JPS6330520A - Epoxy resin composition for laminated sheet - Google Patents

Abstract

PURPOSE:To obtain the title epoxy resin composition excellent in heat resistance, adhesiveness, water resistance, etc., and suitable for the production of laminated sheets used in the electrical field, etc., by mixing a specified polyglycidyl ether compound with an epoxy resin curing agent. CONSTITUTION:At least one compound selected from among polyglycidyl ether compounds of formulas I, II and III (wherein X is H or a halogen, R is H or an alkyl, R<1>-R<10> are each H, alkyl, phenyl or a halogen and l, m and n are each >= 0) is mixed with an epoxy resin curing agent (e.g., dicyadiamide) to obtain the purpose epoxy resin composition for laminated sheets. The compound of formula I, II or III can be obtained by reacting a bisphenol epoxy resin of formula IV with a bisphenol derivative of formula V (e.g., 4,4'- bishydroxybiphenyl) in the presence of a catalyst (e.g., tert. amine).

Description

Detailed Description of the Invention (a) Purpose of the Invention (Field of Industrial Application) The present invention provides a laminate that can be used as a seed layer that has excellent heat resistance, adhesiveness, and water resistance, and in particular, a laminate that has excellent heat resistance. The present invention relates to an epoxy resin composition for electromagnetic laminates.

(Prior Art) Generally, in electrical laminates, an inorganic fiber woven fabric such as a glass cloth is used as a base material, and a phenol resin, epoxy resin, or polyimide resin is used as a resin.

Epoxy resins have excellent mechanical strength and adhesive properties, and generally have excellent adhesive properties between base material layers and between a base material and metal foil. In particular, bisphenol A type epoxy resins and halodanated bisphenol A type epoxy resins exhibit particularly high adhesive properties and are therefore frequently used in this type of application. However, when only bisphenol A type epoxy resin is used, the crosslinking density is low, and the lath transition temperature is low.
For example, when drilling the obtained seed laminate, the epoxy resin is softened by the frictional heat generated by the drill, resulting in a so-called drill smear phenomenon. Therefore, in order to improve this drawback, conventionally, phenol nodela, resin or cresol resin has been used. Um, nodera of resin etc., mold work? A portion of the resin is blended to increase the crosslinking density of the resin. However, as the amount of blending of the novolac molding resin increases, the adhesive strength of the resin decreases rapidly, so there is a limit to the size of the blend, and sufficient heat resistance cannot be obtained.

Furthermore, polyimide resins have a high glass transition temperature and therefore can sufficiently satisfy heat resistance, but their use is limited to special fields because of their poor adhesive strength.

(Problems to be Solved by the Invention) The present invention has improved all the above-mentioned drawbacks of conventional epoxy resins and polyimide resins for laminates, that is, it has excellent heat resistance, adhesion and water resistance, and particularly It is an object of the present invention to provide an epoxy resin composition for laminates, particularly an engineered resin composition for FC laminates which has excellent heat resistance and is suitable for manufacturing laminates used in the electrical field.

(b) Structure of the Invention (Means for Solving All Problems) The epoxy resin composition for laminates of the present invention has the following formula: is a hydrogen atom or an alkyl group, and R-R are each a hydrogen atom, an alkyl group, a phenyl group, or a halodane atom, and may be the same or different from each other.A, m,
Each n is an integer of 0 or more. ] A polyglycisol ether compound represented by the general formula - [wherein, Groups or halodane atoms may be the same or different from each other e Z
Each of s m @n is an integer greater than or equal to 0. ] A polyglycidyl ether compound represented by the general formula [wherein, , phenyl group, or halokene atom, and may be the same or different from each other.

L+nl and fi are each integers greater than or equal to 0. ] This is a composition containing at least one compound selected from the group consisting of polyglycisol ether compounds represented by the following and (B) an epoxy resin curing agent.

The epoxy resin composition of the present invention can be used to produce various epoxy resin laminates (laminates, metal foil-clad laminates, etc.) for audio equipment, electronic components, and electrical equipment that have improved heat resistance and adhesive properties. board, multilayer board, etc.). For example, it is possible to obtain an electrical laminate that does not cause the measling phenomenon or peeling between the eyebrows caused by heating by far infrared rays, infrared rays, soldering, etc., and has excellent through-hole connection reliability with extremely little warpage or dimensional change.

The bisphenol skeleton constituting the molecule of the polyglycidyl ether compound represented by the general formula (1), (n) or (II) to be contained in the epoxy resin composition of the present invention includes nine bisphenol A skeletons. , bisphenol F-based skeleton, tetrabromobisphenol A
Examples include a mixed skeleton of two or more of these bis-7-enol-based skeletons, and the like.

In addition, the biphenol skeleton constituting the molecules of these polyglycidyl ether compounds includes, for example, 4,4
'-bishydroxybiphenyl skeleton, 4,4'-bishydro medium 3.3%s, s'-tetramethylbiphenyl skeleton, 4,4'-bishydroxy-3,3', 5゜5'
-tetramethyl-2-chlorobiphenyl skeleton, 4.4'
-bishydroxy-3,3',5.5'-tetramethyl-2-bromobiphenyl skeleton, 4,4'-bishydroxy-3,3-5,5'-tetraethylbiphenyl skeleton,
Examples include a 4,4'-bishydroxy-3,3', 5,5'-tetraphenylbiphenyl skeleton, and a mixed skeleton of two or more of these biphenyl skeletons.

Represented by the general formula (1), (n) or (DI) contained in the epoxy resin composition of the present invention,
The je IJ glycidyl compound and the mixture of these compounds can be produced by various methods, and the following three methods are listed as typical production methods.

The first method is based on the general formula [wherein R, X, R, R and t all represent the same as those in the above general formula (1). ] A bisphenol-type epoxy resin represented by the formula [In the formula, R-R each represents the same thing as in the general formula CI). ], such as 4,4'-bishydroxybiphenyl, 4,4'-bishydroxy-3,3',5,5
'-tetramethylbiphenyl, 4,4'-bishydroxy-3,3', 5,5'-tetramethyl-2-chlorobiphenyl, 4,4'-bishydroxy-3,3', 5.
5'-tetramethyl-2-bromobiphenyl, 4.4'
-bishydroxy-3,3', 5,5'-tetraethylbiphenyl, 4,4'-bishydroxy-3,3;s,
Examples include a method of reacting s'-tetraphenylbiphenyl or a mixture thereof at 120 to 190° C. for 2 to 5 hours by adding tertiary amines, imidazoles, or quaternary ammonium salts as a catalyst. According to this method, a compound (including a mixture thereof) corresponding to the polyglycidyl ether compound represented by the general formula (1) can be obtained.As the raw material bisphenol-type epoxy resin in the first method of Uko, commercially available Bisphenol type epoxy resins, such as Epicote 828, Epicote 1
001 (the above are bisphenol A-type epoxy resins, all trade names of Yuka Shell Epoxy Co., Ltd.), etc., Epicor 807 (bisphenol F-type epoxy resin, trade names of Yuka Shell Epoxy Co., Ltd.), etc., Epicort 5050.
Epicote 5051FC and above are brominated bisphenol A
Type epoxy resin, Yuka Shell Epoxy Co., Ltd. product name)
etc. can be used.

In addition, as the second method, the general formula [wherein R3-
R10, and t (-1, both of the above - general formula (n)
Represents the same thing as those in K. A biphenol-type epoxy resin represented by the formula (wherein, A
Tertiary amines, 1-bisphenol F, tetrabromo-bisphenol A, etc., or a mixture thereof as a catalyst.
An example is a method in which all imidazoles or quaternary ammonium salts are added and reacted at 120 to 190°C for 2 to 5 hours. According to this method, a polyglycidyl ether compound represented by the general formula (If) is obtained.

The biphenol-type epoxy resin used as a raw material in this second method is a commercially available resin such as Epicor YX40.
00 (Product name of Yuka Shell Epoxy Co., Ltd., 4,4'
The amount of epoxy resin having -bishydroxy-3,3-5,5'-tetramethylbiphenyl skeleton, etc. can be used.

As the third method, a bisphenol type epoxy resin represented by the general formula (IV) and a bisphenol type epoxy resin represented by the general formula (■
), a biphenol derivative represented by the general formula (V) and/or a bisphenol represented by the general formula [■] is mixed with a mixture of biphenol-type epoxy resins represented by the formula (V), and tertiary amines and imidazole are added as a catalyst. 12 by adding quaternary ammonium salts, etc.
A method of reacting at 0 to 190°C for 2 to 5 hours is exemplified.

According to this third method, the general formula (III)
It is expressed as A mixture of compounds of the 751J spider layer is obtained.

The composition of the present invention includes general formulas (I) to (II) described above.
One type of polyglycidyl ether compound represented by I) may be contained alone, or two or more types thereof may be contained as a mixture. Furthermore, these polyglycidyl ether compounds can be used in combination with a relatively small amount of other epoxy compounds within a range that does not significantly impair the cured physical properties of the composition of the present invention. Furthermore, in the polyglycidyl compounds represented by the general formulas (I) to (II) in the present invention, a portion of the terminal epoxy groups of these compounds may be reacted with a monophenol compound to prepare a relatively small amount. The polyglycidyl ether compound used in the present invention containing such a phenol-modified epoxy compound may be used in a small amount in the reaction system during the production process of the polyglycidyl ether compounds (I) to (III) of the present invention. It can be obtained by adding a phenol compound.

Various kinds of epoxy resin curing agents (B) can be used as the epoxy resin curing agent (B) to be added to the composition of the present invention. Examples include a variety of curing agents including known curing agents such as dicyandiamide, aromatic amines, novolac type phenolic resins, and acid anhydrides. Two or more types of epoxy resin curing agents may be used in combination.

Furthermore, the epoxy resin composition of the present invention does not contain curing accelerators, solvents, fillers, etc., which are usually blended in epoxy resin compositions for laminates, especially electrical laminates, without deteriorating the cured physical properties of the epoxy resin composition. It can be blended within the range. Examples of the curing accelerator include benzyldimethylamine, 2-(dimethylaminomethyl)phenol,
Examples include 2,4,6-tris(dimethylaminomethyl)phenol, various imidazoles, and BF3 amine salts.

Examples of the solvent include methyl ethyl ketone, acetone, ethylene glycol monomethyl ether,
Examples include dimethylformamide.

In order to manufacture a laminate using the epoxy resin composition of the present invention, various conventionally used methods can be used. For example, a solvent is added to the epoxy resin composition of the present invention containing component (A) and component (B), and other components blended as necessary, and the composition is dissolved to form a resin face. This resin face has a resin amount of, for example, 50
A glass cloth is impregnated to a desired amount such as weight %, and this is heated and dried to form a B-stage! Get all the relegs.

Next, a predetermined number of prepreg sheets are stacked together and heated and pressed to obtain a laminate with excellent adhesiveness and workability. Sincerely,
At the time of lamination molding, metal foil such as copper foil may be laminated as necessary.

(c) Effects of the Invention If the NIXY resin composition of the present invention is used, a laminate with excellent heat resistance, adhesion, water resistance, and workability can be obtained, and in particular, it is extremely excellent in heat resistance and has no deformation or glabella due to heating. without causing m
A laminate with good drillability can be obtained.

(Examples etc.) Below, epoxy resin production examples, examples, and comparative examples are given and further detailed. In these examples, "parts" refer to parts by weight.

Epoxy resin production example A 4. 100 parts of diglycidyl ether of 4'-bis-3,3',5,5'-tetramethylbiphenol (trade name Epiny, Yuka Shell E4XI Co., Ltd.) YX4000, epoxy equivalent 186), 0.03 part of tetramethylammonium iodide was added as a catalyst to 54 parts of tetrabromobisphenol A, and the mixture was heated at 170°C for 3 hours.
After reacting for a period of time, a 4-oxy resin having an epoxy equivalent weight of 450 and a solid at room temperature was obtained.

In this epoxy resin, in the general formula (n), R is a hydrogen atom, and R'l R2, R3, R5, R8, R
" is a methyl group, R, R, R, R are hydrogen atoms, and X is a bromine atom. This is a polyglycidyl ether compound corresponding to a compound. Hereinafter, this is referred to as "epoxy resin A."

Epoxy resin production example B 100 parts of diglycidyl ether of 4.4'-bis-3,3',5.5'-tetramethylbiphenol (Yuka Shell Epoxy Co., Ltd. trade name Epicote YX4000. Epoxy equivalent conductor 86), and Bisphenol A 2
To 9 parts, 0.03 part of 2-methylimidazole was added as a catalyst, and the mixture was reacted at 170°C for 3 hours to obtain an epoxy resin having an epoxy equivalent of 450 and solid at room temperature.

In the general formula (II), this epoxy resin has R
is a hydrogen atom, R', R2e R3, R5, R8
, R10 is a methyl group, R, R, R, R are hydrogen atoms, and X is a hydrogen atom. Hereinafter, this will be referred to as "epoxy resin B."

Nyxy resin production example C 4,4'-bis-3,3',5,5'-tetramethylbiphenol diglycidyl ether (Yuka Shell Epoxy Co., Ltd. trade name Epiny) YX4000. To 100 parts of epoxy equivalent (186) and 87 parts of tetrabromobisphenol A, 0.03 part of tetramethylammonium iodide was added as a catalyst, and
After reacting for a period of time, an epoxy resin having an epoxy equivalent weight of 870 and a solid at room temperature was obtained.

In the general formula (If), this epoxy resin has R
is a hydrogen atom, R't R2t R3+ R5,R
8, R10 is a methyl group, R4, R6, R7, R9
was a hydrogen atom, and X was a bromine atom. Hereinafter, this will be referred to as "epoxy ratio compound C."

Epoxy resin production example D Epichlorohydrin-bisphenol A type epoxy resin (Yuka Shell Ef!Yashi Co., Ltd. Product name Epicote 82
8, epoxy equivalent 187) 100 parts, and 4,4'-bis-3,3',s,s'-tetramethylbiphenol 3
To 0 part, 0.03 part of 2-methylimidazole was added as a catalyst, and the mixture was reacted at 170°C for 3 hours to obtain an epoxy resin having an epoxy equivalent of 410 and solid at room temperature.

In the above general formula (1), R is a hydrogen atom, and R1, R2, R3, R5, R13, R
This was a polyglycisol ether compound corresponding to a compound in which oo was a methyl group, R4, R6, R7, and R9 were hydrogen atoms, and X was a hydrogen atom. Hereinafter, this will be referred to as "epoxy resin D."

Epoxy resin production example E Epichlorohydrin-bisphenol A type epoxy resin (Product name: Epicote 828, Yuka Shell Edoxy Co., Ltd.
, epoxy equivalent of 187), and 23 parts of 4,4'-biphenol, 0.03 part of 2-methylimidazole was added as a catalyst, and the mixture was reacted at 170°C for 3 hours to give an epoxy equivalent of 440 at room temperature. A solid epoxy resin was obtained.

This epoxy resin is a polyglycyl resin corresponding to a compound in the general formula (I), where R is a hydrogen atom, R1-R2 are a methyl group, X is a hydrogen atom, and R3 to H10 are hydrogen atoms. It was a sol ether compound. Hereinafter, this will be referred to as "epoxy resin E."

Engineering? Kinsei Seishin Production Example F In a three-neck flask with an internal volume of 11 equipped with a stirrer, a thermometer, and a condenser, 4,4'-bis-3,3-5,5'-tetramethylbiphenol 121.2. FCo, 5 mol],
Epichlorohydrin 370!9 (4 mol) and tetramethylammonium iodide 2.42!i (2 parts by weight based on piphenyl) were charged, the oil bath was heated to 130°C, and an addition reaction was carried out under reflux for 2 hours. .

The contents were then cooled to 60°C, a water removal device was attached, and the reactor was charged with 42.9 (1,
05 mol) at a temperature of 50 to 65°C and a degree of vacuum of 100 to 65°C.
The produced water was continuously azeotropically removed under the conditions of 200 fiI (H) to prevent the ring-closing reaction. The reaction was terminated when the produced water reached 131 nl (approximately 1.5 hours).

After recovering the excess epichlorohydrin under reduced pressure, 500 d of toluene was added and washed three times with 1 liter of water to remove the formed common salt, remaining alkali, and catalyst. Toluene was removed under reduced pressure using a rotary evaporator to obtain a pale brown solid epoxy resin.

This epoxy resin had an epoxy equivalent weight of 187.

In the general formula (II), this epoxy resin has R
is a hydrogen atom and R, R, R, R are a methyl group,
There were polyglycisol ether compounds corresponding to compounds in which R, R, R, and R are hydrogen atoms. Hereinafter, this will be referred to as "epoxy resin F."

Epoxy resin production example G Epichlorohydrin-bisphenol A epoxy resin (Yukaken L Epoxy Co., Ltd. trade name Epicote 828
, epoxy equivalent 187) 50 parts, and 4,4'-bis-
Diglycidyl ether of 3,3',5,5'-tetramethylbiphenol (Yuka Shell Epoxy Co., Ltd. trade name: Epiny) YX4000. Epoxy equivalent weight 186)
To 50 parts, 29 parts of bisphenol and 0.03 parts of tetramethylammonium iodide as a catalyst were added, and the mixture was reacted at 170°C for 3 hours to give an epoxy equivalent of 470.
An epoxy resin which was solid at room temperature was obtained.

In the general formula (III), this epoxy resin has the following formula:
R is a hydrogen atom, R-R is a methyl group, X is a hydrogen atom, p, R3, R5, R8, Hlo are methyl groups, and R', R6, R', R' are hydrogen atoms It was a polyglycisol ether compound corresponding to the compound. Hereinafter, this will be referred to as "epoxy resin G."

Examples 1 to 14 Comparative Examples 1 to 5 Epoxy resin A- obtained in the above epoxy resin production example
After impregnating a glass cloth in an epoxy resin varnish (resin component: 60% by weight) obtained by blending G and commercially available epoxy resin with various materials as shown in Table 1,
Dry the varnish-impregnated cloth for 2 minutes in a drying room at 0°C,
A B-steno-like grippreg was obtained.

8 pieces of Noripreg obtained by cutting this prepreg and 1 piece of copper foil
The sheets were stacked together and heated under pressure at 175° C. for 120 minutes while applying pressure at 4 oyu/cm” to form a laminate.

The physical properties of the obtained cured laminate are shown in Table 1, and the laminate using the resin of the example has extremely good overall heat resistance (glass transition temperature), boiling water resistance, and adhesion. Met.

Note 2 to Table 1 (1) Molding conditions Examples and comparative examples: 175°C x 120 minutes x 40 Yu/13 (2) Test method and evaluation of cured physical properties (1) Glass transition temperature measured by DSC (11) Boiling resistance Water-based disk-shaped cured product (diameter 501 x thickness 3-1 hardened at 80°C)
×10 hours + 120°C × 2 hours + 175°C × 2 hours)t
After being immersed in boiling water at -98° C. or higher for 4 hours, the presence or absence of abnormalities was visually determined and evaluated according to the following criteria.

A...No abnormality B...-Discolored to white at 6 C... Discolored to white on the entire surface (111) Adhesiveness The laminate after molding was visually judged and compared to the following criteria. Please make sure to evaluate it.

Human: Good adhesion 3: Slightly poor adhesion C: Poor adhesion 3) The nine commercially available epoxy resins used are as follows.

Epinye) 5049 Yuka Shell Epoxy Co., Ltd. trade name, brominated bisphenol A type Niexy resin, engineering 4-oxyequivalent 760. Bromine content 26 heavy T4 Epicor) 1001 Yuka Querue I Kishi Co., Ltd. Product name, Bisphenol A
Type Nyxy resin, epoxy equivalent Epicoat 180 Yuka Shell Eqi Co., Ltd. Product name, cresol novolac type epoxy resin, epoxy equivalent Epicoat 5046

Claims (1)

[Claims] (1) (A) General formula▲ Numerical formulas, chemical formulas, tables, etc.▼ [In the formula, X is a hydrogen atom or a halogen atom, R is a hydrogen atom or an alkyl group, and R^1~R^1^ 0 represents a hydrogen atom, an alkyl group, a phenyl group, or a halogen atom, and may be the same or different from each other. l, m, and n are each integers of 0 or more. ] Polyglycidyl ether compound represented by the general formula ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is a hydrogen atom or a halogen atom, R is a hydrogen atom or an alkyl group, and R^1 to R^1^0 are a hydrogen atom, an alkyl group, They are phenyl groups or halogen atoms, and may be the same or different. l, m and n are each integers of 0 or more. [In the formula, X is a hydrogen atom or a halogen atom, R is a hydrogen atom or an alkyl group, and R^1~ R^1^0 each represents a hydrogen atom, an alkyl group, a phenyl group, or a halogen atom, and may be the same or different. l, m, and n are each integers of 0 or more. ] An epoxy resin composition for a laminate, comprising at least one compound selected from the group consisting of polyglycidyl ether compounds represented by the following: and (B) an epoxy resin curing agent.