JPH09302058A - Heat-resistant phenol resin excellent in thermosetting properties and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phenol resin excellent in heat resistance, moisture absorption resistance, and thermosetting properties by selecting a phenol resin comprising repeating units formed by bonding a xylylene component, a phenylmethine component, and a methylene component to a phenol component in a specified ratio. SOLUTION: This phenol resin comprises repeating units formed by bonding a xylylene component (B) represented by formula I, a phenylmethine component (C) represented by formula II, and a methylene component (D) represented by formula III to a phenol component (A) derived from a phenol compd. and has a molar ratio of (B+C+D)/A of 0.4-0.95, a molar ratio of D/(B+C+D) of 0.1-0.9, and a number average mol.wt. of 500-5,000. In those formulas, R1 is methyl or ethyl; a is 0, 1, or 2; and Ar is phenyl or a di-or tricyclic arom, group provided one or two hydrogen atoms of each arom. nucleus of Ar may be substd. by a group or groups selected from among 1-4C alkyl, halogen, and hydroxyl groups.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is useful as a molding material, a laminate material, various binders, a coating material, etc.
The present invention relates to a phenolic heat-resistant resin which has excellent functions such as heat resistance and low hygroscopicity, and also has excellent thermosetting properties, and therefore has excellent moldability.

[0002]

2. Description of the Related Art Phenol-formaldehyde resin (hereinafter also simply referred to as "phenol resin"), which is a typical phenol resin, is widely used for various purposes as an inexpensive heat-resistant resin.

Phenolic resins are produced by reacting phenol with excess formaldehyde in the presence of a basic catalyst, which is a thermosetting resol resin itself, and excess phenol in the presence of formaldehyde and an acid catalyst. It is roughly classified into a novolac type phenol resin obtained by reacting with.

The novolac type phenol resin is a thermoplastic resin by itself, but it is used as a thermosetting resin by adding a curing agent (eg, hexamethylenetetramine, resole resin, etc.) to heat curing. ing.

When a divalent metal salt (which may be an oxide or hydroxide of a divalent metal or a trivalent metal oxide) is used as a catalyst in place of the acid catalyst in the production of a novolac type phenol resin, phenol is It is known that a high ortho novolac type phenolic resin containing a large proportion of components bonded with o, -methylene is obtained, and its curability is higher than that of a novolac type phenolic resin obtained with an acid catalyst (that is, it is a fast curable type). Has been.

Phenolic resin shows an initial heat resistance of 200 ° C. or more when sufficiently post-cured, but the long-term heat resistance is 150 ° C. or less because the resin itself is easily oxidized due to the phenolic hydroxyl group. , Not enough. Further, due to the presence of the phenolic hydroxyl group, water resistance and alkali resistance are relatively weak. These drawbacks limit the uses of phenolic resins.

For the purpose of improving this drawback, the phenolic hydroxyl group is protected by etherification or esterification (using a catalyst such as boron, silicon, phosphorus or heavy metal) or p-aminophenol is used in place of phenol. It is generally known that nitrogen is denatured by such means as using bisphenol S, or sulfur is modified by using bisphenol S, and some methods are used. However, even with these methods, the long-term heat resistance is limited to 220 ° C., and even if the long-term heat resistance is improved, there is a problem that the curability is deteriorated, and the application is still limited.

On the other hand, a phenol aralkyl resin produced in the same manner as the novolac type phenol resin was proposed by using a xylylene type aralkyl compound (hereinafter referred to as a xylylene compound) such as p-xylylene glycol dimethyl ether instead of formaldehyde ( Japanese Patent Publication 47-15
111, JP-A-4-142328). This resin is also used as a thermosetting resin with a curing agent such as hexamethylenetetramine, and has improved heat resistance, water resistance, alkali resistance, etc. as compared with a phenol resin.

However, this phenol aralkyl resin is inferior in curability when it is heat-cured by adding a curing agent, and therefore, it is necessary to take a sufficient time for heat-curing, and there is a great limitation in practical use in terms of productivity. There is.

Further, for the purpose of improving the curability of the phenol aralkyl resin, a resin in which formaldehyde is used in combination with a xylylene compound (JP-A-4-142324), or phenol-formaldehyde during or after the reaction between the phenol and the xylylene compound Resins modified by adding a resin (Japanese Patent Application Laid-Open No. 4-173834, Japanese Patent Publication No. 58-58378) are also known.

However, although these resins have improved curability, they are inferior in heat resistance to the original phenol aralkyl resin, and are therefore insufficient as heat resistant resins with improved moldability.

A resin produced by co-condensing a phenol compound, an aromatic aldehyde, and a xylylene compound in a specific constitutional ratio in the presence of an acid catalyst (JP-A-6-184258 and JP-A-6-184258).
-136082) and a resin prepared by reacting phenol and an aromatic aldehyde under an acid catalyst with a phenol aralkyl resin in a specific ratio (Japanese Patent Publication No.
47-15111, JP-A-4-142328, JP-A-6
-322234) was also proposed.

These resins have a heat resistance equal to or higher than that of the phenol aralkyl resin but have greatly improved curability, and have both high heat resistance and good moldability and have practical value. There is. However, its curability is
It is still inferior to general-purpose novolac type phenolic resin. Therefore, in order to obtain molding processability equivalent to that of this phenol resin, it is necessary to devise a method such as setting the molding temperature to a high level, which has the drawback that it cannot be used under the general-purpose phenol resin usage conditions. Is limited.

[0014]

The object of the present invention is to solve the above-mentioned problems of the phenolic resin, and specifically,
When it is cured with a curing agent such as hexamethylenetetramine, it has the same curability as general-purpose novolac type phenolic resin, so it is easy to mold, and at the same time it has long-term heat resistance, water resistance, alkali resistance and other functions. It is to provide a heat-resistant phenolic resin which is as excellent as an aralkyl resin and a method for producing the same.

[0015]

DISCLOSURE OF THE INVENTION The present inventors have proposed a phenol-based co-condensation resin obtained by reacting the phenol compound described in JP-A-6-1841258 previously proposed with an aromatic aldehyde and an aralkyl compound. Although it is still inferior to general-purpose novolac type phenolic resin in excellent water resistance and alkali resistance and curability, it was noted that it is improved compared to phenol aralkyl resin.

As a result of repeated studies to improve the curability while maintaining the above-mentioned physical properties such as heat resistance and water resistance of the phenol-based co-condensed resin, phenol compounds, aromatic aldehydes and aralkyl compounds were obtained. In addition, it was found that by co-condensing formaldehyde, the curability was remarkably improved, and other properties such as heat resistance were maintained or decreased only slightly. Further, they have found that the use of a catalyst used for the production of high ortho novolac during the reaction of formaldehyde improves the reactivity with a curing agent such as hexamethylenetetramine, and further improves the curability, and has reached the present invention.

Here, the present invention provides the following phenolic heat-resistant resins and methods for producing the same.

A phenol component (A) derived from a phenol compound is added to a xylylene component (B) represented by the formula (1), a phenylmethine component (C) represented by the formula (2), and a formula (3). ) Is composed of a repeating unit to which a methylene component (D) is bound, and [(B) + (C) + (D)] /
The molar ratio of (A) is within the range of 0.4 to 0.95, and (D) /
A phenolic heat-resistant resin having a number average molecular weight of 500 to 5000, wherein the molar ratio of [(B) + (C) + (D)] is in the range of 0.1 to 0.9.

[0019]

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In the above formula, R ₁ is a methyl group or an ethyl group, a is 0, 1 or 2, Ar is a phenyl group or a 2-3 ring polycyclic aromatic group, and each of Ar is 1 to 2 hydrogen atoms of the aromatic nucleus may be substituted with a substituent selected from an alkyl group having 1 to 4 carbon atoms, a halogen group and a hydroxyl group.

The method for producing a phenolic heat-resistant resin as described above, which comprises reacting a phenol compound with xylylene glycol or a reactive derivative thereof, an aromatic aldehyde, and formaldehyde or a derivative thereof in the presence of an acid catalyst.

After reacting a phenol compound with xylylene glycol or its reactive derivative and an aromatic aldehyde in the presence of an acid catalyst, the reaction mixture is neutralized, and then a salt of divalent metal, hydroxide and oxidation are added. And a derivative thereof in the presence of a catalyst selected from the group consisting of compounds and trivalent metal oxides.

The phenol compound is reacted with formaldehyde or its derivative in the presence of a catalyst selected from the group consisting of divalent metal salts, hydroxides and oxides, and trivalent metal oxides, and then the reaction mixture. The method for producing a phenolic heat-resistant resin as described above, comprising reacting xylylene glycol or a reactive derivative thereof and an aromatic aldehyde in the presence of an acid catalyst.

When the xylylene glycol or its reactive derivative is a xylylene dihalide, the xylylene dihalide is a reaction partner phenol compound or reaction mixture prior to the other reaction components being reacted together. Can be reacted in advance without catalyst.

The phenolic resin of the present invention comprises a divalent phenol component (A) derived from a phenol compound,
Three types of divalent components, that is, xylylene components of formula (1)
(B), a phenylmethine component of formula (2) (C) (more precisely, an arylmethine component), and a methylene component of formula (3)
It is a copolymer (recondensation product) having a repeating unit which is condensation-bonded with each of (D) as a constitutional unit. A typical structure of this copolymer is represented by the following formula (4).

[0026]

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In the above formula, both ends have a phenol component (A).
And m, n, p, and q each independently represent a positive integer. The copolymerization mode of this copolymer is block copolymerization,
Either one of random copolymerization and alternating copolymerization may be used,
It may also be a combination of these. The copolymer represented by the formula (4) preferably contains a large amount of random copolymers and alternating copolymers.

In addition to the copolymer having the structure represented by the formula (4), one or more polymers or copolymers represented by the following formulas (5) to (10) are contained. Good.

[0029]

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In the above formula, m _{1 to} m ₃ , n _{1 to} n ₃ , p _{1 to} p ₃ , q ₁ to
q ₃ is a positive integer independently of each other. However, equation (5) ~
The polymer or copolymer represented by (10) is inferior to the copolymer represented by formula (4) in at least one of the properties such as heat resistance, water resistance, alkali resistance, and curability.
It is preferable that the ratio is as small as possible.

The molar ratio of [(B) + (C) + (D)] / (A) is in the range of 0.4 to 0.95. Since this molar ratio is directly linked to the molecular weight and determines the softening point, melt viscosity, etc., it may be selected so as to obtain the desired softening point and melt viscosity according to the intended use. This molar ratio is preferably 0.5 to 0.9.
, And more preferably within the range of 0.7 to 0.9.

When the reaction is carried out at the above molar ratio, a phenol resin having a number average molecular weight of 500 to 5000 is generally obtained.
The number average molecular weight is preferably 800 to 3500, more preferably 1300 to 2500.

The molar ratio of (D) / [(B) + (C) + (D)] is in the range of 0.1 to 0.9. The higher the molar ratio, the higher the curability, but the physical properties of the cured product such as heat resistance tend to decrease. Therefore, the value may be determined according to the required physical properties such as curability and heat resistance. This molar ratio is preferably in the range of 0.2 to 0.7, more preferably 0.2 to 0.5.

The phenolic heat-resistant resin of the present invention mainly having the structure represented by the above formula (4) is a triphenyl represented by -ACA-, which is formed by binding an aromatic aldehyde and a phenol compound. The methine structure (in a broader sense, a triarylmethine component) enhances the rigidity during heating, and therefore has a significantly higher curability than the phenol aralkyl resin [resin having only ((A) -B] as a repeating unit). Moreover, since this triphenylmethine structure and the structure containing a xylylene bond represented by (AB) coexist, heat resistance,
It has excellent physical properties such as water resistance and alkali resistance.

Further, by introducing a repeating unit having a high crosslink density represented by (AD) into the copolymer structure, the crosslink density can be increased while substantially maintaining the physical properties such as heat resistance. The curing rate (curability) when the composition is thermally cured by adding a curing agent such as hexamethylenetetramine is remarkably improved. Although it is possible to simply blend a phenol-formaldehyde resin (phenol resin) for the purpose of increasing the crosslink density, the blending method can improve the curability, but significantly lowers the physical properties such as heat resistance.

The excellent performance of the phenolic heat-resistant resin of the present invention is schematically shown in FIG. In FIG. 1, a curve A indicates a phenol component (A) -xylylene component (B) -of the present invention.
A phenylmethine component (C) -methylene component (D) co-condensation resin. Specifically, it is a polycondensate of phenol / xylylene glycol dimethyl ether / benzaldehyde / formaldehyde in the presence of an acid catalyst; curve B
Is a co-condensation resin of phenol component (A) / xylylene component (B) / phenylmethine component (C), that is, a polycondensation product of phenol / p-xylylene glycol dimethyl ether / benzaldehyde, and a high ortho type novolak type phenol- A mixture of formaldehyde resin blended; curve C is for a phenol aralkyl resin (phenol / benzaldehyde polycondensate, that is, a polymer of a phenol component (A) and a xylylene component (B)),
It is a mixture of high ortho type novolak type phenol-formaldehyde resin blended.

The mole ratio of --CH ₂ --bonds on the horizontal axis of the figure is the proportion of formaldehyde copolymerized in curve A,
Curves B and C are the proportions of formaldehyde in the blended phenolic resin.

As shown in this figure, in the mixture of curves B and C, the curability is improved almost in proportion to the increase of --CH ₂ --bond (that is, the increase of the mixing amount of the phenol resin). , Proportional to this, long-term heat resistance (for example, 25
Bending strength at 0 ° C and 1000 hours, retention rate) tends to decrease. Therefore, both curability and long-term heat resistance cannot be achieved at the same time.

On the other hand, in the co-condensation resin of the present invention shown in the curve A, when compared at the same molar ratio of —CH ₂ — bonds,
Both curability and heat resistance are superior to curves B and C. Moreover, while the curability sharply improves as the molar ratio of —CH ₂ — bonds increases, the decrease in long-term heat resistance is caused by —CH ₂ —
Not noticeable until the bond molar ratio is significantly higher. Therefore, the co-condensation resin that is the blend component of curve B and the phenol aralkyl resin that is the blend component of curve C are
The excellent long-term heat resistance obtained when used alone is retained in a considerable range. That is, it becomes possible to achieve both curability and heat resistance.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION The phenol compound as a raw material of the phenol component (A) is an aromatic compound having one or more phenolic hydroxyl groups. Specific examples thereof include phenol, p-cresol, o-cresol,
m-cresol, p-ethylphenol, o-ethylphenol, p-isopropylphenol, pn-propylphenol, p-sec butylphenol, o-sec-
Butylphenol, p-tert-butylphenol, o-
tert-butylphenol, p-tert-amylphenol, p-tert-octylphenol, nonylphenol, dodecylphenol, p-cyclohexylphenol, o-phenylphenol, p-phenylphenol, p-cumylphenol, p-α-methylbenzylphenol , P-chlorophenol, p-bromophenol, α-naphthol, β-naphthol, resorcin, catechol, hydroquinone, pyrogallol, phloroglucinol, p-aminophenol, m-aminophenol and the like, but are not limited thereto. Not something. The preferred phenolic compound is phenol.

Xylylene glycol or its reactive derivative (hereinafter referred to as "xylylene compound"), which is a raw material of the xylylene component (B), is a compound represented by the following formula (11).

[0042]

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In the formula, R ₁ is a methyl group or an ethyl group, a
Is 0, 1 or 2, X may be the same or different, and each is -OH (hydroxyl group), halogen atom, -OR.
Alternatively, it is —OCOR, and R is an alkyl group, preferably an alkyl group having 4 or less carbon atoms.

Specific examples of the xylylene compound include xylylene glycol, xylylene glycol dimethyl ether, xylylene glycol monomethyl ether, xylylene glycol diethyl ether, xylylene glycol diacetoxy ester, xylylene glycol dipropoxy ester, and xylylene dichloride. , Xylylene dibromide, and their monomethyl xylylene, monoethyl xylylene, dimethyl xylylene, and diethyl xylylene derivatives (for example, monomethyl xylylene glycol and its dimethyl ether, etc.), but are not limited thereto. is not.
Of these, xylylene glycol, xylylene glycol dimethyl ether, and xylylene dichloride are preferable.

The aromatic aldehyde which is a raw material of the phenylmethine component (C) is an aromatic compound having one aldehyde group directly bonded to the aromatic ring. Specific examples thereof include benzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, halogenated benzaldehyde,
Examples thereof include, but are not limited to, hydroxybenzaldehyde, phenylbenzaldehyde, naphthaldehyde and the like. Preferred is benzaldehyde.

Formaldehyde or its derivative which is a raw material of the methylene component (D) includes, but is not limited to, formaldehyde, paraformaldehyde, trioxane, cyclic formal, hexamethylenetetramine, butyl hemiformal and the like. . Of these, formaldehyde and paraformaldehyde are preferable. Formaldehyde is convenient to use as its aqueous solution, formalin. Hereinafter, formaldehyde or its derivative is simply referred to as formaldehyde.

The acid catalyst may be any of inorganic acids such as phosphoric acid, sulfuric acid and hydrochloric acid, and organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid. The preferred acid catalyst is a strong acid.

The acid catalyst acts as a catalyst for all polycondensation reactions of the phenol compound with each of the formaldehyde, xylylene compound and aromatic aldehyde. However, when the xylylene compound is a dihalide (e.g., xylylene dichloride), the hydrogen halide generated by the polycondensation reaction between the phenol compound and the xylylene compound functions as an acid catalyst. During the reaction with the reaction mixture of the compound and formaldehyde, the polycondensation reaction proceeds even without a catalyst.

In the polycondensation reaction of formaldehyde and a phenol compound, a metal compound can be used as a catalyst instead of an acid catalyst in order to generate a high ortho structure. The catalyst is selected from the group consisting of divalent metal salts, hydroxides and oxides, and trivalent metal oxides. Hereinafter, this catalyst is referred to as a "metal compound catalyst".

The divalent metal salt useful as a metal compound catalyst is an inorganic acid salt or organic acid salt of divalent ions such as Mg, Ca, Cd, Pb, Co, Ni and Zn (eg, lower carboxylate, oxalate). Acid salts, etc.). Specific examples include zinc acetate, cobalt acetate, calcium chloride and the like. Examples of divalent or trivalent metal oxides that can be used as metal compound catalysts include M
It is an oxide of a metal such as g, Ca, Cd, Pb, Co, Ni, Al or B, and an example of the divalent metal hydroxide is a hydroxide of Mg, Ca, Sr or Ba. Of these, particularly preferred metal compound catalysts are zinc acetate, cobalt acetate, magnesium acetate, zinc chloride, magnesium oxide, and calcium oxide.

Each of the polycondensation raw materials and catalysts described above may be used alone or in combination of two or more. Further, these do not have to be pure products, and may contain by-products produced in the synthetic reaction as long as they do not have a significant adverse effect on the reaction or product used in the present invention.

The phenolic heat-resistant resin of the present invention can be manufactured by the above-mentioned three types of methods (in order, referred to as first to third manufacturing methods). These manufacturing methods will be described below.

First Production Method ( Method Above) In this production method, four kinds of reaction components, that is, a phenol compound, an aromatic aldehyde, a xylylene compound, and formaldehyde are all reacted in the presence of an acid catalyst.

As a reaction procedure, these four kinds of raw materials may be charged into a reaction vessel (steam heating vessel) all at once, an acid catalyst may be added, and they may be reacted together at an appropriate temperature. Alternatively, a method in which a phenol compound having a relatively high reactivity is reacted with formaldehyde first and then an aromatic aldehyde and a xylylene compound are added and reacted, or conversely, a phenol compound, an aromatic aldehyde and a xylylene compound are first reacted Alternatively, three kinds of polycondensation raw materials may be reacted in sequence with the phenol compound in two steps, for example, by reacting under heating with an acid catalyst and then reacting by adding formaldehyde. When divided into two times, it is preferable to react formaldehyde, which has relatively high reactivity as described above, separately from other raw materials.

Further, a method of separately reacting three kinds of polycondensation raw materials with the phenol compound is also possible. However, this method produces a relatively large amount of block polymer. On the other hand, if the method of reacting three kinds of polycondensation raw materials all at once is adopted, although a block polymer having a methylene bond derived from formaldehyde is partially produced due to the difference in reactivity, the proportion of random or alternating polymers increases. .
Therefore, a batch reaction or a reaction method divided into at most two times is preferable.

In the case of a batch reaction, a part of the total of the three polycondensation raw materials is first charged together with a part or all of the phenol compound, an acid catalyst is added and reacted, and the rest is divided or continuously. It is also possible to adopt a method of adding and reacting. Further, some or all of the raw materials may be added dropwise or added little by little. Such a method can also be adopted when the formaldehyde and other raw materials are divided and reacted with the phenol compound.

In the case of the splitting reaction, heat generation due to a rapid reaction is prevented, and the reaction proceeds at a high productivity rate. Therefore, in the case of a reaction with a relatively weak acid such as formaldehyde, a reaction with an aromatic aldehyde or a xylylene compound is required. You may take measures such as using a relatively strong acid. Alternatively, the same catalyst may be used to react with formaldehyde in a relatively small catalytic amount, and when reacting with an aromatic aldehyde or a xylylene compound, the catalytic amount may be increased to react.

The xylylene compound is a dihalide (eg,
(Xylylene dichloride), a splitting reaction is carried out by first reacting the xylylene dihalide with a phenol compound in the absence of a catalyst in advance, and then adding an acid catalyst to react the remaining components in a batch or in splits. You can also

The reaction temperature is 50 to 200 ° C., preferably 80 to 200 ° C.
It is 150 ℃. In the case of split reaction, the reaction temperature may be changed for each reaction. By-products of the polycondensation reaction are, in addition to water, alcohol, depending on the type of xylylene compound,
Hydrohalic acid such as carboxylic acid or hydrochloric acid is produced. In the polycondensation reaction, it is basic to proceed the reaction while removing such by-products to the outside of the reaction system, but in a part of the reaction step, the by-products are partially or wholly refluxed to carry out the reaction. Good.

The polycondensation reaction proceeds even without solvent, but a solvent inert to the reaction (eg, water, alcohol, ketone, etc.) may be used. For example, it is preferable to use a solvent when some of the raw materials do not melt at the reaction temperature. When using formalin as formaldehyde,
Since water and a small amount of methanol contained in formalin serve as a solvent, it is usual not to use any other solvent. When formalin is not used, it is preferable to use a solvent depending on the state of the reaction system. The polycondensation reaction is preferably continued until the xylylene compound, the aromatic aldehyde and the formaldehyde are almost completely reacted, and for example, the reaction may be ended when the generation of by-products is almost completed.

After completion of the polycondensation reaction, it is preferable to remove unreacted phenol from the reaction mixture by distillation. If necessary, the solvent is also removed at the same time. Further, the catalyst may be removed from the produced resin by appropriately combining neutralization, filtration, washing with water, or by evaporating after the reaction using a volatile acid catalyst (for example, the resin having a high insulating property is used). When used for required purposes). The phenolic resin of the present invention can be granulated before being cooled after being taken out from the reaction kettle, or can be crushed after cooling to be a product.

Second Production Method ( Method Above) After reacting a phenol compound with a xylylene compound and an aromatic aldehyde in the presence of an acid catalyst, the reaction mixture is neutralized and then in the presence of a metal compound catalyst. It is a method of reacting formaldehyde with.

Phenol component (A) and methylene component
Binding mode (D), i.e. -D-A-D-binding mode (hereinafter, -CH ₂ - that the binding mode), as shown in the following equation, phenol o, o'was methylene linkage There are an o-substituted product and a p-substituted product in which o, p'-methylene bond is bonded to phenol. According to the above-mentioned second production method, formaldehyde is used as a metal compound catalyst to cause polycondensation. Compared with the production method of No. 1, the ratio of the o-substitution product is significantly higher. As a result, many of the p-positions of the phenol nucleus remain unreacted, and the p-position is more reactive than the o-position, so that reaction with a curing agent such as hexamethylenetetramine occurs faster, and the curability is further improved. To be done.

[0064]

[Chemical 6]

In the polycondensation reaction of the second production method, the phenol compound is reacted with an aromatic aldehyde and a xylylene compound in the presence of an acid catalyst, and the reaction mixture obtained in the first step is neutralized. After deactivating the acid catalyst,
This reaction mixture is divided into a second step of reacting formaldehyde using a metal compound catalyst.

The first step can be carried out by charging a phenol compound, an aromatic aldehyde, and a xylylene compound together into a reaction vessel, adding an acid catalyst, and reacting at an appropriate temperature. Alternatively, both or part of the aromatic aldehyde and the xylylene compound are charged into a reaction kettle together with the phenol compound, an acid catalyst is added, and the mixture is reacted at an appropriate temperature, and then the rest of the aromatic aldehyde and the xylylene compound is continuously added. The reaction may be carried out by adding the target or dividedly.

Also in this case, the aromatic aldehyde and the xylylene compound can be completely divided and added and reacted in order, but the ratio of the random copolymer or the alternating copolymer which is a preferable copolymer is Less. Therefore, both the aromatic aldehyde and the xylylene compound are added to the phenol compound at once or little by little together to react, or even in the case of divided addition, at least a part of the aromatic aldehyde and the xylylene compound is simultaneously reacted with the phenol compound. It is preferred to add some at the same time so that they react.

However, the xylylene compound is a dihalide
In the case of (eg, xylylene dichloride), it is also possible to first react a phenol compound with a xylylene dihalide without catalyst and then add an acid catalyst to react with an aromatic aldehyde.

The reaction temperature in this first step may be substantially the same as that in the first production method, specifically 50 to 200 ° C, preferably 80 to 180 ° C. This reaction is preferably carried out until the aromatic aldehyde and the xylylene compound are almost completely reacted.

The reaction mixture obtained is neutralized. This neutralization can be carried out, for example, by adding an appropriate base to the reaction kettle as it is or in the form of a solution. As the base, relatively high-boiling organic compounds such as ethanolamine, methylamines, ethylamines, propylamines, benzylamines, DBU (1,8-diazabicyclo [5.4.0] -7-undecene), and imidazoles Amine is preferred, but inorganic base
(Alkali) can also be used.

In the second step, the neutralized reaction mixture of the first step is kept in the same reaction kettle as in the first step or transferred to another reaction kettle, and then formaldehyde and a metal compound catalyst are added and heated. It can be implemented by Formaldehyde may be added all at once, or may be added in portions or continuously. The pH during the reaction is preferably in the range of 4-8. The reaction temperature is 50 to 200 ° C, but it is preferable to carry out the reaction at a relatively high reaction temperature (eg, 100 ° C or higher).

Handling of by-products and use of a solvent in the first and second steps of the second method may be the same as in the first production method. Also in the second step using a metal compound catalyst, this metal compound once reacts with phenol, which is an acidic substance, to form a salt (further chelation is considered to occur), so the reaction proceeds even without a solvent. However, if desired, an inert solvent may be used. The reaction product obtained after the completion of the second step may be treated in the same manner as the reaction product of the first production method.

Third Production Method ( Method Above) After reacting a phenol compound with formaldehyde in the presence of a metal compound catalyst, the reaction mixture is reacted with xylylene glycol and an aromatic aldehyde in the presence of an acid catalyst. Is the way.

As in the second production method, formaldehyde is also polycondensed using a metal compound catalyst in the third production method, so that the bonding mode of --CH _2- , that is, the methylene component to the phenol component (A) is used. The bond of (D) is o,
The proportion of o-substitutes, which are o'-bonds, increases, and the reactivity with a curing agent such as hexamethylenetetramine increases,
The curability is further improved.

The polycondensation reaction of the third production method comprises the first step of reacting a phenol compound with formaldehyde using a metal compound catalyst, and the obtained reaction mixture containing an aromatic aldehyde and a xylylene compound in the presence of an acid catalyst. It is divided into a second step of reacting with.

The first step can be carried out by charging a phenolic compound and formaldehyde into a reaction kettle, adding a divalent metal salt as a catalyst and heating. The total amount of formaldehyde may be charged all at once, or may be added in portions or continuously. This reaction has a p within the range of 4-8.
It is preferable to carry out the reaction with H at a relatively high reaction temperature (preferably 100 ° C. or higher) and proceed the reaction until the formaldehyde is almost completely reacted. After the reaction, the divalent metal salt catalyst may be left in the reaction product as it is, or may be removed by neutralization, washing with water or the like.

In the second step, an aromatic aldehyde and a xylylene compound are added to a reaction kettle containing the product of the first step (the same as the first step or a different reaction kettle),
An acid catalyst is also added and the reaction is carried out at an appropriate temperature. The addition of the aromatic aldehyde and the xylylene compound may be such that the total amount of both is added at once, or both or part of one of them is added and reacted, and the rest is continuously or dividedly added,
The reaction may proceed.

In this case as well, the aromatic aldehyde and the xylylene compound can be added completely separately and reacted separately, but the ratio of the random copolymer or the alternating copolymer which is a preferable copolymer Is less. Therefore, the product of the first step may be reacted with the aromatic aldehyde and the xylylene compound all at once, or the aromatic aldehyde and the xylylene compound may be reacted at least partially at the same time without completely dividing them. Preferably.

However, the xylylene compound is a dihalide.
(Eg, xylylene dichloride), the first
It is also possible to first react the reaction mixture obtained in the step without catalyst with xylylene dihalide, and then add an acid catalyst to react with an aromatic aldehyde.

In both the first step and the second step, the reaction temperature is
The temperature is 50 to 200 ° C, preferably 80 to 180 ° C. Handling of by-products and use of a solvent in the first step and the second step of the third method may be the same as in the first production method. The reaction product obtained after the completion of the second step may be treated in the same manner as the reaction product of the first production method.

In any of the first to third manufacturing methods described above, the proportion of each raw material used is such that the proportion of each component derived from it is [(B) + (C) + (D)] / The molar ratio of (A) is within the range of 0.4 to 0.95, and (D) / [(B) + (C)
+ (D)] molar ratio is selected within the range of 0.1 to 0.9. As can be seen from the first equation, the phenolic compound is used in excess with respect to the sum of the other components.

The amount of the catalyst used varies depending on the acid strength of the acid catalyst and the reactivity of the main raw material used, so it is preferable to set an appropriate amount by experiments. Phenol compound is phenol, xylylene compound is p-xylylene glycol dimethyl ether, aromatic aldehyde is benzaldehyde, formaldehyde is formalin, acid catalyst is p-.
In the case of toluenesulfonic acid, the amount of the acid catalyst is appropriately 0.1 to 1.0% by weight based on the total amount of the raw materials charged. The amount of metal compound catalyst used depends on the amount of phenol compound charged.
It is preferably within the range of 0.1 to 1.0% by weight.

The phenolic resin of the present invention can be used as a thermosetting resin by adding a curing agent (crosslinking agent) like the general-purpose novolac type phenolic resin. Hexamethylenetetramine is preferable as the curing agent, but other various curing agents known to be usable for novolac type phenolic resins can be used. Examples of such curing agents include resol-type phenolic resins, resins such as epoxy resins, and paraformaldehyde, trioxane and the like.

In the case of hexamethylenetetramine, the addition amount of the curing agent is appropriately 5 to 20 parts by weight with respect to 100 parts by weight of the resin. Further, like the general-purpose novolac type phenolic resin, magnesium oxide, calcium carbonate or the like can be used as a thermosetting aid, and the addition amount thereof is 100
0.1 to 5 parts by weight is suitable with respect to parts by weight.

The phenolic resin of the present invention is another phenolic resin, for example, a general-purpose novolak type phenolic resin, or a phenol aralkyl resin (polycondensation resin of a phenol compound and a xylylene compound) or JP-A-6-184258. The phenolic resin / xylylene compound / aromatic aldehyde co-condensation resin described in 1. can be used in combination with other phenolic heat-resistant resins, whereby the mixed resin has excellent properties of the phenolic resin of the present invention, For example, physical properties such as curability and heat resistance are improved.

The phenolic resin of the present invention can be used in the same applications as ordinary phenolic resins.

For example, a fibrous reinforcing material such as glass fiber, carbon fiber, aramid fiber and cellulose fiber, and glass powder, in addition to the phenol resin of the present invention to which a curing agent is added,
Wood powder, calcium carbonate, mica, silica powder, graphite, PT
One or more fillers selected from powdered fillers such as FE powder and molybdenum disulfide can be added and used as a molding material.

As the base material, paper, cotton cloth, glass fiber mat or woven cloth, synthetic fiber woven cloth or non-woven cloth is used, and the phenolic resin of the present invention (with a curing agent added) is used alone or in an organic solvent for varnishing. It can be used as a laminated material by making a prepreg with the material.

Since such a molding material or laminated material is superior in physical properties such as heat resistance, water resistance, and alkali resistance and is also excellent in insulation property as compared with the case where a phenol resin is used, mechanical parts and electronic / electric parts Can be used for a wide range of applications.

The phenolic resin of the present invention is also used for friction materials such as brake pads and brake linings, abrasive materials,
It can be used as a binder in the production of refractories and the like. It can also be used as a paint, an adhesive or an insulating varnish. Also in these applications, it is preferable to add a curing agent.

The phenolic resin of the present invention can be used as various carbon materials because it becomes glassy carbon when it is heated to a high temperature and carbonized after adding a curing agent such as hexamethylenetetramine to heat the resin. . Further, it can be used for the production of C—C composites by compounding with a carbon material such as carbon fiber and then carbonizing or graphitizing.

Further, the phenolic resin of the present invention can be used as a curing agent for epoxy resin, and can also be used for electronic materials such as sealants for electronic parts such as printed circuit boards and IC packages. In this case, no curing agent such as tetramethylenehexamine is required.

The phenolic resin of the present invention has the following features when it is made into a thermosetting resin by adding a curing agent such as hexamethylenetetramine.

(1) Curability at the same temperature (speed and degree of cure)
However, it is equivalent to the average value of general-purpose novolac type phenolic resin and has excellent curability. In particular, the curability of the resin produced by the second or third production method is high.

(2) Physical properties such as heat resistance, water resistance, and alkali resistance are far superior to those of general-purpose novolac type phenol resin, and phenol aralkyl resin (polycondensation product of phenol / xylylene compound) and phenol / aromatic aldehyde / xylylene It is equivalent to other phenolic heat-resistant resins such as compound co-condensation resins.

(3) The above other phenolic heat-resistant resin is
In order to use many relatively expensive xylylene compounds,
Although the resin price is high and the use is limited, since the resin of the present invention uses inexpensive formaldehyde, the amount of the relatively expensive xylylene compound used can be small, and the resin can be produced at a relatively low raw material cost. it can.

(4) As a result of the above, the resin price is close to that of a general-purpose phenol resin, the curability is equivalent to that of a general-purpose phenol resin, and the heat resistance, water resistance, and alkali resistance are higher than those of a general-purpose phenol resin. The present invention can provide a phenolic resin excellent in

The application advantages of the phenolic heat-resistant resin of the present invention will be illustrated below. (A) For molding materials and laminated materials, heat resistance, water resistance,
A molding material and a laminated material can be produced with the same composition and treatment conditions as in the case of using a general-purpose phenol resin while the alkali resistance and the like are remarkably superior to those of a general-purpose phenol resin.
In addition, molded products and laminated products can be produced by adopting molding processing conditions equivalent to the case of using a general-purpose phenol resin. In other words, it was not necessary to use special measures and restrictions during compounding and molding, which were necessary when using other phenolic heat-resistant resins, and the existing equipment for phenolic resins was almost the same. Since it can be used under conditions, it is extremely useful as a phenolic heat-resistant resin with good productivity.

(B) When used as a curing agent for epoxy resin in electronic materials such as encapsulants for electronic parts and printed circuit boards, it has a low water absorption rate and a suitable glass transition temperature and elastic modulus under heat. However, it has an advantageous feature that it has high curability.

[0100]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but it goes without saying that the present invention is not limited to these examples. In the examples, parts and% are parts by weight and% by weight, unless otherwise specified.

In the examples, [(B) + (C) + (D)] /
The molar ratio of (A) is defined as "crosslinking component molar ratio", (D) / [(B)
The molar ratio of + (C) + (D)] is referred to as the [D component molar ratio]. These molar ratios are values calculated from the amount of each raw material used at the time of charging the raw materials, the amount of unreacted raw materials after the reaction, and the resin yield. The calculated value thus obtained is H-NM
It has been confirmed that the values almost match the analytical values of the R analysis and the IR analysis.

Further, the number average molecular weight of the phenolic resin synthesized in the example is as follows: Shimadzu high performance liquid chromatographic column (KF-802 or KF-804, column layer: CTO-6).
A, detector: differential refractometer RID-6A, standard substance: polystyrene, solvent: THF).

(Example 1) Synthesis of resin of the present invention by the first production method A four-necked flask equipped with a stirrer, a thermometer, a cooler and a N ₂ gas introduction tube was charged with 561.1 parts of phenol and 120.2 parts of benzaldehyde. , P-xylylene glycol dimethyl ether 277.5 parts, 37% formaldehyde aqueous solution (formalin) 111.4 parts, and acid catalyst p-toluenesulfonic acid 3 parts were charged and heated to 80 to 140 ° C for 4 hours while dehydration and methanol removal were carried out. After the reaction, unreacted phenol was removed by a vacuum distillation method to obtain a phenolic resin A containing 3% of free phenol. The cross-linking component molar ratio of this resin was 0.85, the D component molar ratio was 0.32, and the number average molecular weight was 2000.

(Example 2) Synthesis of resin of the present invention by the first production method 597.2 parts of phenol, 134.7 parts of benzaldehyde, p-
Xylylene glycol dimethyl ether 210.9 parts, 37%
Using 154.6 parts of an aqueous formaldehyde solution and 3 parts of p-toluenesulfonic acid, a reaction was carried out in the same manner as in Example 1 to remove unreacted phenol to obtain a phenolic resin B containing 3% of free phenol. The crosslinking component molar ratio of this resin is 0.86, D
The component molar ratio was 0.42, and the number average molecular weight was 2020.

(Example 3) Synthesis of resin of the present invention by the first production method 678.0 parts of phenol, 76.5 parts of benzaldehyde, 167.6 parts of p-xylylene glycol dimethyl ether, 210.5 parts of 37% aqueous formaldehyde solution, p-toluenesulfonic acid 3 Was reacted in the same manner as in Example 1 to remove unreacted phenol to obtain a phenolic resin C containing 3% of free phenol. The crosslinking component molar ratio of this resin was 0.73, the D component molar ratio was 0.60, and the number average molecular weight was 1270.

(Example 4) Synthesis of resin of the present invention by the second production method In the same reactor as in Example 1, 561.1 parts of phenol, 120.2 parts of benzaldehyde, 277.5 parts of p-xylylene glycol dimethyl ether, p of the acid catalyst were added. -Toluenesulfonic acid (3 parts) was charged, heated to 80 to 140 ° C, and allowed to react for 3 hours while dehydrating and removing methanol.

The reaction mixture is then neutralized with an aqueous solution of diethylamine and then with a 37% aqueous formaldehyde solution 111.4.
Parts and 2 parts of zinc chloride as a metal compound catalyst were added, and the mixture was refluxed to 2 parts.
After reacting for a period of time, the temperature was raised to 150 ° C. over 3 hours while dehydrating, and the temperature was maintained at 150 ° C. for 30 minutes to further react. Then, the pressure was reduced to remove unreacted phenol to obtain a phenolic resin D containing 2% of free phenol. The crosslinking component molar ratio of this resin is 0.87, the D component molar ratio is 0.33, and the number average molecular weight is
It was 2100.

(Example 5) Synthesis of resin of the present invention by the second production method 597.2 parts of phenol, 134.7 parts of benzaldehyde, p-
Xylylene glycol dimethyl ether 210.9 parts, 37%
Using 154.6 parts of an aqueous formaldehyde solution, 3 parts of p-toluenesulfonic acid, and 2 parts of zinc acetate as a metal compound catalyst, the reaction was carried out in two steps in the same manner as in Example 4, and then unreacted phenol was removed to release the compound. Phenol resin E containing 2% phenol was obtained. The crosslinking component molar ratio of this resin is 0.8
8, the D component molar ratio was 0.43, and the number average molecular weight was 2340.

(Example 6) Synthesis of resin of the present invention by the second production method Phenol 632.0 parts, benzaldehyde 111.5 parts, p-
Xylylene glycol dimethyl ether 180.8 parts, 37%
After using 194.0 parts of an aqueous formaldehyde solution, 3 parts of p-toluenesulfonic acid, and 3 parts of zinc acetate as a metal compound catalyst, a two-step reaction was carried out in the same manner as in Example 4, and then unreacted phenol was removed to release the compound. Phenol resin F containing 3% of phenol was obtained. The crosslinking component molar ratio of this resin is 0.8
2, the D component molar ratio was 0.52, and the number average molecular weight was 1800.

Example 7 Synthesis of Resin of the Present Invention by Second Production Method Phenol 678.0 parts, benzaldehyde 76.5 parts, p-xylylene glycol dimethyl ether 167.6 parts, 37% aqueous formaldehyde solution 210.5 parts, p-toluenesulfonic acid 3 Parts and 3 parts of a metal compound catalyst, zinc acetate, were reacted in two steps in the same manner as in Example 4, and then unreacted phenol was removed to obtain a phenolic resin G containing 3% of free phenol. . The crosslinking component molar ratio of this resin is 0.7
5, the D component molar ratio was 0.60, and the number average molecular weight was 1350.

(Example 8) Synthesis of resin of the present invention by the second production method 704.2 parts of phenol, 99.5 parts of benzaldehyde, 79.4 parts of p-xylylene glycol dimethyl ether, 316.0 parts of 37% aqueous formaldehyde solution, p-toluenesulfonic acid 3 Parts and 3 parts of the metal compound catalyst zinc acetate,
After reacting in two steps in the same manner as in Example 4, unreacted phenol was removed to obtain a phenolic resin H containing 2% of free phenol. The crosslinking component molar ratio of this resin is 0.82, D
The component molar ratio was 0.73, and the number average molecular weight was 1810.

Example 9 Synthesis of Resin of the Present Invention by Second Production Method In this example, a xylylene compound was first reacted with phenol without catalyst. The same reactor as in Example 1 was charged with 587.1 parts of phenol and 269.4 parts of p-xylylene chloride, heated to 120 ° C without a catalyst, and dehydrochlorinated while 4
Allowed to react for hours. Continuously, benzaldehyde 111.0g
And 2.8 parts of p-toluenesulfonic acid as an acid catalyst are added, and the mixture is reacted under reflux for 1 hour, and then dehydrated.
The reaction in the first step was completed by heating at 0 to 140 ° C. for 2 hours.

The reaction mixture is then neutralized with an aqueous solution of diethylamine and then with a 10% aqueous solution of formaldehyde 109.9%.
Parts and 3.0 parts of zinc oxide as a metal compound catalyst were added, and the mixture was reacted under reflux for 2 hours, then heated to 150 ° C. in 3 hours while dehydrating, and kept at 150 ° C. for 30 minutes for further reaction. Then, the pressure was reduced to remove unreacted phenol, and a phenol resin I containing 3.8% of free phenol was obtained. The cross-linking component molar ratio of this resin was 0.79, the D component molar ratio was 0.34, and the number average molecular weight was 1410.

(Example 10) Synthesis of resin of the present invention by the third production method In the same reactor as in Example 1, 561.1 parts of phenol, 37%
111.4 parts of aqueous formaldehyde solution and 1 part of zinc acetate as a metal compound catalyst were charged, reacted for 2 hours under reflux, then heated to 150 ° C for 3 hours while dehydrating, and then heated to 150 ° C for 30 minutes.
The reaction was held for a further time to further react, and the first step was completed.

Benzaldehyde 1 was added to the resulting reaction mixture.
20.2 parts, p-xylylene glycol dimethyl ether 2
77.5 parts, p-toluenesulfonic acid 2 parts were charged, dehydrated,
After the reaction was carried out at 100 to 140 ° C. for 3 hours while removing methanol, unreacted phenol was removed by a vacuum distillation method to obtain a phenolic resin J containing 4% of free phenol. The cross-linking component molar ratio of this resin was 0.85, the D component molar ratio was 0.32, and the number average molecular weight was 1980.

(Example 11) Synthesis of resin of the present invention by the third production method 626.2 parts of phenol, 84.7 parts of benzaldehyde, 199.1 parts of p-xylylene glycol dimethyl ether, 243.1 parts of 37% aqueous formaldehyde solution, p-toluenesulfonic acid 2 Parts and 1 part of zinc acetate, the reaction was carried out in two steps in the same manner as in Example 10, and then unreacted phenol was removed to obtain a phenolic resin K containing 3% of free phenol. The cross-linking component molar ratio of this resin is 0.88, and the D component molar ratio is
It was 0.60 and the number average molecular weight was 1950.

(Example 12) Synthesis of resin of the present invention by the third production method 761.6 parts of phenol, 44.7 parts of benzaldehyde, 103.5 parts of p-xylylene glycol dimethyl ether, 243.8 parts of 37% aqueous formaldehyde solution, p-toluenesulfonic acid 2 Parts and 1 part of zinc acetate, the reaction was carried out in two steps in the same manner as in Example 10, and then unreacted phenol was removed to obtain a phenolic resin L containing 3% of free phenol. The crosslinking component molar ratio of this resin is 0.65, and the D component molar ratio is
The number average molecular weight was 0.74 and 805.

Comparative Example 1 Synthesis of general-purpose phenol-formaldehyde resin In the same reactor as in Example 1, 817.4 parts of phenol and 37% were added.
493.5 parts of formaldehyde aqueous solution and 0.5 part of p-toluenesulfonic acid were charged and reacted under reflux for 3 hours, then heated to 150 ° C while dehydrating and further reacted. Then, the unreacted phenol was removed by vacuum distillation to obtain a novolac-type phenol-formaldehyde resin having a free phenol of 3% and a number average molecular weight of 2060 (coupling mode was that the o-substituted product and the p-substituted product coexist randomly). It was This resin is referred to as comparative resin a. (Comparative Example 2) Synthesis of high orthophenol-formaldehyde resin In the same reactor as in Example 1, 817.4 parts of phenol and 37% were added.
Charge 493.5 parts of formaldehyde aqueous solution and 1.5 parts of zinc acetate, react under reflux for 3 hours, and then dehydrate. The reaction was further heated by heating to 160 ° C. for an hour. Then, unreacted phenol was removed by a vacuum distillation method to obtain a novolac type phenol-formaldehyde resin having a free phenol of 3% and a number average molecular weight of 2130 (coupling mode was a high ortho type having a large proportion of o-substituted product). This resin is referred to as comparative resin b.

(Comparative Example 3) Synthesis of phenol aralkyl resin In the same reactor as in Example 1, 447.2 parts of phenol, p-
Xylylene glycol dimethyl ether 552.8 parts, p-
After charging 4 parts of toluenesulfonic acid and reacting for 3 hours at 100 to 140 ° C while removing methanol, unreacted phenol was removed by vacuum distillation to obtain 3% free phenol and phenol aralkyl resin having a number average molecular weight of 1850. Got This resin is referred to as a comparative resin c.

Comparative Example 4 Phenol / benzaldehyde / xylylene compound co-condensation
Synthesis of compound resin In the same reactor as in Example 1, 496.8 parts of phenol, p-
307.1 parts of xylylene glycol dimethyl ether, 196.1 parts of benzaldehyde, and 4 parts of p-toluenesulfonic acid were charged and allowed to react for 3 hours at 100 to 140 ° C while dehydrating and removing methanol, and then unreacted phenol was removed by vacuum distillation. Thus, a resin having 2% free phenol and a number average molecular weight of 1830 was obtained. This resin is referred to as comparative resin d.

Comparative Example 5 Phenol / formaldehyde / xylylene compound shrinkage
Synthesis of compound resin In the same reactor as in Example 1, 525.3 parts of phenol, p-
Xylylene glycol dimethyl ether 436.1 parts, 37%
Charge 104.2 parts of formaldehyde aqueous solution and 2 parts of p-toluenesulfonic acid, and 100-140 while removing methanol.
After reacting for 3 hours at 0 ° C., unreacted phenol was removed by vacuum distillation to obtain a resin having 4% free phenol. This resin is referred to as a comparative resin e. The D component molar ratio of this resin is 0.
33, the number average molecular weight is 1800.

Comparative Example 6 Blend of Comparative Resin a and Comparative Resin d (25:75) 75 parts of phenol / benzaldehyde / xylylene compound co-condensation resin synthesized in Comparative Example 4 and random bond synthesized in Comparative Example 1 25 parts of the novolac-type phenol-formaldehyde resin of was mixed to obtain a comparative blend resin (a). The proportion of —CH ₂ — bonds in this blend resin
(That is, the D component molar ratio) is 0.33.

Comparative Example 7 Blend of Comparative Resin b and Comparative Resin d (25:75) 75 parts of phenol / benzaldehyde / xylylene compound co-condensation resin synthesized in Comparative Example 4 and high ortho type synthesized in Comparative Example 2 25 parts of the novolac-type phenol-formaldehyde resin of was mixed to obtain a comparative blend resin (b). The proportion of —CH ₂ — bonds in this blend resin
(That is, the D component molar ratio) is 0.33.

Comparative Example 8 Blend of Comparative Resin b and Comparative Resin d (50:50) 50 parts of phenol / benzaldehyde / xylylene compound co-condensation resin synthesized in Comparative Example 4 and high ortho type synthesized in Comparative Example 2 50 parts of the novolac type phenol-formaldehyde resin of No. 3 was mixed to obtain a comparative blend resin (C). The proportion of —CH ₂ — bonds in this blend resin
(That is, the molar ratio of D component) is 0.60.

Comparative Example 9 Blend of Comparative Resin b and Comparative Resin d (62:38) 38 parts of phenol / benzaldehyde / xylylene compound co-condensation resin synthesized in Comparative Example 4 and high ortho type synthesized in Comparative Example 2 And 62 parts of the novolac type phenol-formaldehyde resin of Comparative Example 2 were mixed to obtain a comparative blend resin (d). The proportion of —CH ₂ — bonds in this blend resin
(That is, the D component molar ratio) is 0.73.

Comparative Example 10 Blend of Comparative Resin b and Comparative Resin c (50:50) 50 parts of phenol aralkyl resin synthesized in Comparative Example 3,
Comparative blend resin (e) was obtained by mixing with 50 parts of the high ortho type novolak type phenol-formaldehyde resin synthesized in Comparative Example 2. In this blend resin,
CH ₂ - bond ratio of (i.e., D component molar ratio) is 0.60.

The curability, water resistance (moisture absorption rate), moldability, bending characteristics, long-term heat resistance, and gelling time of each resin or blend resin obtained in the above Examples and Comparative Examples were determined as follows. Tested.

(Test method) (1) Curastometer Curability test Add 15 parts of hexamethylenetetramine to 100 parts of the resin sample and grind to 150 mesh or less, and then weigh 3.5 g of curastometer (Orientec VPS type). Set to 170
The maximum torque (kg ・ cm) and the torque when the torque rises to 20% and 80% of the maximum torque are shown in the chart at 20 ° C with a load of 3.5 kgf / cm ³ and an amplitude angle of ± 1/4 °. The ascent rate (kg · cm / min) was calculated from the chart. The curability was evaluated using the maximum torque as the degree of cure and the torque increase rate as the cure rate.

(2) Moisture absorption rate (water resistance) 15 parts of hexamethylenetetramine was added to 100 parts of the test resin, and the mixture was ground to 150 mesh or less, and then heated at 200 ° C for 3 hours and then at 250 ° C for 2 hours. After curing, the resulting cured resin is crushed and sieved to a particle size of 16 to 30 mesh, and placed under an atmosphere of relative humidity of 85% and temperature of 30 ° C until a constant weight is reached, and the weight is increased. The rate of moisture absorption was calculated as the moisture absorption rate.

(3) Moldability test 100 parts of resin sample was mixed with hexamethylenetetramine 12
Part, 80 parts of glass fiber, 80 parts of calcium carbonate and 2 parts of zinc stearate were mixed and kneaded on a hot roll to produce a trial molding material having a constant flowability.

This molding material was molded in a transfer molding machine into a flat plate having a length of 80 mm, a width of 10 mm and a height of 4 mm under the conditions of a mold temperature of 175 ° C., a holding time of 20 seconds, 30 seconds and 60 seconds. Immediately after demolding, the Barcol hardness (JIS-K7060, type:
GYZJ935) was measured and the moldability was evaluated from the hardness value. If the hardness is low, defective demolding or deformation during demolding occurs, and a good quality molded product cannot be produced with good workability.

(4) Bending Property The molded product prepared in (3) was heated to 180 ° C. for 2 hours to be cured, and subsequently heated at 200 ° C. for 2 hours, 230 ° C. for 2 hours, and further 250 ° C. for 5 hours. Then, it was post-cured. The flexural strength and flexural modulus of the obtained cured product were measured according to JIS-K6911.

(5) Long-term heat resistance The molded product produced in (3) was heat-cured and post-cured in the same manner as the above bending test piece, and then 1,000 times in air at a temperature of 250 ° C.
Left for hours. Then, measure the weight of the test piece, and
The same bending test as in (4) was performed, and the long-term heat resistance was evaluated by obtaining the weight retention rate, flexural strength retention rate, and flexural modulus retention rate.

(7) Gelation time According to JIS-K6910, the gelation time was measured at temperatures of 150 ° C and 170 ° C. The contents of the resins of Examples and Comparative Examples are summarized in Tables 1 and 2, and the test results are summarized in Table 3.

[0135]

[Table 1]

[0136]

[Table 2]

[0137]

[Table 3]

As is apparent from Table 3, the phenolic resins A to L of the present invention synthesized in Examples 1 to 12 have the following features as compared with the phenolic resins or blended resins of Comparative Examples. .

(1) Other curable curable phenols such as phenol aralkyl resin of Comparative Example 3, phenol / benzaldehyde / xylylene compound co-condensation resin of Comparative Example 4, phenol / formaldehyde / xylylene compound co-condensation resin of Comparative Example 5 Superior to heat-resistant resins. In particular, the resins C, G, H, and L are the random phenols of Comparative Example 1-
Excellent curability similar to formaldehyde resin.

(2) Due to its excellent curability, the moldability represented by the Barcol hardness immediately after molding is superior to the other phenolic heat-resistant resins of Comparative Examples 3-5. Resin C, F, G,
H, K, and L have the same moldability as the random type phenol-formaldehyde resin of Comparative Example 1.

(3) On the other hand, a phenol aralkyl resin of Comparative Examples 6 to 10 or a blend resin of a phenol / benzaldehyde / xylylene compound co-condensation resin and a phenol-formaldehyde resin (ie, a conventional phenol containing no methylene component derived from formaldehyde). When the heat-resistant resin and a blend of a phenol-formaldehyde resin are compared at the same D component molar ratio, the phenolic resin of the present invention is excellent in curability and moldability, which shows the significance of the present invention.

(4) The moisture absorption rate is about 1/2 of that of the phenol-formaldehyde resins of Comparative Examples 1 and 2, and the moisture resistance is excellent.

(5) Long-term heat resistance is remarkably superior to the phenol-formaldehyde resins of Comparative Examples 1 and 2. Excellent long-term heat resistance, which is almost equal to or higher than that of the conventional phenolic heat-resistant resin having the best heat resistance, such as the phenol aralkyl resin of Comparative Example 3 and the phenol / benzaldehyde / xylylene compound co-condensation resin of Comparative Example 4, is obtained. There is. In detail, due to the increase in the proportion of —CH ₂ — groups due to the copolymerization of formaldehyde, the heat resistance may slightly decrease, but the resins C, G, H,
K and L are slightly inferior to Comparative Example 4, and in other cases, they are equal to or higher than the conventional phenolic heat-resistant resin. The long-term heat resistance of the phenol / formaldehyde / xylylene compound co-condensation resin of Comparative Example 5 is
Although much higher than the phenol-formaldehyde resin, it is lower than the phenolic resin of the present invention and the phenolic resins of Comparative Examples 3 and 4.

(6) On the other hand, the long-term heat resistance is compared with the conventional phenolic heat-resistant resins containing no methylene component derived from formaldehyde of Comparative Examples 6 to 10 and phenol-formaldehyde resin blends at the same D component molar ratio. Thus, the phenolic heat-resistant resin of the present invention is considerably high (in particular, the retention rate of bending properties), which shows the significance of the present invention.

[0145]

EFFECTS OF THE INVENTION Conventional phenolic heat-resistant resins, which are generally excellent in heat resistance and moisture resistance, like the phenolic heat-resistant resins taken up in Comparative Examples, have poor curability, and therefore have a much better moldability than phenol-formaldehyde resins. It was common to be inferior. Contrary to this wisdom, the phenolic heat-resistant resin of the present invention has remarkably improved moldability while maintaining the same level of heat resistance and moisture resistance as conventional phenolic heat-resistant resins. That is, both heat resistance and curability of the phenolic resin could be realized.

Moreover, since formaldehyde is added as a reaction component, the raw material cost is lower than that of the conventional phenolic heat-resistant resin. As described above, the present invention contributes to the expansion of applications of the phenolic resin, and opens the way to use the phenolic resin even in the field where a very expensive resin such as a polyimide resin has been conventionally used.

[Brief description of drawings]

1 (a) and 1 (b) are schematic views showing curability and heat resistance of a phenolic heat-resistant resin of the present invention and a comparative blend resin, respectively.

Claims (5)

[Claims] 1. A phenol component (A) derived from a phenol compound, a xylylene component (B) represented by the formula (1), a phenylmethine component (C) represented by the formula (2), and a formula. It is composed of a repeating unit in which a methylene component (D) represented by (3) is bonded, and [(B) + (C) + (D)] /
The molar ratio of (A) is within the range of 0.4 to 0.95, and (D) /
A phenolic heat-resistant resin having a number average molecular weight of 500 to 5000, wherein the molar ratio of [(B) + (C) + (D)] is in the range of 0.1 to 0.9. Embedded image In the above formula, R ₁ is a methyl group or an ethyl group, a is 0, 1 or 2, Ar is a phenyl group or 2 to
A tricyclic polycyclic aromatic group having 1 to 2 of each aromatic nucleus of Ar.
Each hydrogen atom may be substituted with a substituent selected from an alkyl group having 1 to 4 carbon atoms, a halogen group and a hydroxyl group. 2. The phenolic heat-resistant resin according to claim 1, wherein the phenol compound is reacted with xylylene glycol or a reactive derivative thereof, an aromatic aldehyde, and formaldehyde or a derivative thereof in the presence of an acid catalyst. Production method. 3. A phenol compound is reacted with xylylene glycol or a reactive derivative thereof and an aromatic aldehyde in the presence of an acid catalyst, the reaction mixture is neutralized, and then a salt or hydroxide of a divalent metal. The method for producing a phenolic heat-resistant resin according to claim 1, wherein formaldehyde or a derivative thereof is reacted in the presence of a catalyst selected from the group consisting of an oxide, an oxide, and an oxide of a trivalent metal. 4. A phenol compound is reacted with formaldehyde or a derivative thereof in the presence of a catalyst selected from the group consisting of salts of divalent metals, hydroxides and oxides, and oxides of trivalent metals. The method for producing a phenolic heat-resistant resin according to claim 1, wherein the reaction mixture is reacted with xylylene glycol or a reactive derivative thereof and an aromatic aldehyde in the presence of an acid catalyst. 5. A xylylene glycol or a reactive derivative thereof is a xylylene dihalide, which is a reaction partner phenol compound or reaction mixture prior to other reaction components with which the xylylene dihalide is reacted together. The method according to any one of claims 2 to 4, wherein the reaction is carried out in advance without a catalyst.