JPH02229041A - Heat-resistant laminated sheet - Google Patents

Abstract

PURPOSE:To make solubility of varnish favorable, enable lengthening of usable time of the varnish or a prepreg, become superior in heat resistance, moisture resistance, adhesion, mechanical properties and processability and contrive especially an improvement in ply adhesion, by making use of specific pure polyimide resin free from modification. CONSTITUTION:A heat-resistant resin composition constituted of organic solvent- soluble polyether imide shown by a formula I, and N, N'-bisimide compound of unsaturated dicarboxylic acid shown by a formula IIa, aminophenol of a formula IIb and an additional reaction matter of aromatic diameter of a formula IIIc is used for a heat-resistant laminated sheet. Where R<1> and (n) in the formula I show respectively a formula III and an integral number of at least 2. R<2> and R<3> in the formula IIa show respectively a bivalent group having at least two carbon atoms and the bivalent group containing double bond between the carbon atoms. R<4> in the formula IIb shows a hydrogen atom or a halogen atom or an alkyl group. X<1>, X<2>, X<3> and X<4> in a formula IIc show the same or different halogen atom.

Description

[Detailed Description of the Invention] [Objective of the Invention] (Industrial Application Field) The present invention provides a heat-resistant laminate with excellent interlayer adhesion using pure polyimide that has not been modified with other resins such as epoxy resin modification. Regarding.

(Prior Art) In recent years, the development of electronic devices has been remarkable, and the uses and processing conditions for copper-clad laminates have become diverse, and excellent properties are required. In particular, as wiring density increases, wiring boards become more multi-layered and through-holes become smaller in diameter.
There is a demand for copper-clad laminates with good workability, such as less smearing during drilling.

On the other hand, with the demand for improved productivity and lower costs, increasingly strict conditions have been added to the wiring board mounting process, such as pot air refilling and flow soldering.
Under these circumstances, copper-clad laminates that serve as substrates are required to have better heat resistance and moisture resistance than ever before. In recent years, in order to meet these demands, epoxy resins have been widely used in copper-clad laminates.
Addition reaction type polyimide resins have come into use. When this polyimide resin is used in prepreg for copper-clad laminates, the occurrence of smear during drilling becomes almost zero, and the heat resistance during processing and long-term tests is significantly improved.

However, the conventionally used addition reaction type polyimide resins have had various problems as described in 4' below. That is, a product made by reacting N,N'-bisimide, an unsaturated dicarboxylic acid, with diaminodiphenylmethane is excellent for use in laminates, but on the other hand, diaminodiphenylmethane is highly reactive and is not suitable for use in varnishes and prepregs. The problem is that the usage time is short. Products containing N,N'-bisimide, an unsaturated dicarboxylic acid, and aminophenol as the reaction components have well-balanced properties and excellent processability for use in laminates, but have poor moisture resistance, such as For long-term storage of the obtained prepregs and laminates, special attention must be paid to moisture absorption. A product obtained by reacting an unsaturated dicarboxylic acid N,N'-bisimide with amine benzoic acid is suitable for use in laminates, but
It has poor solubility in low-boiling point solvents, making it difficult to apply to crow cloth, etc., and also requires care in storing the resin solution. Maleimide-based compounds that are not polymerized alone have poor thermal properties, but their molecular structure inevitably leads to inferior mechanical strength, so it is not possible to improve mechanical strength even at the cost of sacrificing thermal properties to some extent. The current situation is that In addition, organic solvent-soluble polyetherimide is attracting attention as a high-performance engineering plastic that can be injection molded, and is used in various applications such as films and molding materials. was there.

Additionally, a common problem with pure polyimide resin laminates is that the adhesive strength with silver foil and the interlayer adhesive strength between crow cloth are weak.

(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned drawbacks. The present invention aims to provide a heat-resistant laminate that uses a pure polyimide resin with excellent properties and moldability and also has good interlayer adhesion.

[Structure of the Invention] (Means for Solving the Problems) As a result of extensive research in an attempt to achieve the above object, the present inventor has discovered that organic solvent-soluble polyetherimide and unsaturated dicarboxylic acid N,N' - We have found that the above object can be achieved by using a heat-resistant resin composition consisting of a hisimide compound, an amine phenol, and an addition reaction product of an aromatic diamine, and have completed the present invention.

That is, the present invention comprises an organic solvent-soluble polyetherimide represented by <A>-clothing cost, n represents an integer of 2 or more), and (B) <a)-clothing cost (wherein R2 is A N,N'-bisimide compound of an unsaturated dicarboxylic acid represented by a divalent group having at least 2 carbon atoms (R3 represents a divalent group containing a double bond between carbon atoms); Aminophenol represented by the formula (R4 represents a hydrogen atom, a halogen atom or an alkyl group), (C)-Fukudai (wherein x', x2, x3, x' represent the same or different halogen atoms) ) A heat-resistant laminate characterized by comprising a pure polyimide-based thermal resin composition containing as an essential component an addition reaction product of an aromatic diamine, and a base material.

The present invention will be explained in detail below.

Examples of the organic solvent-soluble polyetherimide (A) used in the present invention include ULTEM polyetherimide (trade name, manufactured by CGE). This is shown by the general formula mentioned above, and is a polyether production reaction (
obtained by aromatic nucleophilic substitution polymerization with elimination of nitro group), dimethylformamide, dimethylacetamide,
It is soluble in aprotic organic solvents such as N-methyl-2-pyrrolidone. Here, as polyamines when synthesizing the nitro group-containing polyimide intermediate, 4.4
Examples include '-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diamino-3,3'-dichlorodiphenylmethane, and 3-talolophenylenediamine.

The addition reaction product (B) used in the present invention includes <a> an N,N'-bisimide compound of an unsaturated dicarboxylic acid;
) amine phenol and (C) aromatic diamine are used.

(a) As the N,N'-bisimide compound of unsaturated dicarboxylic acid, one having the following general formula is used.

However, in the formula, R2 is 2 having at least 2 carbon atoms.
The valent group R3 does not represent a divalent group containing a double bond between carbon atoms. In other words, R2 is a linear or branched alkylene group, a cycloalkylene group having a ring of 5 to 6 carbon atoms, or a divalent heterocycle containing at least one of oxygen, nitrogen, or sulfur atoms. -NHCO+, -NR5 including formula group, phenylene group or divalent polycyclic aromatic group
Examples include a plurality of aromatic groups and alicyclic groups bonded by -3iR6R'- or -802-. Incidentally, R', R6, and R' represent an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having a ring having 5 to 6 carbon atoms, or a phenyl group.

Further, R3, that is, a divalent group containing a double bond between carbon atoms, includes, for example, a maleic acid residue, a citraconic acid residue,
Examples include tetrahydrophthalic acid residues. Therefore,
Specifically, the N,N'-bisimide compounds of unsaturated dicarboxylic acids that satisfy the above-mentioned conditions of R2 and R3 include the following, and each of these can be used singly or in a mixed system of two or more. I can do that. maleic acid N
, N'-4,4'-diphenylmethane hisimide, N maleic acid, N'-44'-diphenyl ether bisimide, N maleic acid, N'-paraphenylene bisimide, N maleic acid, N'-benzidine pisimide I ', maleic acid N, N'-metaxylene hisimide, maleic acid N, N'-15-naphthalene-hisimide, maleic acid N, N'-4,4'-diphenylsulfone-bisimide, maleic acid N, N'-2,2'-4,4'-dimethylene-cyclohexane-bisimide, maleic acid N,
N'-4,4'-dicyclohexyl-methane bisimide, N maleic acid, N'-44'-diphenylcyclohexane-bisimide, N maleic acid, N'-44'-
Diphenyl-phenylamine-bisimide, N maleic acid, N'-44'-diphenyl-diphenylsilane-
Bisimide, maleic acid N, N'-44'-diphenyl sulfur-hisimide, maleic acid NN'-2,2'-(4
, 4'-diphenyl)-propane-bisimide, malein IN, N'-metaphenylene bisimide, maleic acid N, and N'-3,3'-(NN'-metaphenylene-bisbenzamide) pisimide.

Moreover, as the amine phenol (b), one having the following general formula is used.

However, in the formula, R4 represents a hydrogen atom, a halogen atom, or an alkyl group. Specific examples of these compounds include 0-aminephenol, m-aminophenol, p-aminophenol, 2-amino-4-ri00phenol, 2-amino-4-methylphenol, etc. Alternatively, two or more types can be used in combination.

Further, as the aromatic diamine (C), an aromatic diamine having the following general formula is used.

However, in the formula, X1 and X4 represent the same or different halogen atoms, and specific compounds include, for example, 4,4'-diamino-3,3', 5.5'
Examples include -te1herachlordiphenylmethane, 4,4'-diamino-33', and 55'-tetrabromidiphenylmethane, and these can be used alone or in a mixture of two or more.

The above-mentioned (a) N,N'-bisimide compound of unsaturated dicarboxylic acid, (b) aminophenol, and (C) aromatic diamine are heated and reacted in a solvent-free or inert solvent to produce an addition reaction product. can do. These 3
As for the blending ratio of the components, it is desirable to blend 0.1 to 1.0 moles of amine phenol and aromatic diamine in a total amount of #1 to 1 mole of N,N'-bisimide compound of unsaturated dicarboxylic acid. If the proportion is less than 0.1 mole, the reaction will not proceed and properties such as heat resistance and toughness will deteriorate, while if it exceeds 1.0 mole, unreacted amine will remain, which is not preferable since the heat resistance will be significantly reduced. The order of blending the three components, the reaction temperature, and the solvent can be selected as appropriate and are not particularly limited.

The addition reaction product (B) thus produced can be blended with the organic solvent-soluble polyetherimide (A) to produce a heat-resistant resin composition. It is desirable that the addition reaction product be blended in an amount of 20 to 95% by weight based on the entire resin composition. This is because if the blending amount is less than 20% by weight, processability will decrease, and if it exceeds 95% by weight, mechanical strength will decrease, which is not preferred.

Next, a typical manufacturing process will be explained as an example.

N,N'-bisimide compounds of unsaturated dicarboxylic acids, aminophenols, and aromatic diamines are charged into a reaction vessel in a predetermined ratio, and the contents are melted by heating to 100 to 200°C to achieve a predetermined viscosity. , proceed the reaction until cure time. An organic solvent-soluble polyetherimide is blended with this reaction product and further dissolved in a solvent such as acetone, methyl edyl ketone, dioxane, tetrahydrofuran, dimethylformamide, etc. to produce a resin solution having properties suitable for use in laminates. be able to. It is also possible to use a solvent from the beginning. For example, an unsaturated dicarboxylic acid N,N'-bisimide compound, aminophenol, and aromatic diamine are charged together with dioxane into a reaction vessel, and the dioxane is refluxed to a predetermined viscosity and cure time, and then dimethylformamide is added. A resin composition solution for a laminate can be produced by adding a solvent such as the following and cooling it. The resin composition solution thus prepared can be blended with various additives and fillers depending on the intended use. For example, a catalyst such as imidazole may be added to adjust the curing rate, and a coupling agent may be added to provide adhesiveness. In addition, a filler that imparts flame retardant properties, a flame retardant, and an inorganic filler may be appropriately blended.

The heat-resistant resin composition produced as described above is coated and impregnated onto a base material such as glass cloth or glass nonwoven fabric, and then dried in a drying tower within a temperature range of 100 to 200°C to form a prepreg for heat-resistant laminates. can be manufactured. This prepreg can be heated and pressed by a predetermined method and used for manufacturing a laminate, a copper-clad laminate, or a printed wiring board.

(Function) The heat-resistant laminate of the present invention uses a heat-resistant resin composition comprising an organic solvent-soluble polyetherimide and an addition reaction product of an N,N'-bisimide compound, an aminophenol, and an aromatic diamine. Therefore, the effects of the present invention were achieved.

Based on organic solvent-soluble polyetherimide, it maintains good moldability and solubility, and by introducing an addition reaction product consisting of an N,N'-bisimide compound, aminophenol, and aromatic diamine, it can be used as a prepreg. In addition to improving the time, the heat resistance of organic solvent-soluble polyetherimide was also improved. In addition, we improved the mechanical strength of bismaleimide homopolymerization, and by using a specific aromatic diamine, we were able to improve adhesive strength and moisture resistance, and at the same time, we were able to maintain the conventional advantages of processability. It is something.

(Example) Next, the present invention will be specifically explained using examples.

Example 1 In a flask equipped with a stirrer and a thermometer, maleic acid N, N
358 g of '-44'-diphenylmethane bisimide,
2-amino-4-talolophenol 45[and 4.4'
-Diamino-3,3',5.5'-tetrachlorodiphenylmethane 25 () was charged and heated while stirring.

When the temperature exceeds 100°C, it gradually begins to dissolve and becomes a brown liquid. This liquid was heated to 120°C and stirred for 1 hour. In this way, the amine phenol and the aromatic diamine were completely added to hismaleimide to obtain an addition reaction product.
This addition reaction e140 parts by weight and Ultem 1000 (G
Manufactured by Company E, trade name) 60 parts was dissolved in a mixed solvent of dioxane and dimethylformamide to make a 50% solution, and stirred.
It was made into a similar varnish.

Next, a glass cloth having a thickness of 180 μm was coated and impregnated with the prepared varnish and dried at a temperature of IEO'C to produce a prepreg having a resin content of 43% by weight. Using 8 sheets of this prepreg and 2 sheets of silver foil with a thickness of 18 μι, they were heated and pressed together at a temperature of 170°C and a pressure of 40 kg/am2 for 90 minutes to form a heat-resistant copper-clad laminate with a thickness of 1.6 nm. was manufactured. The properties of the obtained laminate were tested and are shown in Table 1. The present invention exhibits excellent characteristics, and the effects of the present invention have been confirmed.

Example 2 N maleic acid, 358 g of N'-4,4'-diphenylmethane bisimide, and 16 g of 0-amine phenol.
55 g of 4.4'-diamino-3,3',5.5'-tetrachlorodiphenylmethane was charged into a flask, and an addition reaction product was produced in the same manner as in Example 1. Fifty parts by weight of this addition reaction product and 50 parts by weight of Ultem 1000 (mentioned above) were dissolved in a mixed solvent of dioxane and dimethylformamide to form a 50% solution, and the mixture was stirred to form a -like varnish.
Next, a prepreg and a heat-resistant laminate were manufactured using this varnish in the same manner as in Example 1.

In addition, the same properties as in Example 1 were tested, and the results are shown in Table 1. The products of the present invention were superior in all cases, and the effects of the present invention were confirmed.

Example 3 Maleic acid N, N'-4,4'-diphenylmethane, 358 g of simide, and ■-aminophenol 45 (
J and 4,4'-diamino-3,3',5,5'-terachlorodiphenylmethane 30 (I) were charged into a flask and an addition reaction product was prepared in the same manner as in Example 1. 65 parts by weight of the reactant and 35 parts by weight of Ultem 1000 (mentioned above) are dissolved in a mixed solvent of dioxane and dimethylformamide to make a 50% solution, and stirred to form a --like varnish.Next, using this varnish, A prepreg and a heat-resistant laminate were manufactured in the same manner as in Example 1. Also, as in Example 1, the elastic properties were tested, so the results were
Show it in the table. The products of the present invention were superior in all cases, and the effects of the present invention were confirmed.

Comparative Example 1 Maleic acid N, 358 g of N'-4,4'-diphenylmethane bisimide, 2-amino-4-chlorophenol 45(], and ]4,4'-diamino-3.3',55
25 (l) of '-tetrachlorodiphenylmethane was charged into a flask, and an addition reaction product and varnish were produced in the same manner as in Example 1. Using this varnish, prepregs and heat-resistant laminates were produced in the same manner as in Example 1. , the cord properties were also tested and the results are shown in Table 1.

Comparative Example 2 Maleic acid N, 358 g of N'-4,4'-diphenylmethane bisimide, 16 g of 0-aminophenol, and 55 g of 4,4'-diamino-3,3', 5.5'-tetrachlorodiphenylmethane. Pour g into the flask,
The addition reactant and varnish were prepared in the same manner as in Example 2.

Using this varnish, a prepreg and a heat-resistant laminate were manufactured in the same manner as in Example 2. In addition, the characteristics of the cord were also tested and the results are shown in Table 1.

Comparative Example 3 N maleic acid, 358 g of N'-4,4'-diphenylmethane bisimide, and 45 g of ■-aminophenol,
30q of 4.4'-diamino-3,3',5.5'-tetrachlorodiphenylmethane was charged into a flask, and an addition reaction product and varnish were produced in the same manner as in Example 3.

A prepreg and a heat-resistant laminate were manufactured in the same manner as in Example 3 using this varnish. In addition, the same characteristics were tested and the results are shown in Table 1.

[Effects of the Invention] As is clear from the above explanation and Table 1, the heat-resistant laminate of the present invention has good varnish solubility due to the use of a specific unmodified pure polyimide resin. It is not possible to extend the pot life of prepreg. In addition, the laminate has excellent heat resistance, moisture resistance, adhesive strength, mechanical properties, and workability, and particularly good interlayer adhesive strength, making it suitable for meeting the strict demands of recent years.

Claims (1)

[Claims] 1 (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^1 in the formula ▲ There are ▲ mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. , tables, etc.▼ (However, in the formula, R^2 represents a divalent group having at least two carbon atoms, and R^3 represents a divalent group containing a double bond between carbon atoms.) N,N'-bisimide compound of unsaturated dicarboxylic acid, (b) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^4 represents a hydrogen atom, a halogen atom or an alkyl group) Aminophenol represented by (c) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, X^1, X^2, X^3, and X^4 represent the same or different halogen atoms) 1. A heat-resistant laminate comprising a pure polyimide-based heat-resistant resin composition containing as an essential component an addition reaction product of an aromatic diamine, and a base material.