JP2000219716A - Production of amino-modified phenol-aralkyl resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an amino-modified phenol-aralkyl resin excellent in resistances to heat and water, flame retardance, strengths, etc., in high productivity and yield by reacting a phenolic hydroxy-containing compound with a triazine derivative and an aldehyde. SOLUTION: A phenolic hydroxy-containing compound of the formula is used. In the formula, Ar1 is a 6-14 aryl; Ar2 is a 6-14C aryl or biphenyl; R1 and R2 are each a 1-6C alkylene; R is H or a 1-10C organic group; and n is 0-8. A triazine derivative, preferably a guanamine derivative, is used preferably in an amount of 1-20 wt.% of the phenolic hydroxy-containing compound. The amount of an aldehyde used is 1-10 mol per mol of the triazine derivative. Preferably, the reaction is conducted at 60-250 deg.C for about 1-20 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for molding materials, friction materials, paints, coating materials, adhesive sealing materials, laminated materials, FRP, carbon material raw materials, etc. having excellent heat resistance, strength, flame retardancy, etc. The present invention relates to a method for producing an amino-modified phenol-aralkyl resin.

[0002]

2. Description of the Related Art Phenol resins and melamine resins are excellent in heat resistance, chemical resistance, strength, etc.
Used as a binder for friction materials, laminates, FRP and carbon products. In addition, heat-curable phenolic and melamine resins can be cured by heating alone without adding an expensive curing agent such as an epoxy resin. No mixing step is required. A heat-curable phenolic resin is superior in heat resistance and water resistance to melamine resin, but is inferior in flame retardancy. On the other hand, the heat-curable melamine resin is superior in flame retardancy to phenol resin, but is inferior in water resistance. Therefore, attempts have been made to obtain a resin having excellent heat resistance, water resistance, and flame retardancy with respect to a mixture of a compound having a phenolic hydroxyl group and a triazine derivative and a reaction product thereof (JP-A-8-31142, However, there is a problem that the heat resistance and water resistance are not always satisfied, and the strength of the molded product is not sufficient.

[0003]

The object of the present invention is to provide an amino-modified phenol which can produce an amino-modified phenol / aralkyl resin excellent in heat resistance, water resistance, flame retardancy, strength and the like with good productivity and high yield. It is intended to provide a method for producing an aralkyl resin.

[0004]

The present invention provides a compound represented by the general formula (I):

Embedded image (Wherein, Ar ¹ represents an aryl group having 6 to 14 carbon atoms, Ar ² represents an aryl group or a biphenyl group having 6 to 14 carbon atoms, and R ¹ and R ² each independently represent 1 ~ 6
R is a hydrogen atom or a carbon number of 1 to
Wherein n represents an organic group of 10 and n is an integer of 0 to 8), a triazine derivative and an aldehyde, and a method for producing an amino-modified phenol-aralkyl resin.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (I), examples of the aryl group having 6 to 14 carbon atoms of Ar ¹ include a phenyl group, a naphthyl group and an anthryl group. Ar ²
Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and the like. These are an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom. May be substituted. R ¹
And the alkylene group having 1 to 6 carbon atoms for R ² includes, for example, a methylene group, ethylene, propylene group, isopropylene group, butylene group, pentylene group, hexylene group and the like. Examples of the hydrocarbon group having 1 to 10 carbon atoms for R include a branched or straight-chain alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms,

Embedded image And the like.

As the compound represented by the above general formula (I), a commercially available compound is a phenol-aralkyl resin Millex XLC-4L manufactured by Mitsui Chemicals, Inc. (in the general formula (I),
Ar ¹ is a phenyl group, Ar ² is a phenyl group, R ¹ and R ² are methylene groups, R is a hydrogen atom, and the average of n is about 3.)
Is mentioned.

The triazine derivative in the present invention is a compound having a triazine nucleus in the molecule, and examples thereof include guanamine derivatives such as melamine, benzoguanamine and acetoguanamine, and cyanuric acid derivatives such as cyanuric acid and methyl cyanurate. These can be used alone or
Used in combination of more than one species. Among these, guanamine derivatives such as melamine and benzoguanamine are preferred from the viewpoint of heat resistance and the like.

[0008] Examples of the aldehyde in the present invention include formaldehyde, formalin, paraformaldehyde and the like.

The use amount of the triazine derivative to the compound represented by the formula (I) is preferably 1 to 20% by weight, more preferably 2 to 15% by weight.
If it is less than 1% by weight, the resulting amino-modified phenol-aralkyl resin tends to have insufficient flame retardancy,
If the amount is more than 10% by weight, the obtained amino-modified phenol / aralkyl resin tends to have an excessively high softening point. The amount of the aldehyde used is 1 to 1 mole of the triazine derivative.
It is preferably from 10 to 10 mol, more preferably from 1 to 5 mol. 1
If the amount is less than the mole, the reaction between the compound represented by the general formula (I) and the triazine derivative tends to be difficult to proceed, and
If it exceeds 0, it tends to gel during synthesis.

[0010] The reaction is preferably carried out at a temperature of 60 ° C to 250 ° C. If the temperature is lower than 60 ° C., the reaction becomes insufficient, the molecular weight does not increase, and the heat resistance, water resistance, flame retardancy, strength and the like tend to be poor. If the temperature exceeds 250 ° C., the compound represented by the general formula (I) The reaction of the triazine derivative tends to be insufficient. The reaction time is about 1 to 20 hours. Also,
The pH of the reaction is preferably from 1 to 10. If the pH is less than 1, the resin tends to gel during the synthesis, and if it exceeds 10, the resin has the general formula (I)
The reaction of the compound represented by with the triazine derivative tends to be difficult to proceed.

If necessary, an amine catalyst such as trimethylamine or triethylamine, sodium hydroxide,
An alkali catalyst such as potassium hydroxide, an acid catalyst such as phosphoric acid, p-toluenesulfonic acid, oxalic acid, and
You may use about 0.00001-0.01 mol with respect to mol.

In this way, after reacting the compound represented by the general formula (I) with the aldehyde and the triazine derivative, unreacted aldehyde, water and the like can be removed by heating under reduced pressure. Has a temperature of 80 to 180 ° C,
The pressure is preferably 100 mmHg or less, more preferably 60 mmHg or less, and the time is preferably 0.5 to 10 hours.

The amino-modified phenol-aralkyl resin of the present invention comprises, as a raw material, a compound represented by the general formula (I):
An aldehyde and a triazine derivative are essential, and can be produced by reacting each of these materials.

The amino-modified phenol-aralkyl resin of the present invention has a number average molecular weight (Mn) (measured by gel permeation chromatography, converted to standard polystyrene, and the same weight average molecular weight) of 300 to 2,000. It is more preferably from 450 to 15,000, and particularly preferably from 500 to 1,200. If it is less than 300, the strength of the obtained cured product tends to be inferior. If it exceeds 2,000, synthesis becomes difficult,
In addition, handling properties tend to be poor. Weight-average molecular weight (M) of the amino-modified phenol-aralkyl resin of the present invention
w) is 1,000 to 10,000, and 900 to
9,000, preferably 800 to 8,000
Is more preferable. If it is less than 1,000, the strength of the obtained cured product is inferior. If it exceeds 10,000, synthesis becomes difficult, and handleability is inferior.

Mw / Mn of the amino-modified phenol-aralkyl resin of the present invention is 1.6 to 15, and 1.8 to 1.8.
More preferably, it is 10. If it is less than 1.6, heat resistance, water resistance, flame retardancy, strength and the like are inferior.
Synthesis tends to be difficult.

The amino-modified phenol-aralkyl resin of the present invention is characterized by heat resistance, water resistance, flame retardancy, strength and the like.
The ratio a / b of the intensity a at the point corresponding to the molecular weight of 2,050 of the standard polystyrene (on the graph measured by gel permeation chromatography) to the intensity b at the point corresponding to the molecular weight of 655 is 0.2 to 1. It is preferably 2.

The amino-modified phenol / aralkyl resin of the present invention has a binuclear phenol derivative content of 10 to 10.
Preferably it is 40% by weight. If it is less than 10% by weight, the softening point tends to increase, and if it exceeds 40% by weight, the flame retardancy tends to deteriorate.

The phenol-amino condensation resin of the present invention preferably has a softening point of 40 ° C. to 150 ° C.,
The temperature is more preferably 120 ° C. If the temperature is lower than 40 ° C., the strength of the obtained cured product tends to be inferior. If the temperature exceeds 150 ° C., the workability during synthesis tends to be inferior.

The unreacted phenol derivative contained in the amino-modified phenol / aralkyl resin of the present invention is preferably 3% by weight or less from the viewpoint of safety and health and odor. The amino-modified phenol-aralkyl resin of the present invention preferably has a nitrogen content of 1 to 20% by weight in terms of flame retardancy, easy synthesis, and the like.

The amino-modified phenol / aralkyl resin of the present invention is blended with an epoxy resin, an inorganic filler, a curing accelerator and the like to form a molding material having excellent heat resistance, strength, flame retardancy, etc.
It can be a composition used for a friction material, a paint, a coating material, an adhesive sealing material, a laminated material, FRP, a raw material for carbon products, and the like.

[0021]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, “parts” means “parts by weight” and “%” means “% by weight”.

Example 1 In a flask equipped with a stirrer, a reflux condenser and a thermometer, a phenol-aralkyl resin Millex XLC-4L100 was added.
g, 6.3 g (0.05 mol) of melamine and 8.1 g (0.1 mol) of 37% formalin water, adjust the pH to 2 using 10% oxalic acid, and reflux to dehydration up to 150 ° C.
The temperature was raised over time, and the reaction was carried out at 150 ° C. for 4 hours. Thereafter, unreacted aldehyde and water were removed at 180 ° C. under reduced pressure. The amount of the purified amino-modified phenol-aralkyl resin was 110 g, and the softening point was 90 ° C.

Example 2 A flask equipped with a stirrer, a reflux condenser and a thermometer was charged with a phenol-aralkyl resin Millex XLC-4L100.
g, benzoguanamine 17.6 g (0.1 mol), 37
% Formalin water (24.34 g, 0.3 mol)
After adjusting the pH to 2 using 0% oxalic acid, 1
The temperature was raised to 50 ° C. in 2 hours and reacted at 150 ° C. for 4 hours. Thereafter, unreacted aldehyde and water were removed at 180 ° C. under reduced pressure. The amount of the purified amino-modified phenol-aralkyl resin was 125 g, and the softening point was 95 ° C.

Comparative Example 1 In a flask equipped with a stirrer, reflux condenser and thermometer, 94 g (1 mol) of phenol and 25.1% of 37% formalin water were used.
g (0.3 mol) and 4.34 g (0.034 mol) of melamine, and after adjusting the pH to 8 using triethylamine,
While refluxing dehydration, the temperature was raised to 140 ° C. in 4 hours, and then the reaction was performed at 140 ° C. for 5 hours. Thereafter, unreacted phenol and water were removed at 140 ° C. under a reduced pressure of 60 mmHg. The amount of the purified resin was 40.8 g and the softening point was 80
° C.

Number average molecular weight, weight average molecular weight, weight average molecular weight of the resins obtained from Examples 1 and 2 and Comparative Example 1
The ratio a / b between the intensity a at the point corresponding to the molecular weight of 2,050 of the standard polystyrene (retention time = 26 min) and the intensity b at the point corresponding to the molecular weight 655 (retention time = 30 min), diphenol phenol Table 2 shows the results of body content, softening point and nitrogen content. Here, the number-average molecular weight and the weight-average molecular weight were calculated by gel permeation chromatography using a calibration curve using standard polystyrene. The weight-average molecular weight / number-average molecular weight, phenol binuclear content, and unreacted phenol content were also calculated by gel permeation chromatography using an area method. Table 2 shows the results of the softening point and the nitrogen content obtained from the elemental analysis.

The gel permeation chromatography was performed under the following conditions. Column: Gel Pack (manufactured by Hitachi Chemical Co., Ltd.) GL-R4
20 + GL-R430 + GL-R440 Column temperature: 40 ° C. Detector: RI Eluent: Tetrahydrofuran Flow rate: 1.6 ml / min The calibration curve is a standard polystyrene having a molecular weight shown in Table 1 (trade name: TSK standard, Tosoh Corporation). Co., Ltd.)
The retention time (min) was plotted on the horizontal axis and the logarithm of the molecular weight was plotted on the vertical axis.

[0027]

[Table 1]

[0028]

[Table 2]

Application Example 1 100 parts by weight of a cresol novolak type epoxy resin having an epoxy equivalent of 220 and a softening point of 78 ° C., 50 parts by weight of a melamine-modified phenol / aralkyl resin synthesized in Production Example 1,
1.5 parts by weight of benzylmethylamine, 2 parts by weight of carnauba wax, 8 parts by weight of antimony trioxide, 1.5 parts by weight of carbon black, 3 parts by weight of r-glycidoxypropyltrimethoxysilane, and 360 parts by weight of fused silica And
Using a 10-inch diameter heating roll, kneading temperature 80-9
Kneading was performed at 0 ° C. for 7 minutes. Thereafter, the mixture was pulverized using a Horai type pulverizer to produce an epoxy resin molded material.
Table 4 shows the characteristics.

Application Examples 2 and 3 and Comparative Application Example 1 A molding material was produced in the same manner as in Application Example 1. The amounts are shown in Table 3. Table 4 shows these characteristics.

The test method for the coating film is as follows. (1) Gel time: Measured at a temperature of 180 ° C. using Curast Meta manufactured by JSR Corporation manufactured by Imanaka Seisakusho. (2) Spiral flow: Measured at a mold temperature of 180 ° C. and a transfer pressure of 70 KGF / CM2 according to EMMI1-66. (3) Tg: using a TMA device manufactured by Rigaku Denki Co., Ltd.
The temperature at the inflection point of the thermal expansion curve was defined as Tg. (4) Flame retardancy: evaluated by the VB method according to UL-94. (1/8 inch test piece) (5) Izod impact: Performed by a method based on ASTM-D256. (V notch, 1/8 inch test piece)

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

The amino-modified phenol according to claim 1
The aralkyl resin manufacturing method is heat-resistant, water-resistant, flame-retardant,
An amino-modified phenol / aralkyl resin having excellent strength and the like can be produced with good productivity and yield.

[Brief description of the drawings]

FIG. 1 is a GPC chart of an amino-modified phenol / aralkyl resin obtained in Example 1.

FIG. 2 is a GPC chart of the resin obtained in Comparative Example 1.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoshiki Inoue Oyama Goban, Kashima-gun, Kashima-gun, Ibaraki Pref. I Hitachi Hitachi Chemical Co., Ltd. Kashima Plant F-term (reference) 4J033 FA01 FA06 FA11 HA02 HA04 HA14 HB01 HB02 HB04 HB06 HB08 HB09

Claims (1)

[Claims] 1. A compound of the general formula (I) (Wherein, Ar ¹ represents an aryl group having 6 to 14 carbon atoms, Ar ² represents an aryl group or a biphenyl group having 6 to 14 carbon atoms, and R ¹ and R ² each independently represent 1 ~ 6
R is a hydrogen atom or a carbon number of 1 to
Wherein n represents an organic group of 10, and n is an integer of from 0 to 8), a triazine derivative and an aldehyde, and a method for producing an amino-modified phenol / aralkyl resin.