JPH06322123A - Resin for heat-resistant laminate and heat-resistant laminate - Google Patents

Abstract

PURPOSE:To provide the subject resin comprising a specific oligomer, etc., excellent in heat resistance, moisture resistance and electrical characteristics, and useful for copper-clad laminates, etc. CONSTITUTION:The objective resin comprises an oligomer of formula I and/or an oligomer of formula II [Ar1 is trivalent organic group; Ar1' is organic group; Ar2 is divalent group; Ar3 is tetravalent organic group; Y is S, SO2, O, CO, CO-O, CH=N, HNCO, CR2 (R is H, phenyl, lower alkyl, etc.), etc.; X is trivalent bond group such as a group of formula III; n is 0-20; M is -CR2, -C#cCR, -CR2=CR2]. The resin is impregnated into a substrate comprising an organic or inorganic fibrous material is provide a heat-resistant laminate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin for a heat-resistant laminated material having excellent heat resistance, moisture resistance and electric characteristics, and a heat-resistant laminated material using the resin.

[0002]

2. Description of the Related Art In recent years, the development of electronic devices has been remarkable, and the use of copper-clad laminates used as wiring boards has been diversified, and excellent properties are required. In particular, as wiring density has increased due to high-density mounting of electronic components, multilayer wiring boards and through-hole diameters are becoming smaller. For this reason, there is a demand for a copper-clad laminate having good workability such as less smear during drilling.
On the other hand, with the demand for improved productivity and cost reduction, increasingly stringent processing conditions such as hot air levelers and reflow soldering are being added in the wiring board mounting process. In these demands, the copper clad laminate as a substrate is required to have more excellent heat resistance and moisture resistance than ever before.

In order to meet these requirements, in recent years, an addition-curable polyimide resin has come to be used in place of an epoxy resin which is widely used as a laminate material for a copper clad laminate. When this polyimide resin is used as a laminated material for copper clad laminates, it has the advantage that smearing during drilling is almost eliminated, and the heat resistance in the machining process and long-term tests is significantly improved. It is known.

[0004]

However, the addition-curing type polyimide resin which has been used conventionally has various problems as described below. That is, the one obtained by reacting bismaleimide with diaminodiphenylmethane is excellent for laminates, but on the other hand, diaminodiphenylmethane has high reactivity and has a problem that the pot life of varnish or prepreg is short. Furthermore, the toxicity of diaminodiphenylmethane to the living body may be a problem. Moreover, since diaminodiphenylmethane is used as a curing agent, there is a problem that the moisture resistance is poor,
Special attention must be paid to moisture absorption for long-term storage of the obtained laminate.

[0005]

SUMMARY OF THE INVENTION The present inventors have arrived at the present invention as a result of intensive studies in order to solve these technical problems in view of the above circumstances.

That is, the gist of the resin for heat-resistant laminated material according to the present invention is that the general formula (1) MY-Ar ₁ = X-(-Ar ₂ -X = Ar ₃ =) _n = X-Ar ₂ -X = Ar ₁ -YM ₍₁₎ and / or the general formula _{(2) MY-Ar 1 '} -X = (= Ar 3 = X- Ar 2 -) n -X = Ar 3 = X- Ar 1' -YM (2) [wherein Ar ₁ is a trivalent organic group, Ar _{1 ′} is a divalent organic group, Ar
₂ is a divalent organic group, Ar ₃ is a tetravalent organic group, Y is S, SO
₂ , O, CO, -CO-O-, none, -O-CO-, C
_{H = N, HNCO, CR 2} (R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) represents a. X is a trivalent bond,

[Chemical 3] Selected from the above, and may be one kind or different. n represents a positive integer of 0-20. M is a functional group having reactivity, -CR ₂ -C≡CR _{or, -CR 2 -CR = CR 2 (} R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) is selected from among. ] Consists of.

Next, the gist of the heat-resistant laminated material according to the present invention is that a base material made of an organic or inorganic fibrous material is used, and the general formula (1) MY-Ar ₁ = X-(-Ar ₂ -X = Ar ₃ =) _n = X- Ar ₂ -X = Ar ₁ -YM (1) and / or general formula (2) MY-Ar _{1 '} -X = (= Ar ₃ = X- Ar _2- ) _{n -X = Ar 3 = X- Ar 1} '-YM (2) wherein, Ar ₁ is a trivalent organic group, Ar _1' is a divalent organic group, Ar
₂ is a divalent organic group, Ar ₃ is a tetravalent organic group, Y is S, SO
₂ , O, CO, -CO-O-, none, -O-CO-, C
_{H = N, HNCO, CR 2} (R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) represents a. X is a trivalent bond,

[Chemical 4] Selected from the above, and may be one kind or different. n represents a positive integer of 0-20. M is a functional group having reactivity, -CR ₂ -C≡CR _{or, -CR 2 -CR = CR 2 (} R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) is selected from among. ] Is impregnated with a resin.

In the heat resistant laminate resin and the heat resistant laminate material, in the divalent organic group Ar ₂ , 2 mol% or more of all the Ar ₂ groups is -Ph-CO-OTO-OC-Ph- (formula In the formula, Ph is a divalent aromatic group, and T is a divalent organic group.).

In the resin for heat resistant laminate and the heat resistant laminate as described above, in the above-mentioned tetravalent organic group Ar ₃ , all Ar ₃
At least 2 mol% of the group is = Ph-CO-OTO-OC-Ph = (wherein Ph represents a trivalent aromatic group and T represents a divalent organic group). is there.

Further, in the resin for heat resistant laminate and the heat resistant laminate described above, the bonding group Y is —O—.

[0011]

EXAMPLES Next, the heat-resistant laminated material according to the present invention will be described in detail together with its manufacturing method.

In an atmosphere in which the reaction tank is sufficiently dried and replaced with an inert gas such as argon or nitrogen, the compound represented by the general formula (3)

[Chemical 5] (In the formula, Ar ₃ represents a tetravalent organic group.) Or a dianhydride represented by the general formula (4)

[Chemical 6] (In the formula, Y is hydrogen or an alkyl group selected from 1 to 5 carbon atoms, and may be one kind or different. Ar ₃
Represents a tetravalent aromatic group, and may be one type, or may be selected from multiple components. ) Any one of the acid dianhydride derivatives represented by the formula (1) is dissolved in a polar organic solvent, and the solution of the general formula (5) H ₂ N-Ar ₂ -NH ₂ (5) (wherein Ar ₂ is An organic diamine compound represented by a divalent organic group) is added in a solution prepared by dissolving it in the same polar solvent as described above, or is added as a powder while paying attention to heat generation and thickening. An oligomer is obtained.

At this time, the general formula (1) MY-Ar ₁ = X-(-Ar ₂ -X = Ar ₃ =) _n = X- Ar ₂ -X = Ar ₁ -YM (1) [wherein Ar ₁ is a trivalent organic group, Ar ₂ is a divalent organic group, Ar
₃ is a tetravalent organic group, Y is S, SO ₂ , O, CO, —CO
-O-, none, -O-CO-, CH = N, HNCO, C
R ₂ (in the formula, R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl). X is a trivalent bond,

[Chemical 7] Selected from the above, and may be one kind or different. n represents a positive integer of 0-20. M is a functional group having reactivity, (wherein, R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) -CR ₂ -C≡CR or -CR ₂ -CR = CR ₂ is selected from the. ] To obtain the oligomer represented by the formula (6), the reaction solution of the telechelic oligomer obtained above can be used.

[Chemical 8] [Wherein Ar ₁ is a divalent organic group, Y is S, SO ₂ , O, C
O, -CO-O-, none, -O-CO-, CH = N, H
NCO, CR ₂ (R is hydrogen, phenyl, lower alkyl,
Lower fluoroalkyl). Further, M is a reactive functional group, and is selected from -CR ₂ -C≡CR or -CH ₂ -CR = CR ₂ (R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl). ] A primary amine having a thermosetting group represented by the following is added to terminate the terminal,
An amic acid solution which is a precursor of a reactive oligomer is obtained.

[0014] In general formula _{(2) MY-Ar 1 '} -X = (= Ar 3 = X- Ar 2 -) n -X = Ar 3 = X- Ar 1' -YM (2) wherein, Ar _{1 'is} a divalent organic group, Ar ₂ represents a divalent organic group, Ar
₃ is a tetravalent organic group, Y is S, SO ₂ , O, CO, —CO
-O-, none, -O-CO-, CH = N, HNCO, C
R ₂ (R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) is represented. X is a trivalent bond,

[Chemical 9] Selected from the above, and may be one kind or different. n represents a positive integer of 0-20. M is a functional group having reactivity, -CR ₂ -C≡CR or -CR ₂ -CR = CR ₂ (R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) is selected from among. In order to obtain an oligomer represented in], general formula to the reaction solution _{(7) MY-Ar 1 '} - NH 2 (7) wherein, Ar _1' is a divalent organic group, Y S, SO ₂ , O, C
O, -CO-O-, none, -O-CO-, CH = N, H
NCO, CR ₂ (R is hydrogen, phenyl, lower alkyl,
Lower fluoroalkyl). M is a functional group having reactivity, -CR ₂ -C≡CR or -CH ₂ -CR = CR ₂ (R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) is selected from among. ] A primary amine having a thermosetting group represented by the following is added to terminate the terminal to obtain an amic acid solution which is a precursor of a reactive oligomer.

The reaction temperature at this time is preferably 0 to 120 ° C, preferably 0 to 100 ° C, more preferably 4
0-100 degreeC is suitable. The reaction time is preferably about 1 to 5 hours.

The heat resistant laminate according to the present invention is obtained by coating and impregnating an organic or inorganic fibrous base material with a resin solution. As a method of applying and impregnating this resin solution to obtain a heat-resistant laminated material, the above-obtained amic acid solution was directly used as an impregnating varnish, and the organic or inorganic fibrous base material was applied and impregnated with the amic acid solution. After that, it can be converted into an imide resin. Alternatively, after converting the amic acid solution into an imide resin, the imide resin can be dissolved in an organic solvent to form an impregnating varnish, which can be applied and impregnated on an organic or inorganic fibrous base material before use.

In order to thermally ring-close and dehydrate the obtained amic acid solution to convert it into an imide resin, a non-solvent is added to the amic acid solution and then converted into an imide resin under reflux and azeotropy. Can be disclosed as an example. As the non-solvent used here, xylene / toluene, which is an aromatic hydrocarbon, can be used, but toluene is preferably used.

A specific example of the reaction for thermally ring-closing / dehydrating the amic acid solution will be described. The water to be azeotropically distilled off is refluxed using a Dean-Stark reflux device until a theoretical amount of water is collected. Let me do it. For the dehydration ring-closing reaction to this imide structure, an applied method based on the knowledge of those skilled in the art can be used, such as using a chemical ring-closing method together. After the reaction, the imide resin can be precipitated as a powder by pouring the imide solution into water or an alcohol solvent with vigorous stirring. Then, the obtained imide resin powder is collected by filtration, and then dried at 80 ° C. under reduced pressure for 48 hours to obtain a powder.

Here, the Ar ₁ group of the acid anhydride represented by the general formula (6) used in the present invention is trivalent based on general knowledge of those skilled in the art within a range not departing from the spirit thereof. Any organic group can be used. Specific examples of the Ar ₁ group include the following chemical formulas.

[Chemical 10]

Further, 2 Ar _{1 'group} primary amine represented by the above general formula for use in the present invention (7), based on general knowledge of those skilled in the art within a range not departing from its gist Any valent organic group can be used. As a specific example of the Ar _{1 ′} group, the following chemical formula 11 can be mentioned.

[Chemical 11]

Next, the Ar ₂ group of the diamine represented by the general formula (5) used in the present invention is a divalent organic compound based on the general knowledge of those skilled in the art within a range not departing from the spirit thereof. Any base can be used. Specific examples of the Ar ₂ group include the following chemical formulas 12, 13 and 14.

[Chemical 12]

[Chemical 13]

[Chemical 14]

The divalent organic group Ar ₂ group is preferably at least one selected from the following Chemical formulas 15.

[Chemical 15]

More preferably, as the divalent organic group Ar ₂ group, among all Ar ₂ groups, the following formula -Ph-CO-OTO-OC-Ph- (wherein Ph is a divalent aromatic group and T is An organic group represented by the formula:

[Chemical 16] Content of 2 mol% or more is desirable in order to obtain good electric characteristics.

The Ar ₃ group of the acid dianhydride represented by the general formula (3) or the acid dianhydride derivative represented by the general formula (4) used in the present invention does not depart from the gist thereof. Any tetravalent organic group can be used within the scope based on the general knowledge of a person skilled in the art. Specific examples of the Ar ₃ group include the following chemical formulas 17 and 18.

[Chemical 17]

[Chemical 18]

The tetravalent organic group Ar ₃ group is preferably at least one selected from the following Chemical Formulas 19:

[Chemical 19]

More preferably, as the tetravalent organic group Ar ₃ group, among all Ar ₃ groups, the following formula = Ph-CO-OTO-OC-Ph = (wherein Ph is a trivalent aromatic group, T Represents a divalent organic group), particularly an organic group represented by

[Chemical 20] Content of 2 mol% or more is desirable in order to obtain good electric characteristics.

Furthermore, the linking group Y linking the functional groups M and trivalent organic group Ar ₁ group or a divalent organic group Ar _{1 'group} having reactivity
_{Is, S, SO 2, O,} CO, -CO-O-, no, -O
-CO-, CH = N, HNCO, CR 2 (R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) illustrate like, it is possible to use, -O terms of matching costs and properties It is desirable to select −.
The bonding group Y is “none” means that the compound represented by the general formula (1)
Alternatively, it represents that the Ar ₁ group or Ar _{1 ′} group in (2) and the functional group M are directly bonded.

The reactive functional group M used in the present invention for terminating the terminal is -CR ₂ -C≡CR or -CR ₂ -CR = CR ₂ (R is hydrogen, phenyl or lower alkyl). , Lower fluoroalkyl), and specifically a reactive functional group M is

[Chemical 21] Can be mentioned.

Examples of the organic solvent used in the reaction for producing the amic acid solution include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and N, N'-.
Examples thereof include formamide solvents such as dimethylformamide and N, N′-diethylformamide, acetamide solvents such as N, N′-dimethylacetamide and N, N′-diethylacetamide. These may be used alone or as a mixed solvent of two or three or more. Further, these polar solvents can be used as a mixed solvent with a non-solvent of an amic acid such as methanol / acetone / tetrahydrofuran / ethanol / isopropanol / benzenemethylcellosolve.

Further, it is obvious that the oligomer of the present invention is based on thermal polymerization when inducing a curing reaction, but if necessary, a so-called peroxide catalyst or a reactive diluent may be used. Both or one of the reaction aids can be used in combination.

Examples of preferable organic peroxide catalysts include, as peroxyketals, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like, 1,1-. Bis (t-butylperoxy) cyclohexanes, dialkylperoxides include di-t-butylperoxide, and peroxyesters include t-butylperoxybenzoate. These are used in several parts per 100 parts of the resin composition. The curing catalyst is not limited to these, and a known curing catalyst such as a curing catalyst sensitive to light or a curing catalyst sensitive to radiation or electron beams may be used together with an organic peroxide. It is self-evident that you can.

As the reactive diluent which is a reaction aid, a polyfunctional allyl compound can be specifically exemplified. Specifically, triallyl isocyanurate, trimethallyl isocyanurate, tri-β-ethylallyl isocyanurate, tri-β-propylallyl isocyanurate, triallyl cyanurate, trimethallyl cyanurate, ethyl diallyl isocyanurate, propyl diallyl. Cyanurate, N-allyl-5-norbornene-
2,3-dicarboximide, N-methallyl-methyl-
5-norbornene-2,3-dicarboximide, N,
N'-diallylbenzophenone-3,3 ', 4,4'-
Examples thereof include tetracarboxydiimide and N, N-diallyldiphenyl ether-3,3 ′, 4,4′-tetracarboxydiimide.

Thermal polymerization or thermal polymerization in the presence of a reactive diluent is 100 ° C. or higher, more preferably 150.
It is preferable that the heating is carried out at a temperature of not lower than 1 ° C. for 1 minute or longer, preferably for 5 minutes or longer, while being melted while circulating hot air or under vacuum. When an organic peroxide catalyst is used in combination, 100 ° C or higher and 200 ° C or lower, more preferably 100 ° C or higher and 170 ° C.
It is good to carry out at a temperature of not higher than 1 ° C. for 1 minute or longer, preferably 5 minutes or longer, while being melted, while circulating hot air, or under vacuum.

When a curable resin is obtained from the amic acid that is the curable oligomer of the present invention, known epoxy resins and epoxy resin curing agents, curing accelerators, fillers, flame retardants, reinforcing agents, and surfaces may be added as necessary. Treatment agents, pigments, various elastomers, etc. can be used alone or in combination of two or more kinds.

Next, the manufacturing process of a typical heat-resistant laminated material will be described by way of example. First, the above general formula (1) or (2)
The varnish-shaped resin composition is uniformly obtained by dissolving and stirring the imide oligomer represented by the above with a predetermined amount of an organic solvent so as to have a predetermined resin concentration. At this time, it is preferable to dissolve the imide oligomer in powder form in an organic solvent. The resin composition thus produced is applied to and impregnated with a reinforcing material such as glass cloth, glass nonwoven cloth, glass paper, etc., and then 50 to 250 in a hot air circulation drying furnace.
C, preferably 50 to 200 C, more preferably 100.
Within a temperature range of 200 ° C to 200 ° C, the residence time in the furnace is set so as to obtain a predetermined residual solvent concentration and drying is performed to produce a prepreg for a laminated plate.

Examples of the organic solvent used here include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N'-dimethylformamide and N, N'-diethylformamide, N, N'-dimethylacetamide, N, N'-
Examples thereof include acetamide solvents such as diethylacetamide, ether solvents such as dimethyl ether, diethyl ether and dioxane, and ketone solvents such as acetone and methyl ethyl ketone. These may be used alone or as a mixed solvent of two or more kinds. Furthermore, with these organic polar solvents, methanol, ethanol,
An alcohol solvent such as isopropanol may be mixed and used as a mixed solvent.

The resin concentration upon dissolution and dilution in an organic solvent is 5-75% by weight, preferably 15-65% by weight, more preferably 35-65% by weight, in relation to the resin concentration during prepreg.
It is desirable to use it in the range of% by weight. The residual solvent concentration of the prepreg, that is, the residual solvent / resin ratio calculation is 1 to 20% by weight, preferably 1 to 10% by weight, more preferably 1 to 5%.
It is desirable to adjust in the range of weight%. If it exceeds the above range, there arises a problem that the mechanical properties of the laminated plate after the prepreg molding are deteriorated. On the other hand, if the amount is smaller than the above range, the residual solvent is volatilized during the molding of the prepreg, so that the void is generated.

Next, a method for producing a double-sided copper-clad laminate using the heat-resistant prepreg obtained as described above will be described. A double-sided copper-clad laminate is produced by inserting a cushioning material, a predetermined copper foil, and a prepreg between two stainless sheets whose surfaces are mirror-finished, and then heating and pressing under a predetermined time, temperature and pressure. be able to. Also,
It is also effective to use after-cure together to improve heat resistance and mechanical strength.

The imide oligomer represented by the general formula (1) or (2), which is the resin for heat-resistant laminate according to the present invention, or a solution prepared by dissolving a composition obtained by mixing these imide oligomers in an organic solvent, or these imides. As a base material made of an organic or inorganic fibrous material on which an amic acid that is a precursor of an oligomer is applied and impregnated, carbon fiber, glass fiber,
Aramid fiber, liquid crystal polyester fiber such as Vectra,
Examples thereof include woven cloth, non-woven cloth, mat, paper (paper) made of polybenzothiazole (PBT) fiber and alumina fiber, or a combination thereof. In addition, various fillers and the like can be used in applying and impregnating these base materials with a solution such as an imide oligomer. Examples of the filler include aluminum hydroxide, antimony trioxide, red phosphorus and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples, and the present invention is applicable within the scope of the invention. It can be implemented in a mode in which various modifications and improvements are added based on the knowledge of the trader.

Example 1 A 500 ml three-necked flask was equipped with a three-way cock, a Dean-Stark distiller, a Dimroth reflux condenser and a searum cap, and the reactor was dried under reduced pressure.
After adding 7.31 g (25 mmol) of 1,3-bis (3-aminophenoxy) benzene, it was thoroughly replaced with nitrogen,
Subsequently, 30 ml of dry dimethylformamide (hereinafter abbreviated as DMF) was added and cooled. Then 1
4.41 g (25 mmol) of bisphenol-A bistrimellitic acid dianhydride and 8.01 g (25 mmol) of 3,
A mixture of 3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride (hereinafter abbreviated as BTDA) was dissolved in 60 ml of DMF, and the solution was placed in a dropping funnel. Then, while paying attention to heat generation, they were added all at once to the reaction system and reacted at 0 ° C. for 1 hour and at 80 ° C. for 0.5 hour.

Next, 7.45 g (50 mmol) of 4-aminophenylpropargyl ether dissolved in 15 ml of DMF was added and reacted for 1 hour. afterwards,
200 ml of toluene was added, 5.5 ml (theoretical amount; 5.4 ml) of water of reaction was distilled off at 150 ° C. (bath temperature) under azeotropy, and dehydration ring closure was performed to obtain an imide oligomer. After the reaction, pour the reaction solution into 1.5 liter of methanol with vigorous stirring,
The resulting imide oligomer was precipitated as a powder. This was filtered under reduced pressure and dried in vacuum at 80 ° C. for 48 hours to give 42.2 g (yield; 93.1).
%) As a pale yellow powder. The spectral data of the obtained oligomer were examined. The results are shown below.

[Spectral data] IR (neat, c
m ⁻¹ ) ν = 3000, 2950, 1780, 1750,
1700, 1630, 1600, 1580, 1495,
1440, 1350, 1295, 1220, 1160,
990,910,860,780,735,690.

The obtained powdery imide oligomer 1
Dissolve 00g in 100g DMF (resin concentration: 50wt% /
DMF). 20x20 cm E-glass cloth (WE
8 sheets of A-18W 7628; Nitto Boseki Co., Ltd. were impregnated. It was dried in a hot air circulation drying oven at 150 ° C. for 120 minutes to prepare a prepreg having a resin concentration of 45 wt% (per glass cloth) and a residual solvent concentration of 4.2%.

Eight prepregs thus prepared were sandwiched between two electrolytic copper foils (18 μm, manufactured by Furukawa Electric Co., Ltd.) and the temperature was adjusted to 2
A double-sided copper-clad laminate having a plate thickness of 1.62 mm was obtained by integrally molding by heating and pressurization at 00 ° C. for 2 hours under a pressure of 40 kg / cm ² .

Various mechanical and electrical characteristics of the obtained double-sided copper clad laminate were examined. As mechanical properties, the peel strength of the copper foil is based on JIS-C6481 and the glass transition temperature (Tg) is SDM560 manufactured by Seiko Denshi KK
It was measured using 0H DMS110, and the bending strength was measured based on the JIS method. Regarding the solder heat resistance, the blister after the solder bath (260 ° C, 30 seconds) was observed, and the pressure cooker test (PCT) was
After treating under the conditions of 121 ° C., 2 atmospheres, and 5 hours, blister after the solder bath (260 ° C., 30 seconds) was observed. The observation results are good (no blistering), good (no blistering).
Is represented by x. The results of these measurements are shown in Table 1.

[Table 1]

Further, as electric characteristics, the dielectric constant and the dielectric loss tangent were measured with a Q meter, and a value of 1 MHz was shown. The results of these measurements are shown in Table 2.

[Table 2]

Example 2 In the same manner as in Example 1, a powdery imide oligomer was obtained. However, 8.01 g (25 mmol) of acid dianhydride
BTDA was used instead of 1,3-bis (3-aminophenoxy) benzene to yield 62.79 g (50 mmol).
Of bisaminobenzyloxyphenylpropane, and 10.1 g (50 mmol) of propargyloxyphthalic anhydride was used in place of 4-aminophenylpropargyl ether. The spectral data of the obtained oligomer were examined. The results are shown below.

[Spectral data] IR (neat, c
m ⁻¹ ) ν = 3200, 3030, 2950, 1780,
1750, 1700, 1630, 1600, 1580,
1495, 1450, 1350, 1295, 1220,
1160, 990, 905, 860, 780, 735,
690.

Using 100 g of the above imide oligomer, a double-sided copper clad laminate having a plate thickness of 1.6 mm was obtained under the same conditions as in Example 1. The mechanical and electrical characteristics of the obtained double-sided copper-clad laminate were examined in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 3 50 g of the imide oligomer synthesized in Example 1 and 50 g of the imide oligomer synthesized in Example 2 were used and the same conditions as in Example 1 were used. Got The mechanical and electrical characteristics of the obtained double-sided copper-clad laminate were examined in the same manner as in Example 1. The results are shown in Table 1.
And shown in Table 2.

Comparative Example 1 Commercially available thermosetting imide oligomer (Kelimide 601)
Dissolve 100g in 100g DMF (resin concentration: 50wt%
/ DMF). 20 x 20 cm E-glass cloth (W
8 sheets of EA-18W 7628; Nitto Boseki Co., Ltd. were impregnated. Dry in a hot air circulation drying oven at 150 ° C for 120 minutes to obtain a resin concentration of 45 wt% (per glass cloth),
A prepreg having a residual solvent concentration of 4.2% was produced.

Eight prepregs thus prepared were sandwiched between two electrolytic copper foils (18 μm, manufactured by Furukawa Electric Co., Ltd.) at 200 ° C.
・ 2 hours ・ 40 kg / cm ² ) under the conditions of heating and pressure integral molding to obtain a double-sided copper clad laminate having a plate thickness of 1.63 mm. The mechanical and electrical characteristics of the obtained double-sided copper-clad laminate were examined in the same manner as in Example 1. The results are shown in Table 1 and Table 2.
Shown in.

[0054]

EFFECT OF THE INVENTION The resin for heat resistant laminate of the present invention enables production of a prepreg for heat resistant laminate and a laminate having high humidity resistance, excellent mechanical strength and excellent electrical characteristics.
Furthermore, a laminated material such as a single-sided or double-sided copper clad laminate produced using the prepreg is excellent in industrially valuable moisture resistance and heat resistance and electrical characteristics,
Its usefulness is extremely large.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // C08F 299/02 MRU

Claims (5)

[Claims] 1. A general formula (1) MY-Ar ₁ = X-(-Ar ₂ -X = Ar ₃ =) _n = X- Ar ₂ -X = Ar ₁ -YM (1) and / or a general formula _{(2) MY-Ar 1 '} -X = (= Ar 3 = X- Ar 2 -) n -X = Ar 3 = X- Ar 1' -YM (2) wherein, Ar ₁ is a trivalent organic group, Ar _{1 'is} a divalent organic group, Ar
₂ is a divalent organic group, Ar ₃ is a tetravalent organic group, Y is S, SO
₂ , O, CO, -CO-O-, none, -O-CO-, C
_{H = N, HNCO, CR 2} (R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) represents a. In addition, X is a trivalent bonding mode, Selected from the above, and may be one kind or different. n represents a positive integer of 0-20. M is a functional group having reactivity, -CR ₂ -C≡CR _{or, -CR 2 -CR = CR 2 (} R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) is selected from among. ] The resin for heat resistant laminated materials which consists of these. 2. A substrate comprising an organic or inorganic fibrous material,
General formula (1) MY-Ar ₁ = X-(-Ar ₂ -X = Ar ₃ =) _n = X- Ar ₂ -X = Ar ₁ -YM (1) and / or general formula (2) MY- _{Ar 1 '-X = (= Ar} 3 = X- Ar 2 -) n -X = Ar 3 = X- Ar 1' -YM (2) wherein, Ar ₁ is a trivalent organic group, Ar _{1 '} Is a divalent organic group, Ar
₂ is a divalent organic group, Ar ₃ is a tetravalent organic group, Y is S, SO
₂ , O, CO, -CO-O-, none, -O-CO-, C
_{H = N, HNCO, CR 2} (R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) represents a. In addition, X is a trivalent bonding mode, Selected from the above, and may be one kind or different. n represents a positive integer of 0-20. M is a functional group having reactivity, -CR ₂ -C≡CR _{or, -CR 2 -CR = CR 2 (} R is hydrogen, phenyl, lower alkyl, lower fluoroalkyl) is selected from among. ] The heat resistant laminated material characterized by being impregnated with the resin consisting of. 3. In the divalent organic group Ar ₂ , the total Ar ₂
2 mol% or more of the group is -Ph-CO-OTO-OC-Ph- (in the formula, Ph represents a divalent aromatic group, and T represents a divalent organic group). The heat-resistant laminated material according to claim 1 or 2, which is characterized. 4. In the tetravalent organic group Ar ₃ , all Ar ₃
2 mol% or more in the group is = Ph-CO-OTO-OC-Ph = (wherein Ph represents a trivalent aromatic group, and T represents a divalent organic group). The heat-resistant laminated material according to any one of claims 1 to 3, which is characterized. 5. The heat resistant laminate according to claim 1, wherein the bonding group Y is —O—.