JP2657291B2 - Thermosetting resin composition containing petroleum heavy oils or pitch-modified phenolic resin and compression molded article from the modified phenolic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin set containing a novel petroleum heavy oil or pitch-modified phenolic resin.
The present invention relates to a molded product and a compression molded product from the modified phenol resin . More specifically, the thermosetting resin set of the present invention
Compression molded product from the product and the modified phenolic resin
Since the novel modified phenolic resin itself has a relatively low softening point, it can be advantageously used as a molding material such as a molding chip, especially molding powder, and has a relatively low curing temperature. To provide a denatured phenolic resin molded article, particularly a compression molded article , which is dense and excellent in heat resistance, oxidation resistance, mechanical properties and the like.

[0002]

2. Description of the Related Art Phenol resins have excellent mechanical properties and have been widely used for a long time. However, light resistance and alkali resistance are slightly low, and dimensional and electric resistance are easily changed by absorbing moisture or alcohol. However, there is a problem that the heat resistance, particularly the oxidation resistance at a high temperature, is slightly low. In order to solve such a problem, various modifications of the phenol resin itself have been studied. In particular, there has been interest in denaturation with oils and fats, rosin, or neutral aromatic compounds to impart resistance to changes due to light, chemicals, oxidation, and the like.

Have studied the reaction of m-xylene-formaldehyde resin with novolak and have shown that m-xylene-formaldehyde resin can be used as a curing agent for novolak. Further, even if low molecular weight phenols are added and reacted after reacting m-xylene and formaldehyde, the phenols are not completely thermally cured, indicating that the phenols have a low ability as a curing agent. [Industrial Chemistry Magazine, Vol. 60, p. 1579 (195
7)].

Further, Japanese Patent Publication No. 53-5705 discloses that
A dry oil-modified aromatic hydrocarbon obtained by modifying an aromatic hydrocarbon resin obtained by reacting an aromatic hydrocarbon such as alkylbenzene containing mesitylene as a main component with formaldehyde with a drying oil and phenols and further resolving the resin. -A resin composition useful as a printed circuit board comprising a phenol-formaldehyde resin (A) and a usual drying oil-modified phenol resin (B) and a water-soluble phenol resin (C) is disclosed. The synthesis of the aromatic hydrocarbon-phenol-formaldehyde resin (A) is disadvantageous in terms of cost, and the obtained phenolic resin molded product itself has insufficient performance.

According to JP-A-61-235413, a phenol-modified aromatic hydrocarbon resin having excellent heat resistance can be obtained by selecting a reaction component of the phenol-modified aromatic hydrocarbon resin. It discloses that a heat-resistant resin having a high glass transition temperature can be obtained by mixing with a curing agent such as hexamine, but has the disadvantage that curing is slow and a high temperature and a high pressure are required to obtain a molded article. In addition, Tokiko Sho 6
JP-A-36209 discloses a phenolic resin modified with polycyclic aromatic hydrocarbons such as acenaphthene and acenaphthylene. In this case, the polycyclic aromatic hydrocarbon has high reactivity with formaldehyde. By selectively using compounds, it is possible to obtain a modified phenolic resin with excellent properties.However, none of the pyrolysis products of petroleum and coal contains these compounds in large amounts, and is produced in large quantities. For this purpose, it is necessary to synthesize, and there is a disadvantage that the cost is high, and there is also a problem that it is not easy to perform the hot-press molding in a relatively easy and short time.

[0006]

As a result of studying the above-mentioned problems of the prior art, the present invention has found that the drawbacks of the conventional phenolic resin are that the heat resistance and oxidation resistance are rather low; The drawbacks of phenolic resins modified with reactive aromatic hydrocarbons are that the reactivity is often low and the thermosetting is difficult unless special raw materials are used. A problem that the xylene resin is not sufficiently cured even when the phenol is used as a curing agent to cure the resin; Japanese Patent Publication No. 53-570.
JP-A-61-235413, as disclosed in Japanese Patent Application Laid-Open No. 5-235413, is that even if a normal phenol resin is blended with a phenol-modified mesitylene resin, the performance of the molded article itself is not sufficient;
Discloses that a phenol-modified aromatic hydrocarbon resin is cured with a curing agent such as hexamine, but the curing speed is slow and a high temperature and a high pressure are required;
No. 6209 discloses a polyphenolic aromatic hydrocarbon-modified phenol resin, which is intended to solve the problem that it is not easy to perform hot-press molding in a relatively easy and short time. is there. Further, the present invention relates to a thermosetting resin containing a novel modified phenol resin having excellent heat resistance, oxidation resistance, and mechanical properties that cannot be obtained with conventional modified phenol resins.
Fat composition and molded article from the modified phenolic resin, especially
A compression molded article is provided.

[0007]

The present invention provides: (A) 1 to 10 mol of formaldehyde polymer in terms of formaldehyde per 1 mol of petroleum heavy oils or pitches; 5 moles of phenols
Obtained by polycondensation in the presence of an acid catalyst, and petroleum heavy oil or pitch such modified phenolic resin and (B) Fe is a softening point measured by the flow tester is forty-two to one hundred thirty-two ° C.
A thermosetting resin composition comprising a curing agent for a knol resin . Further, the modified phenolic resin (A) is 1 to 1 in terms of formaldehyde with respect to 1 mol of a petroleum heavy oil or pitch mainly composed of a condensed polycyclic aromatic hydrocarbon having 2 to 4 rings.
10 mol of formaldehyde polymer and 0.3 to 5 mol of phenol, cresol, xylenol, and one or more phenols selected from the group of resorcinol are polycondensed in the presence of an acid catalyst. The heat which is obtained and whose softening point measured by a flow tester is 42 to 132 ° C.
It is also characterized in terms of the curable resin composition . A tree containing the modified phenolic resin (A)
Modified phenolic resin compression molded with excellent heat resistance, oxidation resistance, and mechanical properties by hot-pressing a fat material by a known method.
Offer goods .

Hereinafter, the present invention will be described in detail. (A) Production of petroleum-based heavy oils or pitch-modified phenolic resins: (a) Petroleum-based heavy oils or pitch-based materials: one of the raw materials for producing the novel modified phenolic resin of the present invention. As the petroleum heavy oils or pitches, those having an aromatic hydrocarbon fraction fa value of 0.40 to 0.95 and an aromatic ring hydrogen content Ha value of 20 to 80% are preferable. The aromatic hydrocarbon fraction fa value and the aromatic ring hydrogen amount Ha value are represented by the following equations.

[0009]

(Equation 1)

The fa value can be determined by ¹³ C-NMR. The Ha value can be determined by ¹ H-NMR. In the present invention, when the fa value of the petroleum heavy oils or pitches as the raw material decreases, the aromatic content decreases, so that the effect of modifying the performance of the resulting modified phenolic resin, especially the heat resistance and oxidation resistance, are improved. Quality effects tend to be small. In particular, when the fa value is 0.40 or less, the reforming effect becomes extremely small, which is not preferable.

In the case of petroleum heavy oils or pitches having a fa value larger than 0.95, the reactivity between the aromatic ring hydrogen and formaldehyde decreases, which is not preferable. Therefore, in the present invention, the fa value is 0.40-0.
95 is desirable, and more preferably, it is 0.50 to 0.80.

In the present invention, when the Ha value of the petroleum heavy oils or pitches as the raw material is reduced, the amount of aromatic ring hydrogen which reacts with formaldehyde is reduced and the reactivity becomes poor. This is not preferred because the quality effect is poor. The practical value of the Ha value is considered to be 20% or more. As the Ha value increases, the reactivity of the aromatic hydrogen content tends to gradually decrease. Ha
Use of petroleum heavy oils or pitches having a value of more than 80% as a raw material is not preferred because the strength of the modified phenolic resin tends to decrease. In the present invention, H
The a value is preferably from 20 to 80%, more preferably from 25 to 80%.
60%.

In the petroleum heavy oils or pitches used in the present invention, the number of condensed rings is not particularly limited.
Preferably, it is mainly a fused polycyclic aromatic hydrocarbon having 2 to 4 rings. In the case of a condensed polycyclic aromatic hydrocarbon having five or more rings, the boiling point exceeds 450 ° C. in most cases, so that it is difficult to collect those having a narrow boiling point range and the quality is not stable. In addition, in the case of mainly a monocyclic aromatic hydrocarbon, there is a problem that the reactivity with formaldehyde is low, and the effect of modifying the performance of the phenol resin is small.

The petroleum heavy oils or pitches, which are the raw materials of the modified phenolic resin of the present invention, include crude oil distillation residue, hydrogenolysis residue, catalytic cracking residue, and reduced-pressure distillate or heat treatment of these residue oils. The appropriate one of the fa value and the Ha value is selected from these and used.

(B) Formaldehyde polymer raw material: The formaldehyde polymer used in the present invention is paraformaldehyde, polyoxymethylene (particularly, oligomer)
And a cyclic polymer such as trioxane. The mixing ratio of the petroleum heavy oils or pitches to the formaldehyde polymer is such that the formaldehyde polymer is 1 in terms of formaldehyde with respect to 1 mol of an average mole calculated from the average molecular weight of the petroleum heavy oils or pitches.
It is preferably from 10 to 10 mol.

When the molar ratio is less than 1, it is not preferable because the strength of the cured product of the modified phenolic resin obtained is low. On the other hand, when it is 10 or more, both the performance and yield of the obtained cured product hardly change, so it is considered useless to use more formaldehyde polymer. The mixing molar ratio of the petroleum heavy oils or pitches and the formaldehyde polymer in the present invention is more preferably 2 to 7.

(C) Acid catalyst: As the acid catalyst used in the present invention, use of a Bronsted acid or Lewis acid is preferred, and more preferred is a Bronsted acid. As the Bronsted acid, toluenesulfonic acid, xylenesulfonic acid, hydrochloric acid, sulfuric acid, formic acid and the like can be used, and p-toluenesulfonic acid and hydrochloric acid are particularly excellent. The amount of the acid catalyst to be used is 0.1 to 0.1 to the total amount of petroleum heavy oils or pitches, formaldehyde polymer and phenols.
30% by weight is desirable, more preferably 1 to 10% by weight
It is. When the amount of the acid catalyst used is small, the reaction time tends to be long, and the reaction tends to be insufficient unless the reaction temperature is increased.

On the other hand, even if the amount of the acid catalyst used is large, the reaction rate is not so high, which may be disadvantageous in cost. Further, it may be necessary to recover or neutralize and remove the acid catalyst, which may result in extra costs.

(D) Phenols: As the phenols used in the present invention, any phenols can be used, and one or more phenols selected from the group consisting of phenol, cresol, xylenol, and resorcinol Compounds are preferred. In the present invention, phenols are added and mixed little by little by a method such as dropping. The rate of addition is 0,0 to the total weight of the reaction mixture.
It is preferably from 0.5 to 5% by weight / minute, more preferably from 0.1 to 5% by weight.
２2% by weight / minute.

If the rate of addition is 0.05% by weight / minute or less, the time required for addition is too long, and the cost increases, which is not preferable. On the other hand, the rate of addition is 5% by weight /
In the case of more than minutes, the added phenol rapidly reacts with free formaldehyde, so that it is difficult to form a uniform mixture or co-condensate, which is not preferable. The reason why such non-uniformity occurs is that the reactivity of phenols with formaldehyde is significantly higher than that of petroleum heavy oils or pitches, and unless the initial concentration of phenols is kept low. It is presumed that this is because formaldehyde selectively reacts with phenols or a condensate of phenols formed by the reaction with formaldehyde and becomes hardly soluble in the system.

Alternatively, petroleum heavy oils or pitches or petroleum heavy oil formed by the reaction is consumed before the formaldehyde is consumed by the reaction between the phenols or the phenols formed by the reaction and the condensate of formaldehyde. It is presumed that the condensate of oils or pitches with formaldehyde cannot be further reacted with formaldehyde, and may be separated from the reaction system.

In the present invention, the timing of starting the addition of phenols is not particularly limited, but the reaction rate of formaldehyde estimated from the amount of remaining free formaldehyde is 7%.
It is desirable to add phenols at a time point of 0% or less, preferably 50% or less. The start of the addition may be a point in time when the reaction between petroleum heavy oils or pitches and formaldehyde has not substantially proceeded. When the reaction rate of formaldehyde is 70% or more, the amount of formaldehyde that reacts with phenols decreases, so that the performance of the produced resin is significantly reduced.
Unless a curing agent is added, a cured product cannot be obtained, which is not preferable.

The amount of the phenol to be added is from 0.3 to 3 moles of the phenol relative to 1 mole of the average mole calculated from the average molecular weight of the petroleum heavy oils or pitches.
5 is desirable. When the addition amount is 0.3 or less, the reactivity between petroleum heavy oils or pitches and formaldehyde is inferior to the reactivity between phenols and formaldehyde. ,
There is a problem that the strength of the cured body is lower than that of a general phenol resin. In particular, it has low impact resistance and is brittle.

On the other hand, when the amount of the phenol added is 5 or more, the effect of modification by the phenol resin is small, which is not preferable. The addition amount of phenols in the present invention is more preferably 0.5 to 3.

(D) Reaction conditions: the reaction temperature is 50 to 1
60 ° C is desirable, and more preferably 60 to 120 ° C. The reaction temperature is suitably determined in consideration of the raw material composition, the reaction time, the properties of the resin to be produced, and the like. The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours. The reaction time is determined in consideration of the raw material composition, the reaction temperature, the addition rate of phenols, the properties of the resin to be formed, and the like.

In the present invention, when the reaction is carried out batchwise, it can be carried out in one step, and it is preferable to carry out the reaction in one step. In the case of performing a continuous process, it is not necessary to use a device that is difficult to control, such as a continuous mixing of two or more types of reaction products, which is used in a conventional modified phenol resin, in a constant amount. Place a complete mixing type reaction vessel,
What is necessary is just to feed in the phenol added to it at a fixed amount. Such devices are relatively inexpensive,
Operability is good.

In the present invention, a solvent can be used during the reaction. The reaction can be carried out without a solvent, in which case it is necessary to pay attention to the uniformity of the reaction.
The use of a solvent lowers the viscosity of the reaction system and improves the uniformity of the reaction. However, the solvent must be removed before curing, which generally increases costs, except for special ones.

Examples of the solvent include halogenated aromatic hydrocarbons such as chlorobenzene, nitrated aromatic hydrocarbons such as nitrobenzene, nitrated aliphatic hydrocarbons such as nitroethane and nitropropane, perchrene, trichlene, carbon tetrachloride And the like can be used.

(B) Petroleum heavy oils or pitches modified phenolic resin of the present invention: The novel modified phenolic resin (A) of the present invention is obtained by using petroleum heavy oils or pitches to form a phenolic resin. Since it is modified, it can be synthesized in a single step in a process, is inexpensive as a raw material, and can be easily thermoformed at a relatively low temperature and a low pressure.

Since the modified phenolic resin (A) of the present invention has a softening point in a range suitable for thermoforming the modified phenolic resin itself, it can be used as a molding material such as a molding chip, particularly a molding powder. The modified phenolic resin alone can be thermoformed (cured) because it is advantageous because it has sufficient thermosetting properties. Further, the modified phenolic resin of the present invention
(A ) is a thermosetting resin composition blended with a conventionally known curing agent (B) for a phenol resin such as an epoxy resin.
It can also be easily thermoformed (curing).

The modified phenolic resin (A ) of the present invention
Has excellent heat resistance, oxidation resistance, electrical insulation properties, moisture resistance, etc., and thus has little deterioration in electrical properties at high temperatures, and exhibits excellent performance as an electrical insulating material for printed wiring boards and the like.

The modified phenolic resin (A ) of the present invention has a glass transition point of several tens of times that of the conventional phenolic resin.
It is about 0 ° C. to 100 ° C. higher and has better heat resistance than conventional phenolic resins. Since the modified phenolic resin (A ) of the present invention has excellent light resistance, it can be used as a base resin for black paint.

Since the modified phenolic resin (A ) of the present invention has extremely high heat resistance, it is excellent as a matrix resin of a composite material using carbon fiber as a reinforcing material. The modified phenolic resin (A ) of the present invention has a high rate of carbonization and remaining when heated at a high temperature, and can be used as a binder for a carbon molded article. In particular, it can be used as a binder for molding carbon fibers, carbonized and processed into a carbon-carbon composite material.

(C) Others: The novel modified phenolic resin (A) of the present invention and phenol
Molding material formed of a composition comprising a resin curing agent (B) is
Thermoplastic resins such as glycidyl ether type, glycidyl ester type, glycidyl amine type, mixed type, alicyclic type epoxy resin and other phenolic resins, polyethylene, polypropylene, vinyl acetate resin etc. which are well-known as components to be blended with phenolic resin May be mixed, and hexamine or the like can be used as a curing agent.

Further, in order to enhance various properties such as strength and dimensional stability of the obtained molded product, especially a compression molded product , glass fibers and carbon fibers, which are well known as additives for phenolic resins, are used.
An inorganic filler such as aluminum carbonate and magnesium carbonate, an internal release agent such as silicone and wax, a flame retardant, a light stabilizer, an antioxidant, a pigment, a filler, a coupling agent, and the like may be mixed.

(D) Molding material comprising a composition containing the modified phenolic resin of the present invention and a molded article thereof The modified phenolic resin (A ) of the present invention has a softening point within a range suitable for thermoforming the modified phenolic resin itself. It is advantageous since it can be used as a molding material such as a molding chip, especially molding powder, and has sufficient thermosetting properties so that it can be thermoformed (cured) even with a modified phenol resin alone.
You . Further, the modified phenolic resin (A ) of the present invention is a known phenolic resin curing agent (B) such as an epoxy resin.
Even thermosetting resin composition containing a readily thermoformed (curing). The modified phenolic resin molded article of the present invention ,
In particular, the compression-molded article is characterized by having excellent heat resistance, oxidation resistance, and mechanical properties as compared with a conventional molded article made of a modified phenolic resin.

For example, the present inventionNew modified phenol tree
Resin containing fat (A)Material obtained by molding
Molded productsIn particular, known compression molding means (for example, 197
June 15, 2001 First edition of the Industrial Research Committee published, plastic technology
Refer to Phenol Resins, pages 67-72, especially page 69
The compression molded product obtained by hot pressing, Such as
It has excellent physical properties. Bending strength room temperature 6-22kgf / mm²  150 ℃ 3-14kgf / mm²  Flexural modulus room temperature 400-1800kgf / mm²  150 ° C 200-1500kgf / mm²  Tg (° C) 130 to 260 ° C Thermal deformation temperature 190 to 300 ° C or higher Antioxidant Insulation resistance Normal 1.0 × 10¹⁴~ 1.0 × 10^FifteenΩ boiling 1.0 × 10¹²~ 1.0 × 10¹³Ω New modified phenolic resin of the present inventionResin material containingThan
MoldingGoodsIn order to obtain a phenolic resin,
Forming means such as compression molding, injection molding, extrusion molding,
Spher molding and the like can be applied.

[0038]

Since the modified phenolic resin of the present invention has been modified with a condensed polycyclic aromatic hydrocarbon such as petroleum heavy oils or pitches, the modified phenolic resin itself has a relatively low softening point. It is advantageous because it can be used as a molding material such as chips, especially molding powder, and can be thermoformed at a relatively low curing temperature in a short time, and is dense and has excellent heat resistance, oxidation resistance, mechanical properties, etc. Modified phenolic resin moldings , especially compression molding
Goods can be provided.

In the present invention, polycyclic aromatic hydrocarbons such as petroleum heavy oils and pitches as modifiers have extremely different reactivity with formaldehyde as compared with phenols. By paying attention to the point, in the production of the modified phenol resin, a homogeneous phenol resin can be obtained by adjusting the timing and amount of the petroleum heavy oils or pitches to be added.

[0040]

The present invention is illustrated by the following examples, which do not limit the scope of the invention. Table 1 shows the properties of the reaction raw materials used in the examples. The feedstock and the pitch are obtained by distilling the bottom oil obtained by fluid catalytic cracking (FCC) of vacuum gas oil.

[0041]

[Table 1] (Properties of raw material oil for reaction pitch)

Note) Average molecular weight: Value by vapor pressure osmosis method, Boiling point: Value by ASTM D-1160, Ratio of condensed polycyclic aromatic hydrocarbon having 2 to 4 rings: Mass spectrometer (FI method) Softening point: value by flow tester, (Example 1) 200 g of raw material oil shown in Table 1 (0.74 mo
l), 90 g of paraformaldehyde (mole number in terms of formaldehyde, 3.0 mol, the same applies hereinafter), and 17.8 g of p-toluenesulfonic acid (monohydrate) were charged into a glass reactor, and the temperature was raised to 80 ° C. while stirring. did. 1 at 80 ° C
After reacting for 5 minutes, 66 g of phenol (0.7 g)
0 mol) at 1 cc / min (to the total weight of petroleum heavy oils or pitches and formaldehyde polymer).
34% / min, the same applies hereinafter).
The reaction continued for minutes. After the completion of the dropwise addition of phenol, the reaction was further continued for 2 hours while stirring. After completion of the reaction, the reaction product was taken out and cooled to obtain 364 g of a modified phenol resin.

The softening point of the resulting modified phenolic resin was 42 ° C. as measured with a flow tester (CFT-20, manufactured by Shimadzu Corporation). This modified phenolic resin is
When treated at 00 ° C. for 20 minutes, a thermosetting body was obtained.
Also, this modified phenolic resin was placed in a mold,
When maintained at 200 ° C. for 1 hour under a pressure of 0 kg / cm ² · G, a dense molded product was obtained and the oxidation resistance was good. The results are shown in Table 2 together with the physical properties of the compact.

(Example 2) 300 g of the feedstock oil shown in Table 1 (1.
1 mol), 180 g of paraformaldehyde (6.0 m
ol), p-toluenesulfonic acid (monohydrate) 30.6
g and 165 g of chlorobenzene were charged into a glass reactor and heated to 80 ° C. while stirring. After reacting at 80 ° C. for 20 minutes, phenol 130 g (1.4 m
ol) at a rate of 2 cc / min (0.42% / min), and reacted for 60 minutes. After dropping, 2 more
The reaction was continued while stirring for 0 minutes. After completion of the reaction, the reaction mixture was poured into 1700 g of n-hexane to precipitate a modified phenol resin. After the precipitate is filtered and washed,
And dried under reduced pressure to obtain 500 g of a modified phenol resin.

The softening point of the resulting modified phenol resin was measured by a flow tester and found to be 99 ° C. When this modified phenolic resin was treated at 200 ° C. for 10 minutes, a thermosetting product was obtained. This modified phenolic resin was placed in a mold and kept at 200 ° C. for 30 minutes under a pressure of 400 kg / cm ² · G to obtain a dense molded product. The results are shown in Table 2 together with the physical properties of the compact.

(Example 3) 150 g of raw material oil shown in Table 1 (0.
55 mol) and 100 g of paraformaldehyde (3.3
mol), 23.3 g of hydrochloric acid and 110 g of chlorobenzene were charged into a glass reactor and heated to 90 ° C. while stirring. When the temperature reached 90 ° C., 60 g of phenol (0.
64 mol) was added dropwise at a rate of 1 cc / min (0.40% / min), and after the completion of the addition of phenol, the mixture was further reacted by stirring for 15 minutes. At the end of the reaction, the reaction mixture was
The mixture was poured into 0 g of n-hexane to precipitate a modified phenol resin. The precipitate was filtered and washed, and dried under reduced pressure at 25 ° C. to obtain 175 g of a modified phenol resin.

The softening point of the resulting modified phenol resin was measured by a flow tester and found to be 92 ° C. When this modified phenol resin was treated at 250 ° C. for 20 minutes, a thermosetting product was obtained. This modified phenolic resin was placed in a mold and kept at 250 ° C. for 1 hour under a pressure of 400 kg / cm ² · G to obtain a dense molded product. The results are shown in Table 2 together with the physical properties of the compact.

Example 4 150 g of raw material oil shown in Table 1 (0.
55 mol), 90 g of paraformaldehyde (3.0 m
ol), p-toluenesulfonic acid (monohydrate) 15.3
g, chlorobenzene 83 g was charged into a glass reactor,
The temperature was raised to 95 ° C. while stirring. When the temperature reached 95 ° C, 1 cc of 65 g (0.60 mol) of p-cresol was added.
The reaction was carried out for 60 minutes while dropping at a drop rate of 0.42% / min (0.42% / min). After the addition of p-cresol, one more
The mixture was stirred for an hour to react. After completion of the reaction, the reaction mixture was
The mixture was poured into 80 g of n-hexane to precipitate a modified phenol resin. The precipitate was filtered and washed, and dried under reduced pressure at 25 ° C. to obtain 241 g of a modified phenol resin.

The softening point of the produced resin was measured by a flow tester and found to be 69 ° C. When this modified phenol resin was treated at 200 ° C. for 20 minutes, a thermosetting product was obtained. This modified phenolic resin was placed in a mold and kept at 200 ° C. for 1 hour under a pressure of 400 kg / cm ² · G to obtain a dense molded product. The results are shown in Table 2 together with the physical properties of the compact.

(Example 5) Pitch 186 obtained in Table 1
g (0.50 mol), paraformaldehyde 60 g
(2.0 mol), 13.9 g of p-toluenesulfonic acid (monohydrate) and 110 g of chlorobenzene were charged into a glass reactor, and the temperature was raised to 70 ° C. with stirring. 70
When the temperature reached 0 ° C., 32.5 g of phenol (0.35 m
ol) was added dropwise at a rate of 1 cc / min (0.41% / min). After the completion of the dropwise addition of phenol, the reaction was further stirred for 15 minutes. After completion of the reaction, the reaction mixture was poured into 1020 g of n-hexane to precipitate a modified phenol resin. The precipitate is filtered and washed, and dried under reduced pressure at 25 ° C.
243 g of a modified phenol resin was obtained. The softening point of the resulting modified phenolic resin was 132 ° C. as measured with a flow tester.

The modified phenolic resin was cured at 200 ° C. for 20 minutes.
After the treatment for minutes, a thermosetting body was obtained. The modified phenolic resin was put into a mold and charged at 400 kg / c.
When maintained at 200 ° C. for 1 hour under a pressure of m ² · G, a dense molded product was obtained. The results are shown in Table 2 together with the physical properties of the compact.

(Example 6) Raw material 225 obtained in Table 1
g (0.83 mol) and 60 g of trioxane (mol number in terms of formaldehyde, 2.0 mol) were charged into a glass reactor, and the temperature was raised to 60 ° C. while stirring. At 60 ° C., p-toluenesulfonic acid (monohydrate) 1
7.8 g was added, and the temperature was raised to 95 ° C. with further stirring. At 95 ° C., 40 g of phenol (0.4 g)
2 mol) was added dropwise at a rate of 1 cc / min (0.35% / min). After the completion of the dropwise addition of the phenol, the reaction product is taken out of the reaction vessel and cooled, and the modified phenol resin 331 is removed.
g was obtained. The softening point of the produced resin was measured at 69 ° C. by a flow tester.

The modified phenolic resin was treated at 200 ° C. for 15 minutes.
After the treatment for minutes, a thermosetting body was obtained. The modified phenolic resin was put into a mold and charged at 400 kg / c.
When maintained at 200 ° C. for 1 hour under a pressure of m ² · G, a dense molded product was obtained. The results are shown in Table 2 together with the physical properties of the compact.

[0054]

[Table 2] * Note: Tg (glass transition point) was measured by TMA method (thermomechanical analysis method). Other physical property values are based on JIS K6911.
It measured according to.

[0055]

Thermal hard including modified phenolic resin of the present invention
Resin composition and molding containing the modified phenolic resin
The article, in particular the compression molded article, does not undergo any substantial alteration when heated at 300 ° C. for several hours in an inert atmosphere and in air. Further, the mechanical strength is almost the same as that of the conventional phenol resin. Glass transition point is higher than that of conventional phenolic resin.
It is higher by several tens to 100 ° C., and is superior in heat resistance to the conventional phenol resin. It exhibits little deterioration in electrical properties at high temperatures and shows excellent performance as an electrical insulating material for printed wiring boards and the like.

Further, the present inventionofModified phenolic resinitself
Has excellent light resistance and is used as a base resin for black paint.
Can be used. It has excellent heat resistance and is made of carbon fiber and other reinforcing materials.
Excellent as a matrix resin for composite materials. Also, when heated at high temperatures, the rate of carbonization and residual
And can be used as a binder for carbon molded products. Especially,
Used as a binder to mold carbon fiber, carbonized
Can be processed into carbon / carbon composite material.

Claims (3)

(57) [Claims] 1. An acid catalyst comprising: (A) 1 to 10 moles of a formaldehyde polymer and 0.3 to 5 moles of a phenol in terms of formaldehyde per mole of a petroleum heavy oil or pitch. obtained by polycondensation in the presence of, and petroleum heavy oil softening point measured by the flow tester is forty-two to one hundred and thirty-two ° C. or pitch such modified phenolic resin 及
And (B) a thermosetting resin composition comprising a phenolic resin curing agent . 2. The modified phenolic resin (A) is used in an amount of 1 to 10 moles in terms of formaldehyde per mole of a petroleum heavy oil or pitch mainly composed of a condensed polycyclic aromatic hydrocarbon having 2 to 4 rings. A formaldehyde polymer;
3-5 moles of phenol, cresol, xylenol,
It is obtained by polycondensing one or more phenols selected from the group of resorcinol in the presence of an acid catalyst, and has a softening point of 42 to 13 measured by a flow tester.
The thermosetting composition according to claim 1, wherein the temperature is 2 ° C.
Resin composition . 3. A resin material containing the modified phenolic resin (A) according to claim 1 or 2, which is subjected to heat by known compression molding means.
Characterized in that the pressure molding, heat resistance, oxidation resistance, excellent modified phenolic resin compression molded product mechanical properties.