WO2002018469A1

WO2002018469A1 - Epoxy resin mixture with a phosphor-modified epoxy resin

Info

Publication number: WO2002018469A1
Application number: PCT/DE2001/003326
Authority: WO
Inventors: Peter GRÖPPEL; Wolfgang Von Gentzkow
Original assignee: Siemens Aktiengesellschaft
Priority date: 2000-09-01
Filing date: 2001-08-29
Publication date: 2002-03-07
Also published as: DE10043205A1

Abstract

The invention relates to an epoxy resin mixture, more particularly an epoxy resin mixture suitable for producing prepregs and halogen-free, non-inflammable printed circuit board materials produced therefrom. Composite materials based on epoxy resins and inorganic or organic reinforcement materials have become extremely important in many technical fields and day-to-day life. The expensive hardener PAIC, which is used in phosphor-containing epoxy resin mixtures for the production of halogen-free, non-inflammable laminates, is replaced by a less expensive, aminic or amidic hardener. Surprisingly, the resulting epoxy resin exhibits an equally high nonflammability as the costly hardener.

Description

description

EPOXY RESIN MIX WITH A PHOSPHOROMODIFIED EPOXY RESIN

The invention relates to an epoxy resin mixture, in particular one which is suitable for the production of prepregs.

Composites based on epoxy resins and inorganic or organic reinforcement materials have become very important in many areas of technology and everyday life. The reasons for this are, on the one hand, the relatively simple and safe processing of the epoxy resins and, on the other hand, the good level of mechanical and chemical properties of the hardened epoxy resin materials, which allows adaptation to different purposes and an advantageous use of the properties of all materials involved in the composite.

The processing of epoxy resins into composite materials is advantageously carried out using prepregs. For this purpose, inorganic or organic reinforcement materials or intercalation components in the form of fibers, nonwovens and fabrics or in the form of surface materials are impregnated with the resin. In most cases this is done with a solution of the resin in an easily evaporable or volatile solvent. The prepregs obtained in this way must no longer be adhesive, but also not yet cured after this process; rather, the resin matrix should only be in a prepolymerized state.

In addition, the prepregs must be sufficiently stable in storage. For example, a shelf life of at least three months is required for the production of printed circuit boards. In the further processing to composite materials, the prepregs must also melt when the temperature rises and combine with the reinforcement materials or storage components and with the materials provided for the composite Connect the pressure as firmly and permanently as possible, ie the cross-linked epoxy resin matrix must develop a high level of interface adhesion to the reinforcing materials or intercalation components as well as to the materials to be connected, such as metallic, ceramic, mineral and organic materials.

In the hardened state, the composite materials are generally required to have high mechanical and thermal strength as well as chemical resistance and heat resistance or aging resistance. For electrotechnical and electronic applications, there is also the need for permanently high electrical insulation properties and for special purposes, a large number of additional requirements. For use as printed circuit board material, for example, high dimensional stability over a wide temperature range, good adhesion to glass and copper, high surface resistance, low dielectric loss factor, good processing behavior (punchability, drillability), low water absorption and high corrosion resistance are required.

Another requirement is that it be flame retardant. In many areas, this requirement has top priority because of the risk to people and property, for example in the case of construction materials for aircraft and motor vehicle construction and for public transport. In electrotechnical and in particular electronic applications, the flame resistance of circuit board materials is indispensable because of the high value of the electronic components mounted on them. To assess the burning behavior, one of the toughest material test standards must be passed, namely the V-0 rating according to UL 94V. In this test, a test specimen is flamed vertically at the bottom with a defined flame. The sum of the burning times of 10 tests must not exceed 50 s. This requirement is difficult to meet, especially when thin Wall thicknesses exist, as is the case in electronics. The epoxy resin used worldwide for FR4 laminates only fulfills these requirements because - based on the resin - it contains approx. 30 to 40% core-brominated aromatic epoxy components, ie approx. 17 to 21% bromine. Comparably high concentrations of halogen compounds are used for other purposes and are often combined with antimony trioxide as a synergist. The problem with these compounds is that on the one hand they are extremely effective as flame retardants, but on the other hand they also have very questionable properties. For example, antimony trioxide is on the list of carcinogenic chemicals, and aromatic bromine compounds not only split off bromine radicals and hydrogen bromide during thermal decomposition, which lead to severe corrosion, but when decomposed in the presence of oxygen, the highly brominated aromatics in particular can also cause the highly toxic polybromodibenzofuran and form polybromodibenzodioxins. The disposal of old materials containing bromine also presents considerable difficulties.

There has been no shortage of attempts to replace the bromine-containing flame retardants with less problematic substances. For example, fillers with an extinguishing gas effect, such as aluminum oxide hydrates ("J. Fire and Flammability *, Vol. 3 (1972), pages 51 ff.), Basic aluminum carbonates (" Plastics Engineering "', Vol. 32 (1976), pages 41 ff.) And magnesium hydroxides (EP-OS 0 243 201), and glazing fillers, such as borates (“Modern Plastics, Vol. 47 (1970), No. 6, pages 140 ff.) And phosphates (US Pat. No. 2,766 139 and 3 398

019). However, all of these fillers have the disadvantage that they sometimes significantly deteriorate the mechanical, chemical and electrical properties of the composite materials. They also require special, usually more complex processing techniques because they tend to sediment and increase the viscosity of the filled resin system.

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Containing dicyandiamide and / or an aminobenzoic acid derivative as hardener (EP 0 779 905) or an aromatic sulfonic acid amide or hydrazide containing amino groups as hardener (EP 0 779 906).

Laminates made from these epoxy resin mixtures require approx. 3 to 3.5% phosphorus in the epoxy resin matrix, i.e. approx. 1% phosphorus more than when using PAIC as a hardener, in order to achieve flame retardancy according to UL 94 V-0, which supports the thesis, that PAIC contributes significantly to flame retardancy.

These high phosphorus concentrations prove to be extremely problematic, since they impair the storage stability of the modified epoxy resins and the prepregs made therefrom and significantly increase the water absorption of the laminates, so that they have to be subjected to drying before each thermal load. Apart from this, it is known that phosphorus compounds are comparatively expensive and therefore increase the laminate price in such a way that they are only of limited use for industrial use.

Printed circuit boards are the basis for the production of electronic printed circuit boards. They are used to connect a wide variety of electronic and microelectronic components to form electronic circuits. The components are connected to the circuit board by gluing or soldering using complex, highly automated assembly processes. There is also a trend towards ever more rational production methods for assembling flat assemblies. Therefore, IR reflow soldering is increasingly being used in SMD technology, which will largely replace the other soldering processes in the future. But only laminates with low water absorption and very good interlaminar adhesion survive IR soldering processes without being destroyed by delamination. In order to reduce this risk, complex conditioning processes have been proposed (see: “Galvanotechnik *, Vol. 84 (1993), pages 3865 to 3870). co co MK) F »F» Cπ o Cπ o Cπ O Cn

(A) polyepoxide compounds with at least two epoxy groups per molecule

(B) at least one compound from the group of phosphinic acids, phosphonic acids and pyrophosphonic acids,

• Dicyandiamide and / or an aromatic amine of structure I and / or structure II as a hardener

Structure I Structure II

where the following applies: X is an H atom and Y is an alkyl group with 1 to 3 C atoms and m or n denotes an integer from 0 to 4 with the proviso m + n = 4,

R is an OH or an NR ¹ R ² group and the radicals R ¹ and R ² - independently of one another - have an H atom, an alkyl group with 1 to 3 C atoms or one of the radicals R ¹ and R ² has them Meaning and the other radical is an NR ³ R ⁴ group with R ³ or R ⁴ = H or alkyl with 1 to 3 C atoms,

• a hardening accelerator.

The phosphorus-modified epoxy resins are produced by reacting commercially available polyepoxy resins (polyglycidyl resins) with the following phosphorus compounds:

Phosphonic acids: phosphonic acids with alkyl radicals, preferably with 1 to 6 carbon atoms, or with aryl radicals, co O t \ - F ¹ F ¹

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and cresol / aldehyde resins, resorcinol diglycidyl ether, tetrakis (p-glycidylphenyl) ethane, di- and polyglycidyl esters of phthalic, isophthalic and terephthalic acid as well as tri-lithic acid, N-glycidyl compounds of aromatic amines and heterocyclic nitrogen compounds N, N-diglycidylaniline, N, N, 0-triglycidyl-p-aminophenol, triglycidyl isocyanurate and N, N, NN-tetraglycidyl-bis- (p-aminophenyl) -methane, hydantoin epoxy resins and uracil epoxy resins and di- and polyglycidyl compounds of polyhydric aliphatic alcohols, such as 1,4-butanediol, trimethylolpropane and polyalkylene glycols. Oxazolidinone-modified epoxy resins are also suitable. Such compounds are already known (see: "Angew. Makromol. Chem. '", Vol. 44 (1975), pages 151 to 163, and US Pat. No. 3,334,110); the reaction product of bisphenol A diglycidyl ether is an example of this With

Diphenyl ethane diisocyanate (in the presence of a suitable accelerator). The polyepoxy resins can be present individually or as a mixture in the preparation of the phosphorus-modified epoxy resin. An epoxidized novolak is preferably used as the polyepoxy resin.

The following compounds in particular are used as the phosphorus component for the production of the phosphorus-modified epoxy resins:

Phosphonic acids: methanephosphonic acid, ethanephosphonic acid,

Propanephosphonic acid, hexanephosphonic acid and benzenephosphonic acid;

• Phosphinic acids: dirnethylphosphinic acid, methylethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, ethylphenylphosphinic acid and diphenylphosphinic acid;

• Pyrophosphonic acids: methane pyrophosphonic acid, propane pyrophosphonic acid and butane pyrophosphonic acid. The phosphorus-modified epoxy resins are prepared in such a way that the polyepoxide compounds with the phosphorus-containing acids are preferably in an inert solution or. Diluent or - if the reaction is adapted - also be implemented in bulk. The phosphorus-modified epoxy resins have an average molecular weight M _n up to 10,000; preferably M _{N is} 200 to 5000 and in particular 400 to 2000.

If solvents or diluents are used, they are aprotic and preferably have a polar character. Examples include N-methylpyrrolidone; dimethylformamide; Ethers, such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monoether and diether, propylene glycol monoether and diether and butylene glycol monoether and diether, the alcohol component of the mono- or diether being monoalcohols with an optionally branched alkyl radical from 1 to 6 hydrocarbon atoms derived; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl glycol acetate and methoxypropyl acetate; halogenated hydrocarbons; (cyclo) aliphatic and / or aromatic hydrocarbons, such as hexane, heptane, cyclohexane, toluene and the various xylenes; aromatic solvents in the boiling range of approx. 150 to 180 ° C (higher-boiling mineral oil fractions, such as Solvesso ^R ). The solvents can be used individually or in a mixture. The reactions take place at -20 to 130 ° C, preferably at 20 to 90 ° C.

For the production of prepregs, the equivalent ratio between the epoxy function used and the amine hydrogen function used in the epoxy resin mixtures according to the invention can be 1: 0.2 to 1: 1.1.

The epoxy resin mixtures according to the invention can also contain accelerators which are known to cure CO co fr

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Φ Φ Ω 3 φ NP Φ p: q P φ vq F ¹ rt φ P Φ, ^ <o 3 0 P 1 0 F-, F tr hd P- F 0 0 F- Ω φ 3 NF Φ _^ 0 Φ 0 cn cn J-- F ¹ H P- NF ¹ Φ co

Φ 1 0 o 0 rt cn Ω 0 tr cn F- g 0 Φ F - _^ 0 cn Ω 1 a F- o φ er F- Ω p: tr vq φ rt a P 3 F- α P Φ tr cn J- - PF ¹ 0 Ω Φ

Φ iX • cn rt φ 0 Φ rt 0 tr F- vq 0 1 F ¹ 1 1 N ^ rt F- s: rt φ P Φ N * 1 1 P- ¹ Φ P- O: 1 F- φ Hi o \ o φ o J-- • <vq Φ

1 0 F- Φ Φ F- hd F vq 1 Φ 1 0 F "1 F- 0 F

1 0 0 F- 1 o F- rt 1 1 Φ 1 P φ 1 1 1 1 1 1 0

co o IV) r-υ F ¹ F ¹

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Φ 0 P tr H 0 F- Φ 0 P O F- F- φ O 0 "> Φ F P φ F- φ 0 F- 0 0 P 0 Φ Φ 0 F- F- Φ

F cn cn Φ Φ F Φ F cn 0 0 Ω rt F 0 0 F- Φ 0 F P * tr a φ Hl Hl rt 0 F- F 0 Ω r

F-. cn 3 F- Ω 3 er Ω a tr 0 cn vq er cn vq er F- F Z F- vq cn vq tr

P φ F- 0 tr P P- Φ tr Φ rt Φ • d 0 cn 0 rt er φ P a O cn Φ rt cn H 3

F "ö F X Φ 0 0 cn Φ F P F- 3 F- 0 N F- r rt 0 pj: Φ F 0 F- 0 3 F p: vq P 3 F-

F- F- PP 0 Φ cn a O 0 cn F ¹ 0 p- vq P o φ P Φ a rt P P- tr a Φ p- tr F Φ 0 * d rt φ Φ 0 F ¹ F- vq Φ 0 rt cn Φ rt Φ Ω vq HF ä ^• vq P cn a rt O: iX 3 Ω F

0 Fl F- rt Φ F as: rt F 0 tr φ cn iX i Φ P φ PÖ N Φ Φ rt tr 0 p: tr p: Φ t 0 Φ tr Φ tr rt Φ P- 0 er Φ 0 -S Φ Φ F 0 FP rt 0 cn Φ rf 0 EP vq P-

F- P P 0 Φ 0 p: F Ω X φ cn p- Hi C φ F- F X Hi cn Φ S! F "Φ vq hd 0 0 cn Hi ET er FF F- X F- o P- 0 tx P F- rt P cn • rt 3 0 Φ φ HF cn tr F F- Φ rt rt p Φ 3 0: rt cn cn o Ω φ P 0 cn rt rt P rt Φ F F- 3 Φ 3 Φ φ φ 3

0 Φ cn F- er Φ rt N 0 Ω 0 tr F 3 VJ3 Hi φ P 0 O O er Φ 0 N cn Xi 0 Fl P F • d F

P 0 rt cn Φ rt. 0 0 tr a φ 0-- 0 F Hi P- F- F- φ F rt Φ rt cn F * i

0 vq 0 p: Ω F Φ vq Φ Φ F -3 jE <a Q cn Φ Hi φ Xi tu Φ p: Fi 3 Φ rt φ O: F ¹ cn 0 0 tr 0 er * • «0 F φ P φ PN 0 φ _^ Φ Φ F ¹ Φ vq Φ Ό F Φ vq cn p: q N aa Φ Φ F cn 0 0 H 1 cn P Φ 0 F cn er F- 0 F Φ F- cn 0 Ω φ 0 P- P- <! o F- CΛ a cn F- <! P a P Ω P 0 F- 0 FPF ¹ 0 tr

N ω vq 0 Φ 3 3 Xi <! <cn φ O tr vq Ω O <! cn rt tr F φ rt P M Φ 3 vq Φ φ a Φ iX to Φ F tr P o 1 rf tr P φ tr 0 Φ cn tr 0 P- Φ P F rt F- 0 F- φ 0

F- Φ tr Φ 0 0 er P <P * F o p: a 0 3, 0 F φ • F Ω 0 0 tr s: 0 Φ • rt 0 vq

Ω 0 F P- cn 0 F "φ rt rt 1 F Φ Φ F- Φ φ IV * d 0 tr EP P P- F 0 φ tr rt as: 0 rt F • d Φ Cd i 0 0 er 0 F cn Fi rt Cd φ FF α vq as:

0 vq " _^ Φ Φ a F- vq F P- F- Φ NP Φ • F ^> Φ ω F- 0: 0 F- FN a vq er F- Φ Φ F-

Φ Φ 0 tr F- zq OP ^J 0 CSJ 0 rt co cn F- Φ F 0 vq o φ Φ N Φ FF Ω rt F rt i 0 rt Φ Φ Φ a tr cn <0 cn _^ 3 S! O cn Ω vq φ F cn 0 rt ^• K F- tr

• cn φ o 0 Φ F 0 P- 0 P rt O cn P F- φ Φ tr Ξ a φ a 0 F • P- 0 <i rt rt F 0 0 X Ω Fi 0 0 P rt <! rt F o 0 φ F- 0 cn Φ φ a O 3 vq o tu p: φ F vq cn Cd tr r r r rt Fi rt N Φ a O "• er P- Φ Ω 0 F Ω Cd X3 φ F

Φ FF ¹ O cn Fl rt • d φ 0 P ^> NF Φ φ Φ cn 0 tr rt Fi PX P- F 0 cn

F- rX φ cn iX Φ O O N 0 cn <i s: F- 0 0 a F- φ σ 0 P o 0 0 0 p: rt ϊ 0J

Φ iX P- O 3 Fi X 0 vq a vq σ. rt O Φ 0 0 F- 0 P a Hi P- F ¹ a Φ vq 1 Φ

<0 rf 0 Φ * Ü H F- Φ PO 0 Φ P a φ F3 0 rt Ω q Φ rt P 0 F ¹ ^

Φ a F 0 Fi Φ Φ a P er EP er 9 i a 3 Φ φ Φ hd φ tr rt F vq F- p: Φ Cπ

F φ F- ω Hi F tr 0 F- Φ p Fl tu Φ cn a ω 3 P- F F • Φ Φ Φ Ω 0

≤ 0 cn er F- P N P a IV cn Φ P rt g 0 F- • d 0 φ vq F s: F F tr a er

Φ Ω Φ N rt φ F Φ a Φ rt O 0 F- »P Cd F Ω Φ φ <i 0: H cn o 0 rt φ F-

0 0 tr cn F- 0 F- NF Φ F- P a O cn F- Ω tr FOF 0 0 Φ er 0 Φ 0 vq cn a 0 φ rt Φ F Ω Hi φ rt 0 0 Φ q cn cn 0 tr PP 0 φ cn cn F- Φ v 0 vq φ

0 ap: 0 er tr o 0 Φ a F cn φ O Φ F ¹ a rt 0 vq rt vq rt F- cn φ 0 ro

0 Cd 0 rt Φ 0 F s: φ Φ 0 PP P- 0 0 cn a cn P- φ cn 1 O s: P o vq N P- a Φ F φ 3 hd Φ rX 0 cn F "<s: 0 vq 0 FFFF vq cn Φ X ¹ a F- 0 o

0 vq F- 0 Φ 0 cn O F o O er φ F- rt φ tr Ω Φ Φ Φ cn Φ P Φ P- o Φ Ω 0

Φ ιq P- rt a F vq cn FF Φ F p: tr 0 P- F- F- cn 3 F- 0 3 F tr rt vq o <\ X cn Ω cn o * -a Φ F ö P rt er a P- 0 F Ω 0 rt 0 Φ • d rt φ \

Φ ω φ O tr F- Hi p 0 O P F F- F "0 Φ tr er tr g a <Φ F o er Φ 0 3

F Ω P- -S Ω Hi Φ cn er er 0 a vq 0 o P- Φ o Φ Φ cn 0 Φ 0

<! he tr rt P- rX tr Φ F 0 F- Φ <! Φ a P- <cn rt tr cn 0 0 F F <J φ Φ cn φ F- P - <Φ o 0 ϊ 0 O F- 0 φ O

Fi <F- 3 Φ Φ a P F- tr vq o P- Ω P F Φ

F 0 Hi ** φ a Φ P κ> Φ rt Ω P = P- F rt rt tr 0 rt F- cn a rf vq a cn Φ F 0 Φ hd vq tu rt CΛ Q r Φ tr F ¹ er • d cn Φ F- Fi 0 rt Φ n φ 0 rt F cn X a F o F φ F ri Φ Ω F ¹ ot 0 rt rt rt o 0 Ω O vq p: 0 s: FFP 0 rt cn F- O s: • 0: 0 Φ σ F tr PPX ¹ 0 F ¹ a tr FP φ

F a Φ F- O 0 φ P rt Φ a Φ 00 Hi 0 F- -S cn o vq 0 F ¹ P- cn P -S rf a cn cn iX Φ F 0 tr rt FFO Φ F- X o 0 er P φ 0: n φ 0 Φ cn F- cn φ φ Φ cn φ

0 rt vq iX Hi F cn O: a Xi P- F ¹ F er F a σ Ω Φ F rf 1 Φ rt

0 Φ φ tr Hi rt p F Φ F ω 1 Φ N cn Φ <tr F tr a Φ 0 N

vq go Φ er 1 F 0: F 0 rt 0 O F- O: 0 rt ω P tr 0 Φ Φ 1 1 cn 1 P a 0 1 1 0 * 1 1 Φ 1 cn) 1

co o ⁾ fv> F ¹ F ¹

Cπ σ Cπ O cπ O Cπ

Interlaminar adhesion and the adhesion to copper are significantly improved,

• an extremely cost-effective solution is made possible.

The epoxy resin system according to the invention also results when using dicyandiamide, e.g. in a quantity of 1 to 10 mass? -, as hardener good results in the high-pressure cooker test. This could not be expected on the basis of the moderate results which were described with the epoxy resins modified with phosphonic and phosphinic anhydrides in the patents EP 0 779 905 and EP 0 779 906.

The invention will be explained in more detail using exemplary embodiments.

Production of the phosphorus-modified epoxy resins

Example 1: Preparation of the phosphinic acid-modified epoxy resin MEPS / EP resin

400 parts by weight (MT) of an epoxidized novolak (epoxy value: 0.56 mol / 100 g, average functionality: 2.6), dissolved in 170 MT methyl ethyl ketone, are mixed with 100 MT ethylmethylphosphinic acid. The solution is stirred under reflux at an oil bath temperature of 100 ° C. for 60 min. After the solution has cooled, 40 MT of sodium carbonate are added, the mixture is stirred for a further 12 hours and the solid constituents are then filtered off. The reaction product has an epoxy value of 40 mol / 100 g, which stabilizes to a value of 0.22 mol / 100 g after a short storage period. The phosphorus content of the reaction product is 5.9%.

Example 2: Production of the phosphonic acid-modified epoxy resin EPS / EP resin 400 parts by weight (MT) of a bisphenol-F-diglycidyl ether (epoxide value: 0.61 mol / 100 g), dissolved in 250 MT methyl ethyl ketone, are mixed with 92 MT ethanephosphonic acid. The solution is stirred for 60 min at an oil bath temperature of 100 ° C under reflux. After the solution has cooled, 40 parts by mass of sodium carbonate are added, the mixture is stirred for a further 12 hours and the solid constituents are then filtered off. The reaction product has an epoxy value of 0.38 mol / 100 g, which stabilizes at a value of 0.20 mol / 100 g after a short storage period. The phosphorus content of the reaction product is 5.4%.

Example 3: Preparation of a phosphinic acid-modified epoxy resin without subsequent addition of sodium carbonate, analogous to Example 1 of EP 0 689 559 B1

400 parts by weight (MT) of an epoxidized novolak (epoxy value: 0.56 mol / 100 g, average functionality: 3.6), dissolved in 170 MT methyl ethyl ketone, are mixed with 50 MT ethylmethylphosphinic acid. The solution is stirred for 60 min at an oil bath temperature of 100 ° C under reflux. After a short storage period, the reaction product has an epoxy value of 0.40 mol / 100 g. The phosphorus content of the reaction product is 3.2%.

The phosphorus-modified epoxy resins prepared in Examples 1-3 are examined for their stability at room temperature. Figure 1 shows the result. While the epoxy value of the epoxy resins produced in Examples 1 and 2 remains stable or only decreases slightly, the epoxy value of the epoxy resin produced in Example 3 is reduced by almost 50% within 12 weeks.

6 7 10 11 12

Time [weeks]

Fig. 1: Stability of the epoxy resins produced in Examples 1-3 at room temperature

Manufacture of prepregs

Examples 4 and 5

A solution of A parts by mass (MT) dicyandiamide (Dicy) - in J MT dimethylformamide (DMF) - is mixed with a solution of D (I) MT of the phosphorus-modified epoxy resin (MEPS / EP resin) described in Example 1 (epoxy value: 0, 22 mol / 100 g; phosphorus content: 5.9%), obtained from an epoxidized novolak (epoxy value: 0.56 mol / 100 g; average functionality: 3.6) and methyl ethylphosphinic acid, in G MT methyl ethyl ketone (MEK ) and I MT ethyl acetate (EA) added; E MT 2-methylimidazole (MelM) is then added to the resin solution, and F (l) MT of an epoxidized novolake (epoxy value: 0.56 mol / 100 g; average functionality: 3.6; EP resin 1) or F ( 2) MT of a bisphenol A diglycidyl ether (EP resin 2) was added to obtain a phosphorus content in the resin matrix of 2.5%. With the impregnating resin solution obtained, which is mixed with H MT DMF to set the correct viscosity. glass fabrics (glass fabric type 7628; basis weight: 197 g / m ² ) are continuously impregnated using a laboratory impregnation system and dried in a vertical drying system at temperatures of 50 to 160 ° C. Prepregs produced in this way are tack-free. The composition of the impregnation resin solution and the properties of the prepregs are shown in Table 1.

Example 6

A solution of A parts by mass (MT) of dicyandiamide (Dicy) - in J MT of dirnethylformamide (DMF) - is mixed with a solution of D (2) MT of the epoxidized novolak in Example 2 (epoxy value: 0.56 mol / 100 g; average functionality: 3.6) and ethanol-modified phosphorus-modified epoxy resin (EPS / EP resin) (epoxy value: 0.24 mol / 100 g; phosphorus content: 5.4%) in G MT methyl ethyl ketone (MEK) and I MT ethyl - added acetate (EA); F (3) MT bisphenol-F-diglycidyl ether is then added to the resin solution in order to obtain a phosphorus content of 2.5% in the resin matrix. With the impregnating resin solution obtained, which is mixed with H MT DMF to set the correct viscosity, glass fabrics (glass fabric type 7628; basis weight: 197 g / m ² ) are continuously i-impregnated using a laboratory impregnation system and in a vertical drying system at temperatures from 50 to Dried 160 ° C. Prepregs produced in this way are tack-free. The composition of the impregnation resin solution and the properties of the prepregs are shown in Table 1.

Examples 7 and 8

The procedure is as in Examples 4 and 5. However, the impregnating resin solution is mixed with B MT sulfanilamide (SAM) in J MT dimethylformamide (DMF) instead of dicyandiamide. With the impregnation resin solution obtained, which is still used to set the correct viscosity with H MT DMF is added, glass fabrics (glass fabric type 7628; basis weight: 197 g / m ² ) are continuously impregnated by means of a laboratory impregnation system and dried in a vertical drying system at temperatures from 50 to 160 ° C. Prepregs produced in this way are tack-free. The composition of the impregnation resin solution and the properties of the prepregs can be found in Table 1.

Example 9

The procedure is as in Example 6. However, instead of dicyandiamide, B MT sulfanilamide (SAM) in J MT dirnethylformamide (DMF) is added to the impregnating resin solution. With the resulting impregnation resin solution, which is mixed with H MT DMF to adjust the correct viscosity, glass fabrics (glass fabric type 7628; basis weight: 197 g / m ² ) are continuously impregnated using a laboratory impregnation system and in a vertical drying system at temperatures from 50 to Dried 160 ° C. Prepregs produced in this way are tack-free. The composition of the impregnation resin solution and the properties of the prepregs are shown in Table 1.

Example 10

The procedure is as in Examples 4 and 5. However, a mixture of A parts by mass (MT) dicyandiamide with B MT sulfanilamide (SAM) in J MT dirnethylformamide (DMF) is added to the impregnating resin solution. The resulting impregnation resin solution is used to continuously impregnate glass fabrics (glass fabric type 7628; basis weight: 197 g / m ² ) using a laboratory impregnation system and dry them in a vertical drying system at temperatures from 50 to 160 ° C. Prepregs produced in this way are tack-free. The composition of the impregnation resin solution and the properties of the prepregs are shown in Table 1. Examples 11 (Comparative Example 3 from EP 0 689 559)

A solution of 75 parts by weight (MT) of the reaction product prepared in Example 3 (epoxy value: 0.40 mol / 100 g) in 60 MT of methyl ethyl ketone is mixed with a solution of 25 MT of polyamino aryl isocyanurate (PAIC) in J MT of dimethylformamide (DMF) , offset. The further processing is carried out analogously to Examples 4 and 5. With the impregnating resin solution obtained, glass fabrics (glass fabric type 7628; basis weight: 197 g / m ² ) are continuously impregnated by means of a laboratory impregnation system and in a vertical drying system at temperatures of 50 to 160 ° C dried. Prepregs produced in this way are tack-free. The composition of the impregnating resin solution and the properties of the prepregs are shown in Table 1.

Example 12 (Comparative Example 1 from EP 0 779 905)

A solution of A parts by mass (MT) dicyandiamide (Dicy) - in J MT dimethylformamide (DMF) - is mixed with a solution of D (3) MT of a phosphorus-modified epoxy resin (EPS / EP resin) in the form of a reaction product (epoxy value: 0, 32 mol / 100 g; phosphorus content: 3.8%) from an epoxidized novolak (epoxy value: 0.56 mol / 100 g; average functionality: 3.6) and propanephosphonic anhydride in G MT methyl ethyl ketone (MEK) and I MT ethyl acetate (EA) offset; E MT 2-methylimidazole is then added to the resin solution. With the impregnation resin solution obtained, glass fabrics (glass fabric type 7628; basis weight: 197 g / m ² ) are continuously impregnated using a laboratory impregnation system and dried in a vertical drying system at temperatures of 50 to 160 ° C. Prepregs produced in this way are tack-free. The composition of the impregnation resin solution and the properties of the prepregs are shown in Table 1. Example 13 (Comparative Example 7 from EP 0 779 905)

The procedure is the same as in Example 12, but the impregnating resin solution - instead of A MT dicyandiamide (Dicy) - is mixed with B (2) MT 4-aminobenzoic acid (ABS), dissolved in J MT dimethylformamide (DMF). In addition, no curing accelerator (E) is added. The composition of the impregnation resin solution and the properties of the prepregs are shown in Table 1. The prepregs produced in Examples 4, 7 and 11 are examined for their stability by storage at room temperature. Figure 2 shows the result. While the remaining gel time of the prepregs produced in Examples 4 and 7 remains stable or only decreases slightly, the remaining gel time of the prepregs produced in the comparative example (Example 11 with hardener PAIC) is reduced by more than 50% within 12 weeks. The remaining gel time in this example is therefore completely inadequate. In Example 12 (comparative example from EP 0 779 905), a comparatively large amount of phosphorus (3.6%) is required in order to achieve the required flame retardancy. In example 13 (comparative example from EP 0 779 905) prepregs are obtained which do not reach the prescribed shelf life of 3 months.

Table 1 Composition of the impregnation resin solutions.

Stability of the prepregs

6 7 10 11 12

Time [weeks]

Fig. 2: Stability of the prepregs produced in Examples 4, 7 and 11

Production and testing of laminates

Examples 13 to 23

Eight of the prepregs produced according to Examples 1 to 7 (glass fabric type 7628; basis weight: 197 g / m ² ), laminated on both sides with a 35 μm Cu foil, are pressed in a press at 175 ° C. and 20 bar. The 1.5 to 1.6 mm thick laminates are removed from the press after 40 minutes and then post-annealed at 175 ° C. for 2 hours. The glass transition temperature Tg, the flammability according to UL 94 V, the adhesion of the copper foil, the measuring test, the high-pressure cooker test and the solder bath resistance are determined on the bodies obtained in this way - by means of dynamic mechanical analysis (DMTA). The values obtained are shown in Table 2.

The tests carried out on the laminates proceed as follows: • Heat resistance on the solder bath

The test is carried out in accordance with DIN IEC 249 Part 1, Section 3.7, using a solder bath in accordance with Section 3.7.2.3. Test specimens of size 25 mm x 100 mm are to be used, which are placed with the copper side on the solder bath. There must be no delamination and no formation of measlings, stains or blisters under the lamination.

• Adhesion of the copper cladding

A 25 mm wide and 100 mm long strip of copper foil is detached from the glass hard tissue over a length of 20 mm and pulled off vertically by means of a suitable device at a take-off speed of 50 mm / min. The force F (N) required for this is measured.

• The water absorption was measured in accordance with MIL-P-13848 G.

• Examination of interlaminar liability

A 25 mm wide and 100 mm long strip of the uppermost glass hard fabric layer is detached over a 20 mm length from the next glass hard fabric layer underneath and pulled off vertically by means of a suitable device at a take-off speed of 50 mm / min. The force F (N) required for this is measured.

• Measing test

The test is carried out on test specimens measuring 20 mm x 100 mm without copper cladding. The test specimens are immersed in a 65 ° C LT26 solution (composition: 850 ml deionized H ₂ O, 50 ml HCl pa, 100 g SnCl ₂ .2 H ₂ 0, 50 g thiourea), rinsed with running water and then placed in boiling water for 20 min. After air drying the sample (2 to 3 min), it is immersed in a 260 ° C solder bath for 10 s. The laminate must not delaminate. Properties of the laminates

Table 2

In example 22 (comparative example from EP 0 779 905), the prepregs produced from the impregnating resin solution 12 neither passed the required solder bath resistance nor the high-pressure cooker test.

Claims

claims

1. Epoxy resin mixture for the production of a composite material, characterized in that it comprises the following components:

• a phosphorus-modified epoxy resin with an epoxy value of 0.02 to 1 mol / 100 g, obtainable by reacting

(A) polyepoxide compounds with at least two epoxy groups per molecule

DR2

Structure I Structure II

the following applies:

X is an H atom and Y is an alkyl group with 1 to 3 C atoms and m or n is an integer from 0 to 4 with the proviso m + n = 4,

R is an OH or an NR ^X R ² group and the radicals R ¹ and R ² - independently of one another - have an H atom, an alkyl group with 1 to 3 C atoms or one of the radicals R ¹ and R ² has them Meaning and the other radical is an NR ³ R group with R ³ or R ⁴ = H or alkyl with 1 to 3 C atoms,

a hardening accelerator,

2. Epoxy resin mixture according to claim 1, characterized in that it comprises a phosphorus-free epoxy resin.

3. Epoxy resin mixture according to claim 1 or 2, characterized in that the phosphorus-free epoxy resin comprises aromatic, heterocyclic and / or cycloaliphatic components.

4. Epoxy resin mixture according to one of the preceding claims, characterized in that an aromatic and / or an aliphatic glycidyl compound is used as the phosphorus-modified epoxy resin.

5. Epoxy resin mixture according to one of the preceding claims, characterized in that the proportion of phosphorus-modified epoxy resin in the overall mixture is between 30-98% by weight.

6. Epoxy resin mixture according to one of the preceding claims, characterized in that a proportion of phosphorus-free epoxy resin of up to 70% by weight is included.

7. Epoxy resin according to one of the preceding claims, characterized in that the total phosphorus content is between 2 and 5% by weight.

8. Epoxy resin according to one of the preceding claims, characterized in that the total phosphorus content is between 2.5 and 3.5% by weight.

9. Prepreg or composite material based on inorganic or organic reinforcement materials in the form of fibers, nonwovens or fabrics or surface materials made from an epoxy resin mixture according to one or more of claims 1 to 8.

10. Printed circuit board material made of prepregs, made of glass fiber fabric and an epoxy resin mixture according to one or more of claims 1 to 8.