the other hand, despite the above-mentioned conventional thinking, based on recent advances in synthetic resin application technology, there has been a demand for more polymerized 9-novo and lac-type phenolic resins. Ta. From this point of view, the present inventors (as a result of 81 studies) found that a novolac having a molecular weight of a higher level than previously expected and an extremely wide molecular weight distribution can be obtained, and that this type of novolak can be obtained. The present inventors have discovered that the present invention has unique and useful characteristics, and have come up with the present invention. 6. The novel polyfunctional phenols (P
) and/f or a carbonyl compound (F), the novolac type phenolic leather resin has an average functionality per molecule of P (f, ) and an average functionality per molecule of F (f,
) is 2.5≧(f, -1,00) (f, -1,00)
The rice satisfies ≧1.20, contains as little unreacted P as possible, and has a value of 500 or more after excluding unreacted P,
All of them are fusible and soluble, characterized by an M/MN ratio of 4°0 or more, calculated as a value excluding unreacted P. That is, the novel novolac type phenolic resin of the present invention is a thermosetting resin type that itself becomes three-dimensional and insoluble by the action of a curing agent that generates formaldehyde, such as hexaone or paraform. Mw (unreacted P
The Mw/MM ratio (both excluding unreacted The molecular weight distribution (converted to a value calculated as 4.0) is abnormally large, and therefore the width of the molecular weight distribution is extremely wide.

Therefore, the novolac type phenolic resin of the present invention has a high weight average molecular weight of 2,000 or more, and GK analysis shows that the proportion of molecular weights of 2,000 or more reaches 5°96 (weight) or more. , further molecular weight 1
The proportion of 0,000 or more categories is several 10% (weight)
The major %01 characteristic is that it contains a large amount by weight of extremely high molecular weight substances, which are difficult to obtain with conventional products.

This means that it has completely different characteristics from conventional products both in terms of physical properties and curing properties.

That is, the novel novolac-type phenolic resin of the present invention falls within the category of typical polymeric substances, and has significantly higher melt viscosity and solution viscosity than conventional products. Moreover, in a solution state, it significantly exhibits abnormal viscosity such as the Weisenberg effect and stringiness. Furthermore, regarding the intrinsic viscosity, M is clearly higher than that of conventional products having approximately the same level. Furthermore, in terms of chemical properties, the novel novolak type phenolic resin of the present invention has completely different characteristics.

In other words, it has the property of becoming unstable and quickly insolubilized when exposed to high temperatures of 200°C or higher in the air, not only in its bulk state but even in its solution state, and forms a tough cured film. It is characterized by being easy. In terms of curing properties, the novolak type phenolic resin of the present invention shows that the novolac type phenolic resin of the present invention has Compared to conventional products, ■ Gelation is generally faster.

■ Even if the amount of curing agent is too small, the speed of gelation will not be slowed down very much.

■ There is 41111, which has excellent physical properties such as toughness and heat resistance when cured.

Since the novel Novo2-type 7-enol resin of the present invention has both surface-forming properties and a wide molecular weight distribution as described above, K is the main component P, IF molecules my average functionality 'p, ' y li mutual K 2.50≧(f,
-1°Go)(fC1.00)≧1.20 must be satisfied. If it is lower than this, it is not desirable because good curing properties cannot be obtained. Also, if the temperature is higher than this, gelation tends to occur, making it difficult to control the reaction, so this is not desirable.

In summary, the novolac type phenolic resin of the present invention has a molecular weight and molecular weight distribution in a balance with curability that is in a range that cannot be reached by conventional Novo 2 Tsuk manufacturing technology. Based on its structural characteristics, it has superior physical and chemical properties not found in conventional products, making it extremely valuable industrially.

Further, it is desirable that the novolac type phenol resin of the present invention contains as little unreacted phenol as possible, preferably less than 1 tt. b) If there is a large amount of unreacted phenol remaining in the lac, the effect of polymerization will be significantly reduced, which is undesirable. - Therefore, you may wash with warm water as appropriate. □The resin used in the novolac type powder of the present invention is usually in the form of a solid lump or powder at room temperature.Is there any other resin besides Rally's P? , solvent i1
It is desirable to contain as little water as possible. However, depending on the application, it may be used in the form of a solution dissolved in an organic solvent such as ketones or cellosolves.

The method for measuring the novolak fraction 4* and the soy cloth of the present invention is as follows. MN was measured by vapor pressure osmosis method (abbreviated as VPO, the same hereinafter) using methyl ethyl ketone solvent.

In the present invention, the molecular weight is calculated by excluding unreacted P. The ratio of M and 7M was measured by Gel Permeation Chromadog 2F (abbreviated as GPC, the same hereinafter).

The GPC measurement conditions are as follows.

Separation column: polystyrene gel with an average pore diameter of 102 angstroms (abbreviated as 1, hereinafter the same), 10 angstroms, 104 angstroms
Two columns each with an inner diameter of 7.5 mm and a length of 60 scratches filled with 7.
Mainly connected, running force 2 m, number of theoretical plates of separation column: 30 cm, ooo plate, pre-column: number of theoretical plates is 30 scratches, 6
Inner diameter 7 filled with polystyrene gel of s, ooo stage or more
．． 5 mm, 1 column with a length of 5 as, eluent: nat2hydrofuran, flow rate: inn/min, detector: differential refractometer type, separation column temperature: 40°C, sample injection amount: about 1.8
A monodisperse standard polystyrene was used to create a calibration curve for molecular weight standardization. was calculated by multiplying the value of 4 measured by vpo by the value of (MW/MN) determined by KGPC. In calculating the molecular weight, the area of each section of the chromatogram was treated as follows. The peaks of unreacted monomers are excluded and are dangerous to use in molecular weight calculations. To calculate the molecular weight, start from an elution count that is one count smaller than the elution count at the top of the unreacted phenol peak, and take into account the broadening of the peak width, and use the elution count that is two counts larger than the minimum elution count as the end point. We used classification. Sectional quadrature for each category was performed by measuring the peak height for each count interval, but only for elution counts that are one count smaller than the unreacted phenol monomer peak peak, the influence of the spread of the unreacted phenol peak was corrected. Therefore, a height half the peak height was used.

In the present invention, the nine GPC devices used to measure molecular weight and molecular weight distribution are 801 type scissor set manufactured by Toyo Ichikai Kogyo Co., Ltd. ()
The PC separation column is manufactured by Toyo Ichida Kogyo Co., Ltd., 'rsh-
GILG-2000H8, G-3000H8゜G-40
There are four, 00H8 and G-5000H8.

The details of the method for producing the Novo 2 type phenolic resin having a high molecular weight and an extremely wide molecular weight distribution according to the present invention are as follows.

That is, thermal condensation of a mixture of P and 1 under acidic catalyst00)
(fF-1,0,0) -0,2)ノM (fP-
1,00) (fc 1.00), conduct the first 9-condensation reaction at medium temperature for a short time, and then remove the volatile components sequentially under neutral to weak acidity, and the viscosity of the system increases significantly. The second polymerization reaction is carried out at high temperature for a long period of time until the reaction is completed.

In the production method of the present invention, the second stage polymerization reaction is carried out at 41K]ll! ! In this case, M, which is converted to a value excluding reaction P, is 500 or more, and no reaction P
A new feature of MW/M ratio of 4.0 or more when converted to the value excluding vr. It is 9.

The key to the novolac of the present invention! The average functionality fpofy taste per molecule of each raw material P%F, 2.50≧(f
, -1,00) (f, -1,00)≧1.20 must be satisfied.

Moreover, in the novolak type phenolic resin, the range of the equivalent ratio (ratio of reaction points) of P/F to be blended is ((f
P 1.00) (fy 1.00.),
Q, 2.0 ) to (fp 1.00) (fF
1.00). If the P/F ratio is larger than this range, the system will not gel abnormally, and if you try to achieve high polymerization without gelling as in the present invention, it will be extremely difficult to adjust the reaction conditions. I don't want to do this because it will be difficult. Conversely, if the equivalent ratio of IF/P is smaller than this range, gelation is less likely to occur, but the rate of increase in molecular weight becomes extremely slow, which is not desirable.
7. As long as the phenol used in the present invention satisfies the above-mentioned average functionality per molecule condition, C is P of monofunctionality, difunctionality, trifunctionality, or higher polyfunctionality.

They may be appropriately selected from among them and used alone or in combination.

The most common polyfunctional phenols used in the present invention are unsubstituted phenols and cresols, but other polyhydric phenols such as resorcinol, catechol, and hydroquinone, and polynuclear phenols such as bisphenol A and bisphenol ν and various other substituted phenols.

The phenols used in the present invention are the O-position, m
- position or p-f Substituted with one to several substituents such as alkyl group, alkenyl group, aryl group, aralkyl group, halogen group, carboxyl group, alkyloxycarbonyl group, alkyloxy group, dialkylamino group, etc. It is a phenol having a functionality of 1 to 3 or more relative to formaldehyde.

The optimum range for the softening point of novolak obtained by the method of the present invention varies depending on the purpose of use, but at least the softening point is so low that even if it is powdered and left at 40°C, it will stick and become dangerous. and 200℃ or less, preferably 160℃
It is preferable for the material to have a softening point of 0.degree. C. or less for use in various applications. In the novolak of the present invention, the softening point tends to increase significantly as the molecular weight increases.

The carbonyl compounds used in the present invention may be used alone or in combination, as long as they satisfy the above average functionality per molecule condition. In addition, the above-mentioned phenols may be suitably methylolated and used as the same effective substance.

As the carbonyl compound which is the other raw material for the novolac of the present invention, formaldehyde is most preferred. Formaldehyde can be used alone or in the form of an aqueous solution such as formalin, a solid form such as paraformaldehyde, polyoxymethylene, etc., a liquid form such as trioxane, dioxane, metheral, etc., or a reactive acetal form. They can be used in combination as appropriate. In addition to formaldehyde, acetaldehyde, paraldehyde, glyoxylic acid, furfural,
Other aldehydes such as glyoxal and acrolein, and ketones such as acetatone, methylethylketone, and cyclohexanone may also be used alone or in appropriate combinations with formaldehyde. In the novolac type phenolic resin, the carbonyl compound of Ni et al. mainly forms a methylene bridge or a mono- or dialkyl-substituted methylene bridge, and connects the above-mentioned phenols in a long chain. It may also contain a small amount of a by-product macrocyclic compound. As a reaction catalyst, an acid is sufficient, but in order to avoid side reactions as much as possible in the secondary polymerization reaction at high temperatures, K can be substituted with sulfuric acid, para-toluenesulfonic acid, etc. It is undesirable to use a catalyst exhibiting strong acidity, and if such a strong acid is used, the system should be washed with water to remove most of the catalyst after the first stage resin production reaction, or the catalyst should be washed with alkali. It is desirable to once neutralize it to make it weakly acidic or neutral, and then conduct the second reaction at high temperature. Organic acids, which are weakly acidic catalysts, are preferable because they do not require such a process, and further, if they are oxalic acid, which thermally decomposes at 120°C to 200°C, no catalyst will remain. Even more preferred.

In the present invention, a solvent may be used if necessary.

The solvent used is preferably a mixture of aromatic hydrocarbons and cellosolves. The aromatic hydrocarbons used as solvents include benzene, toluene, xylene, and other alkylpe/zene compounds, which have the effect of rapidly removing water present in the reaction system from the system by azeotropic distillation. However, since it is non-polar and has a rather low affinity and compatibility with formaldehyde and water, it is desirable to use it in combination with a high-boiling point, polar solvent such as cellosolves. Cellosolves are monoethers of lower alkyls such as methyl, ethyl, propyl, butyl, and amyl of glycols such as ethylene glycol, propylene glycol, or di- and tri-t, so-called polyethylene glycol and polypropylene glycol. It is a kind. In general, all cellosolves are alcoholic O
Since it has an H group and an alkyl ether group, and has an appropriate balance of hydrophilic groups and hydrophobic groups and has an appropriate upper boiling point, it is extremely suitable for the purpose of the present invention.

The lower alkyl diethers of the above-mentioned gelcols have appropriate boiling points and solubility, and can be used in the same way as Habo. It is slightly inferior in this respect. Only a portion of the 74-solves etc. may be used as a solvent at first, and may be added sequentially as the viscosity increases as the reaction progresses ◇The total amount of solvent used is based on the weight of the bulk resin to be produced. 1
00 parts, preferably 20 to 300 parts (by weight), preferably 50 to 150 parts (by weight). Novolak solution viscosity is extremely high due to too small amount of solvent11
If you try to raise the temperature of the reaction system, a part of the resin may become overheated and insolubilized, causing it to burn on the vessel wall, which is not desirable. On the other hand, it is not preferable to carry out the reaction in the presence of a large amount of solvent from the beginning, as this will significantly reduce the reaction rate.

The first condensation reaction is a step in which a low-molecular novolac is produced by the reaction between P and 1.

The necessary conditions in this case are as follows.

(1) Be weak to strong acidic.

(2) There must be an appropriate amount of 1 that balances the rate of gelation and polymerization.

(2) Preferably, a solvent is present, and more preferably, the dehydration is performed sequentially by azeotropic distillation of the solvent 12.

Temperature in ship, short time reaction, preferably 90-100°C, 1
The reaction time should be ~4 hours.

(To) At the end of the reaction, unreacted P should be as low as possible, preferably 1% (by weight) or less.

(b) In the latter half of the reaction, water is removed appropriately and the reaction system is as homogeneous as possible.

The second polymerization reaction is a stage in which the produced low-molecular-weight Novo2s are reacted at high temperature for a long period of time under controlled mild conditions, thereby significantly increasing the viscosity of the system.

The necessary conditions in this case are as follows.

(1'> Must be neutral to weakly acidic.

ω) There should be as few unreacted p and y as possible.

(to) Preferably a solvent is present, more preferably added sequentially as the viscosity of the system increases.

(conversion) High temperature, long time reaction, preferably 120 to 200
℃, 10 to 100 hours of successive temperature raising reaction.

(g) The viscosity of the system must increase significantly at the end of the reaction, that is, the reaction must proceed to the extent that the solution exhibits stringiness and the Weizenperg effect (however, under such conditions Once set, the reproducibility is quite good.)
.

(To) The end point of the reaction can be phenomenologically adjusted as a significant increase in viscosity as described above, but in reality, the reaction should be carried out until the molecular weight and molecular weight distribution of the produced novolak show the desired values. .

(To) It is preferable that the heating be as uniform as possible, and localized heating is not preferable as it may cause partial insolubilization.

The monopolymerization reaction is preferably carried out gradually in stages in order to suppress side reactions and improve reproducibility.

Preferably, at the end of the reaction, the produced resin is rapidly cooled to stop the reaction.

Conventionally, the distinction between such a mild polymerization reaction and a reaction that causes rapid gelation has not been clearly distinguished, and therefore, as in the present invention, novolac polymerization while suppressing gelation has not been made clearly. It is thought that Uta was not able to achieve the goal of achieving change.

That is, as long as the %(1)P/F(2) equivalent ratio is within the above range KTo, the average molecular weight of the group will gradually increase due to the main reaction between P and 1. The system should not gel even when most of the reaction is consumed and the reaction is almost complete, and if the system gels, it is because a side reaction other than the main reaction is occurring.

(II) Under harsh reaction conditions such as reactions at high temperatures of 150°C or higher under strong acidity, side reactions (m-position reaction, decomposition and recombination of methylene bonds, formation and polymerization of quinone methide, etc.) are unlikely to occur. The gelation progresses significantly and therefore gels rapidly! It is easy to gel.

(2) In the reaction under neutral to weak acidity, the side reactions mentioned above proceed slowly, so polymerization should proceed gradually without gelation. However, as long as M is measured only, the limit of the molecular weight that can be reached is approximately 1.000. No matter how long the reaction time is, no further increase in molecular weight will be detected, and the present invention It is impossible to control the reaction step of polymerization such as 0 ω The novolak polymerized as in the present invention may behave as if it were supergelled depending on the conditions, e.g. If there is little solvent and the temperature is low, the Weizenperk effect will be exhibited, and if the heating method is uneven and locally heated to over 200°C, insolubilization will be partial even if a solvent is present.
This means that it gradually spreads throughout the system. In short, until now there has been no organized and integrated view of these chemical and physical phenomena, reaction conditions, and their regulation, and therefore accurate knowledge and technology regarding polymerization conditions have not been established. There wasn't.

It is natural that the novolak type phenol resin of the present invention, which has a high molecular weight and an extremely wide molecular weight distribution, has not been obtained at all in the past.

Furthermore, from the above point of view, the novel novolak type phenolic resin of the present invention is not limited to the above-mentioned method as a manufacturing method.

For example, there are many possibilities such as solid-phase two-stage reaction, interfacial polycondensation reaction, and many others. Furthermore, if necessary, two or more types of novolacs may be appropriately blended and prepared to meet the conditions of the present invention.

That is, no matter which method is used to manufacture the O! !
It can be used effectively as well if it has the following requirements. .

The novolak type phenolic resin of the present invention has a large average molecular weight and an extremely wide distribution, so it has various industrial advantages.

(1) It has excellent curability due to the combination of a curing agent such as hexamine, the cured product is strong and strong, and its physical properties such as heat resistance are also superior to conventional products.

01) Despite the molecular weight K, the softening point is not that high.

(2) Excellent solubility in solvents despite the large molecular weight.

(Foundation) The weight percentage of the category with molecular weight of about 2,000 or more is large, and the weight percentage of the category with molecular weight of about 10,000 or more is also included.

(To) Good compatibility with various thermosetting resins, thermoplastic resins, rubbers, etc.

Furthermore, there are the following applications that take advantage of these characteristics.

(1) It is more curable in fixed installations than the conventional 7-point 2-pot for applications where phenolic resins have traditionally been used, such as molding materials, stacked boards, festival boards, adhesives, binders, and paints. Since the cured product has excellent physical properties, it can be advantageously applied as is.

1) Polymer properties that utilize the reactivity of phenolic OH groups (
2) Application to polymeric antioxidants utilizing properties as polyphenols (e.g. for polypropylene); Application to fire-resistant fibers due to (trans)flammability and low smoke generation properties (e.g. novoloid fibers); .

■ Baking in the air at temperatures above 200°C will result in insolubilization.
Application to insulating paints and powder paint bases due to its strong film-forming action; (b) Application to thickeners due to its high viscosity and excellent compatibility1; In comparison, the fact that it is highly polymerized means that it exhibits the characteristics of a typical polymer that is clearly superior in terms of toughness, heat resistance, and durability, so its industrial value is extremely high. It is clearly different from conventional novolacs in terms of its action and effect. .

Examples will be explained below.

Comparative Example 1゜Phenol 125.2f (1.33 mol), formaldehyde (30-wt.) 10 (1 (1.0 mol)), oxalic acid 5
f is reacted at 90 to 100°C for 2 hours while stirring and refluxing. Next, after vacuum dehydration, take out the soba and leave it open for 1 hour.
Stir at 20°C to 140°C for about 5 hours while dissipating volatiles, then rapidly raise the temperature to 180°C within 1 hour,
It is taken out of the pot, rapidly cooled and solidified, and then crushed. The yield was 1032.

In this example, fP=3. Since f'r=2, (fp-
1,00)<t,-1,00)=2. It becomes OO. That is, 2.00≧P/F (equivalence ratio)≧1.80.

The combination of P/F (molar ratio) = 1.33/1.00 is P/ν
(Equivalence ratio') -1,33X3/1.00X2-2.00
In addition, since the conditions of the present invention are satisfied, gelation is unlikely to occur during polymerization. For example, P/a (molar ratio)-1
, 10/41. In the case of OO formulation, 'P/F' (equivalence ratio) -1,10X 3/1.00 X 2= 1.6
5. Since the conditions of the present invention are not met, gelation tends to occur during the reaction, which is undesirable.

Note that the above reaction does not particularly require uniform heating such as heating in an oil bath, and the reaction can be similarly carried out by heating with a mantle heater. The molecular weight distribution of the obtained novolac is narrow and <'v is low, so the melt viscosity is low and the intrinsic viscosity is also low.

(Intrinsic viscosity (T111ν solvent, 30°C) 0.048) Comparative example 71.4 f (0.66 mol), P
-Cresol 476f (0.44 mol), formalin (
83.3f (1.-00 mol), 5F oxalic acid, and 20 CC of xylene are reacted at 90 to 100°C with stirring for about 1 hour while successively dehydrating. After completing Habo dehydration,
React at 120°C to 140°C for about 2 hours, then rapidly raise the temperature to 220°C within 1 hour while sequentially removing the solvent.
Crystallize. After cooling and solidifying, it is pulverized and vacuum dried to remove volatile components. The yield was 124t.

In this example, f, = 3 x O, 6+ 2 x O,
4=2.6t f,=2, so (fp 1.0
0) ('y 1.00) The value becomes 1.60. That is, 1.60≧P/F (proper quantity ratio)≧1°40. P/F
(Mole ratio”) = (0,66+ 0.44)/1.0
The formulation of 0=1.10/1.00 is P/F (roaring ratio)=
(3X0.66+2X0.44)/2X1.00-1
．． 43, which satisfies the conditions of the present invention, so gelation is unlikely to occur during polymerization.

Example 1 Phenol 125.59 (1,33 mol), Formalin (3696 weight) 83.3 f (1,00 mol), Oxalic acid 5 f, ) Luene 20 CC 1 Methyl cellosolve 20 CC
are reacted at 90 to 100°C while stirring and successively dehydrating.

After the spinach dehydration is completed, the mixture is allowed to react at 12.degree. C. to 0.degree. C. to 140.degree. C. for about 2 hours. During this time, the viscosity increased significantly, so 20 cc of butyl cellosolve was added six times in response to the increase in viscosity. Then, the mixture is reacted for an additional 20 hours at 150 to 180°C to form a seed. Next, the solvent is removed in vacuum, cooled, solidified, crushed, and further vacuum dried to remove volatile components. Yield is 9
It was 5f.

The obtained resin has an abnormally wide molecular weight distribution, has a high melt viscosity, and has an abnormally high intrinsic viscosity.

(Intrinsic viscosity (Ti!F solvent, 30°C)) is the same, but
Their molecular weight distributions differ significantly from each other due to their different reaction methods. Therefore, the viscosity and softening point of the former are clearly higher, and the curing properties due to the addition of hexamine are much better in the former, and the cured product is also tougher and has better heat resistance. Also, when we use this to make a wood flour-based molding material and compare it, it is clear that the former has faster curing and may be more effective with a smaller amount of hexamine (approximately 50% or less). Advantageously, it can be hardened.

Example 2 m-cresol 71.49 (0.66 mol), P-
Cresol 47.6 f (0.44 mol), -1-formalin (36 mw) 83.3 f (1,00 mol), oxalic acid 5F.

xylene 20cc, butyl cellosolve 20cc 90~
The reaction is carried out at 100°C with stirring and successive dehydration. After completion of dehydration, the mixture is reacted at 120°C to 140°C for about 2 hours. During this time, the viscosity increases significantly, so four 20 cc portions of butyl cellosolve are added as the viscosity increases. Then 150
The reaction was continued for an additional 20 hours at ~180°C and plated out.

Next, the solvent is removed in a vacuum, and after cooling and solidifying, it is pulverized, and the volatile matter of the perilla is further removed in a vacuum. The yield was 135t.

Example 20 Novolak was applied as a hot melt adhesive in combination with a polyamide resin using the Novolac of Comparative Example 2 as a comparative sample. As a result, the workability of the two novolaks was good, with no major difference, but
Adhesion strength (peel strength, impact strength in %) Fi Example 2 was significantly improved compared to Comparative Example 2. The heat resistance was also relatively improved by at least 30°C.

Example 3 Bisphenol A 93.6f (0.41 mol), phenol 91.3 f (0.97 mol), formaldehyde (361 weight) 83.3 f (1,00 mol)
, g acid 4 f.

Toluene 20cc, ethyl cellosolve 20cc 90cc
The reaction is carried out at ~100°C with stirring and successive dehydration. After the strawberry dehydration is completed, the mixture is reacted at 120 to 140°C for about 5 hours. During this time, the viscosity gradually increases, so 20 cc of ethyl cellosolve is added 8 times in response to the increase in viscosity. Then 1
The reaction is further carried out for about 5 hours at 50 to 160°C for crystallization. Next, vacuum desolvation is performed, and after cooling and assimilation, pulverization is carried out.
Further, vacuum drying is performed to remove volatile components.

Yield was approximately 1872.

In this example, fP= (4X0.30+3X0.70)=3
．． Since 30°f, = 2.00, (tp −1, O
O) (f, -1°00) = 2.30.

That is, 2.30≧P/F (equivalence ratio)≧2.10.

P/IF (molar ratio) = (0,41+0.97)
/, 1. OO-1, 38/1.00 Ashi, P/F
(Yellow ratio) = (4XO, 41+3 Xo, 97) /
(2X 1.00) -2,28. Therefore, the P/F of this example fully satisfies the conditions of the present invention.

The above reaction was carried out using a heating method such as heating in an oil bath that did not cause local overheating, and the difference between the temperature of the reaction system and the bath temperature was maintained at 20 to 40°C. If this heating method is used, such as a mantle heater, which tends to cause local overheating, the wood resin layer will become locally insolubilized on the walls of the reaction flask as the viscosity increases, and the wood resin layer will burn. This spreads rapidly as the reaction progresses. Also, in the case of oil bath heating, if the system temperature is heated with a large temperature difference of 40° C. or more, the insolubilized resin layer similarly burns. If the reaction is continued at 120 to 140° C. without adding a solvent, the viscosity will increase significantly and the resin will eventually cling to the stirrer, exhibiting the so-called Weisenberg effect. However, in this case, if a large amount of solvent is added immediately, most of the resin will dissolve and the resin solution will show normal viscosity.
ni 4 do. However, in order for the reaction to proceed smoothly, the system must be ζO
It is desirable to add a solvent to lower the viscosity before such a Weizenpelg effect is exhibited.

When Example 30 Novotsk was blended with NBR and used as a structural adhesive, the adhesive strength under heat and the fatigue strength of the adhesive strength were clearly improved compared to conventional products.

Example 4 Phenol 9.4f (0.10 mol), o-cresol 9G,! $ f (0,92 mol), formaldehyde (36-wt) 79.2F (0,95 mol), glyoxal (40-wt) 7.3 f (0,05 mol), oxalic acid 4f.

90 cc of toluene, 20 cc of butyl cellosolve
0haboP is reacted at ~100°C with stirring and sequential dehydration.
After completely reacting, the mixture is allowed to react at 120 to 150°C for about 5 hours. During this time, the viscosity increases significantly, so add 20 CC of butyl cellosolve 7 times depending on the viscosity. Then, it is reacted for an additional 40 hours at 150 to 200 DEG C. until it exhibits remarkable Weizenperg effect and stringiness, and is immediately cast out. Next, the solvent is removed in vacuum, cooled and solidified, and then pulverized, further washed with water and dried to remove volatile components. The yield was 115f.

In this example, f,=3xO,1+2x0.9=t2.1+
f,=4X O,05+ 2X 0.95=2.1
and therefore (f, -1) ('F 1) = 1
．． I X 1.1-1.21-following, 1.21≧P/
? (Equivalent ratio)≧1.01.

In this example, p7p (molar ratio') = (0,10+0.92
)/ (0,0!$+0.95)-1,02/1.00
Adashi, P/1 (equivalence ratio) = (3X0.10+2X0
．． 92)/(4XO,0B+2x0.95)=1.0
2, and the novolac of P/Example 4 above is Comparative Example 1
9. Novolak was used in comparison. As a result, there was no major difference in the compatibility and reactivity of the two novolacs with the epoxy resin, and both of them were found to have good properties, but the mechanical properties of the resulting composites (
%) and heat resistance, Example 1 was far superior to Comparative Example 1, and was extremely useful as an epoxy resin-based material for encapsulating electronic materials. there were.

[Brief explanation of the drawing]

FIG. 1 shows a GPC sunset madogram of a phenolic novolac resin. M indicated by a solid line excludes unreacted A. The broken line shows the sample □G1'C chromatogram with a value of 9M, /M, of 3°2. 6.9
This shows the GPC chromatogram of the sample. In the figure, * indicates unreacted P, and b indicates t, which shows two peaks. In addition, Figure 1 shows the GPC chromadogtum normalized so that the areas of M and B are equal.

Claims (1)

[Claims] U) In a novolac type solid resin which is a condensation product of phenol (abbreviated as P, the same below) and carbonyl compound (abbreviated as 1, the same below) under acidic catalyst, The average functionality of the molecular weight of the constituent phenols (abbreviated as fy, hereinafter referred to as B) and the molecule a of the carbonyl compound! &b
The average functionality (abbreviated as f, hereinafter the same) is 2. S
O≧(f, -1,00) (f, =1;00)≧1
It satisfies the relationship of ゛20, does not include unreacted P as much as possible, and has a number average molecular weight (abbreviated as M, hereinafter the same) of 500 or more when converted to a value excluding unreacted 5P. The weight average molecular weight (My
A soluble fusible phenolic resin having a logarithmic average molecular weight ratio (Mv/M, abbreviated as ratio, the same hereinafter) of 4.0 to 1. (2) In the heating condensation reaction of a mixture of P and 1 under acidic catalyst, 'P%'F is 250≧(f, -1,00)
Cfv-1,00) ≧ 1.20, and the range of the roaring ratio (ratio of the number of reaction points) of 'h is ((fp 1.00
) (fy 1-00)-0,20) to (fp
'1.00) (fy 1.00), the first condensation reaction is carried out at medium temperature for a short time, and then the viscosity of the system is noticeably increased while neutral to weakly acidic 7f volatiles are sequentially removed. The secondary polymerization reaction was carried out at a high temperature and for a long time until the temperature reached 500 or more, and the MW/MW ratio was calculated as a value excluding unreacted P. 4.
0 or more manufacturing method (3) The second polymerization reaction continues until the viscosity of the system significantly increases and the system significantly exhibits stringiness and Weizenperg effect. Apologies) Ring 1 - Method for producing novolac type phenolic resin.