JPH0693118A - Heat-resistant laminate material and production thereof - Google Patents

Abstract

PURPOSE:To obtain a material excellent in mechanical and electrical properties and moisture resistance by using a polyimide resin composition comprising a specific thermoplastic polyimide and one or two specific heat-curable oligomers. CONSTITUTION:The material is produced from a polyimide resin composition comprising a thermoplastic polyimide represented by formula I [wherein R1 and R2 each is H or a 1-18C (halogenated) aliphatic or aromatic group and Ar1 is a tetravalent aromatic group] and either or both of two heat-curable oligomers respectively represented by formulae II and III [wherein Ar2 is a divalent aromatic group; Ar3 is a tetravalent aromatic group; X is a trivalent group represented by formula IV, V, or VI; n is 1-30; and R3 is a reactive functional group which may have an aliphatic or aromatic group]. Since this material has has moisture and heat resistances as well as excellent mechanical and electrical properties, it is usable over a wide range of applications.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat resistant laminated material using a novel polyimide resin composition and a method for producing the same. More specifically, the present invention relates to a novel heat-resistant laminated material using a polyimide-based resin composition having excellent heat resistance and good solubility in an organic solvent, which is optimum for lamination and molding.

[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 has been diversified, and excellent properties have been demanded. In particular, there is a demand for a copper-clad laminate having good workability such as a multilayer wiring board, a through hole having a smaller diameter, and less smear during drilling as wiring density increases. On the other hand, with the demand for improved productivity and cost reduction, increasingly severe processing conditions such as hot air levelers and reflow soldering are being added in the wiring board mounting process. Among these, the heat resistance and moisture resistance of the copper clad laminate, which is the substrate, have been required to be more excellent than ever. In order to meet these requirements, in recent years, an addition-curable polyimide resin has been used in place of an epoxy resin which is widely used for copper-clad laminates. When this polyimide resin is used for a copper clad laminate, it has almost no smear during drilling, and has the advantage that the heat resistance in the machining process or long-term test is significantly improved. Are known. However, the addition-curing type polyimide resin that has been used conventionally has various problems as described below. That is, the one obtained by reacting N, N'-bisimide of unsaturated dicarboxylic acid with diaminodiphenylmethane is excellent for laminates, but on the other hand, diaminodiphenylmethane has high reactivity,
There was a problem that the pot life of varnish and prepreg was short. Furthermore, the toxicity of diaminodiphenylmethane to living bodies may be a problem. Further, those containing N, N'-bisimide of unsaturated dicarboxylic acid and aminophenol as reaction components show well-balanced properties for laminates and have excellent processability but poor moisture resistance. There are problems, for example long term storage of the resulting laminate requires special attention to moisture absorption. Further, a product obtained by reacting an unsaturated dicarboxylic acid with N, N′-bisimidoaminobenzoic acid is suitable for a laminated plate, but has poor solubility in a low boiling point solvent and is a glass for preparing a prepreg. There is a problem in applying to a cloth or the like, and there is a problem in that the resin solution must be stored carefully. Further, a thermosetting polyimide in which the end is terminated by using propargylamine as a primary amine has also been proposed. [Ube Industries, JP-A-2-284923, JP-A-3-1744
27]. However, the thermal reaction initiation temperature of the propargyl group is 2
It is known that the temperature is as high as 50 ° C., and that the imide oligomer using this as a reactive group also has a high curing temperature and is inferior in terms of processability [St. Clair, Anne K. et al., Polym. Eng. S.
ci., 22 (1), 9-14 (1982)]. In any case, the polyimide resin generally has poor hygroscopicity, and it has been pointed out that the dimensional stability in the processing step is a problem.

[0003]

SUMMARY OF THE INVENTION In view of the above situation, the present invention provides a heat resistant laminated material and a method for producing the same which solve these technical problems.

[0004]

The inventors of the present invention have arrived at the present invention as a result of intensive studies in order to solve these technical problems in view of the above-mentioned circumstances. That is, the first aspect of the present invention is the general formula (1)

[0005]

[Chemical 14]

(In the formula, R ₁ and R ₂ are at least one selected from the group consisting of hydrogen, a C1-18 aliphatic group and an aromatic group and each represents a substituent which may contain a halogen group. R ₁ and R ₂ may be the same or different, and Ar ₁ represents a tetravalent aromatic group and may be _one type or two or more types. The thermoplastic polyimide shown and the general formula (2)

[0007]

[Chemical 15]

Alternatively, the general formula (3)

[0009]

[Chemical 16]

(In the formula, Ar ₂ is a divalent aromatic group and may be one kind or two or more kinds. Ar ₃ is a tetravalent aromatic group. X is a trivalent bonding mode, represented by the general formula (4)

[0011]

[Chemical 17]

It is selected from among the above and may be the same or different. n represents a positive integer of 1 to 30. R ₃ is a functional group having reactivity and may have an aliphatic group or an aromatic group. ), A heat-resistant laminated material characterized by using a novel polyimide resin composition having one or both of thermosetting oligomers as constituent components, (5)

[0013]

[Chemical 18]

An acid dianhydride represented by the general formula (6)

[0015]

[Chemical 19]

(In the formula, Y ₁ to ₄ are at least one selected from the group consisting of hydrogen and C ₁ to C 5 alkyl groups, and they may be the same or different. Ar ₁ is tetravalent. Which represents an aromatic group, and may be one kind or two or more kinds) in an inert gas atmosphere in a temperature range of 50 to 150 ° C. from a tetracarboxylic dianhydride and a corresponding alcohol. Then, under the same conditions, the general formula (7)

[0017]

[Chemical 20]

(Wherein R ₁ and R ₂ are hydrogen, C 1-18
At least one kind selected from the aliphatic group and the aromatic group described above may each contain a halogen group. Also R ₁ ,
R ₂ may be the same or different. ), A polyamic acid prepolymer is synthesized by mixing the organic diamine of

[0019]

[Chemical 21]

Alternatively, the general formula (3)

[0021]

[Chemical formula 22]

(In the formula, Ar ₂ is a divalent aromatic group, and may be one kind or two or more kinds. Ar ₃ is a tetravalent aromatic group. X is a trivalent bonding mode and has the formula (4)

[0023]

[Chemical formula 23]

Selected from the group represented by: and may be the same or different. n represents a positive integer of 1 to 30. R ₃ is a functional group having reactivity and may have an aliphatic group or an aromatic group. ) To prepare a resin solution obtained by blending the thermosetting oligomer,
Next, a reinforcing material is applied and impregnated with the resin solution, and then dried to obtain a predetermined residual solvent concentration to prepare a prepreg, and a predetermined number of the prepreg is heated and pressed to be integrally molded. The method for producing a heat-resistant laminated material is described below.

A method for producing a resin composition which is a constituent component of the heat resistant laminated material of the present invention will be described. After sufficiently drying the reaction tank, the reaction tank was replaced with an inert gas such as argon or nitrogen, and a predetermined amount of a non-aqueous polar solvent was charged, and then the reaction mixture was subjected to the general formula (5) under an inert gas atmosphere.

[0026]

[Chemical formula 24]

An acid dianhydride represented by the following formula or a general formula (6)

[0028]

[Chemical 25]

(In the formula, Y ₁ to ₄ are at least one selected from the group consisting of hydrogen and a C1-5 alkyl group, and may be the same or different. Ar ₁ is 4
The valent aromatic group may be one kind or two or more kinds. 1) in an inert gas atmosphere in a temperature range of 50 to 150 ° C., preferably 50 to 100 ° C., particularly preferably 80 ° C. ± 5 ° C., from an alcohol corresponding to tetracarboxylic dianhydride, Synthesis is performed within 5 hours, preferably within 2 hours. Next, under the same conditions, the general formula (7)

[0030]

[Chemical formula 26]

(Wherein R ₁ and R ₂ are hydrogen, C 1-18
At least one kind selected from the aliphatic group and the aromatic group may be contained in each halogen group. Also R
₁ and R ₂ may be the same or different. ) Is mixed with the organic diamine to synthesize a polyamic acid prepolymer. To complete the reaction,
1 to 10 hours, preferably 1 to 5 at the same temperature as above
Time, more preferably within 2 hours. Furthermore, the general formula (2)

[0032]

[Chemical 27]

Alternatively, the general formula (3)

[0034]

[Chemical 28]

(In the formula, Ar ₂ is a divalent aromatic group, and may be one kind or two or more kinds. It may be selected from multiple components. Ar ₃ is a tetravalent group. It is an aromatic group, in which X is a trivalent bond, and has the formula (4)

[0036]

[Chemical 29]

It is selected from the group represented by and may be the same or different. n represents a positive integer of 1 to 30. By blending the thermosetting imide oligomer represented by (4), a resin solution which is an essential component of the present invention can be prepared. As the thermosetting oligomer represented by the general formula (2) or (3), any one can be used as long as it is known as a thermosetting imide oligomer in the constitution of the present invention. However, in order to exert the effect of the present invention, the general formula (2)

[0038]

[Chemical 30]

Alternatively, the general formula (3)

[0040]

[Chemical 31]

(In the formula, Ar ₂ is a divalent aromatic group,
It may be one type or two or more types. Ar ₃
Is a tetravalent aromatic group, wherein X is a trivalent bonding mode, and has the formula (4)

[0042]

[Chemical 32]

It may be selected from the group represented by and may be one kind or different. n represents a positive integer of 1 to 30. It is desirable to use a propargyl ether-terminated imide or isoimide represented by the formula (4), or a thermosetting imide-based oligomer which can be represented in the form of an amic acid. The above-mentioned oligomer can also be easily synthesized by using a known technique such as JP-A-53-119865 by Gulf R & D. As the diamine component, the general formula (7)

[0044]

[Chemical 33]

(In the formula, R ₁ and R ₂ are at least one selected from the group consisting of hydrogen, an aliphatic group selected from C1 to 18 and an aromatic group, and may each contain a halogen group. R ₁ and R ₂ may be the same kind or different kinds, and each of them has an organic diamine represented by the following general formula (8).

[0046]

Embedded image H ₂ N—Ar ₄ —NH ₂ (8)

It is also possible to copolymerize a diamine represented by the formula (wherein Ar ₄ is a divalent organic group). Ar ₄ can be essentially any divalent organic group, and specifically,

[0048]

[Chemical 35]

[0049]

[Chemical 36]

The aromatic group is preferable. In particular,

[0051]

[Chemical 37]

It is preferable to use at least one of the above as the main component. As the organic tetracarboxylic dianhydride that can be used in the present invention as shown in the above-mentioned production method, organic tetracarboxylic dianhydrides having any structure can be used. 5) Ar ₁
The group is a tetravalent organic group, and is preferably an aromatic group. Specific examples of the Ar ₁ group include the following.

[0053]

[Chemical 38]

These organic tetracarboxylic dianhydrides may be used alone or in combination of two or more. More specifically, in terms of the balance of various characteristics,

[0055]

[Chemical Formula 39]

It is preferable to use at least one of the above as the main component. As an example of the reactive functional group R ₃ represented by the general formula (2) or (3) used in the present invention for terminal termination,

[0057]

[Chemical 40]

The following are preferable in terms of cost and handling.

[0059]

[Chemical 41]

Examples of the aprotic polar organic solvent used in the reaction for forming the polyamic acid ester solution include ether solvents such as tetrahydrofuran and dioxane, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N'-dimethylformamide. Formamide solvents such as N, N'-diethylformamide, N, N'-dimethylacetamide, N, N'-
Examples thereof include acetamide-based solvents such as diethyl acetamide. These may be used alone or as a mixed solvent of two or three or more. Furthermore, these aprotic polar solvents can be used as a mixed solvent of a polyamic acid ester solution such as methanol, ethanol, isopropanol, benzenemethylcellosolve and the like and a non-solvent. It is preferable to use dimethylacetamide (hereinafter abbreviated as DMAc) and tetrahydrofuran (hereinafter abbreviated as THF) from the viewpoint of operability.

The number average degree of polymerization of the thermosetting polyimide oligomer which is one of the constituents of the present invention [DP; J. Flory, "Principles of Polymer Chemistry" Cornel
l University Press: I thaca, NY, 91 pages, 195
3 years] to control the degree of polymerization is 1 to 30, preferably 1 to 15, and more preferably 1 to 10. When it is larger than the above, there is a drawback that the solubility in an organic solvent decreases. Further, if it is smaller than the above, there is a problem in mechanical strength.

The molecular weight of the thermoplastic polyimide which is the other component of the present invention is not particularly limited, but in order to maintain the strength of the polyimide resin produced, a number average molecular weight of 50,000 or more, Is preferably 80,000 or more, particularly preferably 100,000 or more, and further preferably 120,000 or more. Although it is often difficult to directly measure the molecular weight of a polyimide polymer, in such a case, it is estimated by an indirect method. For example, when the polyimide polymer is synthesized from polyamic acid or polyamic acid ester, the value corresponding to the molecular weight of the corresponding precursor may be the molecular weight of the polyimide. The thermoplastic resin polyimide of the present invention and the thermosetting oligomer can be mixed in an arbitrary composition ratio, but preferably the thermoplastic polyimide represented by the general formula (1) and the general formula (2) and / or (3 ), The weight fraction of the thermosetting oligomer is 99/1 to 5
The range is / 95. Outside this range, workability tends to deteriorate.

The composition of the present invention contains the above-described reactive polyimide resin as an essential component. If necessary, a known epoxy resin or epoxy resin curing agent,
A curing accelerator, a filler, a flame retardant, a reinforcing agent, a surface treatment agent, a pigment, various elastomers and the like can be used in combination. The epoxy resin is a compound having two or more epoxy (glycidyl) groups in the molecule, and is exemplified by bisphenol A, bisphenol F, hydroquinone, resorcin, flurglycine, tris- (4-hydroxyphenyl) methane, 1,1. , 2,2-Tetrakis (4-hydroxyphenyl) ethane and other divalent or trivalent phenols or glycidyl derived from halogenated polyphenols such as tetrabromobisphenol A and novolac derived from brominated polyphenols Novolac-based epoxy resin, aniline, para-aminophenol, which is the reaction product of phenols such as ether compounds, phenol, orthocresol, and formaldehyde,
Meta-aminophenol, 4-amino-metacresol,
6-amino-metacresol, 4,4'-diaminodiphenylmethane, 8,8'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3- Aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, paraphenylenediamine, metaphenylenediamine, 2,4-toluenediamine, 2,6-
Toluenediamine, para-xylylenediamine, meta-xylylenediamine, 1,4-cyclohexane-bis (methylamine), 1,3-cyclohexane-bis (methylamine), 5-amino-1- (4'-aminophenyl) −
1,8,8-trimethylindane, 6-amino-1-
An amine-based epoxy resin derived from (4-aminophenyl) -1,8,8-trimethylindane or the like, a glycidyl ester-based compound derived from an aromatic carboxylic acid such as paraoxybenzoic acid, terephthalic acid or isophthalic acid,
Hindantoin-based epoxy resin derived from 5,5-dimethylhindantoin or the like, 2,2'-bis (3,4-
Epoxycyclohexyl) propane, 2,2-bis [4
Alicyclic epoxy resins such as-(2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, and 3,4-epoxycyclohexanecarboxylate, and triglycidyl isocyanurate,
1, such as 2,4,6-triglycidoxy-s-triazine
There may be mentioned one kind or two or more kinds.

Examples of the epoxy curing agent include amine type curing agents such as aromatic amines and aliphatic amines such as xylylenediamine, polyphenol compounds such as phenyl novolac and cresol novolac, and hydrazide compounds. Benzyldimethylamine as a curing accelerator,
Amines such as 2,4,6-tris (dimethylaminomethyl) phenol and 1,8-diazabicycloundecene, imidazole compounds such as 2-ethyl-4-methylimidazole, boron trifluoride amine complex, etc. It can be illustrated. Also, addition of various elastomers is effective for improving the mechanical strength. The resin concentration when dissolved and diluted in an organic solvent is 5 to 5 because of the relationship with the resin concentration during prepreg.
It is desirable to use 75% by weight, preferably 15 to 65% by weight, more preferably 35 to 65% by weight.
The residual solvent concentration of the prepreg is 1 to 20% by weight with respect to the resin, preferably 1 to 10% by weight, more preferably 1 to
It is desirable to adjust in the range of 5% by weight. If it is less than 1% by weight, the mechanical properties of the laminated plate after prepreg molding are low. On the other hand, if it exceeds 20% by weight, the residual solvent is volatilized during the molding of the prepreg, which causes the generation of voids.

Next, a method for producing a heat resistant laminated plate using the heat resistant prepreg obtained as described above will be described. Adjust the number of prepregs to obtain the desired thickness. A predetermined laminate can be prepared by inserting a predetermined prepreg between two stainless steel plates or dies whose surfaces are mirror-finished and then heating and pressurizing for a predetermined time and under pressure. Alternatively, the amount of volatile gas can be adjusted by using a vacuum state together. This indicates that the resin system is also suitable for autoclave processing. When used for so-called PWB (printed wiring board) applications, various fillers and reinforcing agents can be used. As a filler,
Examples include aluminum hydroxide, antimony trioxide, red phosphorus, and the like. As the reinforcing material, a woven fabric, a non-woven fabric, a mat, a paper (paper) made of carbon fiber, glass fiber, aramid fiber, liquid crystal polyester fiber such as Vectra, polybenzothiazole (PBT) fiber, alumina fiber or the like, or a combination thereof is used. It can be illustrated. In addition, it is also effective to use after-cure together to improve the mechanical strength. These thermosetting resins are not limited in their usage and can be applied in various modes. Among them, it can be used as a laminated board for electricity and a matrix resin for PWB.

[0066]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples, and the present invention is within the scope of the present invention. The present invention can be implemented with various modifications, improvements and changes.

Reference Example 1 1,3-bis (4,4-dinitrophenoxy) -2,2
- N ₂ inlet tube 4 necked flask 2000ml synthesized thoroughly dried dimethyl propane, bubbler - & Dimroth reflux condenser, fitted with a mechanical stirrer, was flushed with N _2. 146.1 g
(0.920 mol) of 1-nitro-4-chlorobenzene and 45.1 g (0.470 mol) of 2,2-dimethylpropane-1,3-diol were ground well in a mortar and then placed in a reactor. After thoroughly dissolving with 200 ml of dimethylacetamide, 400 g (2.820 mol) of K was added.
₂ CO ₃ was added. The reaction was carried out for 26 hours in a N ₂ stream and under reflux. It was precipitated in 2000 ml of ice water, carefully neutralized with concentrated HCl and the precipitate was filtered off. The precipitate obtained was recrystallized twice from toluene. When sufficiently dried at 65 ° C. under reduced pressure, 133.3 g (yield: 82.0%) of 1,
3-bis (4,4-dinitrophenoxy) -2,2-dimethylpropane (hereinafter abbreviated as BNPDMP) was obtained. The melting point was 165-6 ° C (reported value: 164 ° C). [Spectral data] IR (KBr, cm ^-1 ) ν = 3100, 2950, 168
0, 1600, 1500, 1340, 1290, 117
0, 1120, 1040, 1000, 860, 770,
680. ¹ H-NMR (acetone-d ₆ , ppm) δ = 1.20
_{(S, 6H, -CH 3)} , 4.08 (s, 4H, -CH
_2- O-), 7.19 (m, 4H, aromatic H), 8.
15 (m, 4H, aromatic H) Elemental analysis value was calculated as C17H18O6N2 (%): C; 58.74, H; 23.83 Measured value (%): C; 58.56, H; 23.92 Met.

Reference Example 2 1,3-bis (4,4-diaminophenoxy) -2,2
-Synthesis of dimethyl propane In a well-dried 2000 ml 4-necked flask, bubbler-Dimroth reflux condenser, rotor, 600 g (12.
080 mol) of hydrazine monohydrate in 1000
A ml dropping funnel was attached. 286.44 g (0.8
41 mol) of BNPDMP obtained in Reference Example 1 and 13.
71 g of 5 wt% Pd-C and 1000 ml of dry ethanol were added to the reaction system. Hydrazine was added dropwise under reflux over about 90 minutes. The reaction was carried out under reflux for 24 hours. After the reaction,
The precipitate was filtered under reduced pressure on Celite, and the organic layer was evaporated under reduced pressure. The precipitate was collected and recrystallized from ethanol. 196.8 g (yield; 95.5%) of 1,3-bis (4,4-diaminophenoxy) -2,2-dimethylpropane (whose melting point is 114-5 ° C (reported value: 113 ° C)) Hereinafter, it is abbreviated as BAPDMP). [Spectral data] IR (KBr, cm ^-1 ) ν = 3420, 3350, 320
0,2950,2900,2850,1725,161
0,1510,1460,1410,1250,113
0,1040,820 ¹ H-NMR (acetone-d ₆ , ppm) δ = 1.10.
_{(S, 6H, -CH 3)} , 3.40 (bs, 4H, -N
_{H 2), 3.80 (s,} 4H, -CH 2 -O -), 6.
15 (m, 8H, aromatic H) Elemental analysis value was calculated as C17H22O2N2 (%): C; 73.30, H; 7.91 Actual measurement value (%): C; 73.56, H; 7.78 Met.

Reference Example 3 4-Nitrophenyl-1-propargyl ether A 200 ml dropping funnel, a three-way cock, and a seam cap were attached to a 500 ml three-necked flask, dried under a reduced pressure and replaced with argon. 8.0 g (0.2 mol) of sodium hydroxide was dissolved in 200 ml of water and charged into the reactor. Two
7.82 g (0.2 mol) of 4-nitrophenyl and 6.
After adding 45 g (0.2 mol) of tetra-n-butylammonium bromide, 23.7 from the dropping funnel.
After 9 g (15.1 ml, 0.2 mol) of propargyl bromide was added over about 30 minutes, the mixture was reacted at 80 ° C. for 4 hours, and then stirred overnight at room temperature. The precipitated crystal was filtered and recrystallized from toluene. 30.0 g (yield: 92.0%) of propargyl ether was obtained.

[Elemental analysis value] Calculated value: C; 61.02, H; 3.95, N; 7.9
1. Found: C; 59.82, H; 4.04, N; 7.7.
2. [Spectral data] IR (neat, cm ⁻¹ ) ν = 3600-3000, 30
00, 2950, 1620, 1600, 1580, 14
95, 1450, 1350, 1295, 1220, 11
60,990,905,860,780,735,69
0. ¹ H-NMR (chloroform-d, ppm) δ = 3.
6 (tr., 1H), 5.7 (d., J = 2.0 Hz,
2H), 7.1 & 8.2 (dd., J = 6.0 Hz, 8
H)

Reference Example 4 4-Nitrophenyl-1-allyl ether A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock, and a seam cap, and dried under a reduced pressure and replaced with argon. 8.0 g (0.2 mol) of sodium hydroxide was dissolved in 200 ml of water and charged into the reactor. Two
7.82 g (0.2 mol) of 4-nitrophenyl and 6.
After adding 45 g (0.2 mol) of tetra-n-butylammonium bromide, 24.7 from the dropping funnel.
After 9 g (17.1 ml, 0.2 mol) of allyl bromide was added over about 30 minutes, the mixture was reacted at 80 ° C. for 4 hours, and then stirred overnight at room temperature. The precipitated crystal was filtered and recrystallized from toluene. 30.9 g (yield: 9
(4.2%) of propargyl ether was obtained.

[Elemental analysis value] Calculated value: C; 60.34, H; 5.03, N; 7.8
2. Found: C; 59.75, H; 5.08, N; 8.0.
2. [Spectral data] IR (neat, cm ⁻¹ ) ν = 3600-3000, 30
00, 2950, 1620, 1600, 1580, 14
95, 1450, 1350, 1295, 1220, 11
60,990,905,860,780,735,69
0. ¹ H-NMR (chloroform-d, ppm) δ = 3.
5 (d., J = 2.0 Hz, 2H), 5.1 (m., 2)
H), 5.9 (m., 1H), 7.9 (m., 4H),

Reference Example 5 4-Aminophenyl-1-propargyl ether A 200 ml dropping funnel, a three-way cock, and a seam cap were attached to a 500 ml three-necked flask, dried under a reduced pressure and replaced with argon. 26.91 g (0.16 mol) 4-
Nitrophenyl-1-propargyl ether and 270 ml
Dioxin Sun was charged into the reaction vessel. 260.49 g
(0.16 mol) tin chloride and 270 ml concentrated hydrochloric acid were added dropwise over 2 hours under ice cooling. Keep the reaction vessel under ice cooling 1
After stirring for an hour, the solution was dropped into 1 liter of a 10 wt% sodium hydroxide aqueous solution. After filtering out the precipitated tin hydroxide, the filtrate was extracted from methylene chloride. After dehydration and filtration, the solvent was distilled off and the precipitated crystals were separated by filtration and recrystallized from toluene. 20.12 g (yield: 89.2%)
To give 4-aminophenyl-1-propargyl ether.

[Elemental analysis value] Calculated value: C; 73.46, H; 6.12, N; 9.5
2. Found: C; 73.85, H; 5.98, N; 9.8.
6. [Spectral data] IR (neat, cm ⁻¹ ) ν = 3600-3000, 30
00, 2950, 1620, 1600, 1580, 14
95, 1450, 1350, 1295, 1220, 11
60,990,905,860,780,735,69
0. ¹ H-NMR (chloroform-d, ppm) δ = 2.
5 (tr., 1H), 3.5 (br.s., 2H),
4.75 (d., J = 1.2 Hz, 1H), 6.7
(M., 4H)

Reference Example 6 4-Aminophenyl-1-allyl ether A 500 ml three-necked flask was equipped with a 200 ml dropping funnel, a three-way cock, and a seam cap, and dried and replaced with argon under reduced pressure. 23.67 g (0.14 mol) of 4-
Nitrophenyl-1-allyl ether and 270 ml of dioquinsan were charged to the reaction vessel. 260.49 g (0.
16 mol of tin chloride and 270 ml of concentrated hydrochloric acid were added dropwise over 2 hours under ice cooling. The reaction vessel was stirred under ice cooling for 1 hour and then added dropwise to 1 liter of a 10 wt% sodium hydroxide aqueous solution. After filtering out the precipitated tin hydroxide, the filtrate was extracted from methylene chloride. After dehydration and filtration, the solvent was distilled off and the precipitated crystals were separated by filtration and recrystallized from toluene. 21.62 g (yield: 93.2%) of 4
-Aminophenyl-1-allyl ether was obtained.

[Elemental analysis value] Calculated value: C; 80.74, H; 5.81, N; 13.4
5. Found: C; 80.53, H; 5.98, N; 13.8.
1. [Spectral data] IR (neat, cm ⁻¹ ) ν = 3600-3000, 30
00, 2950, 1620, 1600, 1580, 14
95, 1450, 1350, 1295, 1220, 11
60,990,905,860,780,735,69
0. ¹ H-NMR (chloroform-d, ppm) δ = 3.
5 (tr., 1H), 4.2 (br.s., 2H),
5.15 (d., J = 1.2 Hz, 1H), 6.7
(M., 4H)

Reference Example 7 12.5 g (0.051 mol) of bromophthalic acid (purchased from Bromchemy) and 8.0 g (0.2 mol) of sodium hydroxide were dissolved in 200 ml of water and charged into a reactor.
After adding 6.45 g (0.2 mol) of tetra-n-butylammonium bromide, 2. from the dropping funnel.
After adding 79 g (0.050 mol) of propargyl alcohol over about 30 minutes, the mixture was reacted at 80 ° C. for 4 hours, and then stirred overnight at room temperature. The precipitated crystals were separated by filtration and recrystallized from toluene to obtain 10.5 g (yield: 94.2%) of propargyl ether. The obtained crystals were placed in a reactor substituted with nitrogen together with 100 ml of o-toluene and refluxed for 12 hours. The precipitated crystals were collected by filtration while hot. When purified by sublimation, 5.8 g of 3-propargyloxyphthalic anhydride was obtained.

[Elemental analysis value] Calculated value: C; 65.35, H; 2.99. Found: C; 64.99, H; 3.12. [Spectral Data] IR (neat, cm ⁻¹ ) ν = 3000, 2950, 16
20, 1600, 1580, 1495, 1450, 13
50, 1220, 1160, 990, 905, 860,
780,690. ¹ H-NMR (chloroform-d, ppm) δ = 3.
5 (d., J = 2.4 Hz, 1H), 5.15 (d.,
J = 2.4 Hz, 2H), 6.7 (m., 3H)

Example 1 A 1000 ml 4-neck separable reaction vessel was equipped with a N ₂ introducing tube, bubbler, and mechanical stirrer pressure reducing valve.
N ₂ was flushed. Controlling the reaction system at 76 ± 2 ° C, 38.8863 g (0.12528 mo)
l) oxydiphthalic dianhydride (hereinafter referred to as ODPA
15 ml of N-methylpyrrolidone (N)
MP). Make sure that a homogeneous solution is obtained, and
0.0 ml (1.26 mol) of dry methanol was added dropwise,
Oxydiphthalic acid dimethyl ester was synthesized. After stirring at that temperature for 60 minutes, 34.8610 g (0.
(12526 mol) of the BAPDMP obtained in Reference Example 2 was added to a solution prepared with 100 ml of dry THF at 76 ± 2 ° C. The mixture was stirred for 2 hours while paying attention to temperature control. After that, 14.6 g (42.1 mmol) of benzophenone tetracarboxylic dianhydride and 5.1 g (2
0.7 mmol of bisaminophenyl sulfone and 6.3
25 g of structural formula (9) synthesized from 4 g (42.2 mmol) of 4-aminophenyl-1-propargyl ether

[0080]

[Chemical 42]

The compound represented by the formula: THF60 / NMP1
What was dissolved in 5 ml of the mixed solvent was added, and the mixture was stirred for 2 hours. Brookfield Viscometer
The viscosity of the resin after the reaction was measured using a Viscometer) and was found to be 19 poise. Next, Reseach Tool Co. L
A unidirectional reinforced prepreg was prepared by using two rolls of "RST57PA-535CS" manufactured by Nitto Boseki Co., Ltd. using "Model 30 Prepregger" of td. The prepreg was cut to a predetermined size and then dried. The drying conditions are shown in FIG. 4 inches (vertical) x 3 inches (horizontal)
22 pieces of the prepreg of No. 2 and a heat-resistant laminated material having a thickness of 3.25 mm were prepared by using a precision mold under the press molding condition of FIG. The evaluation results are shown in Table 1.

Example 2 40.0686 g (0.1248 mol) of benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA),
34.7545 (0.1249 mol) of BAPDMP, 1
2.6 g (34.5 mmol) benzophenone tetracarboxylic dianhydride and 6.8 g (17.5 mmol) 2,2-
Bis (4-aminophenyl) hexafluoropropane and 6.1 g (34.9 mmol) 4-aminophenyl-1-
19g structural formula (1
0)

[0083]

[Chemical 43]

Example 1 except that the compound represented by
In the same manner as above, a resin solution having a viscosity of 21 poise was obtained, and a heat-resistant laminated material having a thickness of 3.42 mm was obtained. The evaluation results are shown in Table 1.

Example 3 9.2031 g (0.04220 mol) of pyromellitic dianhydride (hereinafter referred to as PMDA), 20.3560 g
(0.06318 mol) BTDA, 29.3297 g
(0.10539 mol) BAPDMP, 10.6 g (1
7.5 mmol of bisphenol A bistrimellitic dianhydride, 5.6 g (17.5 mmol) of benzophenone tetracarboxylic dianhydride and 6.8 g (17.5 mmol) of 2,2-bis (4-aminophenyl) ) 20 g of structural formula (11) synthesized from hexafluoropropane and 6.1 g (34.9 mmol) of 4-aminophenyl-1-allyl ether.

[0086]

[Chemical 44]

A resin solution having a viscosity of 16 poise was obtained in the same manner as in Example 1 except that the compound represented by the formula (1) was used to obtain a heat-resistant laminated material having a thickness of 3.42 mm. The evaluation results are shown in Table 1.

Example 4 20.8816 g (0.09574 mol) PMDA, 4
4.5310 g (0.14356 mol) ODPA, 6
6.4659 g (0.23883 mol) of BAPDMP,
10.6 g (17.5 mmol) of bisphenol A bistrimellitic dianhydride and 5.6 g (17.5 mmol) of benzophenone tetracarboxylic dianhydride and 4.1 g (1
5.7 mmol of bisaminophenyl sulfone and 7.1
57 g of structural formula (12) synthesized from g (34.9 mmol) of 3-propargyloxyphthalic anhydride

[0089]

[Chemical formula 45]

A resin solution having a viscosity of 28 poise was obtained in the same manner as in Example 1 except that the compound represented by the formula (1) was used to obtain a heat resistant laminated material having a thickness of 3.64 mm. The evaluation results are shown in Table 1.

Comparative Example 1 "Kelimide 601" (manufactured by Nippon Polyimide Co., Ltd.) 9
Dissolve 5g in 120g DMF (resin concentration: 45wt%)
did. It was dried at 120 ° C. for 85 minutes in a hot air circulation drying furnace to prepare a prepreg having a resin concentration of 40.2% by weight and a residual solvent concentration of 6.4%. Eight prepregs prepared in this manner were used and integrally molded by heating at 220 ° C. for 2 hours at 25 kg / cm ² under pressure to obtain a laminated plate having a thickness of 5.7 mm. The evaluation results are shown in Table 1.

Comparative Example 2 165 g of an imide oligomer "Thermid MC-600" (manufactured by Kanebo NSC) was dissolved in 200 g of DMF (resin concentration: 45% by weight). 1 in the hot air circulation drying furnace
It was dried at 20 ° C. for 85 minutes to prepare a prepreg having a resin concentration of 31.2% by weight and a residual solvent concentration of 9.4%. Using 8 sheets of prepreg thus prepared, 220 ° C for 2 hours / 2
5 kg / cm ² heating and pressurizing were integrally molded to obtain a laminated plate having a plate thickness of 6.2 mm. The evaluation results are shown in Table 1.

[0093]

[Table 1]

[0094]

INDUSTRIAL APPLICABILITY As described above, the heat-resistant laminated material of the present invention has excellent mechanical and electrical properties and high moisture resistance and heat resistance, and thus can be used in a wide variety of applications.

[0095]

[Brief description of drawings]

FIG. 1 is a diagram showing a drying condition of a prepreg in an example.

FIG. 2 is a diagram showing press molding conditions in Examples.

Claims (9)

[Claims] 1. A compound represented by the general formula (1): (In the formula, R ₁ and R ₂ are at least one selected from the group consisting of hydrogen, a C1-18 aliphatic group and an aromatic group, and each represents a substituent which may contain a halogen group.
R ₁ and R ₂ may be the same or different. Ar ₁ represents a tetravalent aromatic group, and may be one type or two or more types. ) And a general formula (2) Alternatively, general formula (3): (In the formula, Ar ₂ is a divalent aromatic group, and even if one kind is 2
It may be more than one species. Ar ₃ is a tetravalent aromatic group. Further, in the formula, X is a trivalent bonding mode and is represented by the general formula (4): And may be the same or different. n represents a positive integer of 1 to 30. R ₃ is a functional group having reactivity and may have an aliphatic group or an aromatic group. ) A heat-resistant laminated material comprising a novel polyimide-based resin composition containing one or both of thermosetting oligomers represented by the formula (1). 2. The thermoplastic polyimide represented by the general formula (1) and the thermosetting oligomer represented by the general formula (2) and / or (3) have a weight fraction of 99/1 to 5/95. The heat-resistant laminated material according to claim 1, wherein 3. The heat-resistant laminated material according to claim 1, wherein the thermoplastic polyimide represented by the general formula (1) has a number average molecular weight of 50,000 or more. 4. R ₃ is at least 1 selected from the following:
The heat-resistant laminated material according to claim 1, which is a seed. [Chemical 5] 5. The heat resistant laminated material according to claim 1, wherein Ar ₁ or Ar ₃ is at least one selected from the following. [Chemical 6] 6. The heat-resistant laminated material according to claim 1, wherein Ar ₂ is at least one selected from the following. [Chemical 7] 7. A compound represented by the general formula (5): An acid dianhydride represented by the general formula (6) (In the formula, Y ₁ to ₄ are at least one selected from the group consisting of hydrogen and a C1-5 alkyl group, and may be the same or different. Ar ₁ is a tetravalent aromatic group. Which may be one type or two or more types) in an inert gas atmosphere in the temperature range of 50 to 150 ° C. from tetracarboxylic dianhydride and the corresponding alcohol, and then , Under the same conditions, the general formula (7): (In the formula, R ₁ and R ₂ are at least one selected from hydrogen, a C1-18 aliphatic group or an aromatic group, and may each contain a halogen group. R ₁ and R ₂ are The same kind or different kinds of organic diamines may be mixed to synthesize a polyamic acid prepolymer, and the polyamic acid prepolymer may be synthesized. Alternatively, the compound represented by the general formula (3): (In the formula, Ar ₂ is a divalent aromatic group, and even if one kind is 2
It may be more than one species. Ar ₃ is a tetravalent aromatic group. Further, in the formula, X is a trivalent bond mode and is represented by the formula (4): Selected from the group represented by and may be the same or different. n represents a positive integer of 1 to 30. R ₃ is a functional group having reactivity and may have an aliphatic group or an aromatic group. ), A resin solution obtained by blending a thermosetting oligomer is prepared, and then a reinforcing material is applied and impregnated with the resin solution, and then dried to a predetermined residual solvent concentration to obtain a prepreg. A method for manufacturing a heat-resistant laminated material, which is produced and integrally molded by heating and pressing a predetermined number of the prepregs. 8. The method according to claim 7, wherein the resin solution has a concentration of 5 to 75% by weight. 9. The production method according to claim 7, wherein the residual solvent concentration of the prepreg is 1 to 20% by weight based on the resin.