JP2003212946A - Epoxy resin composition using amino-modified phenol- aralkyl resin, prepreg and laminated board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition using an amino-modified phenol-aralkyl resin, having excellent heat resistance, flame retardance, strength and curability. <P>SOLUTION: The epoxy resin composition contains the amino-modified phenol- aralkyl resin which is characterized by reacting a compound represented by formula (I) [wherein Ar<SB>1</SB>is a 6-14C aryl; Ar<SB>2</SB>is a 6-14C aryl or a biphenyl; R<SB>1</SB>and R<SB>2</SB>are each independently a 1-6C alkylene; R is H or a 1-10C organic group; and (n) is an integer of 0-8] with a triazine derivative and an aldehyde. A prepreg and a laminated board are obtained from each compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a molding material, a friction material, a paint, a coating material, an adhesive, an encapsulating material, a laminated material, an FRP and a raw material for carbon products, which are excellent in heat resistance, strength and flame retardancy. The present invention relates to an epoxy resin composition containing an amino-modified phenol / aralkyl resin used.

[0002]

2. Description of the Related Art Phenolic resins and melamine resins are excellent in heat resistance, chemical resistance, strength, curability, etc.
It is used as a binder for molding materials, friction materials, laminates, FRP and carbon products. Further, since the heat-curable phenol resin and melamine resin are heat-cured by the resin alone without adding an expensive curing agent such as an epoxy resin,
The material cost is low in the production of the molding material, and the curing agent mixing step is not required. The heat-curable phenol resin is superior in heat resistance and water resistance to the melamine resin, but inferior in flame retardancy. On the other hand, the heat-curable melamine resin is superior in flame resistance to the phenol resin but inferior in water resistance. Therefore, an attempt to obtain a resin having excellent heat resistance, water resistance, and flame retardancy has been made for a mixture of a compound having a phenolic hydroxyl group and a triazine derivative and a reaction product thereof (JP-A-8-3114).
No. 2, JP-A-8-183827, etc.), there is a problem that heat resistance and water resistance are not always satisfied, and the strength of the molded product is not sufficient.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an amino-modified phenol / phenol-aralkyl resin which is excellent in heat resistance, water resistance, flame retardancy, strength, curability and the like and which is formed by co-condensation of a triazine derivative. To provide aralkyl resin.

[0004]

The present invention relates to an amino-modified phenol aralkyl resin characterized by reacting a compound represented by the following general formula (I) with a triazine derivative and an aldehyde.

[Chemical 2] (In the formula, Ar ¹ represents an aryl group having 6 to 14 carbon atoms, Ar ² represents an aryl group having 6 to 14 carbon atoms or a biphenyl group, and R ¹ and R ² each independently have 1 carbon atom. ~
6 is an alkylene group, R is a hydrogen atom or a carbon number 1
10 represents an organic group, and n is an integer of 0 to 8)

The present invention relates to an amino-modified phenol / aralkyl resin according to claim 1, wherein the amount of the triazine derivative compounded with respect to the phenol / aralkyl resin is 1% by weight to 30% by weight.

The present invention relates to the amino-modified phenol aralkyl resin according to claims 1 and 2, wherein the molar ratio of the aldehydes to the triazine derivative is 1-10.

The present invention relates to an amino-modified phenol / aralkyl resin characterized by reacting a phenol / aralkyl resin, a triazine derivative and aldehydes at pH 3-9.

The present invention relates to an epoxy resin composition containing an epoxy resin and an amino-modified phenol / aralkyl resin.

In the present invention, the amino-modified phenol / aralkyl resin 20 to 20 is added to 100 parts by weight of the epoxy resin.
It relates to an epoxy resin composition containing 0 part by weight.

The present invention relates to an epoxy resin composition containing 0.01 to 2.0 parts by weight of imidazoles based on 100 parts by weight of epoxy resin.

The present invention relates to a prepreg in which a sheet base material is impregnated with an epoxy resin composition.

The present invention relates to a laminate obtained by heat-molding a laminate in which a plurality of prepregs are laminated or a copper foil laminate in which copper foil is laminated on one side or both sides of the laminate.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the 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, and an anthryl group, and these include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom. May be replaced with. R ¹
Examples of the alkylene group having 1 to 6 carbon atoms for R ² include a methylene group, ethylene, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group. Examples of the hydrocarbon group having 1 to 10 carbon atoms of R include, for example, a branched or straight chain alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms,

[Chemical 3] Etc.

The compound represented by the general formula (I) is
As a product for sale, there is a phenol
Ralkir resin Milex XLC-4L (general formula (I)
Medium, Ar ¹Is a phenyl group, Ar^TwoIs a phenyl group, R¹Over
And R^TwoIs a methylene group, R is a hydrogen atom, and the average of n is about 3
Compound).

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 methylcyanurate. These are either alone or 2
Used in combination of two or more species. Of these, guanamine derivatives such as melamine and benzoguanamine are preferable from the viewpoint of heat resistance.

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

The amount of the triazine derivative used with respect to the compound represented by the general 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 flame retardancy of the resulting amino-modified phenol / aralkyl resin tends to be insufficient, and 20
If the amount exceeds 10% by weight, the resulting amino-modified phenol / aralkyl resin tends to have a too high softening point. The amount of aldehyde used is 1 for 1 mol of the triazine derivative.
-10 mol is preferred, and 1-5 mol is more preferred. 1
If it is less than 1 mol, the reaction between the compound represented by the general formula (I) and the triazine derivative tends to be difficult to proceed, and 1
If it exceeds 0, gelation tends to occur easily during synthesis.

The reaction temperature is preferably 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, etc. tend to deteriorate, and if the temperature exceeds 250 ° C, the compound represented by the general formula (I) is obtained. The reaction of the triazine derivative tends to be insufficient. The reaction time is about 1 to 20 hours. The reaction pH is preferably 1-10. If the pH is less than 1, the resin tends to gel during the synthesis, and if the pH exceeds 10, the reaction between the compound represented by the general formula (I) and the triazine derivative tends to be difficult to proceed. In addition, if necessary, an amine-based catalyst such as trimethylamine or triethylamine,
Alkali catalysts such as sodium hydroxide and potassium hydroxide,
An acid catalyst such as phosphoric acid, p-toluenesulfonic acid, oxalic acid,
From 0.00001 to 1 mol of phenol derivative
You may use about 0.01 mol.

In this way, after reacting the compound represented by the general formula (I) with the aldehyde and the triazine derivative, the unreacted aldehyde, water and the like can be removed under heating and reduced pressure under the conditions. Has a temperature of 80 to 180 ° C,
The pressure is 100 mmHg or less, 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 is a compound represented by the general formula (I) as a raw material,
An aldehyde and a triazine derivative are essential and can be produced by reacting each of these raw materials.

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

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

The amino-modified phenol / aralkyl resin of the present invention has heat resistance, water resistance, flame retardancy and the like, and corresponds to a molecular weight of 2,050 of standard polystyrene (graph measured by gel permeation chromatograph). The ratio a / b for the strength a in the above) and the strength b at the point corresponding to the molecular weight 655 is preferably 0.2 to 1.2.

The amino-modified phenol / aralkyl resin of the present invention has a binuclear content of the phenol derivative of 10 to 10.
It is preferably 40% by weight. Below 10% by weight,
The softening point tends to be high, and if it exceeds 40% by weight, the flame retardancy tends to be poor.

The phenol-amino condensation resin of the present invention preferably has a softening point of 40 ° C to 150 ° C, and 60 to 150 ° C.
It is more preferably 120 ° C. If it is lower than 40 ° C, the strength of the obtained cured product tends to be poor, and if it exceeds 150 ° C, workability tends to be poor at the time of synthesis.

From the viewpoint of safety and health and odor, it is preferable that the unreacted phenol derivative contained in the amino-modified phenol / aralkyl resin of the present invention is 3% by weight or less. Nitrogen content of amino-modified phenol-aralkyl resin of the present invention has flame retardancy 1 to 20 by weight%, from the viewpoint of 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, etc. to form a molding material excellent in heat resistance, strength, flame retardancy, etc.
The composition can be used as a friction material, a paint, a coating material, an adhesive sealing material, a laminated material, an FRP and a raw material for carbon products.

The epoxy resin used in the epoxy resin composition of the present invention includes phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin phosphorus-containing epoxy resin. A general epoxy resin is used and is not particularly limited, and there is no problem even if these epoxy resins are used alone or in combination of several kinds.

The compounding amount of the phenol-amino condensation resin with respect to the epoxy resin is not particularly limited, but it is preferably 20 to 200 parts by weight, and 50 to 150 parts by weight with respect to 100 parts by weight of the epoxy resin. Is more preferable. When the compounding amount of the amino-modified phenol aralkyl resin exceeds 200 parts by weight, the molded article tends to deteriorate in properties such as water resistance and moisture resistance, and when it is less than 20 parts by weight, reactivity, strength, flame retardancy, etc. Characteristics tend to deteriorate.

The epoxy resin composition of the present invention contains a phosphorus-containing compound such as phosphoric acid, phosphoric acid ester, halogen-containing phosphoric acid ester, condensed phosphoric acid ester and polyphosphoric acid ester for the purpose of imparting a flame retardant effect. It can be blended. The phosphorus-containing compound is preferably blended in a ratio of 100 parts by weight or less based on 100 parts by weight of the epoxy resin.
If the blending amount is more than 100 parts by weight based on 100 parts by weight of the epoxy resin, the water absorption of the molded product will be high, and the properties such as water resistance and moisture resistance will tend to deteriorate. Preferably 20 to 1
The compounding amount is 00 parts by weight. Further, when the phosphorus-containing compound is not blended, the flame retardancy of the molded article tends to be lower than when it is not blended, but other properties are less affected.

An inorganic filler and a curing accelerator can be appropriately used in combination with the epoxy resin composition of the present invention. As the inorganic filler, silica, quartz glass powder, calcium carbonate,
Examples thereof include calcium silicate, alumina, aluminum hydroxide, magnesium hydroxide, clay, mica and glass fiber. When using these, usually epoxy resin 1
It is used in an amount of 300 parts by weight or less based on 00 parts by weight. Preferably 100 to 300 parts by weight are blended. Examples of the curing accelerator include imidazoles such as 2-ethyl-4-methylimidazole, tertiary amine, BF ₃ -amine complex, organic phosphines and the like. These are preferably 0. to 100 parts by weight of the epoxy resin.
It is used in an amount of 01 to 2.0 parts by weight.

When the epoxy resin composition of the present invention is impregnated into a sheet-like base material such as glass cloth or glass non-woven fabric with a solvent such as toluene or methanol as required, a prepreg for a laminated board is obtained. The amount of the epoxy resin composition used is appropriately determined depending on the conditions and is not limited. For example, it is used so that the resin solid content of the epoxy resin composition is 10 to 90% by weight with respect to the total of the sheet-shaped substrate.

A laminate such as a copper clad laminate is obtained by thermoforming a laminate in which a plurality of the prepregs are laminated or a copper foil laminate in which copper foil is laminated on one side or both sides of the laminate. You can

[0034]

EXAMPLES The present invention will be described more specifically below by showing Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. <Synthesis of amino-modified phenol aralkyl resin>

Example 1 Phenol aralkyl resin Milex XLC-4L100 was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer.
g, 6.3 g (0.05 mol) of melamine, and 8.1 g (0.1 mol) of 37% formalin water were added, and the pH was adjusted to 2 with 10% oxalic acid, and then refluxed to 150 ° C for 2 hours. The temperature was raised by and the reaction was carried out at 150 ° C. for 4 hours. Then, unreacted aldehyde and water were removed under reduced pressure at 180 ° C. The amount of the purified amino-modified phenol / aralkyl resin was 110 g, and the softening point was 90 ° C.

Example 2 Phenol aralkyl resin Milex XLC-4L100 was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer.
g, benzoguanamine 17.6 g (0.1 mol), 37
Add 24.34 g (0.3 mol) of% formalin water, 1
After adjusting the pH to 2 using 0% oxalic acid, the temperature was raised to 150 ° C in 2 hours while performing reflux dehydration, and the reaction was carried out at 150 ° C for 4 hours. Then, unreacted aldehyde and water were removed under reduced pressure at 180 ° C. Purified amino-modified phenol
The amount of aralkyl resin was 125 g, and the softening point was 95 ° C.

Comparative Example 1 In a flask equipped with a stirrer, a reflux condenser and a thermometer, 94 g of phenol (1 mol) and 37% formalin water 25.1
g (0.3 mol) and melamine 4.34 g (0.034 mol) were added, and after adjusting the pH to 8 using triethylamine, the temperature was raised to 140 ° C. in 4 hours while performing reflux dehydration, and then 5 at 140 ° C. Reacted for hours. Then 14
Unreacted phenol and water were removed under reduced pressure of 60 mmHg at 0 ° C. The amount of purified resin is 40.8g,
The softening point was 80 ° C.

Application Example 1 70 parts by weight of cresol novolac type epoxy resin (epoxy equivalent 220), 30 parts by weight of phosphorus-containing epoxy resin (phosphorus content 3%, epoxy equivalent 300) Amino-modified phenol / aralkyl resin synthesized in Example 1 40 parts by weight and 0.5 parts by weight of 2-methyl-4-methylimidazole were dissolved in methyl ethyl ketone to prepare a mixed solution having a nonvolatile content of 60%. Then, this mixed solution was impregnated into a glass cloth so that the resin solid content was about 50% with respect to the total of the glass cloth, and dried at 180 ° C. for 3 minutes to obtain a prepreg. Eight layers of this prepreg were laminated, 18 μm copper foil was further laminated on both sides, pressure 40 Kg / cm ² , temperature 1
Pressurization and heat molding were carried out under the condition of 80 ° C. to prepare a copper clad laminate. The characteristics are shown in Table 1.

Application Examples 2-3 and Comparative Application Example 1 A molding material was prepared in the same manner as in Application Example 1. An example of the formulation is shown in Table 1. Table 1 shows these characteristics.

The test methods for the epoxy resin composition and the copper-clad laminate are as follows. (1) Evaluation of glass transition temperature (Tg) The tan δ of the molded plate was measured by a viscoelasticity measuring device (RSAII manufactured by Rheometric Scientific FE), and its peak temperature was taken as Tg. (2) Evaluation of peel strength The adhesive strength at 25 ° C. between the inner layer of the molded product and the copper foil is
It was measured by a 180 degree peel test method using Shimadzu Corporation Autograph AGS-100B. (JIS C6
471) (3) Evaluation of Moisture Resistance Solder Resistance The test piece was immersed in a solder bath at 280 ° C. for 30 seconds, and the appearance was evaluated. ◯: No change Δ: Slightly discolored, with blister. X: Discoloration and remarkable blistering. (5) Flame retardancy; evaluated by the VB method according to UL-94. (1/8 inch test piece)

[0041]

[Table 1]

[0042]

The epoxy resin composition of the present invention containing an amino-modified phenol / aralkyl resin gives a prepreg excellent in heat resistance, flame retardancy, strength and curability. The prepreg of the present invention thus obtained can produce a laminate such as a metal-clad laminate with good productivity and yield.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F072 AA07 AB09 AB29 AB30 AD18                       AD21 AD30 AF03 AF04 AF06                       AF16 AG03 AG16 AG17 AG19                       AH02 AH21 AJ04 AK14 AL12                       AL13                 4F100 AB17A AH03B AH03H AK33B                       AK35B AK53B AL05B BA02                       CA02B DH01B GB43 JJ03                       JJ07 JK01                 4J033 EA02 EA03 EA34 EA35 EA36                       EA45 EA46 EB03 FA01 FA06                       FA11 HA02 HA04 HA09 HA12                       HB02 HB03                 4J036 AA01 AA05 AB01 AB19 AD08                       AF06 AF08 BA02 DA01 DA02                       DC05 DC41 DD07 FA02 FA03                       FA04 FA05 FA06 FA09 FA12                       FB06 GA15 GA19 HA12 JA11                       KA01

Claims (9)

[Claims] 1. An amino-modified phenol / aralkyl resin characterized by reacting a compound represented by the following general formula (I) with a triazine derivative and an aldehyde. [Chemical 1] (In the formula, Ar ¹ represents an aryl group having 6 to 14 carbon atoms, Ar ² represents an aryl group having 6 to 14 carbon atoms or a biphenyl group, and R ¹ and R ² each independently have 1 carbon atom. ~
6 is an alkylene group, R is a hydrogen atom or a carbon number 1
10 represents an organic group, and n is an integer of 0 to 8) 2. The amino-modified phenol / aralkyl resin according to claim 1, wherein the compounding amount of the triazine derivative with respect to the phenol / aralkyl resin is 1% by weight to 30% by weight. 3. The molar ratio of aldehydes to the triazine derivative is 1 to 10.
2 amino-modified phenol aralkyl resin. 4. The amino-modified phenol according to claim 1, wherein the phenol / aralkyl resin, the triazine derivative and the aldehyde are reacted at a pH of 3-9.
Aralkyl resin. 5. An epoxy resin composition comprising an epoxy resin and the amino-modified phenol / aralkyl resin according to any one of claims 1 to 4. 6. An epoxy resin composition containing 20 to 200 parts by weight of the amino-modified phenol / aralkyl resin according to claim 1 to 100 parts by weight of the epoxy resin. 7. The imidazoles are contained in an amount of 0.01 to 2.0 parts by weight based on 100 parts by weight of the epoxy resin.
The epoxy resin composition described. 8. A prepreg in which a sheet base material is impregnated with the epoxy resin composition according to any one of claims 5 to 7. 9. A laminate obtained by heat-forming a laminate obtained by laminating a plurality of the prepregs according to claim 8 or a copper foil laminate obtained by laminating copper foil on one side or both sides of the laminate.