JPH0428720A - Heat-resistant laminated material and its production - Google Patents

Abstract

PURPOSE:To readily obtain the subject laminated material excellent in heat resistance, moisture resistance, storage stability, etc., at a low cost by impregnating a basal material with a resin having a specified structural formula, drying the impregnated material and laminating the dried materials. CONSTITUTION:For example, a mixture of an organic diamine compound and a diamine containing an inner acetylene substituent group is dissolved in an organic solvent in an atmosphere of an inert gas, and an organic tetracarboxylic acid dianhydride is added thereto and allowed to be reacted. A primary amine is added thereto and allowed to be reacted. After adding a non-solvent substance thereto, the resultant mixture is subsequently refluxed and azeotropically boiled to obtain a reactive resin having structural formula I (Ar1 is preferably group of formula II, etc.; Ar2 is preferably group of formula III, etc.; Ar3 is preferably group of formula IV, etc.; X is CH3, etc.; (n) and (m) are 1-30; (y) is 1-4). The obtained resin is dissolved in an organic solvent such as dimethyl sulfoxide preferably so as to be 35-65wt.% concentration and a base material such as a glass fabric is impregnated with the resultant solution. After drying, the dried materials are laminated, thus obtaining the objective laminated material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-resistant laminate having excellent heat resistance, moisture resistance, and storage stability, and a method for producing the same.

[Prior Art and Problems to be Solved] In recent years, electronic devices have developed at a remarkable pace, and the use of copper-clad laminates used as wiring boards has become diverse, and those with excellent characteristics are required. In particular, with the increasing density of wiring due to the high-density packaging of electronic components, wiring boards are becoming more multilayered and through-holes are becoming smaller in diameter. For this reason, there is a need for copper-clad laminates with good workability, such as less smear generation during drilling. On the other hand, with the demand for improved productivity and lower costs, increasingly strict processing conditions are required in the process of mounting onto wiring boards, such as using a photo air reherer or flow soldering. Among these demands, copper-clad laminates that serve as substrates are required to have better heat resistance and moisture resistance than ever before.

In order to meet these demands, in recent years, addition-curing polyimide resins have come to be used instead of evoquino resins, which are generally widely used as laminated materials for copper-clad laminates. When this polyimide resin is used as a laminate material for copper-clad laminates, it has the advantage of almost no smearing during drilling, and the heat resistance during processing and long-term tests is significantly improved. It has been known.

However, conventionally used addition-curing polyimide resins have had various problems as described below. In other words, a product made by reacting N,N'-bisimide, an unsaturated dicarboxylic acid, with diaminodiphenylmethane is excellent for use in laminates. There was a problem with the short usage time. Furthermore, diaminodiphenylmethane may pose a problem of toxicity to living organisms.

Further, those containing N,N'-bisimide of unsaturated dicarboxylic acid and aminophenol as reaction components exhibit well-balanced properties for use in laminates and have excellent processability.

However, there is a problem in that the moisture resistance is poor, and for example, special attention must be paid to moisture absorption for long-term storage of the obtained laminate.

Furthermore, a product obtained by reacting N,N'-bisimide of an unsaturated dicarboxylic acid with aminobenzoic acid is suitable for use in laminates, but it has poor solubility in low-boiling point solvents and cannot be used in glass cloth when making prepregs. There were problems in applying it to surfaces such as. Furthermore, there were other problems such as the need to be careful in storing the resin solution.

[Means to solve the problem]

In view of the above circumstances, the present inventor has made extensive studies to solve these technical problems, and as a result, has arrived at the present invention.

That is, the gist of the heat-resistant laminate material according to the present invention is as follows: is a group, ^rz+Ar++Ar
:+ may be of the same type or different types. In addition, n and m are copolymerization ratios, both of which are 1 to 30.
) represents an integer. Furthermore, X is CH3, CHxCl(z,
CHxO, CI, Br, F, CN, NOx,
A substituent selected from Ch, CF+CFz, and CF30ph, which may be the same or different, and y is an integer of 1 to 4. ) is the main component.

Further, it is an Ar14-valent aromatic group in the heat-resistant laminate material of the present invention.

Furthermore, In the heat-resistant laminate material of the present invention, Ar -Q-OG so g @-o coma (I(sawa) small number o-OQ or -oO(door()0k Divalent aroma selected from It is a family group.

Also, In the heat-resistant laminate material of the present invention, Ar.

Ru.

Next, the method for producing a heat-resistant laminate according to the present invention is based on the general formula (1) (wherein 2 is a tetravalent organic group, Ar1 is a divalent organic group, and Ar3 is a monovalent organic group. ,Ar2.Ar,,^r
, may be of the same type or different types. Moreover, n and m are copolymerization ratios, and both represent integers of 1 to 30. Furthermore, X is CH2, CH2CH2, C1
ho, CI, Br, F, CN, NO□, C
F3. A substituent selected from CF3Ch and CF30ph, which may be the same or different.
y is an integer from 1 to 4. ) After impregnating a base material with a reactive resin composition, it is dried to create a prepreg, which is then press-molded.

It is a tetravalent aromatic group in the method for producing a heat-resistant laminate material of the present invention.

Further, in the method for producing a heat-resistant laminate of the present invention, Ar is a divalent aromatic group selected from DOGSOzGOG (剋Q -o-oo Oo Oo-).

Furthermore, the present invention provides a method for manufacturing a heat-resistant laminate material.

[Example 1] Next, an example of a heat-resistant laminate material and a manufacturing method thereof according to the present invention will be described. First, a method for producing a reactive resin composition used in the heat-resistant laminate of the present invention will be described.

In an inert gas atmosphere such as argon or nitrogen, killing (n)
Organic diamine compound represented by; HzN-Ar+-NH
z (II) (wherein, Ar,
is a divalent organic group); and a diamine having an internal acetylene substituent represented by (III);
X is C) l:I, CLCL, Cl130. C.I.
, 8r, FCN, No□, CF,, CF□C
F7. CF30. It is position 11 selected from Ph,
May be the same or different, y is 1 to 4
is an integer. ) was dissolved in an organic solvent,
An organic tetracarboxylic acid dihydride (in the formula, Arz is a tetravalent organic group) represented by general II (IV) is added to the mixed solution, and a telechelic oligomer at the terminal of the tetracarboxylic acid collection is added. I got it.

The reaction temperature at this time is suitably in the range of 5 to 120'C, preferably -15 to 100'C, and more preferably -5 to 50'C.The reaction time is 1
About 5 hours is preferable.

In this reaction solution, a primary amine represented by -killing (V), Ar,, -NHz (
V) was added to terminate the ends to obtain a polyamic acid solution containing all reactive polyimide pieces.

The reaction temperature at this time is suitably 0 to 120°C, preferably 0 to 100°C, and more preferably 40 to 100°C.
]00°C is preferred. The reaction time is preferably about 1 to 5 hours.

Thereafter, a non-solvent was added to thermally ring-close and dehydrate the polyamic acid solution, and then the solution was converted into polyimide under reflux and azeotropy. Here, the nonsolvent used may be an aromatic hydrocarbon such as kiln or toluene, but toluene is preferably used. The reaction was carried out azeotropically, and the water to be distilled off was refluxed using a Dean-Stark reflux device until the stoichiometric amount of water for the reaction was collected. After the reaction, the polyimide solution was poured into a water or alcohol solvent with vigorous stirring to precipitate the polyimide as a powder. After the powder was collected by filtration, it was heated to 80'C.
The mixture was dried under pressure for 48 hours.

As the organic tetracarboxylic dianhydride used in the present invention, organic tetracarboxylic dianhydride having any structure can be used, but the Ar1 group of -rV is a tetravalent organic group, and aromatic A group group is preferred. This^
Specific examples of rzJA include the following.

These organic tetracarboxylic dianhydrides may be used alone or in combination of two or more. More specifically, in terms of the balance of properties, it is preferable that at least one of the following is used as the main component.

Further, as the divalent organic group ^r+ in the organic diamine compound represented by the general formula (II) used in the present invention, essentially any divalent organic group can be used, but specifically, , 0°o0o0°o5″S.

(to SO), Kou (translation) CHZ o-CH2 GS, etc., but aromatic groups are preferable, and specifically, at least one type of Go @-s o z @-o @- is the main group. It is suitable to use it as a component.

Examples of the primary amine Ar3 represented by the general formula (V) used in the present invention for terminal termination are as follows: Q”Q’＝”−〇−〇′o″
c°0H,'1or3-06. . □-〇-0S:5o1
, -〇-5JQLo=o.

-〇-0 core C; C8-◎-CmiCJI etc., but from the point of view of cost and handling, the following is particularly preferred.

The mechanism behind the particularly high heat resistance of the reactive polyimide used in the prepreg of the present invention is not clear, but it is believed that the formation of a benzene skeleton by heat curing of acetylene/acetylene or the formation of phenanthrene by heat curing of acetylene/biphenylene This is thought to be an effect of the formation of aromatic rings due to skeleton formation [for example, J. Steil et al., Macromolecules, Vol. 19, No. 8;
1985 Heidi, 1986].

In addition, the number average degree of polymerization [D P :P, J, Flory P
r1nciples of Polymer Chem
istry:Cornell University
Press: l thaca, NY, 91 pages,
1953], the copolymerization ratio n is 1 to 30, preferably 1 to 15, more preferably 1 to 15.
10 is good. Similarly, the copolymerization ratio m is preferably 1 to 30, preferably 1 to 25, and more preferably 1 to 20. If it exceeds this range, there will be a disadvantage that the solubility in organic solvents will decrease. Moreover, if it is less than that, a problem will arise in terms of mechanical strength.

The composition of the present invention has the polyimide resin having the reactivity described above as an essential component, but if necessary, it may also contain a known epoxy resin, an epoxy resin curing agent, a curing accelerator,
Fillers, flame retardants, reinforcing agents, surface treatment, pigments, various elastomers, etc. can be used in combination.

Known epoxy resins have two or more evoquinones (
Examples include bisphenol A, bisphenol F, hydroquinone, resorcinol, furylglycine, tris-(4-hydroquinophenyl)methane, and 1,1,22-tetrakis(4-hydroquinophenyl)ethane. Glysodylether compounds derived from divalent or trivalent or higher valent phenols such as phenols derived from halogenated polyphenols such as novolak derived from tetrabromobisphenol A and brominated polyphenols, phenols such as orthofuresol, etc. Novolanc epoxy resin, which is the reaction product of 4,4'-diaminodiphenyl ether, 3,
4'-diaminodiphenyl ether, 1,4-bis(4
-aminophenoquino)benzene, 1.4-bis(3-aminophenoxy)benzene, 1.3-bis(3-aminophenoquine)benzene, 2.2-bis(4-aminophenoquinophenyl)propane, para phenylenediamine,
metaphenylenediamine, 2.4-toluenediamine, 2.6-)luenediamine, baraxylylenediamine, metaxylylenediamine, 1,4-cyclohexane-bis(methylamine), l,3-cyclohexane-bis(methylamine) , 5-amino-1-(4'-aminophenyl)-1,8,8-)listylindane, 6-amino-1(4-aminophenyl)-1,8,8-1-listylindane, etc. amine-based epoxy resins derived from , glycidyl ester compounds derived from aromatic carboxylic acids such as paraoxybenzoic acid, terephthalic acid, and isophthalic acid, and hindantoin-based epoxy resins derived from 5,5-dimethylhindantoin, etc. 111.2.
2'-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)
Alicyclic epoxy resins such as cyclohexal 1 propane, vinyl cyclohexane dioxide, 3,4-epoxycyclohexane carboxylate, and one or more of triglycidyl isocyanurate, 2,4゜6-triglycidoxy S-triazine, etc. Two or more types can be mentioned.

Examples of known epoxy curing agents include amine curing agents such as aromatic amines and aliphatic amines such as xylylene diamine, polyphenol compounds such as phenol novolak and cresol novolac, and hydrazide compounds.

As a curing accelerator, benzyldimethylamine, 2.4.
6-1-Lis(dimethylaminomethyl)phenol, 1
．． Amines such as 8-diazabicycloundecene, 2
Examples include imidazole compounds such as -ethyl-4-methylimidazole and boron trifluoride amine complexes.

Addition of known elastomers to improve mechanical strength is also effective. Specific examples of known elastomers include the following.

n85゜ Seagull = 1° R; C00)I (CTBN.

CTB) H The elastomer described above is 5ilastic (LS-
420) Sy Igard (184) is available from Dow Corning, high strength ATBN (1300X16 etc.), CTB (200
0X162), CTBN (1300X13,1300
X8, 1300X31), VTBN (1300X23
) can be purchased from Ube Industries, Ltd., and 3F can be purchased from Monsando.

Further, in order to impart flame retardancy, flame retardants and inorganic fillers can be appropriately blended. The inorganic filler used is water-insoluble and insulating. Examples include metal oxides such as silica, alumina, zirconia, titanium dioxide, and zinc white, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, talc, kaolin, mica, wollastonite, and clay minerals. These include natural minerals and insoluble salts such as calcium carbonate, magnesium carbonate, barium sulfate, and calcium phosphate.

Carbon fiber, glass fiber, aramid fiber,
Examples include woven fabrics, nonwoven fabrics, mats, paper, and combinations thereof made of liquid crystal polyester fibers such as Hectra, polybenzothiazole (PBT) fibers, alumina fibers, and the like. Since these reinforcing materials provide adhesive properties, it is effective to use silane coupling treatment together.

Next, as a method for manufacturing a heat-resistant laminate material containing the reactive resin composition according to the present invention as a main component, a typical coating process will be described by way of example.

- A uniform face-shaped resin composition can be obtained by dissolving and stirring the resin composition represented by Sakuboku (1) in a predetermined amount of an organic solvent to a predetermined resin concentration.

After coating and impregnating a reinforcing agent such as glass cloth, glass nonwoven fabric, glass paper, etc. with the resin composition produced in this way, the resin composition is dried in a drying oven at 50 to 250°C, preferably 50°C.
0 to 200°C1, more preferably 100 to 200'
co) The residence time in the furnace is set so that a predetermined residual solvent concentration is achieved within a temperature range, and the prepreg for a heat-resistant laminate is manufactured by drying.

Examples of the organic solvent used include sulfoxide-based solvents such as dimethyl sulfokide and diethyl sulfoxide, N,N'-dimethylformamide, and N'-
Formamide solvents such as diethylformamide, N,
Examples include acetamide solvents such as N'-dimethylacetamide and N,N'-diethylacetamide, ether solvents such as dimethyl ether, diethyl ether, and dioxane, and ketone solvents such as acetone and methyl ethyl ketone. These solvents can be used alone or as a mixed solvent of two or more.

Furthermore, in addition to these polar solvents, it can also be used as a mixed solvent with alcoholic solvents such as methanol, ethanol, and isopropanol, benzene, methyl cellosolve, and the like.

The resin concentration when dissolved in an organic solvent and diluted is 5 to 75% by weight, preferably 15 to 75% by weight in relation to the resin concentration during prepreg.
It is desirable to use it in an amount of 65% by weight, more preferably in a range of 35 to 65% by weight. It is desirable to adjust the residual solvent concentration of the prepreg in the range of 1 to 20% by weight, preferably 1 to 10% by weight, and more preferably 1 to 5% by weight, based on the reinforcing material/resin ratio calculation. If it is less than that, a problem arises in that the mechanical properties of the laminate after prepreg molding become poor. Moreover, if it is more than that, the residual solvent will volatilize during prepreg molding, resulting in the inconvenience that voids will occur.

Next, a method for producing a double-sided copper-clad laminate using the heat-resistant prepreg obtained as described above will be described.

First, the number of copper foils and pre-reflectors are adjusted to obtain the desired thickness. After inserting the specified copper foil and prepreg between two stainless steel plates with mirror-finished surfaces attached to the press, they are heated and pressurized for a specified time, temperature, and pressure to form double-sided copper plates. A tension laminate is created.

Note that it is also effective to use aftercure in combination to improve mechanical strength.

Next, the present invention will be explained using more specific examples.
The present invention is not limited to these examples in any way, and the present invention may be implemented with various modifications, improvements, and changes based on the knowledge of those skilled in the art without departing from the spirit thereof. It's something you get.

165 g of an imide oligomer having each substituent of general formula (1) was dissolved in 200 g of dimethylformamide (hereinafter abbreviated as O-liver) (resin concentration: 45% by weight/DMF). 20% of this melt
cmX20CIIX180 II- glass cloth (WEA
-105FII7 on 18. Purchased from Nittobo Co., Ltd.)
16 sheets were impregnated. 120°C in a hot air circulation drying oven
After drying for 190 minutes, a prepreg with a resin concentration of 40.8% by weight (per glass cloth) and a residual solvent concentration of 4.0% was produced.

8 sheets of prepreg created in this way were covered with electrolytic copper foil (
35μ thick intestine, 3EC, purchased from Mitsui Kinzoku Kogyo Co., Ltd.) sandwiched between two sheets, 220°C, 2 hours, 25kg/cm
A double-sided copper-clad laminate with a thickness of 10 mm was obtained by heating and pressurizing and integrally molding the product under the following conditions.

The obtained double-sided copper-clad laminate was examined for copper foil peel strength, glass transition temperature, bending strength, and solder heat resistance accompanied by a pressure tsuka test. The results are shown in Table 1.

Back application U 165 g of an imide oligomer in which each substituent of general formula (1) is CF3 ^... * Ar5 = 00 was dissolved in 200 g of DMF (resin concentration: 45% by weight/DMF). x 20cm glass cloth (WEA-
105F117 on 18; purchased from Nittobo Co., Ltd.) 16
The sheet was impregnated. In a hot air circulation drying oven, 120℃, 90℃
After drying for several minutes, a prepreg with a resin concentration of 38.4% by weight (per glass cloth) and a residual solvent concentration of 3.6% was produced.

8 sheets of prepreg created in this way were covered with electrolytic copper foil (
Thickness 35μm, 32C; purchased from Mitsui Kinzoku Kogyo Co., Ltd.) sandwiched between two sheets, 220°C for 12 hours, 25kg/c
A double-sided copper-clad laminate with a uniform thickness of 9 mm was obtained by heating and pressurizing and integrally molding under the conditions of I12.

The resulting double-sided copper-clad laminate was examined for copper foil peel strength, glass transition temperature, bending strength, and solder heat resistance using a plain car test. The results are shown in Table 1.

Susashikan - Lord Each substituent in general formula (1) C.F.

Ar = 165g of imide oligomer, 200g of DMF
(resin concentration: 45% by weight/DMF), this solution was placed on a 20cm x 20c+w glass cloth (WE
A-18 to 105F117; purchased from Nittobo Co., Ltd.)
16 sheets were impregnated. 120° in a hot air circulation drying oven
When dried for 195 minutes, the resin concentration was 39.2% by weight (
A prepreg with a residual solvent concentration of 3.8% (per glass cloth) was produced.

8 sheets of prepreg created in this way were covered with electrolytic copper foil (
Thickness: 35μ, 3EC; purchased from Mitsui Kinzoku Kogyo Co., Ltd.) sandwiched between two sheets, 220°C, 12 hours, 25kg/
Heating, pressurizing and integrally forming the plate under the conditions of
A double-sided copper-clad laminate was obtained.

The obtained double-sided copper-clad laminate was examined for copper foil peel strength, glass transition temperature, bending strength, and solder heat resistance accompanied by a pressure tsuka test. The results are shown in Table 1.

Each substituent of the general formula N) is Ar1.
(resin modification; 45% by weight/DMF).

Spread this solution on four EA glass cloths of 20cw x 20cm.
-18 to 105F117. Purchased from Nittobo Co., Ltd.) 1
Six sheets were impregnated. 120°C1 in a hot air circulation drying oven
After drying for 85 minutes, a prepreg with a resin concentration of 37.2% by weight (per glass cloth) and a residual solvent concentration of 4.4% was produced.

8 sheets of prepreg created in this way were covered with electrolytic copper foil (
Thickness 35μm, 3EC; purchased from Mitsui Kinzoku Kogyo Co., Ltd.) Sandwiched between two sheets, 220°C for 12 hours, 25kg7c
A double-sided copper-clad laminate having a thickness of 1b+w was obtained by heating and pressurizing and integrally molding the product under conditions of 1b+w.

The obtained double-sided copper-clad laminate was examined for copper foil peel strength, glass transition temperature, bending strength, and solder heat resistance accompanied by a pressure tsuka test. The results are shown in Table 1.

165g of Hokukan■-Upper Imide Oligomer Therminodo MC-600 (purchased from hneho-NSC Co., Ltd.), DMF 20
0g of fat was dissolved (#A fat concentration: 45% by weight/DMF). Sixteen pieces of 20c+s x 20cm glass cloth (105F117 in WEA-18; purchased from Nittobo Co., Ltd.) were impregnated with this melt. In a hot air circulation drying oven, 12
After drying for 185 minutes at 0'C, a prepreg with a resin concentration of 31.2% by weight (per glass cloth) and a residual solvent concentration of 9.4% was produced.

8 sheets of prepreg created in this way were covered with electrolytic copper foil (
Thickness 35μ-, 3EC, purchased from Mitsui Kinzoku Kogyo Co., Ltd.) Sandwiched between two sheets, 220℃, 2 hours, 25kg/c1
A double-sided copper-clad laminate with a thickness of 10 m+s was obtained by heating and pressurizing and integrally molding under the following conditions.

The obtained double-sided copper-clad laminate was examined for copper foil peel strength, glass transition temperature, bending strength, and solder heat resistance accompanied by a pressure tsuka test. The results are shown in Table 1.

[Effects of the Invention] According to the heat-resistant laminated material of the present invention, no blisters are observed on the surface of the heat-resistant laminated material even when the heat-resistant laminated material is heated in a solder bath after sufficiently absorbing moisture through a pressure comb test. We were able to obtain a high quality laminated material. Moreover, the heat-resistant laminate material according to the present invention has high characteristic values such as bending strength and copper foil peeling strength, and it has become possible to provide a heat-resistant laminate prepreg with excellent storage stability.

Furthermore, according to the method for producing a heat-resistant laminate according to the present invention, the heat-resistant laminate is produced by impregnating a base material with a resin composition, drying the resin composition to create a prepreg, and then press-molding the prepreg. This makes it possible to easily and inexpensively produce industrially valuable laminates such as double-sided copper-clad laminates with excellent moisture resistance and heat resistance, making them extremely useful.

Claims (8)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Ar_2 is a tetravalent organic group, Ar_1 is a divalent organic group, Ar_3 is a monovalent organic group. , Ar_2, Ar
_1 and Ar_3 may be of the same type or different types. Moreover, n and m are copolymerization ratios, and both represent integers of 1 to 30. Furthermore, X is CH_3, CH
_3CH_2, CH_3O, Cl, Br, F, CN, N
O_2, CF_3, CF_3CF_2, CF_3O, P
A substituent selected from h, which may be the same or different. y is an integer from 1 to 4. ) A heat-resistant laminate material characterized in that the main component is a reactive resin composition consisting of: (2) Ar_2 has ▲mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
The heat-resistant laminate material according to claim 1, wherein the heat-resistant laminate is a tetravalent aromatic group selected from ▲ or ▼ having a mathematical formula, chemical formula, table, etc. (3) Ar_1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
The heat-resistant laminate material according to claim 1 or 2, wherein the heat-resistant laminate material is a divalent aromatic group selected from ▲ or ▼ having a mathematical formula, chemical formula, table, etc. (4) The heat-resistant laminate according to any one of claims 1 to 3, wherein Ar_3 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Material. (5) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, Ar_2 is a tetravalent organic group, Ar_1 is a divalent organic group, and Ar_3 is a monovalent organic group. , Ar_2, Ar
_1 and Ar_3 may be of the same type or different types. Moreover, n and m are copolymerization ratios, and both represent integers of 1 to 30. Furthermore, X is CH_3, CH
_3CH_2, CH_3O, Cl, Br, F, CN, N
O_2, CF_3, CF_3CF_2, CF_3O, P
A substituent selected from h, which may be the same or different. y is an integer from 1 to 4. 1. A method for producing a heat-resistant laminate material, which comprises impregnating a base material with a reactive resin composition consisting of (a) and drying the prepreg to produce a prepreg, which is then press-molded. (6) Ar_2 has ▲mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
6. The method for producing a heat-resistant laminate according to claim 5, wherein the group is a tetravalent aromatic group selected from ▲ or ▼ which has a mathematical formula, chemical formula, table, etc. (7) Ar_1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
The method for producing a heat-resistant laminate according to claim 5 or 6, wherein the divalent aromatic group is selected from ▲ or ▼ which has a mathematical formula, chemical formula, table, etc. (8) The heat-resistant laminate according to any one of claims 5 to 7, wherein Ar_3 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Method of manufacturing wood.