JPH0319837A - Heat-resistant laminated sheet - Google Patents

Abstract

PURPOSE:To extend the usable time of varnish or a prepreg by using a resin composition consisting of org. solvent-soluble polyetherimide and an addition reaction product of an N,N'-bisimide compound of unsaturated dicarboxylic monoamine. CONSTITUTION:A pure polyimide type heat-resistant resin composition containing org. solvent-soluble polyetherimide represented by formula I and an addition reaction product of an N,N'-bisimide compound of unsaturated dicarboxylic acid represented by formula II, aminophenol represented by formula III and aromatic amine represented by formula IV as essential components is used. In the formulae, R<2> is a divalent group having at least two carbon atoms, R<3> is a divalent group containing a C=C double bond, R<4> is a hydrogen atom, a halogen atom or an alkyl group, R<5> is a hydrogen atom or an alkyl group and R<6> is an alkyl group. The org. solvent-soluble polyetherimide is used as a base to hold good moldability and solubility and the addition reaction product of the N,N'-bisimide compound, aminophenol and aromatic amine is introduced to improve the usable time of a prepreg.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to a heat-resistant 8t laminate using pure polyimide that is not modified with other resins such as epoxy resin modification. Technology) In recent years, the development of electronic devices has been remarkable, and fF1-clad laminates have been used in a wide variety of applications and processing conditions, and are required to have excellent characteristics.Especially with regard to higher wiring densities. As 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, productivity is improved and costs are reduced. In response to these demands, increasingly severe processing conditions are being added to the wiring board mounting process, such as hot air levelers and flow soldering.
Under these circumstances, copper-clad laminates serving as substrates are required to have better heat resistance and moisture resistance than ever before. In recent years, in order to meet these demands, #I
Addition-reactive polyimide resins are increasingly being used in place of epoxy resins, which are widely used in stretched laminates. When this polyimide resin is used in copper-clad laminated Itagawa Pre-Breg, the occurrence of smear during drilling becomes almost zero, and the heat resistance during processing and long-term tests is significantly improved. However, the addition reaction type polyimide resins that have been used in the past have had various problems as described below. That is, a product made by reacting N,N'-bisimide, an unsaturated dicarboxylic acid, with diaminodiphenylmethane is excellent for use in laminates. The problem is that the usage time is short. Products containing N,N'-bisimide, an unsaturated dicarboxylic acid, and aminophenol as reaction components have well-balanced properties and are excellent in processing properties for use in laminates, but they have drawbacks in moisture resistance, such as For long-term storage of the obtained Bripregs and laminates, special attention must be paid to moisture absorption. A product prepared by reacting unsaturated dicarboxylic acid N,N'-bisimide with aminobenzoic acid is suitable for use in laminated boards, but it has poor solubility in low-boiling point solvents and is difficult to use in glass cloth, etc. There were problems in application, and in addition, care had to be taken in storing the resin solution. Simple polymerized maleimide compounds have excellent thermal properties, but because of their molecular structure they are inevitably inferior in mechanical strength, so mechanical strength can be improved even if some thermal properties are sacrificed. is the current situation. In addition, organic solvent-soluble polyetherimide is attracting attention as a high-performance engineering plastic that can be molded by injection, and is used in various applications such as films and molding materials, but because it is thermoplastic, its reliability at high temperatures is somewhat inferior. There was a drawback. Additionally, a common problem with pure polyimide resin laminates is that the adhesive strength with #l foil and the interlayer adhesive strength between glass cloth and glass cloth are weak. (Problems to be Solved by the Invention) The present invention was made to solve the above-mentioned drawbacks.The purpose of the present invention is to provide long pot life for varnishes and filipregs, and to improve heat resistance, moisture resistance, and solubility. The present invention aims to provide a heat-resistant laminate that uses pure polyimide resin with excellent mechanical properties and moldability, and also has good interlayer adhesion. [Structure of the Invention] (Means for Solving the Problems) As a result of intensive research to achieve the above object, the present inventor has developed an organic solvent-soluble polyetherimide and an unsaturated dicarboxylic acid N,N' The inventors have discovered that the above object can be achieved by using a heat-resistant resin combination consisting of a -bisimide compound, an amine phenol, and an addition reaction product of an aromatic monoamine, and have completed the present invention. That is, the present invention comprises: (A) an organic solvent-soluble polyetherimide represented by the general formula (wherein R' represents an integer of 2 or more); and (B) (a) a general formula ( f11 L, in which R2 represents a divalent group having at least 2 carbon atoms, R3 represents a divalent group containing a double bond between carbon atoms N of an unsaturated dicarboxylic acid,
N'-bisimide compound, (b) an aminophenol represented by the general formula ((E3 L, in which R' represents a hydrogen atom, a halogen atom, or an alkyl group); and (c) a general formula (f[]L, the formula R5 is a hydrogen atom or an alkyl group, R'
This heat-resistant laminate is characterized by using a pure polyimide-based heat-resistant resin composition in which an aromatic monoamine represented by (represents an alkyl group) and an addition reaction product of are used as an essential component. 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 manufactured by GE, trade name). This is shown by the general formula mentioned above, and is a polyether production reaction (
It is obtained by removing the nitro group by aromatic nucleophilic substitution polymerization, and is soluble in aprotic organic solvents such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. Here, as the polyamines when synthesizing the nitro group-containing polyimide intermediate, 4.
Examples include 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diamino-3,3'-dichlorodiphenylmethane, 3-chlorophenylenediamine, etc. ．． The (B) addition reaction product used in the present invention includes (a) an N,N'-bisimide compound of an unsaturated dicarboxylic acid, (b)
) aminophenol and (C) aromatic monoamine 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 represents a divalent group containing a double bond between carbon atoms. That is, R2 is a linear or branched alkylene group, a cycloalkylene group having a ring of 5 to 6 carbon atoms, or a divalent heterocyclic group containing at least one of oxygen, nitrogen, or sulfur atoms. , phenylene group or divalent polycyclic aromatic group, -NHCO+, -NR'
Examples include a plurality of aromatic groups or alicyclic groups bonded by -SiR'R' or -S02. Note that R7, R8, and R9 have 1 carbon number.
-4 alkyl group, a cycloalkyl group having a ring of 5 to 6 carbon atoms, and a phenyl group. Further, examples of Rl, that is, a divalent group containing a double bond between carbon atoms, include maleic acid residues, citraconic acid residues, Te1-rahydrophthalic acid residues, and the like. Therefore, R2 and R mentioned above
Specific examples of N,N'-bisimide compounds of unsaturated dicarboxylic acids that satisfy condition 3 include the following, and these can be used alone or in a mixture of two or more. Maleic acid N, N'- 4.4'-diphenylmethane bisimide, maleic acid N, N'- 4.4
'-diphenyl ether bisimide, maleic aN,N
'-paraphenylene bisimide, maleic acid N,N'-
Benzidine bisimide, maleic acid N,N'-metaxylene bisimide, maleic acid N,N'-1.5-naphthalene bisimide, maleic acid IN,N'-4.4'-
Diphenylsulfone-bisimide, maleic acid N, N
'- 2.2'- 4.4'-dimethylene-cyclohexane-bisimide, maleic acid NN'-4.4'-dicyclohexy-methane bisimide, maleic acid N, N
'- 4.4"-diphenylcyclohexane-bisimide, maleic acid N, N"- 4.4"-diphenyl-phenylamine-bisimide, maleic IN, N'-
4.4'-diphenyl-diphenylsilane-bisimide, maleic acid N, N'- 4.4'-diphenyl sulfur-bisimide, maleic acid N, N'-2.2'=( 4
．． 4”-diphenyl)-propane-bisimide, maleic acid N,N'-metaphenylene-bisimide, maleic acid N,N'-3.3'-(N,N'-metaphenylene-bisbenzamide)bisimide In addition, as (b) aminophenols, those having the following general formula are used. However, in the formula, R4 represents a hydrogen atom, a halogen atom, or an alkyl group. Specific examples of these compounds include 0 -Aminophenol, m-aminophenol, p-aminophenol, 2-amino-4-aminophenol, 2-amino-4-methylphenol, etc., and these can be used alone or in a mixture of two or more. Furthermore, as the aromatic monoamine (C), an aromatic monoamine having the following general formula is used. However, in the formula, R'' represents a hydrogen atom or an alkyl group, and R6 represents an alkyl group.
Specific examples of these compounds include 0-anisidine (0-methoxyaniline), p-anisidine (p-methoxyaniline), p-phenetidine (p-ethoxyaniline), p-cresidine (5-methyl-101-anidine), ), and these can be used alone or in a mixture of two or more. The aforementioned (a) N,N'-bisimide compound of unsaturated dicarboxylic acid, (b) aminophenol, and (C) aromatic The addition reaction product can be produced by heating the monoamine of the group monoamine without a solvent or in an inert solvent.
It is desirable that the total amount of aminophenol and aromatic monoamine be blended in an amount of 0.1 to 1.0 mol per 1 mol of the '-bisimide compound. If the amount is less than 0.1 mole, the reaction will not proceed and properties such as heat resistance and toughness will deteriorate, and if it exceeds 1.0 mole, unreacted amine will remain, resulting in a significant decrease in heat resistance, which is undesirable. The mixing order of 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 <A) organic solvent-soluble polyetherimide 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 total resin composition. This is because if the blending amount is less than 201Ei%, the processability will decrease, and if it exceeds 95% by weight, the mechanical strength will decrease, which is undesirable. Next, we will explain the typical V-building process as an example. N,N'-bisimide compounds of unsaturated dicarboxylic acids, aminophenols, and aromatic monoamines 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 and cure. Proceed with the reaction until the time is up. Adding organic solvent soluble polyetherimide to this reaction product,
Furthermore, acetone, methyl, ethyl ketone, dioxane,
By dissolving it in a solvent such as tetrahydrofuran or dimethylformamide, a resin solution having properties suitable for use in laminates can be produced. Children can also use solvents from the beginning. For example, in a reaction vessel, an N,N'-bisimide compound of an unsaturated dicarboxylic acid, an aminophenol, and an aromatic monoamine are charged together with dioxane,
A resin composition solution for a laminate can be prepared by reacting dioxane to a predetermined viscosity and air time while refluxing it, and then adding a solvent such as dimethylformamide 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, to impart flame retardancy, flame retardants,
Inorganic fillers can be added as appropriate. The heat-resistant resin composition produced as described above is coated and impregnated onto a base material such as glass cloth or glass non-woven fabric, and then dried within a temperature range of 100 to 200°C in a drying tower to form a prepreg for heat-resistant laminates. can be manufactured. This blibreg can be heated and pressed using a predetermined method and used to manufacture laminates, copper-clad laminates, or printed wiring boards. (Function) The heat-resistant laminate of the present invention uses an aging-resistant resin composition consisting of an organic solvent-soluble polyetherimide and an addition reaction product of an N,N'-bisimide compound, an aminophenol, and an aromatic monoamine. As a result, the effects of the present invention were achieved. Based on organic solvent-soluble polyetherimide, it maintains good moldability and solubility, and by introducing an f-addition reactant consisting of an N,N'-bisimide compound, aminophenol, and aromatic monoamine into the prepreg. In addition to improving pot life, the heat resistance of W-containing solvent-soluble polyetherimide was improved. In addition, we improved the mechanical strength of bismaleimide homopolymerization, and by using a specific aromatic monoamine, 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 a saturation example. Example 1 Maleic acid N, N was added to a flask equipped with a stirrer and a thermometer.
'-4.4'-diphenylmethane bisimide 358Q
, 71 g of 2-amino-4-chlorophenol, and 61 g of 〇1anisidine (0-methoxyaniline) were prepared.
It ripens as it grows. 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 to obtain an addition reaction product. This addition reaction 5/JIIJ 40 parts by weight and Ultem 1000 (G
A uniform varnish was prepared by dissolving and stirring 60 parts by weight of varnish (manufactured by Company E, trade name) in a mixed solvent of dioxane and dimethylformamide. Next, a glass cloth with a thickness of 180 μm was coated and impregnated with the prepared varnish, dried at a temperature of 160°C, and the resin content was 4.
A 3% by weight prepreg was produced. This prepreg 8
A heat-resistant copper clad laminate with a thickness of 1.61 In was formed by heating and pressing two sheets of copper foil with a thickness of 1.61 In at a temperature of 180°C and a pressure of 40 kg/cm' for 90 minutes. The board was manufactured. Example 2 Malein IN,N'- 358 g of 4,4'-diphenylmethane bisimide, O-aminophenol 54 (J), and 689 p-phenetidine (p-ethoxyaniline) were charged into a flask, and the same procedure as in Example 1 was carried out. An addition reaction product was produced by adding 50 parts by weight of this addition reaction product and Ultem 1.
A uniform varnish was prepared by dissolving and stirring 50 parts by weight of 000 (described above) in a mixed solvent of dioxane and dimethylformamide. Next, using this varnish, a Bripreg and a heat-resistant copper-clad laminate were manufactured in the same manner as in Example 1. Practical example 3 358 g of maleic acid N, N'-4.4'-diphenylmethane bisimide, 540 g of aminophenol,
p-cresidine (5-methyl-101-anisidine) 68g
was charged into a flask, and the addition reaction product was prepared in the same manner as in Example 1. ! ! ! I left it behind. 65 parts by weight of this addition reaction product and Uldem 1000 (>35 parts as above) were dissolved in a mixed solvent of dioxane and dimethylformamide to make a 50% solution, and a uniform varnish was prepared by 592 liters.
Next, a prepreg and a heat-resistant copper-clad laminate were manufactured using this varnish in the same manner as in Example 1. Comparative Example 1 358 g of maleic 9N,N'-4,4'-diphenylmethane bisimide and 198 q of 4,4'-diaminodiphenylmethane were charged into a flask, and an addition reaction product and varnish were produced in the same manner as in Example 1. Using this varnish, prepreg and heat resistant #l were prepared in the same manner as in Example 1.
A regional laminate was manufactured. Comparative Example 2 358 g of maleic acid N, N'-4.4'-diphenylmethane bisimide and 109 g of 0-aminophenol
was charged into a flask, and the addition reaction product and varnish were produced in the same manner as in Example 2. Using this varnish, a prepreg and a heat-resistant @stretched laminate were manufactured in the same manner as in Example 2. Comparative Example 3 358 g of maleic acid N, N'-4.4'-diphenylmethane bisimide, 54 g of amine phenol,
61 g of 0-anisidine was charged into a flask, and an addition reaction product and varnish were produced in the same manner as in Example 3. Using this varnish, a prepreg and a #1 heat-resistant laminate were produced in the same manner as in Example 3. Examples 1 to 3 and Comparative Example 1 to
The heat-resistant copper-clad laminate manufactured in step 3 was tested for copper foil peel strength, interlayer adhesion, water absorption, glass transition point, bending strength, drill wear rate, and soldering heat resistance. It is shown in the table. The various properties of the heat-resistant copper-clad laminate of the present invention were excellent, and the effects of the present invention were confirmed. Table 1 $1: According to JIS-C-6481. *2: Measures the peel strength between the Bripreg layer and the prepreg layer. Book 3: Based on JISC-6481. *4
: 2! IIIIX A sample with copper foil cut to 25+111 was floated on solder at 300° C. for 20 minutes, and the situation was evaluated.

○... No blistering ×... Blistering occurred 5: Pc the sample from which the %1 foil was etched away.
1” After being treated at 121°C and 2 atm for 5 hours, the state of blisters was evaluated when immersed in solder at 260°C for 30 seconds. ○... No blisters were found ×... Blisters were found [ [Effects of the Invention] As is clear from the above explanation and Table 1, the heat-resistant stretched laminate of the present invention has good varnish solubility due to the use of a specific pure polyimide resin that is not modified. We were able to extend the pot life of Bripreg.
In addition, the laminate has excellent heat resistance, moisture resistance, adhesive strength, mechanical properties, and workability, and particularly good interlayer adhesion, 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. ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. ▼ where n represents an integer of 2 or more) and (B) (a) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^2 in the formula is a divalent group having at least 2 carbon atoms, and R^3 is a divalent group containing a double bond between carbon atoms.
- Bisimide compound, (b) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^4 represents a hydrogen atom, a halogen atom, or an alkyl group); and (c) General formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R^5 is a hydrogen atom or an alkyl group, R^6
1. A heat-resistant laminate using a pure polyimide-based heat-resistant resin composition containing as an essential component an aromatic monoamine represented by (representing an alkyl group) and an addition reaction product of the following.