JPH1121419A - Phenolic resin composition and method for producing phenolic resin - Google Patents

Abstract

(57) [Summary] [Problem] As an epoxy resin curing agent, flame retardancy, heat resistance,
Can provide a cured product with excellent moisture resistance and metal adhesion, excellent friction and dielectric properties, excellent low-temperature stamping workability, etc., and can be used for glass epoxy laminates, IC sealing materials, friction materials, etc. A phenolic resin composition is provided. SOLUTION: The phenolic resin composition comprising a triazine-modified novolak resin, the resin forming units _{(-NH-CH 2 -Ph -)} / structural units (-NH-CH ₂
A phenolic resin composition comprising -NH-) in a molar ratio of 1.5 or more;
And a binder for an epoxy resin curing agent, a binder for a friction material, and a binder for a paper base laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenolic resin composition and a method for producing a phenolic resin, and more particularly to a curing method which is excellent in flame retardancy, heat resistance, moisture resistance, metal adhesion, etc. when used as an epoxy curing agent. It is suitable for various applications using epoxy resin such as encapsulation, lamination, paint, etc., especially for glass epoxy laminates and IC encapsulants. Furthermore, it has excellent friction and dielectric properties. It is suitable for friction material use and molding material use using a compound containing a compound containing an ethylenically unsaturated group as a curing agent, and also in combination with a resole resin, can provide a cured product excellent in low-temperature punching workability and flame retardancy, The present invention relates to a phenol resin composition suitable for a paper base laminate and a method for producing a phenol resin.

[0002]

2. Description of the Related Art Epoxy resins are widely used mainly in electric and electronic material parts because of their excellent electrical properties.

[0003] These electrical and electronic material parts are required to have high flame retardance as typified by glass epoxy laminates and IC encapsulants, but since epoxy resins alone cannot provide a sufficient effect, these epoxy resins are not used. At present, many halogen-based flame retardants are used in combination.

However, in recent years, the toxicity of organic halogen substances typified by dioxin has become a serious problem, and the adverse effects of halogens on long-term reliability in IC packages have been reduced. There is a strong demand for flame retardants using other compounds that can be substituted for halogens or other flame retardant formulations.

Therefore, for example, a method of adding a flame retardant such as a phosphorus compound has been devised. According to this method, the flame retardancy is improved, but the basic properties of the resin such as heat resistance and moisture resistance are improved. It has the disadvantage of impairing physical properties.

[0006] To solve this drawback, Japanese Patent Laid-Open Publication No. 8-31
No. 1142 proposes to use a phenol composition modified with a compound having a triazine ring as a curing agent as an epoxy resin curing agent.

However, when this compound is used as a curing agent, the bond between the phenol and the triazine compound is not sufficient, so that the resulting cured product exhibits flame retardant effects, but still has insufficient properties such as heat resistance and moisture resistance. However, this does not solve the above-mentioned problem.

In addition, the conventional thermosetting resin composition for a friction material using hexamethylenetetramine as a curing agent also has a so-called “squealing” problem, and the problem has not been solved even by using the above technique. .

Further, when used in a paper base laminate, although it exhibits a flame retardant effect, it has a problem that the low-temperature punching workability is insufficient.

[0010]

According to the present invention, when used as an epoxy resin curing agent, flame retardancy is improved without using halogen, and flame retardancy, heat resistance, moisture resistance, and metal adhesion are improved. Suitable for various applications using epoxy resin such as encapsulation, lamination, paint, etc., especially for glass epoxy laminates and IC encapsulants, containing hexamethylenetetramine and ethylenically unsaturated groups When a compound is used as a curing agent, it has excellent friction and dielectric properties, is suitable for friction materials and molding materials, and when combined with a resole resin, can give a cured product with excellent low-temperature punching workability and flame retardancy. An object of the present invention is to provide a phenol resin composition and a method for producing a phenol resin which are suitable for use as a paper base laminate.

[0011]

Means for Solving the Problems The inventors of the present invention have made intensive studies in view of the above-mentioned circumstances, and as a result, have found that a phenol resin composition containing a novolak resin having a specific ratio of phenols to triazines has the above-mentioned ratio. The inventors have found that solving the problem has been accomplished, and have completed the present invention.

That is, [I] the present invention relates to a phenol resin composition comprising a triazine-modified novolak resin comprising a phenol, a triazine and an aldehyde, wherein the novolak resin comprises a phenol and a triazine. From condensates with aldehydes (a), condensates of triazines with aldehydes (b), condensates of phenols with aldehydes (c), mixtures of phenols (d) and triazines (e) And the condensate (a)
And a state in which, in the condensate (b), the structural unit A represented by the general formula (1) and the structural unit B represented by the general formula (2) satisfy the following formula (3) in a molar ratio. there is provided a phenolic resin composition, characterized in that it contains in, (-NH- -X-NH-CH 2) (1) (-X-NH-CH 2 -Y-) ( 2) (wherein X represents a residue of a triazine, and Y represents a residue of a phenol) B / A ≧ 1.5 (3) [II] The present invention relates to a condensate (a) and a condensate The present invention provides the phenolic resin composition according to the above [I], wherein the molar ratio of the triazines in (b) is 30% or more of the total triazines. [III] [I] is one or more selected from the group consisting of, acetoguanamine and benzoguanamine. Which provides a phenolic resin composition of the formula [I]
V] The present invention further comprises a curing agent, wherein the curing agent is hexamethylenetetramine or a compound having at least two ethylenically unsaturated groups in the molecule. [V] The present invention provides a phenolic resin composition according to the above [I] further comprising a resole resin, and [VI] The present invention provides the above [I] [VII] The present invention provides a binder for a friction material comprising the phenolic resin composition described in the above [I] as a main component. [VIII] The present invention provides a binder for a paper base laminate mainly comprising the phenolic resin composition according to the above [I],
[IX] In the present invention, a step (i) of adjusting a pH of a system of a mixture of phenols, triazines and aldehydes to 5 to 10 and a step of reacting the mixture under conditions in which the aldehydes do not volatilize ( ii) and a step (iii) of removing water of reaction in the system, wherein step (i) step (i)
i) and step (iii) are sequentially performed, and then step (ii) and step (iii) are sequentially performed at a higher temperature than the first step as a second step reaction, and step (ii) is performed as a third step reaction And the step (iii) is carried out at a higher temperature than the second-stage reaction, and further, if necessary, the second-stage reaction and the third-stage reaction are repeatedly carried out to convert the dimethylene ether bond in the molecule into a methylene bond. [X] The present invention provides a method for producing a triazine-modified novolak-type phenol resin, wherein the molar ratio of the phenol or triazine to the aldehyde is 1: 0.2. ~ 0.9
And a process for producing the triazine-modified novolak phenolic resin according to the above [X].

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The phenols for obtaining the phenolic resin composition of the present invention are not particularly limited, and include, for example, phenol or cresol, xylenol, ethylphenol, butylphenol, nonylphenol, octylphenol and the like. Examples include alkylphenols, polyphenols such as bisphenol A, bisphenol F, bisphenol S, resorcin, and catechol, halogenated phenols, phenylphenols, and aminophenols. The use of these phenols is not limited to one kind alone, and two or more kinds can be used in combination.

The compound containing a triazine ring used in the phenolic resin composition of the present invention is not particularly limited, and may have any structure as long as it has a triazine ring. Melamine, acetoguanamine or benzoguanamine is preferred. preferable.

The use of these triazine ring-containing compounds is not limited to one kind, and two or more kinds can be used in combination. Aldehydes for obtaining the phenolic resin composition of the present invention are not particularly limited, but formaldehyde is preferred from the viewpoint of easy handling. Formaldehyde includes, but is not limited to, formalin, paraformaldehyde, and the like as typical sources.

The novolak resin in the present invention refers to a resin substantially not containing a methylol group, and is characterized by containing no unreacted aldehyde. When used as a curing agent for an epoxy resin by substantially not containing a methylol group and not containing an unreacted aldehyde, there is an effect that the mixing stability with the epoxy resin is extremely improved.

The amount of the unreacted monofunctional phenol monomer contained in the novolak resin of the present invention is not particularly limited, but is preferably 3% by weight or less. By reducing the amount of the unreacted monofunctional phenol monomer to 3% by weight or less, the mixing stability with the epoxy resin is improved, and the heat resistance and moisture resistance of the obtained cured epoxy resin are improved.

The term "unreacted monofunctional phenol monomer" as used herein means a phenol monomer containing only one phenolic hydroxyl group capable of reacting with an epoxy group in one molecule. Further, the phenolic resin composition of the present invention contains a triazine-modified novolak resin composed of phenols, triazines, and aldehydes. Among the novolak resins, a condensate of phenols, triazines, and aldehydes (A) In a condensate (b) of a triazine and an aldehyde, a structural unit A represented by the general formula (1)
And the structural unit B represented by the general formula (2) are contained in a state satisfying the following formula (3) in a molar ratio.

(—X—NH—CH ₂ —NH—) (1) (—X—NH—CH ₂ —Y—) (2) (wherein, X represents a residue of a triazine, and Y represents phenol. B / A ≧ 1.5 (3) B / A ≧ 3 is more preferable. B / A
If it is <1.5, the compatibility with the epoxy resin and the reactivity with hexamethylenetetramine and the like become poor, and the heat resistance and the frictional properties are reduced.

Structural units A and B defined in the present invention
The molar ratio to the nuclear magnetic resonance spectrum (hereinafter 13C-N
MR). That is, dimethyl sulfoxide (hereinafter referred to as DM
SO) or heavy acetone, and tetramethylsilane as a reference substance, and measured according to conventional measurement conditions, the peak of the structural unit B appears at 42.5 to 45 ppm in the 13 C-NMR chart, and the structural unit A It has been known that the peak of 47 to 48.5 ppm appears, and the molar ratio between the structural unit A and the structural unit B can be determined by calculating the ratio of the peak integrated values of the two.

In the triazine-modified novolak resin of the present invention, the molar ratio of the triazines in the condensate (a) and the condensate (b) is not particularly limited, but is not less than 30% of all the triazines. Is preferred. Here, if it is 30% or less, heat resistance and moisture resistance are reduced.

The molar ratio of the triazine is the same as that of the structural unit A
Similarly to the case of the structural unit B, it can be determined from a 13 C-NMR chart. That is, 167.2-1 of the chart
A sharp peak appearing at 67.4 ppm can be assigned to unreacted triazines, and the peak integrated value is defined as Tm.
A broad peak appearing at 163 to 167.2 ppm can be assigned to triazines reacted with formaldehyde,
Assuming that the peak integral value is Tr, the molar ratio of the triazines in the precondensate (a) and the condensate (b) in all the triazines can be represented by the following formula (4). The value of this molar ratio is hereinafter referred to as "reaction rate of triazines".

Next, a typical production method for obtaining the triazine-modified novolak resin of the present invention will be described below. That is, a step (i) of adjusting the pH of the system to a mixture of phenols, triazines and aldehydes to 5 to 10; a step (ii) of reacting the mixture under conditions where the aldehydes do not evaporate; Step (iii) of removing the reaction water, and the step (i) of the step (i)
i) and step (iii) are sequentially performed, and then step (ii) and step (iii) are sequentially performed at a higher temperature than the first step as a second step reaction, and step (ii) is performed as a third step reaction And step (iii) is carried out at a higher temperature than in the second stage reaction.

First, a mixture of phenols, triazines, and aldehydes is adjusted to a system pH of 5 to 10 (i), and the mixture is reacted under conditions in which the aldehydes do not volatilize (ii). The step (iii) of removing the reaction water in the system will be described.

In the step (i), the above-mentioned phenol, aldehyde and triazine are mixed and the pH of the system is adjusted to 5 to 5.
10, preferably a step of adjusting the pH to 7 to 9. p
As long as H can be adjusted within the above range, the use of a catalyst is not particularly necessary, but a catalyst composed of a basic compound or a weakly acidic compound can be appropriately added to the system.

As the catalyst, for example, sodium hydroxide,
Hydroxides of alkali metals and alkaline earth metals such as potassium hydroxide and barium hydroxide, and these oxides, basic catalysts such as ammonia, primary to tertiary amines, hexamethylenetetramine and sodium carbonate, zinc acetate ,
Examples include weakly acidic catalysts such as zinc naphthenate and manganese octylate. Among these catalysts, it is more preferable to use amines such as triethylamine and triethanolamine.

The reaction order of the respective raw materials is not particularly limited. Triazines may be added to phenols and aldehydes later, or phenols may be added to phenols and triazines, but the effects of the present invention are achieved. For this purpose, it is preferable to simultaneously add phenols, aldehydes and triazines and react them. At this time, the molar ratio of aldehydes to phenols and triazines is not particularly limited, but is preferably 1: 0.2 to 0.9,
1: 0.4 to 0.7 is more preferable. The weight ratio of the triazine to the phenol is not particularly limited, but is preferably from 10 to 98:90 to 2, and more preferably from 30 to 9
5: 70-5 is more preferred. When the weight ratio of the phenols is 10% by weight or less, it becomes difficult to convert the phenol into a resin.
If the content is more than 10% by weight, a sufficient flame-retardant effect cannot be obtained.

Step (ii) is a step in which the mixture is reacted under the above-mentioned pH conditions and in the presence of the above-mentioned catalyst without volatilizing the aldehyde. The condition under which the aldehyde is not volatilized refers to a distillation condition for returning volatile components in the system to the system, and refers to a case where the reaction is carried out near the boiling point of a low-boiling substance in the system. By reacting all of the aldehydes, a resin designed at a charged molar ratio can be stably obtained with good reproducibility.

At the time of this reaction, the reaction can be carried out in the presence of various solvents from the viewpoint of reaction control. Although it does not specifically limit as a solvent, For example, acetone, MEK, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-
Examples include dimethylformamide, methanol, and ethanol. These solvents can be used alone or as a mixed solvent of two or more kinds as appropriate.

Thereafter, if necessary, washing with water is performed to remove catalyst residues and impurities. Step (iii) is a step of removing reaction water, solvent, and the like in the system according to a conventional method such as atmospheric distillation. In order to remove reaction water and the like, it is preferable to gradually heat the temperature in the system in step (iii) to 120 ° C. or higher.

In the present invention, the above-mentioned step (i), step (ii) and step (iii) are carried out sequentially as a first step reaction, and then step (ii) and step (iii) are carried out as a second step reaction. 1
Steps (ii) and (iii) are carried out at a higher temperature than the second-stage reaction as a third-stage reaction.

That is, the reaction is carried out so that the aldehydes in the system are not volatilized. Then, the reaction water and the solvent in the system are removed according to a conventional method such as atmospheric distillation, and then the aldehydes in the system are not volatilized again. And react
Thereafter, the removal of the reaction water, the solvent, and the like in the system according to a conventional method such as atmospheric distillation is repeated twice or more with the temperature raised from the former stage.

In the third step (iii), the reaction is carried out at 150 ° C.
As described above, preferably, the reaction water and the like are removed by performing distillation at 170 ° C. or more under vacuum. At this time, unreacted formaldehyde and unreacted phenolic monomers can be removed together with the water.

Further, if necessary, step (ii) and step (iii) can be repeated again. By the second and third reactions, the dimethylene ether bond formed by condensation between the methylol groups can be converted into a methylene bond, and the bond ratio between phenols and triazines, which is a feature of the novolak resin of the present invention. Not only can be obtained, but also the molecular weight of the resin can be appropriately controlled.
In the present invention, step (ii) and step (iii) are repeated in a second-stage reaction and a third-stage reaction, and further, if necessary, the number of repetitions is preferably 2 to 3 times. To the third stage reaction or the fourth stage reaction.

The phenolic resin composition of the present invention can be used as a curing agent for epoxy resins. Examples of the epoxy resin in this case include bisphenol A type epoxy resin, polyphenol type epoxy resin, aliphatic epoxy resin, aromatic ester type epoxy resin, cycloaliphatic ester type epoxy resin, aliphatic ester type epoxy resin, and ether ester type. Examples include epoxy resins, non-glycidyl epoxy resins such as epoxidized soybean oil, and halogen-substituted products thereof such as bromine and chlorine. These epoxy resins may be used singly or as a mixture of several types. The solvent used for the epoxy resin composition at this time is not particularly limited, and examples thereof include various solvents described above. Further, various additives, flame retardants, fillers, and the like can be appropriately compounded as needed.

The mixing ratio of the epoxy resin and the phenolic resin composition of the present invention is not particularly limited, but
The phenolic hydroxyl group equivalent of the phenolic resin composition is preferably 0.5 to 2.0 equivalents to 1 equivalent of the epoxy group,
0.9 to 1.4 equivalents are more preferred.

In curing the epoxy resin, various curing accelerators generally used for curing epoxy compounds can be used, if necessary.
Examples of the curing accelerator include imidazole and its derivatives, phosphine compounds, amines, and BF ₃ amine compounds.

Further, the phenolic resin composition of the present invention can be used for a friction material, a molding material or the like by blending a curing agent. The curing agent is not particularly limited,
Examples thereof include substances that generate formaldehyde by heating, such as hexamethylenetetramine and paraformaldehyde, and compounds containing two or more ethylenically unsaturated groups, such as bisallylnadic imide, bismaleimide, and diacrylate. Of these, hexamethylenetetramine or bismaleimide is preferred. If necessary, a curing accelerator can be used in combination with these curing agents. As the curing accelerator, it is possible to use various substances generally used for curing epoxy compounds as described above.

A friction material using the phenolic resin composition of the present invention as a binder for a friction material is obtained by adding a fiber base material and a curing agent to the phenolic resin composition and thermally curing the friction material according to a conventional method. be able to. At this time, as the fiber substrate, for example, glass fiber, ceramic fiber, asbestos fiber, carbon fiber, inorganic fibers such as stainless steel fiber,
Examples include natural fibers such as cotton and hemp, and synthetic organic fibers such as polyester and polyamide. These fibers may be used alone or in combination of two or more. Among these, considering performance, price, etc.,
Those mainly composed of glass fibers are preferred. The shape of the fibrous base material is not limited at all, and any shape such as short fibers, long fibers, yarns, mats, and sheets may be used. As the curing agent, those described above can be used.

The conditions for the thermal curing of the composition are not particularly limited, and the composition can be cured under ordinary conditions for curing a phenol resin. That is, it is usually performed at a temperature of 120 ° C. or more and 200 ° C. or less, which is the temperature at which the resin component softens. In order not to cause molding failure, 130 to 18
It is preferable to carry out in the range of 0 ° C. In order to obtain a friction material having further excellent heat resistance, it is preferable to perform firing after molding.

When the phenolic resin composition of the present invention is used as a friction material, a filler, an additive and the like can be further added. As the fillers and additives, generally known ones can be used, for example, silica, barium sulfate, calcium carbonate, silicon carbide, cashew oil polymer, molybdenum disulfide, aluminum hydroxide, talc, clay, graphite , Graphite, rubber particles, aluminum powder,
Copper powder, brass powder and the like can be mentioned. These fillers and the like may be used alone or as a mixture of two or more. Also, the amounts of these used should be adjusted according to the application and required performance.

The phenolic resin composition of the present invention can be used as a binder for a paper base laminate by adding a resole resin. As the resole resin in this case,
A thermosetting resin containing a methylol group, for example, a low-molecular-weight condensation resin obtained by reacting phenols such as phenol, cresol, butylphenol, nonylphenol, xylenol, and resorcinol with aldehydes such as formaldehyde in the presence of a basic catalyst. It is. In addition, these phenols are tung oil, dehydrated castor oil, linseed oil,
A dry oil-modified resin using phenols modified with a dry oil such as tall oil may be used. And melamine,
A low-molecular-weight condensation resin obtained by reacting guanamine or the like with an aldehyde such as formaldehyde in the presence of a basic catalyst, wherein a part or all of those methylol groups are etherified with a lower alcohol such as methanol or butanol. It may be. The use of these resins is not limited to one type, and two or more types can be used in combination. However, from the viewpoint of achieving both impregnation and punching characteristics, a low molecular weight condensed resin and a dry oil-modified resol are used. It is preferable to use a resin together.

Here, as the basic catalyst, the above-mentioned ammonia, an amine-based catalyst, a metal hydroxide or the like is used. The mixing ratio of the phenolic resin composition of the present invention to the resole resin is not particularly limited, but the weight ratio of the solid content of the phenolic resin composition to the resole resin is 5 to 5.
It is preferable to mix at a ratio of 0: 100.

When used for a paper base laminate, other thermosetting resins can be used as needed. Examples of other thermosetting resins include an epoxy resin, an unsaturated polyester resin, and a thermosetting acrylic resin, and an epoxy resin is preferable from the viewpoint of punching workability.

Further, various additives, flame retardants, fillers and the like can be appropriately compounded as required. Paper base laminate, after dissolving the resin composition obtained as described above in an organic solvent as needed to make a varnish, kraft paper,
It is obtained by applying and impregnating a paper base material such as linter paper, glass cloth, glass nonwoven fabric, polyester cloth, aramid fiber cloth, and canvas, and then drying and forming a laminated material.

At this time, the mixing procedure and the mixing ratio of coating and impregnating the phenol resin composition and the resole resin are not particularly limited, but the phenol resin is coated and impregnated in a two-stage impregnation method. It is preferable to use a low molecular weight resole resin as the impregnating resin, and to use the dry oil-modified resole resin and the phenolic resin composition of the present invention as the second stage impregnating resin.

[0047]

The present invention will be described in more detail with reference to the following examples. Example 1 41.5 was added to 94 parts of phenol and 12 parts of benzoguanamine.
% Formalin and 0.4 parts of triethylamine were added to adjust the pH of the system to 8.2, and the temperature was gradually raised to 100 ° C. while paying attention to heat generation. After reacting at 100 ° C. for 5 hours, the temperature was raised to 120 ° C. over 2 hours while removing water under normal pressure. Next, after reacting for 3 hours under reflux, the temperature was raised to 160 ° C. over 2 hours while removing water under normal pressure. After further reacting for 3 hours under reflux,
The temperature was raised to 180 ° C. over 2 hours while removing water under normal pressure. Next, unreacted phenol was removed under reduced pressure to obtain a phenol resin composition having a softening point of 111 ° C.

Hereinafter, this composition is abbreviated as “N1”. Weight ratio of phenols and triazines in the obtained composition, unreacted formaldehyde amount, presence or absence of methylol group, molar ratio of structural units A and B, unreacted phenol monomer amount, and triazine reaction The rate was determined as follows. <Weight ratio of phenol to triazine (benzoguanamine)> The phenol content in the effluent removed from the reaction system at 180 ° C. under reduced pressure described above was calculated by gas chromatography, and subtracted from the number of phenol parts charged. The amount of phenol present in the product was determined. Benzoguanamine was included in the composition as it was charged.
The ratio between the two was defined as the abundance ratio. Column: 30% Celite 545 carnauba wax 2mx
3 mmΦ Column temperature: 170 ° C. Inlet temperature: 230 ° C. Detector: FID Carrier gas: N ₂ gas 1.0 kg / cm ² Measurement method: Internal standard method <Amount of unreacted formaldehyde> Composition N1 finely pulverized in 50 g of distilled water About 5 g was added and kept at room temperature for 24 hours. Set to a pH meter, add an N / 10 aqueous solution of hydrochloric acid, and add p
H was adjusted to 4.0. To this, 50 ml of a 7% aqueous solution of hydroxylamine adjusted to pH = 4.0 was added, sealed with an aluminum foil or the like, and left for 30 minutes. After that, it is set in a pH meter, and titrated with 1N sodium hydroxide solution until the pH is neutralized to 4.0. The amount of free formaldehyde was determined by the following equation.

[0049] S: Sample amount (g) F: Factor of 1N sodium hydroxide T: Drop amount of 1N sodium hydroxide (ml) <Presence or absence of methylol group> Methylol present in resin composition N1 using 13C-NMR The group was measured. Apparatus: GSX270 manufactured by JEOL Ltd. Proton: 270 MHZ Measurement solvent: DMSO or heavy acetone Reference substance: Tetramethylsilane Measurement conditions Pulse conditions: 45 mm × 10000 times Pulse interval: 2 seconds Peaks are obtained at 60 to 70 ppm in the obtained chart. Appear,
Judgment was made using peaks that could be clearly distinguished from noise.
A case where a peak was observed was evaluated as “present”, and a case where no peak was observed was evaluated as “absent”. <Molar ratio of structural unit A and structural unit B> The molar ratio was calculated using a 13 C-NMR chart measured under the same conditions as in the measurement of the methylol group.

The integral value of the peak appearing at 42.5 to 45 ppm in the chart was Bp, and the integral value of the peak appearing at 47 to 48.5 ppm was Ap, and the molar ratio was determined by the following equation. Structural unit B / Structural unit A = Bp / Ap <Amount of unreacted phenol monomer> The phenol monomer content in the effluent was measured under the same measurement conditions as in the gas chromatography described above. <Reactivity of triazines> Calculated using a 13 C-NMR chart measured under the same conditions as those for measuring the methylol group. The integrated value of the sharp peak appearing at 167.2 to 167.4 ppm in the chart is represented by Tm, 163 to 16
The peak integration value of the broad peak appearing at 7.2 ppm was defined as Tr, and the reaction rate was determined by the following equation.

[0051] Table 1 summarizes the results of the amounts of the components thus obtained.

Example 2 To 94 parts of phenol and 18 parts of melamine, 45 parts of 41.5% formalin and 0.4 part of triethylamine were added.
The pH of the system was adjusted to 8.2, and the temperature was gradually raised to 100 ° C. while paying attention to heat generation. After reacting at 100 ° C. for 5 hours, the temperature was raised to 120 ° C. over 2 hours while removing water under normal pressure. Next, after reacting for 3 hours under reflux, the temperature was raised to 140 ° C. over 2 hours while removing water under normal pressure. After reacting for 3 hours under reflux, the temperature was raised to 160 ° C. over 2 hours while removing water under normal pressure. After further reacting under reflux for 3 hours, the temperature was raised to 180 ° C. over 2 hours while removing water under normal pressure. Next, unreacted phenol was removed under reduced pressure to obtain a phenol resin composition having a softening point of 128 ° C. The weight ratio of phenol and melamine, the amount of unreacted formaldehyde, the presence or absence of a methylol group, the molar ratio of structural unit A and structural unit B, the amount of unreacted phenol monomer, and the conversion of triazines were determined in the same manner as in Example 1. The results are summarized in Table 1.

Hereinafter, this composition is abbreviated as “N2”. Example 3 94 parts of phenol, 70 parts of benzoguanamine, 41.5
% Formalin and 0.5 parts of triethylamine were added to adjust the pH of the system to 7.8, and reacted at 80 ° C. for 3 hours. Next, the temperature was raised to 120 ° C. while removing water under normal pressure, and the reaction was carried out for 2 hours while maintaining the temperature. The temperature was raised to 160 ° C. over 2 hours while removing water under normal pressure. After further reacting for 2 hours while maintaining the temperature, the temperature was raised to 180 ° C. over 2 hours while removing water under normal pressure, and then unreacted phenol was removed under reduced pressure.
A phenol resin composition having a softening point of 135 ° C. was obtained. The weight ratio of phenol to benzoguanamine, the amount of unreacted formaldehyde, the presence or absence of a methylol group, the molar ratio of structural unit B, the amount of unreacted phenol monomer, and the reaction rate of triazines were determined in the same manner as in Example 1, and the results were tabulated. 1 together.

Hereinafter, this composition is abbreviated as “N3”. Example 4 To 94 parts of phenol and 9 parts of melamine, 45 parts of 41.5% formalin and 0.4 parts of triethylamine were added, and the pH of the system was adjusted to 8.2.
The temperature was raised to 00 ° C. After reacting at 100 ° C. for 5 hours, the temperature was raised to 120 ° C. over 2 hours while removing water under normal pressure. Next, after reacting for 3 hours under reflux, the temperature was raised to 140 ° C. over 2 hours while removing water under normal pressure. After reacting for 3 hours under reflux, the temperature was raised to 160 ° C. over 2 hours while removing water under normal pressure. After further reacting under reflux for 3 hours, the temperature was raised to 180 ° C. over 2 hours while removing water under normal pressure. Next, unreacted phenol was removed under reduced pressure to obtain a phenol resin composition having a softening point of 120 ° C. The weight ratio of phenol and melamine, the amount of unreacted formaldehyde, the presence or absence of a methylol group, the molar ratio of structural unit A and structural unit B, the amount of unreacted phenol monomer, and the conversion of triazines were determined in the same manner as in Example 1. The results are summarized in Table 1.

Hereinafter, this composition is abbreviated as “N4”. Comparative Example 1 94 parts of phenol, 12 parts of benzoguanamine, 41.5
45% of formalin and 0.6 part of 48% sodium hydroxide were added to adjust the pH of the system to 8.2, and reacted at 100 ° C. for 2 hours. Next, while removing water under normal pressure, 180
The temperature was raised to 0 ° C, and unreacted phenol was removed under reduced pressure to obtain a phenol resin composition having a softening point of 118 ° C. Weight ratio of phenol to benzoguanamine, amount of unreacted formaldehyde, presence or absence of methylol group, structural unit B
, The unreacted phenol monomer amount, and the triazine conversion were determined in the same manner as in Example 1. The results are shown in Table 1.

Hereinafter, this composition is abbreviated as “N5”. Comparative Example 2 94 parts of phenol, 12 parts of benzoguanamine, 41.5
% Formalin and 0.3 parts of oxalic acid were added to adjust the pH of the system to 5.4, and reacted at 100 ° C. for 2 hours. Next, the temperature was raised to 180 ° C. while removing water under normal pressure, and unreacted phenol was removed under reduced pressure to obtain a phenol resin composition having a softening point of 102 ° C. The weight ratio of phenol to benzoguanamine, the amount of unreacted formaldehyde, the presence or absence of a methylol group, the molar ratio of structural unit B, the amount of unreacted phenol monomer, and the reaction rate of triazines were determined in the same manner as in Example 1. Are shown together.

Hereinafter, this composition is abbreviated as “N6”.

[0058]

[Table 1] Examples 5-7 and Comparative Examples 3-4 Epicron 850 [Epoxy resin Epoxy equivalent 190
Dainippon Ink and Chemicals, Inc.], 100 parts of a compound of N1, N2, N4, N5 and N6 as a curing agent and 2-ethyl 4-methylimidazole (hereinafter abbreviated as 2E4MZ) as a curing accelerator. Table 2)
At the ratios shown in Table 1. At this time, an accelerator was previously added to the curing agent resin, and the mixture was maintained at 170 ° C. and melted. Similarly, add the heated epoxy resin and stir well.
It was poured into a glass mold having a thickness of 3 mm, and was heated and cured at 180 ° C. for 2 hours to obtain a casting plate.

When each physical property test was performed on the cast plate, the results shown in Table 2 were obtained.

[0060]

[Table 2]

* 1: Flame-extinguishing test The time required for a test piece having a width of 12.7 mm to stand vertically and exposed to flame for 10 seconds before self-extinguishing. When the combustion continued for 2 minutes or more, or when the combustion continued to 5 cm from the lower end, it was determined as "combustion".

Example 8 and Comparative Examples 5 to 6 100 parts of N2, N5 and N6 phenolic resin compositions were mixed and pulverized with 10 parts of hexamethylenetetramine to obtain a powdery curable resin composition. For 15 parts of this composition, 55 parts of glass fiber (chopped strand), 5 parts of aramid fiber, 8 parts of cashew oil polymer, 7 parts of graphite
Parts, 5 parts of barium sulfate and 5 parts of calcium carbonate were mixed by a mixer to obtain a thermosetting resin composition for a friction material.

Application Example 1 and Comparative Application Examples 1 and 2 The thermosetting resin compositions for friction materials obtained in Example 8 and Comparative Examples 5 to 6 were molded in a mold at 160 ° C. by a well-known general method. Then, it was subjected to compression molding using a press machine to obtain a molded product. After the mold was removed from the mold,
After heating for a time, firing was performed to obtain a molded product. This molded product is cut into a predetermined size and subjected to a friction performance test (JIS D-44).
11) was performed and comparatively evaluated. Table 3 summarizes the results.

The unit of the wear rate is 10-7 cm / kg
M.

[0065]

[Table 3]

Example 9 and Comparative Examples 7 to 8 Triphenylphosphine was added to the compounds of N3, N5, and N6 and melted at 200 ° C., and imide compounds containing an ethylenically unsaturated group were shown in Table 4. The mixture was melted and mixed according to the ratio, and the mixture was stirred well and poured into a glass mold having a thickness of 3 mm.
For 2 hours to obtain a cast plate. When each physical property test was performed, the results as shown in Table 4 were obtained.

[0067]

[Table 4]

Application Example 2 and Comparative Application Examples 3 to 4 100 parts of Epiclon 850 were mixed with N as a curing agent.
2, N5 and N6 were blended in the proportions shown in Table 5. At this time, the weight of the epicron 850 and the curing agent were previously set to be methyl ethyl ketone / dimethylformamide = 50 /
It was used after being dissolved in 50 mixed solvents. Next, 0.2 parts of 2E4MZ was added as a curing accelerator to each, and the non-volatile content of the solution was adjusted to 55% with methyl ethyl ketone to prepare mixed solutions of Application Example 2 and Comparative Application Examples 3 and 4.

Thereafter, each mixed solution was impregnated into a glass cloth and dried at 160 ° C. for 3 minutes to obtain a prepreg. Eight sheets of this prepreg were stacked, 35 μm copper foil was stacked on both surfaces thereof, and heated and pressed at 170 ° C. and a pressure of 40 kgf / cm 2 for 1 hour to prepare a double-sided copper-clad laminate having a thickness of 1.5 mm.

Next, the laminate was subjected to an etching treatment to remove copper foil, and then subjected to physical property tests. As a result, the results shown in Table 5 were obtained. * 1: Heating rate 3 ° C / min * 2: Preshake cooker test (PCT) is 120
The test piece was treated under steam at ℃ for a predetermined time. * 3: The solder resistance test was performed by immersing in a solder bath at 260 ° C. for 20 seconds after the PCT treatment.

The evaluation was made by visual judgment of the appearance of the test piece, particularly the presence or absence of measling. ：: No abnormality at all △: Slight measling occurred
×: With Meesling

[0072]

[Table 5]

[Application Synthesis Example 1] (Synthesis example of resole resin) 94 parts of phenol, 87 parts of 41.5% formalin and 1.9 parts of trimethylamine were added and reacted at 60 ° C for 2 hours. Next, water was removed under reduced pressure, and methanol / water = 70.
The mixture was diluted with a 30/30 mixed solvent to obtain a low molecular weight resole resin varnish having a resin content of 50%.

Hereinafter, this resin varnish is abbreviated as “W1”. [Application Synthesis Example 2] (Synthesis example of resole resin) 94 parts of phenol, 60 parts of tung oil and 0.5 part of paratoluenesulfonic acid were added and reacted at 80 ° C for 3 hours. Next, 60 parts of toluene and 2 g of triethanolamine were added to dilute and neutralize, and then 40 parts of paraformaldehyde and 2.4 parts of 25% aqueous ammonia were added and reacted at 90 ° C. for 4 hours. To this were added 12 parts of a brominated epoxy resin [Epiclon 153 manufactured by Dainippon Ink and Chemicals, Inc.] and 12 parts of triphenyl phosphate, and then methanol / toluene = 50/5.
The mixture was diluted with a mixed solvent of 0 to obtain a tung oil-modified resin varnish having a resin content of 50%.

Hereinafter, this resin varnish is abbreviated as “W2”. Application Example 3 and Comparative Application Examples 5 to 6 According to the ratios shown in Table 6, W1, W2 and N
2, N5, and N6 and was mixed and dissolved to a homogeneous solution was coated impregnated kraft paper 135 g / m ^2, dried and the resin content was obtained from 52 to 55% of the prepreg. Eight of these were laminated and hot-pressed at 160 ° C. and 80 kg / cm ² for 60 minutes to obtain a laminated plate having a thickness of 1.6 mm.

Table 6 shows the properties obtained for these laminates. The test method was JIS for water absorption and insulation resistance.
Performed according to C6481. Punching workability is ASTM.
According to D-617.

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[Table 6]

[0078]

The phenolic resin composition of the present invention, when used as an epoxy resin curing agent, can give a cured product excellent in flame retardancy, heat resistance, moisture resistance and metal adhesion, and uses halogen. Without flame retardancy, various applications using epoxy resin such as sealing, lamination, paint,
In particular, it can be used for a glass epoxy laminate or an IC sealing material. Furthermore, since it is excellent in friction characteristics and dielectric characteristics, it can be used as a friction material and a molding material. Further, since it is excellent in flame retardancy and low-temperature punching workability, it can be used for a paper base laminate.

Claims (13)

[Claims] 1. A phenol resin composition comprising a triazine-modified novolak resin comprising a phenol, a triazine and an aldehyde, wherein the novolak resin is a condensate of a phenol, a triazine and an aldehyde. (A) a condensate of a triazine and an aldehyde (b), a condensate of a phenol and an aldehyde (c), a mixture of a phenol (d) and a triazine (e), and the condensate In (a) and the condensate (b), the structural unit A represented by the general formula (1) and the structural unit B represented by the general formula (2) are represented by the following formula (3) in a molar ratio. A phenolic resin composition which is contained in a satisfactory state. _{(-X-NH-CH 2 -NH-} ) (1) (-X-NH-CH 2 -Y-) (2) ( wherein, X represents a residue of triazines, Y phenols residues B / A ≧ 1.5 (3) 2. The composition according to claim 1, wherein the molar ratio of the triazines in the condensate (a) and the condensate (b) is 30% or more of all the triazines. 3. The composition according to claim 1, wherein the triazine is at least one member selected from the group consisting of melamine, acetoguanamine and benzoguanamine. 4. The composition according to claim 1, wherein said phenol resin composition further comprises a curing agent. 5. The composition according to claim 4, wherein the curing agent is hexamethylenetetramine. 6. The curing agent according to claim 4, wherein the curing agent is a compound having at least two ethylenically unsaturated groups in a molecule.
A composition as described. 7. The compound having at least two ethylenically unsaturated groups in the molecule is bismaleimide.
A composition as described. 8. The composition according to claim 1, wherein said phenol resin composition further comprises a resole resin. 9. A curing agent for an epoxy resin comprising the phenolic resin composition according to claim 1 as a main component. 10. A binder for a friction material comprising the phenolic resin composition according to claim 1 as a main component. 11. A binder for a paper base laminate comprising the phenolic resin composition according to claim 1 as a main component. 12. A step (i) of adjusting the pH of the system of a mixture of phenols, triazines and aldehydes to 5 to 10, and a step (ii) of reacting the mixture under conditions in which the aldehydes do not volatilize. And step (iii) of removing reaction water in the system, wherein step (i) step (i)
i) and step (iii) are sequentially performed, and then step (ii) and step (iii) are sequentially performed at a higher temperature than the first step as a second step reaction, and step (ii) is performed as a third step reaction And the step (iii) is carried out at a higher temperature than the second-stage reaction, and further, if necessary, the second-stage reaction and the third-stage reaction are repeatedly carried out to convert the dimethylene ether bond in the molecule into a methylene bond. A method for producing a triazine-modified novolak-type phenol resin, which comprises converting. 13. The method according to claim 12, wherein the molar ratio of phenols and triazines to aldehydes is 1: 0.2 to 0.9.