JPH01210431A - Continuous manufacturing method for laminates - Google Patents

Abstract

PURPOSE:To obtain the title sheet improved in a curing rate, performances and productivity, by impregnating a sheetlike base with a specified epoxy resin composition, drying and curing the composition by heating. CONSTITUTION:A mixture of a bifunctional bisphenol epoxy resin (i) with a polyfunctional epoxy resin (ii) having at least two epoxy groups in the molecule is reacted with a bisphenol (iii) to obtain a modified polyfunctional epoxy resin (a) having at least two epoxy groups in the molecule. Separately, component (i) is reacted with a polyfunctional reactive compound (iv) having at least two functional groups reactive with the epoxy group in the molecule to obtain a modified polyfunctional epoxy resin (b) having at least two epoxy groups in the molecule. Component (a) is mixed with component (b) and an epoxy resin curing agent (c) to obtain an epoxy resin composition (B). A sheetlike base (A) is impregnated with component B and dried, and the resin is cured by heating.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a method for continuously manufacturing a laminate for printed wiring boards, etc., by drying a sheet-like base material impregnated with an epoxy resin composition and then curing it by heating. It relates to a manufacturing method.

[Conventional technology]

To form a laminate that will serve as an insulating substrate for a glint wiring board, for example, the base material is impregnated with a varnish made by dissolving an epoxy resin composition in a solvent, the solvent is then dried, and the glint preg is cut to a certain size. Conventionally, a patch method has been used in which a predetermined number of sheets are piled up and then heated and pressed using a multi-stage press, but this requires a long press time, resulting in low productivity, and the curing conditions due to the lid of the multi-stage press. This has the disadvantage that the quality of each individual plate tends to vary due to the difference in quality.

Therefore, in recent years, attention has been paid to a continuous manufacturing method in which the material is continuously cured together with a metal foil such as GriGreg gold-copper foil.

[Problem to be solved by the invention]

However, in a continuous manufacturing method, it is necessary to shorten the heat curing process in order to increase productivity compared to the conventional multi-stage press method. Resin compositions are required.

Since radical polymerization type resins such as non-jull polyester resins and epoxy vinyl ester resins are capable of rapid curing, they have already been put into practical use through continuous production.
When applied to a glass substrate, the adhesion to the glass is poor and 1. The current problem is that the resin shrinks significantly during curing and also has poor adhesion to metal foil.

In addition, as a conventional resin composition for glass epoxy laminates, bisphenol A bifunctional epoxy resin or bifunctional bisphenol A brominated epoxy resin is the main component. Some use a small amount of novolak type polyfunctional epoxy resin in order to improve heat resistance. As a curing agent, a tertiary amine compound or the like is used with dianediamide or the like as a curing accelerator. In this case, the system that uses Nogelac-type epoxy resin will certainly cure faster than the system that does not use it, but
Under the conditions used in a continuous manufacturing method, for example, under heating conditions of several minutes at 190°C, in extreme cases, K may not reach the level of R-ru, or even if the cured product becomes R-R, it will not meet the specified requirements. Currently, post-curing is required to reach performance.

[Means to solve the problem]

As a result of intensive research in view of this situation, the present inventors have determined that bisphenol-type epoxy resins and polyfunctional epoxy resins having more than two epoxy groups in one molecule on average can be combined with bisphenols. A modified polyfunctional epoxy resin having an average of more than two epoxy groups in one molecule obtained by mutual grafting using a polyester resin, and/or a bifunctional bisphenol type epoxy resin and a functional group that can react with the epoxy group. and a polyfunctional reactive compound having more than two in one molecule on average, and further adding the above polyfunctional epoxy resin and/or bisphenols as necessary,
When using an epoxy resin composition consisting of a modified polyfunctional epoxy resin having an average of more than two epoxy groups in one molecule obtained by mutual grafting in advance, and an epoxy resin curing agent, it is possible to carry out the process by a continuous production method. It was discovered that the varnish can be cured even with a short heating time of several minutes at 190°C, for example, and the performance of the cured product is excellent, making it suitable as a varnish for continuously manufactured laminates. , we have completed the present invention.

That is, the present invention provides (A) bifunctional bisphenol type epoxy resin (a-1)
and a polyfunctional epoxy resin (a-2) having an average of more than two epoxy groups per molecule, and bisphenols (i-3) as an essential component. and/or (B) 21 [bisphenol type epoxy resin (a-1)
A bifunctional bisphenol type epoxy resin obtained by reacting a polyfunctional reactive compound (a-4) having an average of more than two functional groups per molecule that can react with an epoxy group as an essential component, or a difunctional bisphenol type epoxy resin. Epoxy group obtained by reacting (a-1), a polyfunctional reactive compound (a-4), and a polyfunctional epoxy resin (a-2) and/or bisphenols (a-3) as essential components (C
5. An epoxy resin composition comprising a hardening agent for epoxy resin and all essential components.
- Provides a method for continuously manufacturing a laminate, which comprises impregnating a tab-shaped base material, drying it, and then curing it by heating.

The bifunctional bisphenol type epoxy resin (a-1) used in the present invention includes, for example, at least one kind selected from bisphenols (a-3), preferably bisphenols, bisphenol F, and tetrabromobisphenol A. Using a compound and epichlorohydrin, for example, "epoxy resin" K published by Shokodo Co., Ltd.
Based on liquid or solid epoxy resins having two glycytyl ether groups in the same molecule, which are easily obtained by known methods as described, or the epoxy resins thus obtained, Pisfe/-kW
IJ (a-3), preferably at least one compound selected from bisphenol A, bisphenol F and tetrabromobisphenol A, is further reacted by a known method as described in "epoxy resin". Generally, resins having an epoxy equivalent of 160 to 800, preferably 160 to 500 are used.

Examples of the polyfunctional epoxy resin (a-2) used in the present invention include cresol, phenol, reso, 11/7
y, an epoxidized product of Tumelac resin obtained by condensation of a phenolic compound such as bisphenol A with formalin; trifunctional epoxy resin such as trishydroxy 7 phenylmethane triglycyl ether, triglycidyl in cyanurate, etc.; or tetrakis 4 such as hydroxyphenylethane tetraglycidyl ether, diaminodiphenylmethane tetraglycidyl compound
The average number of epoxy groups in one molecule is more than 2, preferably 2.5 to 8, including functional epoxy resins.
．． Among them, a no-lac type epoxy resin is preferred in terms of cost, and among these, a tumerac-type epoxy resin based on resorcinol or bisphenol AI paste is preferred.

Among the bisphenols (a-3) used in the present invention, one or more compounds selected from bisphenol A, bisphenol F, and tetrabromobisphenol A are particularly preferable, and they have a flame retardant property. In order to further increase the temperature, tetrabromobisphenol A is preferentially used. However, this does not apply if a tetrabromobisphenol A'1-based bifunctional epoxy resin (a-1) has already been used.

The polyfunctional reactive compound (a-4) used in the present invention is
In (a-2), the average number of reactive functional groups per molecule is more than 2, preferably 2.
Examples include polyfunctional phenolic compounds such as Tumerac resin, trishydroxyphenylmethane, and tetrakishydroxyphenylethane, polyfunctional amine compounds such as diaminodiphenylmethane, and polyfunctional cargokyfur groups such as trimellitic acid. Among the compounds contained therein, polyfunctional phenolic compounds are preferred.

The modified polyfunctional epoxy resin (A) usually has an epoxy equivalent of 200 to 2,000, preferably 300 to 2,000.
800 is used. The modified polyfunctional epoxy resin (
4) is the polyfunctional epoxy resin (
It exhibits much faster curing properties than a simple blend of a-2) at the same weight percent, and also has excellent cured product performance. This is a modified polyfunctional epoxy resin (N is not in the form of a blend of mono-1C difunctional components and other polyfunctional components, but in a good shape as they are grafted together), so the overall curability is sufficient. This is presumed to be because it is fast and a uniform cured product can be obtained without local differences in reactivity occurring during the curing reaction.

The above bifunctional bisphenol epoxy resin (a-
1) The usage ratio of the raw material components of polyfunctional epoxy resin (a-2) and bisphenols (a-3) varies depending on the required performance, but (a-1)
) The ratio (1-1)/(a-2) of the number of epoxy groups in (a-2) to the number of epoxy groups in (a-2) is 9515 to 40/60,
Among them, 80/20 to 50150, and the ratio of the sum of the numbers of epoxy groups in (a-1) and (a-2) to the number of hydroxyl groups in (a-3) ((a-1) + ( a-z))/(a-
a) from 60/40 to 90/10, especially from 65/35
It is preferable to use the ratio in a range of 80/20. If the amount of the polyfunctional epoxy resin (a-2) is too small, the expected effect will not be obtained, and if the amount of the polyfunctional epoxy resin (a-2) is too small, the expected effect will not be obtained. Bisphenol compounds (a-
If 3) is too small, the desired effect will not be obtained.

Conversely, bifunctional bisphenol type epoxy resin (a-1) K
On the other hand, if the amounts of the polyfunctional epoxy resin (a-2) and bisphenols (a-3) are too large, they may be converted during the reaction or impede impregnation into the base material when used as a varnish. Please be careful as the viscosity is high. It is preferable that the phenolic hydroxyl group of the bisphenol (a-3) is completely reacted with the epoxy group.

Next, the modified polyfunctional epoxy resin (B) usually has an epoxy equivalent of 200 to 2,000. Preferably 30o-8
00 is used.

Bifunctional bisphenol type epoxy resin (a-1) used in producing modified polyfunctional epoxy resin (B)
, polyfunctional epoxy 7 resin (a-2), bisphenols (
The usage ratio of the raw material components a-3) and the polyfunctional reactive compound (a-4) is the same as that of the modified polyfunctional epoxy resin (A).
Similarly to , it differs depending on the required performance, so it is not Sea-like, but using components (a-1) and (a-4), (a-
When components 2) and/or (a-3) are not used at all, the usage ratio is the number of epoxy groups in (a-1) and (
The ratio of the number of reactive functional groups in a-4) (a-1)/(a-
4) from 55/45 to 90/10, especially from 60/40
It is preferable to use it within a range of 75/25. If the amount of the polyfunctional reactive compound (a-4) used is too small, the desired effect will not be obtained, and if the amount is too large, there is a risk of oxidation. It is preferable that the reactive functional group of the polyfunctional reactive compound (a-4) is reacted with the epoxy group as completely as possible.

Maku, (a-1), (a-2), (a-3) and (a
-4) When using all of the ingredients, the usage ratio is (
The difference between the number of epoxy groups in a-1) and the number of hydroxyl groups in (a-3), the sum of the number of epoxy groups in (a-2) and the reactive polyfunctional group in (a-4) Ratio ((a-1)-(a-3))
/((a-2)+(a-4)) is 45155 to 65/3
5, especially preferably in the range of 50,150 to 60/40.

When using components (a-1), (a-3) and (a-4), the usage ratio is the number of epoxy groups in (a-1) and the number of hydroxyl groups in (a-3). The ratio of the difference and the number of reactive polyfunctional groups in (a-4) ((a-1)-(a-3))/(
a-4) is 55/45 to 90/10, especially 60/4
It is preferable to use it in a range of 0 to 75/25.

In this case, it is particularly important to adjust the amount of (a-4) used to the optimum amount in order to obtain the desired effect.

Furthermore, when using components (a-1), (a-2) and (a-4), the usage ratio is as follows: (a-1) and (a-2)
) The ratio (a-1)/(a-2) of the number of epoxy groups in ) is 9
515~40/60, especially 90/10~60/4
0, and the ratio of the sum of the numbers of epoxy groups in (a-1) and (a-2) to the number of reactive functional groups in (a-4) ((a-1
)+(a-2))/(a-4) is 55/45 to 90/1
0, especially preferably in the range of 60/40 to 75/25. In this case, since there is a high risk of ruching, care must be taken especially to ensure that the amount of (a-2) used is not greater than necessary.

The reaction for obtaining the modified polyfunctional epoxy resins (A) and (B) is described in the above-mentioned "epoxy resin" and in JP-A-48-8
3199, for example, alkali hydroxides such as sodium hydroxide, tertiary amines such as triethylamine, benzyldimethylamine, and quaternary amines such as tetramethylammonium chloride. It is carried out by heating at 110 to 180° C. using an ammonium salt, an imidazole compound, triphenylphosphine, or the like as a catalyst.

Imidazole compounds, pyridine compounds such as methylpyridine and dimethylaminopyridine, tertiary amines such as dimethylbenzylamine, trisdimethylaminomethylphenol, and diazobicycloundecene, or phenolic compounds and carboxyl group compounds of these amine compounds. salts, boron trifluoride amine complexes, etc.

The curing agent (C) for epoxy resin used in the present invention includes the modified polyfunctional epoxy resin (A) which is the main ingredient and/or
Alternatively, those that do not impair the quick curing properties of (B), have the necessary storage stability as a varnish, and exhibit desirable physical properties of the cured product are preferred, such as dicyandiamide, guanamine derivatives, guanidine crocodile conductors, calgenic acid, etc. Examples include hydrazide compounds, phenolic resins, and boron trifluoride compounds, among which dicyandiamide and phenolic resins are preferred.

Next, in order to assist the reactivity of the curing agent (C), a curing accelerator is generally used in combination, and the fast curing characteristic of the modified polyfunctional epoxy resin (A) and/or (B) in the present invention This is a very effective way to make it even more outstanding.

Examples of the curing accelerator include imidazole compounds such as 2-ethyl-4-methylimidazole, pyridine compounds such as methylpyridine and dimethylaminopyridine,
Tertiary amines such as trismethylbenzylamine, trisdimethylaminomethylphenol, and diazobicycloundecene, or salts of these amine compounds and phenolic compounds, or cal? Examples include salts with xyl group-containing compounds, boron trifluoride amine complexes, and the like.

The epoxy resin composition used in the present invention may further contain solvents such as methyl ethyl ketone, acetone, and methyl selon, pigments, fillers such as aluminum hydroxide, aluminum silicate, colloidal silica, calcium carbonate, mica, and talc. A composition that can be impregnated into a 7-tate base material.

Examples of the sheet-like base material used in the present invention include sheet-like materials using glass fiber, carbon fiber, aromatic polyamide fiber, etc. Among them, continuous mat, cloth, roving cloth, etc. using glass fiber, etc. Non-woven fabric etc. are preferred.

Next, the epoxy resin composition obtained in this way is impregnated into a sheet-like base material as a varnish.
Pre-dry within a few minutes at 0℃! After relegating,
A predetermined number of sheets are stacked together, sandwiched with metal foil such as copper foil as needed, and heated at 130 to 220°C using a hot pressure molding machine such as a double belt press.
By heating and curing preferably at 150 to 200°C for 8 minutes or less, preferably 1 to 5 minutes, a laminate can be obtained continuously. - For boat fishing, it is most efficient to perform the impregnation process on the base material and the dry deregreg process in a continuous manner connected to the continuous pressing process. Of course, continuous press molding is also possible.

The above-mentioned double belt press includes surface pressure methods such as a roll linear pressure method, an air floating method, and a hydraulic method, but is not limited to these methods. Further, the heating and pressurizing zone within the double belt press may be divided into several zones, and should be selected appropriately.

A cooling zone may also be provided if necessary.

〔Example〕

Next, the present invention will be described in more detail with reference to Reference Examples, Examples, and Comparative Examples. In addition, all parts and parts in the examples are based on heavy lids unless otherwise specified.

/ ・ ) / / /' / Reference Example 1 [Preparation of modified polyfunctional epoxy resin (A)] Liquid "Epicron 850J [: Dainippon Ink and Chemicals (
Co., Ltd.) Bisphenol A type epoxy resin on the back, engineering/=? Equivalent ± 190] 46IIS and bisphenol A novolac type epoxy resin (epoxy equivalent ± 190, softening point =
78℃, average number of units per molecule = 6.5)
To a mixture consisting of 20 parts, 34 parts of tetrabromobisphenol A was added, heated to 120°C and stirred, and then 2-
4 at 150°C with the addition of 0.01 part of methylimidazole.
A solid modified polyfunctional epoxy resin (A-
1) was obtained, and 43 parts of methyl ethyl ketone was added to make a methyl ethyl ketone solution with a solid content of 70%.

Reference Example 2 (same as above) 36 parts of Epiclon 850J used in Reference Example 1, and 29 parts of a lac-type epoxy resin containing bisphenol A
! Tetrabromobisphenol AW epoxy resin, epoxy equivalent = 360) To a mixture of 8 parts, 27 parts of tetrabromobisphenol A was added, and Kitafugai was prepared in the same manner as in Reference Example 1. A solid modified polyfunctional epoxy resin with an equivalent weight of 405 and a bromine content of 20 (A-1
1) Add 43 parts of methyl ethyl ketone to the mixture to make a solution with a solid content of 70%.

Reference Example 3 [Preparation of modified polyfunctional epoxy resin CB] “40 parts of Epiclon 850J and semi-solid [Epiclon 1
52J 45 parts and phenol? To 15 parts of lac resin (softening point = 75°C, hydroxyl equivalent = 102.1 average number of phenolic hydroxyl groups per molecule = 4) was further added 10 parts of methyl ethyl ketone, heated to 115°C, stirred, and further triturated. Add 0.02 part of phenylphosphine and heat to 115℃
A solid modified polyfunctional epoxy equivalent (B -1
) was obtained, and 33 parts of methyl ethyl ketone were added thereto to make a solution with a solid content of 70%.

Reference Example 4 (same as above) "A solid with an epoxy equivalent of 701 and a bromine content of 20% was prepared in the same manner as in Reference Example 3, except that the amounts of Epiclon 850J and phenolic nogelac resin were changed to 31 parts and 18 parts, respectively. Modified polyfunctional epoxy resin (B-1
f) and further added 33 parts of methyl ethyl ketone to make a solution with a solid content of 70 parts.

Reference Example 5 (same as above) 50 parts of "Epicron 850" and resorcinol-based nogelac type epoxy resin (resorcin-cresol collinear nogelac-type epoxy resin with a weight ratio of resorcin and orthocresol of 60:40, epoxy equivalent = 172,
Softening point = 79℃, average number of epoxy groups per molecule -7
, 5 pieces)), 34 parts of tetrabromobisphenol A and 5 parts of the phenol black resin used in Reference Example 3 were added, and further 10 parts of methyl ethyl ketone was added.
1 part, heated to 115°C and stirred, further processed with 0.02 part of triphenylphosphine and reacted at 115°C for 5 hours, resulting in an epoxy equivalent of 656. Obtaining a solid modified polyfunctional epoxy resin (B-111) t″ with a bromine content of 20,
Furthermore, 33 parts of methyl ethyl ketone was added to make the solid content 70%.
A solution of

Reference example 6 (same as above) “Epicron 850J 45 parts and “Epicron 152”
” Tetrabromobisphenol A10 in a mixture of 30 parts
and 15 parts of the phenolic resin used in Reference Example 3 were added, further 10 parts of methyl ethyl ketone was added, heated to 115°C and stirred, and 0.02 part of triphenylphosphine was added and reacted at 115°C for 5 hours. In this way, a solid modified polyfunctional epoxy resin (B-IV) having an engineering equivalent of 736 and a bromine content of 20% was obtained, and 33 parts of methyl ethyl ketone was added to prepare a solution with a solid content of 70%.

Reference example 7 (same as above) “Epicron 850 J 30 parts and “Epicron 15
2" 45 parts 1.1.1-) 9 Ene of diphenylethane in hydrochloride? Silicide (hand-shaped, engineering?xy equivalent: 17
In a mixture with 10 parts of 0.1 molecule IU of average number of groups in Epoxy resin, 1,1.1-trishydroxy 7 enyl ethane (molecule 1 = 306, hydroxyl group equivalent; 102.7 per molecule) was added. Add 15 parts of ethanolic hydroxyl groups (number of hydroxyl groups = 3), further add 710 parts of methyl ethyl keto, heat and stir at 115°C, further add 0.02 part of tri-7enylphosphine, and react at 115°C for 5 hours. So, the engineering I xy equivalent is 5
20. Modified polyfunctional epoxy resin with a bromine content of 21% (
B-V)! 33 parts of methyl ethyl ketone was added to obtain a solution with a solid content of 70%.

Examples 1 to 7 and Comparative Examples 1 to 6 The epoxy resin solutions, dicyandiamide (hardening agent for knee and middle resin) and 2-ethyl-4-methylimidazole (hardening accelerator) shown in Table 1 below are shown in the same table. The amount used was used, and methyl ethyl ketone was further added to prepare a mixed solution with a nonvolatile content of 55%.

In this case, the amount of dicyandiamide is set at a ratio of 0.20 mol per epoxy group of the epoxy resin, and the amount of 2-ethyl-4-methylimidazole is set at a ratio of 0.20 mole per 1 epoxy group of the epoxy resin. Te 0.3
The ratio was set to 50%.

The above mixed solution was stored in a resin impregnating tank, and 9 pieces of continuous glass cloth with a width of 1020 mm [WE manufactured by Nittobo (45k)
-18K-104-BZ2) was continuously impregnated with the mixed solution so that the adhesion rate after drying was 44 to 45%, and then each was heated at 165°C for 3 minutes using a drying oven (however,
In Comparative Examples 5 and 6, it was dried for 5 minutes). Next, nine dried impregnated base materials were stacked on top of each other to a thickness of 35 μm.
After stacking electrolytic copper foils from above and below and laminating them with a laminating roll,
Conveyed to a double belt press at 190℃ and continuously heated at 40℃.
Cured under heat and pressure at a pressure of 9 parts cm" for 3 minutes (6 minutes in Comparative Examples 5 and 6), then cooled to 100'C under the same pressure, and cut at 1000x with a guillotine cutter.
It was cut into long pieces to obtain a double-sided copper-clad laminate with a thickness of 1°6cm.

Regarding this double-sided copper-clad laminate, the amount of material flowing out during molding, thickness accuracy, adhesion between substrates, copper foil peel strength, and water absorption were measured as follows. The results are shown in Table 1.

0 Material outflow during molding it (%) -W, /WOX 1
Calculated at 00. However, Wo is a predetermined area of 1020
Weight of copper clad laminate of m (width) Xi 000■ (length),
Wl is the weight of the portion protruding from the 1020j111 width during molding. ) oJ! J precision (m): 50111 position (■) inward from the center of one side on the left side of a 1020 am wide laminate board, and a position (5°n) inward from the center part of one side on the right side (center ■) ■ Measure the thickness of each of the following.

0 Adhesive strength between base materials (kf-cz): 10inX 1
A 00snO test piece was prepared, and the peel strength was measured using a tensile tester Tensilon when the outermost sheet-like base material and steel foil were forcibly peeled together from the laminate at an angle of 90''.

0 Steel foil peel strength (Y-α): JIS C-648
Measured according to 1.

0 Water absorption rate (%): After removing the copper foil on one side of the copper-clad laminate by etching, it was kept at 2 atmospheres for 4 hours! A Rescher cooker test was conducted, and the water absorption rate was calculated based on the following formula.

Water absorption rate (%) = (W'-W)/WX100 friend, W
is the weight of the laminate before the test, and W' is the weight of the laminate after the test.

〔Effect of the invention〕

As is clear from the results of the above Examples and Comparative Examples, according to the production method of the present invention, even though the Nyxi resin composition is used as a varnish, it can be cured in a short time and the performance is improved. Excellent laminates can be manufactured continuously with high productivity.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. (A) difunctional bisphenol type epoxy resin (a-
Epoxy obtained by reacting a mixture of 1) and a polyfunctional epoxy resin (a-2) having more than two epoxy groups in one molecule on average with bisphenols (a-3) as an essential component. Modified polyfunctional epoxy resin and/or (B) difunctional bisphenol type epoxy resin (a-1) having more than two groups in one molecule on average
The epoxy groups obtained by reacting the polyfunctional reactive compound (a-4), which has on average more than two functional groups per molecule that can react with epoxy groups, as an essential component, A sheet-like base material is impregnated with an epoxy resin composition comprising as essential components a modified polyfunctional epoxy resin having more than two epoxy resins, and (C) a curing agent for epoxy resin, and after drying, curing by heating. A method for continuously manufacturing a laminate, characterized by: 2. The modified polyfunctional epoxy resin (B) contains a bifunctional bisphenol type epoxy resin (a-1), a polyfunctional reactive compound (a-4), a polyfunctional epoxy resin (a-2) and/or a bis 2. The continuous production method of a laminate according to claim 1, wherein the modified polyfunctional epoxy resin is obtained by reacting with phenols (a-3). 3. The polyfunctional epoxy resin (a-2) is a polyfunctional epoxy resin having an average of 2.5 to 8 epoxy groups in one molecule, and the bisphenols (a-3) are bisphenol A, bisphenol 3. The method for continuously manufacturing a laminate according to claim 1, wherein the compound is one or more compounds selected from F and tetrabromo bisphenol A. 4. Claim 1, 2 or 3, wherein the polyfunctional compound (a-4) is a polyfunctional compound having an average of 2.5 to 8 reactive functional groups in one molecule. A method for continuous production of laminates. 5. The modified polyfunctional epoxy resin (A) and/or the modified polyfunctional epoxy resin (B) have an epoxy equivalent of 200 to 2.0
00 epoxy resin,
5. The method for continuously manufacturing a laminate according to 2, 3 or 4. 6. The modified polyfunctional epoxy resin (A) and/or the modified polyfunctional epoxy resin (B) have an epoxy equivalent of 300 to 800
Claims 1 and 2, characterized in that the epoxy resin is
5. The method for continuously manufacturing a laminate according to 3, 4 or 5.