JPS6225126A - Addition-type imide resin prepolymer, prepreg and laminated board - Google Patents

Abstract

PURPOSE:To obtain the titled prepolymer suitable for the production of high- density multi-layer printed circuit board, by reacting an unsaturated bis-imide with a diamine in a manner to contain the residual unreacted raw material, a component having a molecular weight falling within a specific range and a high-molecular component at specific respective ratios. CONSTITUTION:The objective prepolymer can be produced by reacting an unsaturated bis-imide with a diamine in a manner to contain 15-55% residual unreacted raw material, 39-80% component having a molecular weight of 400-15,000 and 0.7-6.8% component having a molecular weight of >=15,000. The obtained objective prepolymer is impregnated in a substrate and semicured to obtain a prepreg wherein the contents of the unreacted raw material in the resin is 15-35%, the component having a molecular weight of 400-15,000 is 50-80% and the component having a molecular weight of >=15,000 is 1-15%. The prepreg is laminated to form a laminated board.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to addition-type imide resin prepolymers, prepregs, and laminates used for manufacturing printed wiring boards and the like.

[Background technology]

Conventionally, epoxy resin materials with excellent adhesive properties, chemical resistance, electrical properties, mechanical properties, etc. have often been used as resins for manufacturing multilayer printed wiring boards. When used for this purpose, there are problems with heat resistance during the mounting process, and a reduction in conduction reliability due to smear and thermal expansion in the thickness direction. In order to solve these problems from a material perspective, heat-resistant materials such as imide resins have been developed and put into practical use. In particular, addition-type imide resin made by reacting unsaturated bis-imide with diamine can be used to: ■ Thin wires for high density. j11. Possible for high-precision processing such as drilling small holes, ■Low coefficient of thermal expansion in the thickness direction, and high continuity reliability due to through-hole plating.
■No smear occurs during the drilling process, ■High conductor adhesion and hardness at high temperatures, improving mounting performance, and ■Can withstand continuous use at high temperatures (200℃). As a result, it has come to be widely used as a material for multilayer printed wiring boards.

However, in recent years, there has been a trend toward higher density packaging and higher multilayering of multilayer printed circuit boards for large combi-vinators, etc., and for this reason, there is a strong demand for miniaturization of circuits and reduction in the diameter of through ball holes. In order to meet this requirement, substrates are now required to have even higher levels of dimensional stability and adhesion than before.

That is, the dimensional change of the board directly affects the positional deviation of the inner and outer layer circuits of the multilayer board, and when the multilayer board size is increased, the variation in the dimensional change must be kept to a minimum. For this reason, when manufacturing the substrate, it is preferable to perform the molding process at low pressure. This is because dimensional stability deteriorates when molding is performed under high pressure. On the other hand, regarding adhesion, as circuits become finer, the adhesion between the circuit and the resin must naturally be high, but the adhesion between the base material and the resin must also be high. The adhesion must also be high. This is because, if the adhesion is low, fine peeling will occur between the base material and the resin at the L stage, or peeling will occur between the eyebrows inside the board. This is because such inconveniences may occur. Generally known addition-type imide resins have insufficient adhesion to the base material when viewed at the multi-5Fi level for use in large computers, etc., so minute peeling tends to occur during the drilling process. . Furthermore, when producing a substrate, if the prepreg is molded at low pressure, voids will occur and a uniform substrate will not be obtained, so molding must necessarily be performed at high pressure. This also results in insufficient dimensional stability of the substrate.

[Purpose of the invention]

An object of the present invention is to provide an addition-type imide resin prepolymer, prepreg, and laminate from which a high-density, high-multilayer printed board that enables high-density mounting of electronic components can be obtained.

[Disclosure of the invention]

In order to achieve the above objectives, the inventors first
We investigated the causes of insufficient adhesion to the base material and the generation of voids when molded at low pressure when a commonly known addition-type imide resin binder/polymer is used. As a result, it was found that the cause was that the general addition type imide resin prepolymer contained a large amount of components in the high molecular region. As a result of further research, the inventors discovered an addition-type imide resin with a composition that has sufficient adhesion to the base material and does not generate voids even when molded under low pressure.The inventors have now developed the following three inventions. Completed i:.

However, the first invention is an addition type imide resin prepolymer made by reacting an unsaturated bis-imide with a diamine, and the remaining unreacted raw material is reduced to 15 to 55%2 molecular weight 4
The second invention is an addition-type imide resin prepolymer, characterized in that it contains 39 to 80% of components having a molecular weight of 00 to 15,000 and 0.7 to 6.8% of components having a molecular weight of more than 15,000. Reduce the remaining unreacted raw material to 15 to 5
5%, components with a molecular weight of 400 or more and 15,000 or less from 39 to
80% of components with a molecular weight exceeding 1 sooo 0°7~6
．． Obtained by reacting unsaturated f[ ] bis-imide and diamine with each content in the range of 8% (=1) By impregnating a base material with a moldable imide resin prepolymer and semi-curing, Unreacted raw material is 15-35%1
50-80% of components have a molecular weight of 400 or more and 15,000 or less
9 A prepreg in which the component having a molecular weight exceeding 15,000 is 1 to 15%.The third invention is a laminate formed by laminating and molding prepregs, and as a prepreg,
15% to 55% of remaining unreacted raw materials 39% to 80% of components with a molecular weight of 400 to 15000 2 Molecular weight of 150%
A base material is impregnated with an addition-type imide resin prepolymer obtained by reacting an unsaturated bis-imide and a diamine, each containing a component exceeding 0.00 in the range of 0.7 to 6.8%, and semi-cured. Accordingly, the amount of unreacted raw materials in the resin is 15 to 35%, 3 components with a molecular weight of 400 to 15,000 are 50 to 80%, 1 components with a molecular weight exceeding 15,000 are 1 to 15%. Each of the laminates is summarized as follows.

Below, these inventions will be explained in detail.

Here, the unsaturated bis-imide is represented by the following formula (I), and the diamine is represented by the following formula (II).

(In the formula, A represents a divalent group containing a carbon-carbon double bond, and A represents a divalent group containing at least two carbon atoms.) H2N-B-NR2(Il) (In the formula B is a divalent group having up to 30 carbon atoms) The symbols A and B can be the same or different,
Also 131[IJ is a linear or branched alkylene group having fewer carbon atoms, or a cyclic alkylene group having 5 or 6 carbon atoms in the ring, O, N and S atoms. or a phenylene or polycyclic aromatic group. These various groups may have substituents that do not give rise to unnecessary side reactions under the reaction conditions.

The symbols A and B can also represent numerous phenylene groups or alicyclic groups. In this case,
Adjacent phenylene groups or alicyclic groups may be bonded directly, or may be bonded via a divalent atom such as oxygen or sulfur, or may be bonded via an alkylene group of 1 to 3 carbon atoms or May be connected through one of the following groups: When a plurality of these atoms or groups exist, each of them may be the same or different.

NR4-, -P (0) R3, N=N.

N=N, -Co-0-, -502.

5iR3R4, C0NH.

-N　Y-CO-X　-CO-N　Y　-.

-o-co-x-co-o-.

In the formula, R3, R4 and Y each represent an alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms in the ring, or phenyl or a polycyclic aromatic group, X represents a straight-chain or branched alkylene group having fewer than 13 carbon atoms, a cyclic alkylene group having 5 or 6 carbon atoms in the ring, or a monocyclic or polycyclic arylene group.

The bases are derived from ethylenic anhydrides of the formula; such as maleic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, itaconic anhydride, and cyclodienes and one of these anhydrides. It can also represent the product of the Diels-Alder reaction that occurs between

Preferred examples of the unsaturated bis-imide represented by formula (1) include the following. Malene MN-N
'-Ethylene-bis-imide, maleic acid N-N'-hexamethylene-bis-imide, maleic acid N-N'
-Metaphenylene-bis-imide, maleic acid N-N'
-paraphenylene-bis-imide, maleic acid N-N'
-4,4'-diphenylmethane-bis-imide (N -
N'-methylenebis (also called N-phenylmaleimide)], maleic acid N-N'-4.4'-diphenyl ether-bis-imide, maleic acid N-N'-4.
4'-Diphenylsulfone-bis-imide, maleic acid N-N'-4・4'-dicyclohexylmetal-bis-imide, maleic acid N-N'-α・α′-4・
4'-dimethylenecyclohexane-bis-imide, N-N'-metaxylylene-bis-imide maleate, and N-N'-diphenylcyclohexane-maleate.
Bis-imide.

Preferred examples of diamines of formula (II) include: 4,4'-diaminodicyclohexylmethane, ■,4'-diaminocyclohexane, 2,6
-diamitubiridine, metaphenylenediamine, paraphenylenediamine, 4,4'-diamino-diphenylmethane, 2,2-bis(4-aminophenyl)propane,
benzidine, 4,4'-diaminophenyl oxide,
4,4'-diaminodiphenyl sulfide, 4,4'
-diaminodiphenylsulfone, bis-(4-aminophenyl)diphenylsilane, bis-(4-aminophenyl)methylphosphine oxide, bis=(3-aminophenyl)methylphosphine oxide, bis-
(4-aminophenyl)-phenylphosphine oxide, bis-(4-aminophenyl)pheniramine, ■
- 5-diaminonaphrene, meta-xylylene diamine, para-xylylene diamine, 1-bis-(para-minophenyl) phthalane and hexamethylene diamine.

The addition type imide resin prepolymer according to the first invention is
It can be obtained by reacting a soimide and a diamine as described above using a catalyst. Here, the catalyst used is one that acts as a proton donor in the polar solvent used and promotes Michael addition. Examples of catalysts are shown on the next page.

The obtained prepolymer must have the composition shown below.

That is, the unreacted raw material needs to be 15 to 55%. When it exceeds 55%, when a varnish is prepared by dissolving the prepolymer in a polar solvent such as N-methylpyrrolidone or dimethylacetamide, the solubility in the solvent is low, and precipitates are likely to separate out.

If it is less than 15%, the time it takes for the varnish to harden becomes shorter, resulting in a shorter pot life.

Examples of catalysts triethylamine, tripropylamine, tributylamine, N,N-tetramethylethylenediamine, N,N
-tetramethyl-1,3-butanediamine, triethylenediamine, N-methylmorpholine, pyridine, α-picoline, quinoline, N,N'-dimethylaniline, N,
Tertiary amines such as N'-diethylaniline and dimethylbenzylamine, organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, phthalic acid, isophthalic acid, and terephthalic acid, and water. .

A component having a molecular weight of 400 or more and 15,000 or less is a component that has good solubility and high activity (and exhibits good adhesion to the base material. From this point of view, the more the component, the better.
If it is synthesized to exceed 80%, no matter what catalyst is used, there will be too many components with a molecular weight of over 15,000, resulting in too high a viscosity. It also shortens the time it takes for the resin to harden, shortening the pot life of the varnish and making it impossible to take enough time to dry it.

On the other hand, if it is less than 39%, a large amount of unreacted components will remain, and when the varnish is prepared, the above-mentioned disadvantages such as precipitation becoming more likely to occur will occur. Therefore, this component needs to be 39-80%. Molecular weight 15
Increasing the high molecular weight components above 0.00000000000000 shortens the time to cure of the resin. Therefore, the pot life of the varnish is shortened and the drying time is not sufficient. If the drying time is insufficient, volatile components tend to remain in the varnish.

The adhesion to the base material also decreases. Therefore, the less this component is, the better.

When the inventors separated a component with a molecular weight exceeding 50,000 and dissolved it in d-DMF and subjected it to NMR analysis, almost no diamine component was observed, indicating that it was a homopolymer of unsaturated bis-imide. was recognized. It is known that this polymer has poor flexibility and poor adhesion to the base material, and from this point of view, it is preferable to have as few components as possible with molecules exceeding 115,000. However, once the resin synthesis reaction is started, Since a region with a molecular weight exceeding 15,000 is generated, it is impossible to completely eliminate it. Therefore, components with a molecular itl exceeding 5000 have a molecular itl of 0.7 to 6.
It must be 8%.

If it exceeds 6.8%, the viscosity will increase as mentioned above, and if it is less than 0.7%, the reaction will be insufficient and the varnish will have a low viscosity, making it difficult to use when impregnating a base material such as glass cloth. Inconveniences arise in that resin content cannot be obtained and the varnish tends to precipitate.

Here, the molecular weight distribution was determined using DMF solvent 1 and Showa Denko AD-803/S (8, OX
Gel permeation chromatograph (Toyo Soda HLC-803) equipped with two 25 (1+m, theoretical plates 6000 plates)
D). Calculation of molecular weight is based on the retention time of five types of monodispersed polyethylene glycol and ethylene glycol monomer and the common logarithm of molecular weight.
A regression curve of the following formula was obtained, this was applied to the sample, and the molecular weight was determined inversely from the retention time of the sample. In addition, the proportion (%) of each component is calculated using a differential refractometer (1
28Xlo-8RI units), and the sample concentration was adjusted to 0.5±
0.2%, the sample injection volume was 100 μl, the refractometer output was 0 to 1 ■ The output to the recorder was O to 10 mV, and the chromatogram was divided into the necessary molecular weight categories. , the respective ratios were determined by the cut-out weight method.

The addition type imide resin prepolymer in which each component has the above-mentioned component ratio has high adhesion to the base material and high heat resistance. There are no commercially available products with such ingredient ratios, and they are not generally available. According to the inventors' investigation, compared to the addition-type imide resin prepolymer of the first invention, the proportion of components with a molecular weight exceeding 15,000 in commercially available products is higher (unlikely, if any of the commercially available products does not contain this component) It contained a very large amount.

The prepolymer of the first invention is usually obtained by reacting an unsaturated bis-imide and a diamine in a polar solvent at a low temperature below 95°C, more preferably at a temperature of 60 to 95°C. Although the conventionally commonly used temperature conditions, i.e., melt reaction at 120 to 200°C and solution reaction using polar solvents, can efficiently reduce unreacted raw materials, the reaction proceeds too much and there are many components with molecular weights exceeding 15,000. It will generate. 0 components with a molecular weight exceeding 15,000
．． If the amount is limited to 7 to 6.8%, the reaction will be insufficient and a large amount of unreacted raw materials will remain. This tendency becomes more pronounced as the thermal melting reaction is carried out at higher temperatures; in this case,
There are many unreacted raw materials and many components exceeding 15,000. As a result, the most effective component, the portion with a molecular weight of 400 to 15,000, becomes extremely small. The reaction as described above is usually 0.5 to 10
The specific time is selected depending on the type of raw materials, the type of polar solvent, and the reaction temperature, and may be outside the above range.

The blending ratio of unsaturated bis-imide and diamine is 1°7/1
~2.5/1 molar ratio is preferred, 1.7/1
If it is lower, a large amount of high molecular weight components will be produced, and the time until curing will be shortened, making it difficult to handle. On the other hand, if it exceeds 2°5/1, a large amount of unreacted raw materials tends to remain, especially a large amount of unsaturated imide components. Therefore, precipitation tends to occur during storage of the prepolymer solution. On the other hand, the blending ratio of unsaturated bis-imide and diamine is 1.7
/1 to 2.5/1, hardly any precipitate is formed during normal storage or even when stored refrigerated at -5°C. This blending ratio is the final one,
Both or only one of them may be used twice or more, and may be added in the middle of the reaction, or in some cases, after the reaction is completed.

The addition-type imide resin prepolymer of the present invention can be used to form laminates for printed wiring boards, as well as semiconductor sealing materials, structural materials for high-strength, high-modulus electrical equipment, electromagnetic shielding materials, etc. by combining with various fillers. It can be used for a wide range of electrical applications, such as materials, adhesives for semiconductor devices, adhesives for mounting chip components, and pastes for circuit printing, and when used in these applications, it has high heat resistance, high adhesion, It becomes possible to obtain a molded article with good flexibility.

The prepreg according to the second invention is obtained by impregnating a base material with the addition type imide resin prepolymer according to the first invention, and then performing a secondary reaction of the prepolymer and evaporating the solvent to half the prepolymer. After curing, the resin contains 15 to 35% of unreacted raw materials, 50 to 80% of components with a molecular weight of 400 to 15,000, and 1 to 15% of components with a molecular weight of more than 1 sooo. This prepreg cannot be obtained without using the addition type imide resin prepolymer according to the first invention. The content of unreacted raw materials is less than 15% and the molecular weight is 400 or more and 1500
If the component with a molecular weight of 0 or less exceeds 80% and the component with a molecular weight of over 15,000 exceeds 15%, the amount of components with a molecular weight of over 15,000 increases and the viscosity of the resin becomes too high. Therefore, voids occur during low-pressure molding. Furthermore, the time required for curing is too short, making it difficult to obtain large laminates (molded plates). On the other hand, if the content of unreacted raw materials exceeds 35%, the component with a molecular weight of 400 to 15,000 is less than 50%, and the component with a molecular weight of over 15,000 is less than 1%, the solvent will not remain in the prepreg. This will cause blisters to occur in the laminate.It is preferable that the amount of components having a molecular weight exceeding 15,000 be as small as possible.The reason for this is as stated in the explanation of the prepolymer.

Commercially available addition-type imide resin prepolymers have molecules of 1150
Since the prepreg contains a large amount of components exceeding 0.00, no matter what semi-curing conditions (secondary reaction conditions) are selected, it is not possible to obtain a prepreg with the above-mentioned component ratio.

The type of base material to be impregnated with the addition type imide cedar monofat prepolymer is not particularly limited. Usually, glass cloth or the like is used. In addition, inorganic fiber cloth such as quartz fiber cloth, highly heat-resistant organic fiber cloth such as Kevlar fiber cloth, etc. may be used. These base materials are usually surface-treated with a coupling agent, etc., and the temperature for semi-curing is 130 to 1
Preferably, it is carried out at 55°C. If the temperature exceeds 155°C, the production of components with a molecular weight exceeding 15,000 is promoted, and if it is below 130°C, prepreg cannot be efficiently produced.

The laminate according to the third invention is made using the prepreg according to the second invention. In other words, this prepreg is laminated and molded together with a metal foil such as copper or nickel, or an inner layer material having nine circuits formed thereon, as required. The laminate according to the third invention cannot be formed at low pressure without producing voids unless the prepreg according to the second invention is used. That is, 50cI
When molding a laminate with an area of IIX 50 cm or more without forming voids, prepreg using commercially available prepolymers requires a high pressure of 40 kg/cm2 or more, but the blib 1/g of the second invention requires , 15kg/am2
It is possible to mold at low pressures such as: For this reason,
The laminate according to the third invention can be made extremely dimensionally stable. Further, since this laminate uses the prepolymer according to the first invention, the adhesiveness between the resin and the base material is high. Therefore, by using this laminate, it is possible to obtain a high-density, high-multilayer pudding I-board.

Next, examples of the first to third inventions, comparative examples, and conventional examples will be described.

First, the first invention will be explained.

The prepolymer solution was synthesized and prepared in the following manner.

In Examples 1 to 6 and Comparative Examples 1 to 6, the raw materials with the formulations shown in Table 1, excluding the post-addition of N,N'-methylenebis(N-phenylmaleimide), were added to the 31st and fourth flasks. After weighing, a stirring bar, a thermometer, and a condenser were attached to the flask, nitrogen gas was passed through the side port. After replacing the air in the flask with nitrogen, heating was performed using an oil bath. Stirring was started as the contents dissolved, and the temperature was set as shown in Table 1. After continuing stirring for the time indicated in the table, the mixture was cooled in a water bath, and the temperature was lowered to room temperature in 15 minutes to obtain a prepolymer solution that became a dark liquid. In Example 6, 603 g of bis-imide and 3
A total of 997g was used, divided into two 94g doses.

Then, 603 g of bis-imide was used in the same manner as above, and after reacting the raw materials for 120 minutes, 394 g of bis-imide was used at 90 °C.
g of bis-imide was charged to the flask. After dissolving this, the reaction product was cooled to obtain a prepolymer solution. In Comparative Example 6, a total of 911g was used, divided into two parts: 828g first and 83g later.

In the conventional example, commercially available polyamino bismaleimide was used in the amount shown in Table 1, and by dissolving it in the amount of N-methylpyrrolidone shown in the table at 50°C or less, a reddish-brown color was obtained. A prepolymer solution was obtained.

Prepolymer solution (resin liquid) obtained as described above
The analytical values and characteristic values are shown in Table 2.

From Tables 1 and 2, it can be seen that the prepolymers of the present invention could not be obtained in Comparative Examples 1 to 6 because the combinations of reaction temperature, reaction time, and catalyst amount were not acceptable.

Next, the second invention will be explained.

105g/surface treated using the resin liquid obtained earlier
Impregnation was carried out on a m2 glass cloth under the conditions shown in Table 3. Perform the secondary reaction in the dry product, and the microwave content 47-5
A 0% prepreg was produced. The properties of the obtained prepreg are shown in the lower column of Table 3.

From Table 3, it can be seen that the prepreg of the present invention cannot be obtained by using the prepolymer of the comparative example or the conventional example. Furthermore, even if the prepolymer of the first invention is used, if the molecular weight distribution of the semi-cured resin is out of the range specified in the second invention, it can be seen that the volatile content increases or the gel time becomes short.

Next, the third invention will be explained.

The previously obtained prepreg was made into a size of 30cm x 30c+a, and four sheets were stacked on top of each other, and 1/2 oz/ft2 copper foil of the same size and surface treated was placed on both sides to form a laminate. This was placed in a 1.6 mm thick mold, and while applying a pressure of 5 kg/co+2 using a steam press, it was immediately heated to 130° C. and held for 20 minutes. Thereafter, the pressure was set at 10 kg/cm 2 and the laminate was heated to 170° C. After 90 minutes, the laminate was cooled to room temperature while the pressure was applied to obtain a double-sided copper-clad laminate. This thing costs 200. 'C, 12
After-curing was performed at a temperature of 0 minutes.

The water absorption rate of the obtained laminate was measured based on JIS C6481, and the results are shown in Table 4.

Next, stack 5 sheets of the prepreg with a size of 50C1l
The molding results of the laminates made in the same manner as above except that two types of 5kg/co+2 were used, and the measurement results of the adhesion force when the layers were peeled off in a 90° direction were also shown in the fourth table. Shown in the table.

A primary molded double-sided copper-clad laminate was obtained in the same manner as described above, except that one prepreg of 25C11×25CII and two sheets of copper foil of the same size and 1 oz/ft2 were used. After drilling reference point holes in this material at intervals of approximately 200 TII + 1, the dimensions of Oma were accurately measured, the copper foil on both sides was removed by etching according to the usual method, and prepreg with the same dimensions as above was formed on one side of this (inner layer material). One sheet of copper foil of 1 oz/fL2 with the same dimensions as the two sheets was laminated, and two sheets of prepreg and one sheet of copper foil were laminated on the other side in the same way.
After molding for 1 minute in the same manner as above, it was after-cured at 200° C. for 120 minutes to obtain a laminate. The copper foil on the reference hole of the inner layer material of this laminate was mechanically removed, and the dimensional change in the inner layer material was measured. The above measurements were performed 10 times based on this measurement method. The variation (3σ) of the dimensional change at this time is also shown in Table 4.

From Table 4, the laminate of the example uses the prepreg of the second invention and is molded at low pressure, so compared to the laminate of the comparative example and the conventional example, the water absorption rate and dimensional behavior are more stable. You can see that It can also be seen that the peel strengths of the laminates of Examples were all over 1.4 kg/cI112, which should be fully satisfactory.

〔Effect of the invention〕

Since the addition-type imide resin prepolymer according to the first invention, the prepreg according to the second invention, and the laminate according to the third invention are configured as described above, if these are used, high-density, high-multilayer It becomes possible to obtain printed boards.

That is, when the prepolymer according to the first invention is dissolved in a polar solvent such as N-methylpyrrolidone or dimethylacetamide to prepare a varnish, the varnish does not contain any precipitates of unreacted raw materials or high molecular weight insoluble substances. The varnish is clear, and the varnish takes a long time to harden, so the pot life of the varnish is also extended.

Next, since the prepreg according to the second invention uses the prepolymer according to the first invention, the varnish takes a long time to harden, can be sufficiently dried, and the volatile matter remaining in the prepreg is reduced. It becomes less. Furthermore, since the melt viscosity of the resin is low, this prepreg does not cause fading even when molded at low pressure, making it suitable for molding large-sized laminates.

In addition, since the laminate according to the third invention uses the prepreg according to the second invention, it can be molded at low pressure, resulting in good dimensional stability and an I-layer board with excellent adhesion between the base material and the resin. was gotten.

Agent Patent Attorney Takehiko Matsumoto □ Hoshosho, (Dated October 19, 1985. Court of the Chief of the Anti-Slavery Agency 1, Indication of the case 1985 Patent No. 19 No. 164430 2, Name of the invention (= J Kari-type imide resin prepolymer prepreg and laminate; ], Relationship with 11 amendments Patent applicant Location 1048 Oaza Kadoma, Kadoma-shi, Osaka Name (583) Matsushita Electric Works Co., Ltd. Representative Isei 1 4, Emperor Fujii Keio, no representative, 12., 6, List of documents attached to the application to be amended and column 7, Detailed explanation of the invention in the specification, Contents of amendment (11 Documents attached to the application) Correct the list column as stated in the attached application form.

(2) On page 9, line 5 of the specification, the word "also" is corrected to "or."

(3) "Mokushiha" on page 9, line 7 or line 8 of the specification
Correct the word "or" to "or."

(4) Page 10 of the specification of, I am corrected.

(5) On page 12, lines 3 and 4 of the specification, "dicyclohexylmetal" is corrected to "dicyclohexylmethane."

(6) On page 13, line 5 of the specification, "diaminonaphrene" is corrected to "diaminonaphthalene."

(7) Second from the bottom of the leftmost shelf in Table 3 on page 28 of the specification:
"At 160°C" should be corrected to "At 170°C."

Claims (3)

[Claims] (1) An addition type imide resin prepolymer made by reacting an unsaturated bis-imide and a diamine, with a residual unreacted raw material content of 15-55% and a molecular weight of 400 or more and 15,000.
An addition type imide resin prepolymer characterized by containing the following components in a range of 39 to 80% and a component having a molecular weight exceeding 15,000 in a range of 0.7 to 6.8%. (2) 15-55% remaining unreacted raw material, molecular weight 40
Addition type imide obtained by reacting an unsaturated bis-imide with a diamine, containing 39 to 80% of a component having a molecular weight of 0 to 15,000 and 0.7 to 6.8% of a component having a molecular weight exceeding 15,000. By impregnating the resin prepolymer into the base material and semi-curing it, the unreacted raw material in the resin is 15 to 35% and the molecular weight is 400 to 15,000.
A prepreg containing 50 to 80% of the following components and 1 to 15% of components with a molecular weight exceeding 15,000. (3) A laminate plate in which prepreg is laminated and molded, and the remaining unreacted raw material is 15 to 55% as the prepreg.
%, components with a molecular weight of 400 or more and 15,000 or less are 39 to 8
0%, and components with molecular weights exceeding 15,000 are 0.7 to 6.
By impregnating the base material with an addition-type imide resin prepolymer obtained by reacting unsaturated bis-imide and diamine in a range of 8% and semi-curing, the unreacted raw materials in the resin are reduced to 15 to 35%. %, 50 to 80% components with a molecular weight of 400 to 15,000, and a molecular weight of 15
1. A laminate, characterized in that a component exceeding 0.000 is used in an amount of 1 to 15%.