WO2015014799A1 - Polyorganosiloxane preparation for optical semiconductors - Google Patents

Abstract

The invention relates to silicone resin compositions and to the use thereof for producing optical semiconductor elements.

Description

 Polyorganosiloxane preparation for optical semiconductors

The invention relates to silicone resin compositions and their use for the production of optical semiconductor elements.

The requirements for potting compounds for the production of electrical and electronic components, in particular in the production of optical semiconductor elements such as high-power LEDs

 (= light emitting device) are very extensive and partly contrary, in order to ensure a high luminous efficacy and lifetime of the LED. Desired requirements are for example:

 -good surface hardness and shaping properties;

with flexibility at the same time;

-Good light and thermal stability;

-good weather resistance;

 low gas permeability and thus avoidance of corrosion; -high transparency;

high refractive index;

no yellowing (discoloration by heat);

 -good process properties during processing; -Simple and thus cost-efficient compositions and the resulting more cost-efficient LED manufacturing methods. Many solutions have already been disclosed in the prior art which, however, could only fulfill partial aspects of this requirement.

Many documents disclose the use of addition-crosslinking silicone compositions for the manufacture of LEDs. They consist of at least one organopolysiloxane having at least two aliphatically unsaturated groups in the molecule, and at least one organohydrogenpolysiloxane having two or more Si-H groups in the molecule and at least one hydrosilylation catalyst and often further additives. The following examples refer to proposed solutions for reducing gas permeability.

EP2399961B1, for example, discloses such addition-crosslinking silicone resin compositions for LED production where at least one antioxidant must be present as a further additive. US20120256325A1 discloses silicone resin compositions comprising an aryl-silicone resin having at least 2 vinyl groups, an addition catalyst, and an organohydrogenpolysiloxane mixture consisting of two different organohydrogenpolysiloxanes having chain-bonded Si-aryl units, the first an organohydrogenpolysiloxane oil with alpha-omega terminal Si-Ii - Groups and the second a monofunctional organopolyhydro- gensiloxan oil with only one terminal Si-H group. A disadvantage of both solutions is their relatively complex composition, the sometimes problematic preparative accessibility and the associated reduced cost-effectiveness.

WO2004 / 107458A2 discloses addition-crosslinking organopolysiloxane preparations which may optionally be self-crosslinking containing either self-crosslinking organopolysiloxanes which must contain resin units which contain both aliphatically unsaturated groups and Si-H groups per molecule or an addition-crosslinkable preparation of organopolysiloxanes , which must also contain resin building blocks, as well as a hydrosilylation catalyst. The disadvantage of the preparations described here is that they consist exclusively of oligomeric or polymeric polyorganosiloxanes and thus the setting of certain processing properties, especially the viscosity, which can vary over a wide range depending on the desired processing process, is very difficult. This has the disadvantageous effect that such preparations must each be specifically optimized for a particular processing process, so that with the targeted use of new organopolysiloxanes, these are always associated with adjustments of the processing processes or vice versa. There is therefore a need for silicone compositions that have a simple variability while meeting the requirements shown above. It was therefore an object of the present invention to provide a silicone composition which is as simple as possible, which nevertheless fulfills the above-mentioned requirement for encapsulants for LEDs. This object has been achieved by the addition-crosslinking silicone resin composition according to the invention.

 Contain addition-crosslinking silicone resin compositions according to the invention

(R⁴R⁵Si0₂/₂)D (R⁶Si0₃/₂)_T (Si0₄/₂)Q (D, wobei A) at least one branched, self-crosslinking organopolysiloxane of the general formula (I)

(R ⁴ R ⁵ Si0 _2/2) D (R ⁶ Si0 _{3/2) T} (Si0 _4/2) Q (D, wherein

R ¹ to R ⁶ independently of one another, monovalent, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, an OH group or a hydrogen atom,

 -M, D, T, and Q is a number from 0 to <1,

 mean,

with the proviso that M + D + T + Q = 1 and Q + T> 0, and with the proviso that one molecule A) is selected as R ¹ through R ⁶

 at least two alkenyl groups,

 - At least two hydrogen atoms, and

- At least one aryl group

contains

where the molar ratio of the silicon-bonded alkenyl groups carrying repeating units to the silicon-bonded the hydrogen atoms carrying repeating units is at least 0.75; and

 wherein the mole fraction of the at least one aryl group-carrying silicon atoms to the total number of silicon atoms is at least 30%; and

 wherein the molar fraction of the alkyl groups in the total number of silicon-bonded radicals is at most 70%,

B) at least 0.1 parts based on 100 parts A) of at least one Si-H coupler which contains at least 2 Si-H molecules per molecule

Contains bindings and is selected from the following groups:

Organohydrogensilanes of the general formula

R ⁷ _g (H) _h Si-R ⁸ -Si (H) _i R ⁹ _j (II) where

R ⁷ and R ⁹ independently of one another, monovalent, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, where R ⁷ and R ^{9 are} not an alkenyl group, no OH group and no hydrogen atom,

 -H is a hydrogen atom,

 a Cl to C36 hydrocarbylene group, which may be interrupted by heteroatoms, and such radicals 8 are always bonded to the silicon atoms with a carbon-silicon bond, or an oxygen atom,

 mean,

 -g and j can be 0, 1, 2 and 3, -h and i can be 1, 2 and 3,

 and g + h = 3 and i + j = 3 are respectively satisfied,

Organohydrogensiloxanes of the formula [R ^lu _k (H) ₁ Si0 _1/2 ] ₄ Si (III) where

R ¹⁰ independently of one another are monovalent, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, where R ^{10 is} not an alkenyl group, no OH group and no hydrogen atom,

 -H is a hydrogen atom

 means

 k and 1 have the values 0, 1, 2 and 3, and k + l = 3, C) satisfies a sufficient amount of at least one catalyst which promotes the addition of Si-bonded hydrogen to aliphatic double bonds, wherein in the addition-crosslinking silicone resin composition the molar catalyst Ratio of silicon-bonded alkenyl groups to silicon-bonded hydrogen atoms is between 0.5: 1 and 2: 1.

In the addition-crosslinking silicone resin composition according to the invention, the ratio of Si-alkenyl to Si-H is preferably from 0.5: 1 to 2: 1; preferably 0.6: 1 to 1.8: 1, more preferably 0.6: 1 to 1.6: 1, in particular 0.7: 1 to 1.5: 1.

Depending on the ratio of Si-H to Si-vinyl set in A), the required and preferred amount of B) can thus be determined.

Organopolysiloxanes A) preferably have a molecular weight M w of at least 1000, preferably at least 1300, particularly preferably at least 1800, in particular at least 2000 ha- ben, wherein the polydispersity is at most 15, preferably at most 12, more preferably at most 9, in particular at most 6. Organopolysiloxanes A) have viscosities of at least 1500 mPas, preferably at least 2000 mPas, in particular at least 2500 mPas. In a further preferred embodiment, it is highly viscous A) having a viscosity of at least 8,000 mPas, particularly preferably at least 10,000 mPas, in particular at least 12,000 mPas. In a likewise preferred form, A) is at room temperature of 23 ° C no longer flowable stable masses with still tacky surface or tack-free solids with a glass transition temperature of more than 25 ° C. All information on viscosity is valid at 25 ° C and at normal pressure of 1013 mbar.

Organic groups R ¹ to R ^s may be linear or branched alkyl radicals having preferably 1 to 10 carbon atoms, or alkenyl radicals preferably having 2 to 8 carbon atoms, or aryl radicals having preferably 6 to 8 carbon atoms. The aforementioned may each contain heteroatoms. The heteroatoms may be, for example, oxygen, nitrogen, silicon, phosphorus or halogen, such as F, Cl, Br. Selected examples of alkyl radicals as radicals R ¹ to R ⁶ are the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. -Pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical, and octadecyl radicals such as the n-octadecyl radical, cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals. The methyl and ethyl radicals are the preferred alkyl radicals. Selected examples of alkenyl radicals as radicals R ¹ to R ⁶ are the vinyl radical which may optionally be substituted, the allyl radical, the butenyl radical, the pentenyl radical, the hexenyl radical, the heptenyl radical, the octenyl radical or the cyclohexenyl radical. The vinyl radical is the preferred alkenyl radical.

Selected examples of aryl radicals as radicals R ¹ to R ⁶ are phenyl radical, tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals, such as the benzyl radical and the β-phenylethyl radical.

The molar ratio of the silicon-bonded alkenyl groups carrying repeating units to the silicon-bonded hydrogen atoms carrying repeating units in A) is at least 0.75, preferably 0.8, more preferably 0.9.

The molar fraction of the silicon atoms carrying at least one aryl radical relative to the total number of silicon atoms in A) is at least 30%, preferably at least 40%, in particular at least 50%.

The molar fraction of the alkyl groups in the total number of silicon-bonded radicals in A) is at most 70%, preferably at most 65%, particularly preferably at most 60%, in particular at most 55%.

The molar fraction of the OH groups in the total number of silicon-bonded radicals in A) is at most 3%, preferably at most 2.5%, particularly preferably at most 2.0%, in particular at most 1.5%.

The molar fraction of hydrogen groups in the total number of silicon-bonded radicals in A) is 0.1-45%, preferably 1 - 42%, more preferably 2 - 39%, in particular 2.5 - 36%. The determination is carried out by means of ⁹ Si NMR spectroscopy.

The molar proportion of vinyl groups 2 - 45% is preferably 4 - 42%, particularly preferably 6 - 39%, in particular 8 - 36%. The determination is carried out by ²⁹ Si NMR spectroscopy.

The partial units (R ¹ R ² R ³ Si0 _{1/2) M} according to the general formula (I) in A) is at most 55 mol% present, preferably at most 50 mol%, particularly preferably at most 45 mol%, in particular at most 40 mol%. The radicals R ¹ R ² R ³ are preferably not an aryl group. The radicals R ¹ R ² R ³ are particularly preferably H-, short-chain alkyl, such as methyl, short-chain alkenyl, such as vinyl, and methoxy. Particularly preferred as embodiments of the invention are: (CH ₃ ) ₃ SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 , (CH ₃ ) ₂ (H) SiO _1/2 .

The partial units (R ⁴ R ⁵ Si0 _{2/2) D} according to the general formula (I) in A) is at most 80 mol% present, preferably at most 70 mol%, particularly preferably at most 65 mol%, in particular at most 60 mol%. As radicals R ⁴ R ⁵ are preferably H, methyl, phenyl, vinyl, methoxy, phenoxy. Particularly preferred are as embodiments of the invention are: (CH _{3) 2} Si0 _2/2, (CH ₃₎ (C _e H ₅₎ Si0 _2/2, (CH ₃₎ (H) Si0 _2/2. The partial units (R ⁶ Si0 _{3/2) T} in accordance with the general formula (I) in A) at least 10 mol% are present, more preferably at least 20 mol%, especially at least 25 mol%. Preferably, R ^{6 is} an aryl group and not a hydrogen atom and no alkenyl group. As aryl group R ^s , the phenyl radical is particularly preferred. Of this subunit, at least 1 is preferably present in A), with an aryl radical as R ⁶ , preferably phenyl radical.

The partial units (Si0 _{4/2) Q} of the general formula (I) are present in A) at most to 20 mol%, particularly preferably at most 15 mol%, more preferably no such subunits in A) are present.

 The sum of all 4 aforementioned subunits always gives 100 mol%.

Various processes are known in the prior art with the aid of which A) can be prepared from commercially available educts such as alkoxysilanes, chlorosilanes, or combinations thereof, and further using short-chain organosiloxanes. These methods include selection and appropriate combination of hydrolysis, condensation, and equilibration reactions. Possible production processes are discontinuous stirring processes, continuous stirred-tank cascade processes, quasi-continuous processes by interconnecting continuous processes with discontinuous process steps, continuous processes, such as those in loop reactors or column reactors, which can be designed as double-loop or double-column processes by interconnecting several plants. Likewise, combinations of a loop reactor and a column reactor are conceivable.

A preparation process converts alkoxysilanes, optionally in admixture with short-chain organosiloxanes, in a first reaction step via an acidic hydrolysis, and then condenses optionally stepwise or continuously. The reaction mixture is neutralized either by neutralizing the acid or by neutral washing with demineralized water, and then isolating to the desired purity by a suitable combination of the steps of distillation and filtration.

Further suitable production processes are disclosed, for example, in the following documents: DE 102005003899A1,

DE102005047394, DE102005047395A1, DE102009045930A1,

DE10242418A1 and DE102005003898A1. Residues R ⁷ , R ⁹ , R ^{10 of} the Si-H coupler B) are linear or branched alkyl radicals having preferably 1 to 10 carbon atoms, they may each contain heteroatoms. The heteroatoms may be, for example, oxygen, nitrogen, silicon, phosphorus or halogen, such as F, Cl, Br. Examples of alkyl radicals as R ⁷ , R ⁹ , R ¹⁰ correspond to those mentioned under R ¹ to R ⁶ . The most preferred radical for R ⁷ , R ⁹ and R ¹⁰ is the methyl radical. The radicals R ⁸ are substituted or unsubstituted hydrocarbylene radicals, ie divalent and optionally heteroatom-containing hydrocarbon radicals.

Examples of preferred alkylene and arylene radicals R ⁸ are the methylene radical -CH ₂ -, the ethylene radical -CH ₂ -CH ₂ -, the propylene radical - (CH ₂ ) ₃ -, the butylene radical - (CH ₂ ) ₄ -, the pentylene radical - (CH ₂ ) ₅ -, the hexylene radical - (CH ₂ ) ₆ -, the octylene radical - (CH ₂ ) ₈ -, and the associated isomeric alkylene radicals, cycloalkylene radicals such as the cyclohexylene radical and substituted cyclohexylene radicals, arylene radicals such as the ortho, meta- or para-phenylene radical -

(C ₆ H) -, wherein the para-phenylene radical is particularly preferred and arylene radicals of the form

where x is an integer from 0 to 8.

In addition, the radical R ^{8 may represent} an oxygen atom. Particularly preferred is the para-phenylene radical for R ⁸ .

Typical examples of Si-H couplers (B) according to formula (III) the following organosiloxanes:

[(CH _{3) 2} (H) Si0 _{1/2] 4} Si

[(CH ₃ CH ₂ ) ₂ (H) SiO _1/2 ] ₄ Si

[(CH _{3) 2} (H) Si0 _{1/2] 2} [(CH _{3) 3} Si0 _{1/2] 2} Si [(CH ₃ CH ₂ ) ₂ (H) SiO _1/2 ] ₂ [(CH ₃ ) ₃ SiO _1/2 ] ₂ Si

[(CH _{3) 2} (H) Si0 _{1/2] 2} [(CH ₃₎ (CH ₃ CH _{2) 2} Si0 _{1/2] 2} Si

The Si-H couplers B) according to formula (III) act like a point crosslinker and bring more hardness into the cured molecular structure than the Si-H couplers B) according to formula (II), especially if they are silicon-bonded Contain hydrogen atoms. In particular Si-H coupler B) according to formula (III) with the very high Si-H functional density of 4 Si-H groups per organosiloxane molecule are very well suited to crosslink high molecular weight A) with low vinyl group number to hard moldings , For this reason, the Si-H couplers B) according to formula (III) are particularly preferred for such applications. Suitable catalysts C), all compounds can be used which promote the attachment of silicon-bonded hydrogen to aliphatic double bonds. It is preferably a metal from the group of platinum metals or a compound or a complex from the group of platinum metals. Examples of such catalysts are metallic and finely divided platinum, which may be supported on supports such as silica, alumina or activated carbon, compounds or complexes of platinum such as platinum halides, eg PtCl ₄ , H ₂ PtCl ₆ .6H ₂ O, Na ₂ PtCl ₄ .4H ₂ 0, platinum olefin complexes, platinum alcohol complexes, platinum alkoxide complexes, platinum ether complexes, platinum aldehyde complexes, platinum ketone complexes, including reaction products of H ₂ PtCl ₆ x6H ₂ 0 and cyclohexanone, platinum vinyl siloxane complexes such as platinum 1, 3 divinyl-1, 1, 3, 3-tetramethyldisiloxane Complexes with or without content of detectable inorganic bound halogen, bis (gamma-picoline) -platine dichloride, trimethylenedipyridinium platinum dichloride, dicyclopentadiene platinum dichloride, dimethylsulfoxide-ethylene-platinum (II) dichloride, cyclooctadiene-platinum dichloride, norbornadiene - platinum dichloride, gamma-picoline-platinum dichloride, cyclopentadiene-platinum dichloride, as well as reaction products of P latintetrachlo- with olefin and primary amine or secondary amine or primary and secondary amine, such as the reaction product of dissolved in 1-octene platinum tetrachloride with sec. Butylamine or ammonium platinum complex. The catalyst is preferably present in the formulations according to the invention in amounts of from 5 to 2000 ppm by weight (parts by weight per million parts by weight), preferably in amounts of from 10 to 1000 ppm by weight, in particular in amounts of from 15 to 500 ppm by weight , calculated in each case as elemental platinum and based on the total weight of the polyorganosiloxanes A), B) and the organosiloxanes and / or organosilanes C).

The catalyst used is preferably the Karstedt catalyst (US Pat. No. 3,775,452), which has long been known in the literature and whose active species are described in the Comprehensive Handbook of Hydrosilylation Editor Bogdan Marciniec, Pergamon Press 1992

Pt ₂ {[(CH ₂ = CH) (CH ₃ ) ₂ Si] ₂ 0} ₃ .

The addition-crosslinking silicone resin composition according to the invention may contain as further optional constituent at least one flexiopolymer D) of the general formula (IV)

(R ^u _w R ¹² _x * Si0 _{1/2) M4} (R ¹¹ _y R ¹² _z Si0 _2/2) D * (R ¹³ Si0 _{3/2) * T} (IV), wherein

R ¹¹ and R ¹² and R ^{13 are} independently, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, and no hydrogen atom; -w and x * each a number 0, 1, 2 or 3, with w + x * = 3; -y and z are each a number 0, 1, 2 or 3, with y + z = 2; -M *, D *, and T * and Q is a number from 0 to <1, with

 M * + D * + T * = l

 mean,

 with the proviso that per molecule D)

at least two alkenyl groups as R ¹¹ , and

at least one aryl group as R ¹² or R ¹³ is included.

In the case of flexiopolymer D), low crosslinking is preferred and thus T * is to be kept as small as possible. Particularly preferred are linear polyorganosiloxanes, thus T * = 0 is preferred.

Examples of radicals R ¹¹ 'R ¹² and R ¹³ are the same as those already mentioned for R ¹ , with the exception that they can not be a hydrogen atom atom.

R ¹¹ is preferably an alkenyl, particularly preferably a vinyl radical. Radicals R ¹¹ can be bonded both terminally in D) and chainwise, it being preferred that the R ¹¹ radicals are terminal and more preferably only terminally bonded radicals R ^{11 are present} in D). In a particularly preferred embodiment of the invention, D) has two terminally bonded radicals R ¹¹ , one of the two radicals R ^{11 being} bonded to one terminal silicon atom in each case.

Preferred radicals R ¹² are alkyl and aryl radicals. It is particularly preferred that the radicals R ^{12 are} methyl, ethyl or phenyl radicals, in particular methyl and phenyl radicals. It is particularly preferred that of two radicals R ¹² which are bonded to the same silicon moieties, at most only one represents a phenyl radical and the other represents an alkyl radical, preferably a methyl radical. Two radicals R ¹² which are bonded to the same silicon atom may represent two identical or different alkyl radicals, it being particularly preferred that in the case of two alkyl radicals, these are methyl radicals.

It is preferred that the radicals R ¹³ , alkyl or aryl radicals, with aryl radicals being particularly preferred, in particular the phenyl radical. D) consists of at least 3 Si repeating units, preferably at least 5 Si repeating units, particularly preferably at least 8, in particular at least 10 Si repeat units according to the general formula (IV).

Examples of suitable flexopolymers D) according to the general formula (IV) are given below, the list being given only by way of example for the invention and not by way of limitation:

T ^Ph ₅ D ^ph _V4 D ^vi ₄ D _s M ^v

M ^vi ₂ D ₂₁ D ^Ph ₆

M ₂ M ⁱ ₂ D ₁₆ T ^ph ₂

M ^vi ₂ D ^ph ₂

M ^vi ₂ D ^ph ₃₄ D _v

M ^Vi ₂ D ₁₃ D ^Ph ₄₅

Mean

T ^ph = (C ₆ H ₅ ) Si0 _3/2

D = (CH ₃ ) ₂ Si0 _2/2

D ^ph = (CH ₃ ) (C ₆ H ₅ ) Si0 _2/2

D ^vi = (CH ₃ ) (CH ₂ = CH) Si0 _2/2

M = (CH ₃ ) ₃ Si0 _1/2

M ^vi = (CH ₃ ) ₂ (CH ₂ = CH) Si0 _1/2

The indices indicate how often each unit is present in the polyorganosiloxane.

The linear flexopolymers D) serve for flexibilization in the silicone resin composition according to the invention. They react as a result of their alkenyl groups R ¹¹ , with Si-H groups of the organopolysiloxanes A) and the Si-H coupler B). In this way, hard resin molecules are bridged with flexibilizing chain segments. D) can be used in the silicone resin composition according to the invention in addition to the flexibilization, and also to the viscosity Adjustment can be used, which can lead to both an increase and a reduction in viscosity. In addition, for a catalyzed preparation, it may be advantageous to formulate a two-component system in which a component contains the catalyst to suppress an undesirably early start of the curing reaction, eg, during storage. The use of D) is unnecessary if both the flexibility and the viscosity meet the desired property. If D) is present, then 5 to 200 parts D) are used, preferably 5 to 150 parts, more preferably 5 to 100 parts, in particular 10 to 80 parts, based on 100 parts A).

The addition-crosslinking silicone resin composition according to the invention may comprise further constituents E) which are known to the person skilled in the art. Typical representatives are inhibitors, reinforcing and non-reinforcing fillers, plasticizers, adhesion promoters, soluble dyes, inorganic and organic pigments, fluorescent dyes, solvents, fungicides, perfumes, dispersing aids, rheological additives, corrosion inhibitors, light stabilizers, heat stabilizers, flame retardants, agents for Influence on the electrical properties and means for improving the thermal conductivity.

The invention further provides a process for the preparation of the addition-crosslinking silicone resin compositions according to the invention by mixing all components A), B), C) and, if desired, further optional constituents D) and / or E). While the order of mixing ingredients (A), (B) and (C) and other optional ingredients D) and / or E) is not critical, it has been found useful to include catalyst (C) in the mixture of the other ingredients last to be added.

Another object of the invention is the use of the silicone resin compositions according to the invention as casting compounds for the production of moldings, or encapsulations in electrical and electronic applications such as LEDs. After filling the desired molds, the subsequent curing takes place at elevated temperature. The crosslinking of the silicone resin compositions according to the invention is preferably carried out at 70 to 170.degree. C., preferably at 100 to 150.degree. As energy sources for the crosslinking by heating preferably ovens, eg convection drying cabinets, heating channels, heated rollers, heated plates or heat rays of the infrared range are used.

The crosslinking times are preferably 0.5 to 10 hours, preferably 1 to 6 hours. Shaped bodies produced in this way are, provided that no further additives have been mixed in, crystal clear and have a refractive index of at least 1.50, preferably at least 1.60.

The shaped bodies produced in this way have, after complete curing, without further additives, such as e.g. Fillers or

Plasticizer, a Shore D hardness of at least 5, preferably at least 7, preferably in the range of 8 to 65, in particular in the range of 10 to 60 on. The Shore D hardness is determined according to DIN (German Industrial Standard) 53505 (or ASTM D 2240 or ISO 868). This standard also contrasts the Shore D hardness to Shore A. These high hardnesses are an essential criterion of the invention since the moldings do not allow scratching under mechanical stress and thus also reduce the deposition of dirt so that a high light output is ensured over a long period of time. On account of their temperature and UV resistance, the shaped bodies also show their abilities after 40,000 hours even with HB LEDs (high-brightness LEDs) and LEDs emitting short-wavelength light (380-450 nm) or white light. the operating time no drop in light transmission. For all types of LEDs that require chip cover, the inventive compositions can be used. In addition to the use as potting compounds for the production of moldings, the silicone resin compositions according to the invention can also be used, for example, for coatings and impregnations or can also be used as additives in other compositions. Since the modular system nevertheless allows to set very high as well as very low viscosities, there are also uses as impregnating resin, for example of electrical insulation systems in motors, transformers and cables, in combination with other materials, eg glass fabric, paper, glass-mica tapes, etc possible.

In the present text, substances are characterized by specification of data obtained by instrumental analysis. The underlying measurements are either carried out according to publicly available standards or determined according to specially developed procedures. To ensure the clarity of the teaching taught, the methods used are given here:

Viscosity:

Unless stated otherwise, the viscosities are determined by means of rotational viscometric measurement in accordance with DIN EN ISO 3219. Unless otherwise stated, all viscosity data apply at 25 ° C and atmospheric pressure of 1013 mbar. Refractive index:

 The refractive indices are determined in the wavelength range of visible light, unless otherwise stated at 589 nm at 25 ° C and normal pressure of 1013 mbar according to the DIN standard

51,423th Transmission:

 The transmission is determined by UV VIS spectroscopy. A suitable device is, for example, the Analytik Jena Specord 200.

The measurement parameters used are range: 190-1100 nm

Increment: 0.2 nm, integration time: 0.04 s, measurement mode:

Step operation. The first step is the reference measurement (background). A quartz plate attached to a sample holder (dimension of the quartz plates: HxB approx. 6 x 7 cm, thickness approx. 2.3 mm) is placed in the sample beam path and measured against air. Thereafter, the sample measurement takes place. A quartz plate attached to the sample holder with a sample applied - layer thickness applied to the sample approx. 1 mm - is placed in the sample beam path and measured against air. Internal offsetting against background spectrum is provided by the transmission spectrum of the sample.

Molecule compositions:

Molecular compositions are determined by nuclear magnetic resonance spectroscopy (for terms, see ASTM E 386: High Resolution Magnetic Resonance Imaging (NMR): Terms and Symbols), where the ¹ H and ²⁹ Si nuclei are measured.

Description 1H NMR measurement

Solvent: CDC1 ₃ , 99.8% d

Sample concentration: approx. 50 mg / 1 ml CDC1 ₃ in 5 mm NMR

Tube Measurement without addition of TMS, spectral referencing of residual CHC1 ₃ in CDCl ₃ to 7.24 ppm

Spectrometer: Bruker Avance I 500 or Bruker Avance HD 500 Probe head: 5 mm BBO probe head or SMART probe head (Bruker) Measuring parameters:

 Pulprog = zg30

TD = 64k

 NS = 64 or 128 (depending on the sensitivity of the sample head)

 SW = 20.6 ppm

AQ = 3, 17 s

Dl = 5 s

 SFOl = 500.13 MHz

Oil = 6, 175 ppm

Processing parameters:

SI = 32k

WDW = EM

LB = 0.3 Hz

Depending on the spectrometer type used, individual adjustments of the measuring parameters may be necessary. Description ²⁹ Si NMR measurement

Solvent: C ₆ D ₆ 99, 8% d / CC 1 1: 1 v / v with 1 wt% Cr (acac) ₃ as relaxation reagent

 Sample concentration: approx. 2 g / 1.5 ml of solvent in 10 mm NMR tubes

 Spectrometer: Bruker Avance 300

Sample head: 10 mm ¹ H / ¹³ C / ¹⁵ N / ²⁹ Si glass-free QNP probe head (Bruker)

Measurement parameters:

Pulprog = zgig60

TD = 64k

 NS = 1024 (depending on the sensitivity of the probe head) SW = 200 ppm

AQ = 2, 75 s

Dl = 4 s SFOl = 300.13 MHz

Oil = -50 ppm

Processing parameters:

 SI = 64k

WDW = EM

LB = 0.3 Hz

Depending on the spectrometer type used, individual adjustments of the measuring parameters may be necessary.

Molecular weight distributions:

 Molecular weight distributions are determined as weight average M w and as number average M n, using the method of gel permeation chromatography (GPC or Size Exclusion Chromatography (SEC)) with polystyrene standard and refractive index detector (RI detector). Unless otherwise stated, THF is used as the eluent and DIN 55672-1 is used. The polydispersity is the quotient Mw / Mn.

Glass transition temperatures:

 The glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN 53765, perforated crucible, heating rate 10 K / min.

Examples:

In the following, examples of the preparations according to the invention and their preparation are given.

All percentages are by weight. Unless otherwise stated, all manipulations are carried out at room temperature of about 23 ° C and under normal pressure (1.013 bar). The apparatus are commercially available laboratory equipment such as They are commercially available from numerous equipment manufacturers.

Ph is a phenyl radical = C _S H ₅ - Me is a methyl radical = CH ₃ -.

Me ₂ correspondingly means two methyl radicals.

An essential property of the preparations according to the invention is that it has self-crosslinkable, branched polyorganosiloxane components. The syntheses of such products are described below:

Examples 1-11 describe various processes for the preparation of branched, self-crosslinking organopolysiloxanes A).

Example 1 16116 g of water, 12240 g of toluene and 5436 g of ethyl acetate are weighed into a 60 1 glass stirrer and mixed. A mixture of 1947.3 g of methyldichlorosilane (CH ₃ ) Si (H) Cl ₂ (115 g / mol = weighed 16.93 mol), 7770 g of phenyltrichlorosilane PhSiCl ₃ (211.5 g / mol => Weighed in 36.74 mol) and 2061 g Vinyldimethylchlorsilan (CH ₂ = CH) Me ₂ SiCl (120.5 g / mol = weighed 17.10 mol) uniformly added within 3 hours. The exotherm of the reaction leads to a temperature increase of not more than 47 ° C. The mixture is left to stir for 30 minutes and then to settle for 30 minutes without stirring, so that the phases can separate. 24 kg of hydrochloric acid aqueous phase are then separated off. 12 kg of demineralized water are added to the organic phase, the mixture is stirred for 30 minutes and left to stand for 30 minutes without stirring, so that the phases can separate. The water phase is separated and the organic phase washed in the same way three times with 12 kg of deionized water. Following the last wash, the organic phase is heated to 80 ° C, the apparatus is evacuated to 150 mbar internal pressure. All are distilled at 80 ° C and the specified negative pressure volatile components and receives 8 kg of crude product, which are then further distilled off at 160 ° C and 20 mbar vacuum until no longer volatile under these conditions components are included. This gives 6 kg of product. The product obtained has a viscosity of 5150 mPas at 25 ° C and atmospheric pressure of 1013 mbar. The residual solvent content is 0.06% by weight according to ¹ H-NMR: toluene. The total chloride content is 8 mg / kg. The color number according to APHA is 14, the turbidity according to Sigrist 2.55 ppm. By size exclusion chromatography (SEC) is determined in THF as eluent Mw = 2600 g / mol and Mn = 1500 g / mol. The product has the following molar composition according to ²⁹ Si-NMR spectrum:

Me (H) Si0 _2/2 : 24.3%

Ph (OR) ₂ Si0 _1/2 : 0.4%

Ph (OR) Si0 _2/2 : 17.5%

PhSi0 _3/2: 36.2%

where R is mainly ethyl, as well as hydrogen.

The silanol content can only be estimated roughly and is, according to estimate from the ^ ^"H-NMR spectrum about 6500 ppm because of overlapping signals. The content of vinyl groups according to ¹ H-NMR 1.99 mmol / g, the content of silicon-bonded hydrogen 2 23 mmol / g.

EXAMPLE 2 194.7 g of methyldichlorosilane (CH ₃ ) Si (H) Cl ₂ (115 g / mol = weighed 1.69 mol), 777.0 g of phenyltrichlorosilane PhSiCl ₃ (4) are introduced into a 4 l 4 necked round bottomed glass flask with outlet. 211.5 g / mol => weighed 3.67 mol) and 206.1 g vinyldimethylchlorosilane (CH ₂ = CH) Me ₂ SiCl (120.5 g / mol = weighed> 1.71 mol) weighed out together with 580 g of toluene and mixed.

To this template, 185 g of ethanol are added uniformly within 40 minutes, the temperature of the reaction mixture drops to 16 ° C. It is stirred for 5 minutes. Next, 250 g of deionized water are added within 2 hours. At the beginning, dosing is very slow to avoid excessive hydrochloric acid gas evolution. The incoming reaction is exothermic and is controlled by the water addition mode so that the temperature rises to about 40 ° C. The mixture is stirred after completion of addition of water for 10 minutes at the then given temperature and then heated to reflux (about 83 ° C temperature in the reaction mixture). After refluxing for two hours, 187.5 g of toluene and 170 g of DI water are added without prior cooling, stirring is continued for 10 minutes and the stirrer is then switched off. The phases are allowed to separate within 40 minutes without stirring. The lower hydrochloric acid aqueous phase is separated off. Then 500 g of deionized water are added, stirred for 10 minutes, 45 minutes without stirring separate phases and the water phase separated again. The HCl content in the organic phase is less than 5 ppm. The organic phase is concentrated on a rotary evaporator at 150 ° C oil bath temperature and 10 mbar vacuum for 30 minutes, and then increases the pressure of 10 to 20 mbar and the oil bath temperature of 150 ° C to 160 ° C. The mixture is distilled for a further 3 hours and receives a colorless liquid product having a viscosity of 4510 mPas, a density (according to DIN 51757) of 1.161 g / cm ³ , a flash point (DIN 2719) of 178, 5 ° C and an ignition point EN 14522 from 430 ° C.

According to SEC, Mw = 2400 and Mn = 1300. The APHA color number is 12, the total chlorine content is 13 mg / kg.

According to ¹ H-NMR are still 0.07 wt .-% toluene. The silanol content, which can only be estimated from signal overlays, is about 6400 ppm. The vinyl content is 1.92 mmol / g, the silicon-bonded hydrogen content 2.16 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

(CH ₂ = CH) Me ₂ SiO _2/2 : 21.9%

Me (H) Si0 _2/2: 24, 4%

Ph (OR) ₂ Si0 _1/2 : 0.8%

Ph (OR) Si0 _2/2: 18.3% PhSi0 _3/2: 34.6%

where R is mainly ethyl, as well as hydrogen. EXAMPLE 3 Into a 4 l 4-necked round-bottomed glass-bottomed flask, 588 g of phenyltriethoxysilane PhSi (EtO) ₃ (240 g / mol => weight 2.45 mol), 80 g of 1, 3-divinyl-1, 1, 3, 3 - tetramethyldisiloxane [(CH ₂ = CH) Me ₂ Si] ₂ O (186 g / mol => weight 0.43 mol), 290 g of water and 2.3 g of 20 wt. Weighed in -% - aqueous hydrochloric acid solution and mixed.

 The reaction mixture is heated to 60 ° C. with a heating hood, then the heating is switched off, the heating hood not yet being removed. The temperature continues to rise as a result of the exothermic reaction and reaches 78 ° C. after a short time, during which the mixture becomes clear and homogeneous. Then it cools down again. The mixture is heated until reflux is reached (82 ° C. in the reaction mixture) and kept at this temperature for 30 minutes. The reaction mixture turns milky white.

 It is then distilled off under atmospheric pressure until a top temperature of 83 ° C. (sump temperature 88 ° C.) is reached. This gives 318 g of distillate.

 Then 816 g of toluene are added and 3, 1 ml (4.0 g) 25 wt .-% - aqueous sodium hydroxide solution.

 It is distilled again at atmospheric pressure until a top temperature of 109 ° C (bottom temperature 130 ° C) is reached and allowed to cool. At 90 ° C., 100 g of toluene and 1.9 ml of 20% strength by weight aqueous hydrochloric acid and 64.6 g of DI water are added.

At 40 ° C, 24 g of methyldichlorosilane Me (H) SiCl ₂ (115 g / mol;

Weighed = 0.21 mol) added within 13 minutes. The temperature of the reaction mixture rises without heating

40 ° C to 45 ° C.

The mixture is heated for 1 hour at reflux, which sets from 98 ° C bottom temperature. Then 450 g of toluene and 300 g of demineralized water are added, mixed well and then cooled. let the phases separate. The hydrochloric acid aqueous phase is removed.

 The organic phase is washed by adding 500 g of deionised water. The mixture is stirred, heated to 50 ° C and then turned off the stirrer. After resting for 15 minutes, the phases are separated and the aqueous phase is removed.

 The organic solvent is then partially removed by distillation. Distilled 473 g of toluene, which still contains residual amounts of water, and thereby receives a whitish cloudy mixture, which is allowed to cool to 30 ° C. Filtered through a filter cake Seitz EF filter aid on a Seitz 100 filter plate and receives 335 g of colorless, clear filtrate having a solids content of 78.45 wt .-% (determined by baking 1 g of substance at 200 ° C for 30 min).

The following product characterization data refer to the pure product, not to the 78.45 weight percent solution.

 The following molecular weights were determined by SEC (eluent THF): Mw = 2100 g / mol; Mn = 1600 g / mol.

The silanol content is only approximate in ¹ H-NMR due to signal overlays and is about 2200 ppm. The vinyl content is 1.89 mmol / g, the silicon-bonded hydrogen content 0.25 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

Ph (OR) Si0 _2/2 : 6.3%

PhSi0 _{3 2} : 68.4%

where R is mainly ethyl, as well as hydrogen.

EXAMPLE 4 1176 g of phenyltriethoxysilane PhSi (EtO) ₃ (240 g / mol = weigh-in 4.90 mol), 200 g of 1, 3-divinyl-1,1,3, are introduced into a 4 l 4-necked round bottomed glass flask with outlet , 3-tetramethyldisiloxane [(CH ₂ = CH) Me ₂ Si] ₂ 0 (186 g / mol => weight 1.07 mol) and 580 g of water were weighed out and mixed.

60 g of methyldichlorosilane Me (H) SiCl ₂ (115 g / mol, initial weight = 0.52 mol) are metered into this mixture over the course of 40 minutes at room temperature at about 23 ° C. After 18 minutes, a noticeable reaction occurs, resulting in an exothermic rise in temperature to 40 ° C.

 The mixture is heated to reflux after the end of the dosing (bottom temperature 81 ° C., head temperature 79 ° C. and reflux for 30 minutes). The reaction mixture is whitish cloudy.

 It is then distilled to a sump temperature of 89 ° C and a head temperature of 84 ° C. This gives 810 ml of distillate with a mass of 674.1 g. It is cooled to below 70 ° C and 1632 g of toluene. The mixture is stirred for 15 minutes after the addition is complete, the agitator is stopped and allowed to settle for 30 minutes without stirring, so that the phases can separate. The lower phase is the water phase. It is separated. 1300 g of deionized water are metered into the organic phase, stirred for 20 minutes and again left to separate for 30 minutes without stirring the phases. It separates 1352 g of water phase. The organic phase still contains 7.5 ppm residual HCl.

 It is concentrated by distilling off 1367 g of toluene. Finally, the sump temperature is 128 ° C, the head temperature at 113 ° C. It is cooled to below 60 ° C and then 33 g filter aid Seitz EF added, stirred for 15 minutes and filtered at room temperature with a pressure filter chute over a Seitz K 100 filter plate.

 This gives 987 g of clear colorless filtrate having a solids content of 78.8 g (determined by Ausheitzen of 1 g of substance at 200 ° C for 30 minutes.

 According to SEC (eluent THF), the product has a molecular weight of Mw = 1300 g / mol and Mn = 1100 g / mol.

The silanol content is only approximate in ¹ H-NMR due to signal overlays and is about 4200 ppm. The vinyl content is 2.33 mmol / g, the content of silicon-bonded hydrogen 0.57 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

(CH ₂ = CH) Me ₂ Si0 _1/2 : 27.2%

Me (H) Si0 _2/2: 7.0%

Ph (OR) Si0 _2/2: 19.8%

PhSi0 _3/2 : 46.0%

where R is mainly ethyl, as well as hydrogen.

EXAMPLE 5 Into a 4 l necked glass round-bottomed flask, 588 g of phenyltriethoxysilane PhSi (EtO) ₃ (240 g / mol => weight 2.45 mol), 588 g of a phenylsilicone resin solid at 23 ° C. and atmospheric pressure of 1013 mbar are mixed with a Molecular weight Mw of 2900 g / mol (number average Mn = 1500) and a glass transition temperature of Tg = 52 ° C containing 5.5% by weight of silicon-bonded hydroxy groups and 3.3% by weight of silicon-bonded

Contains ethoxy groups,

and the _3/2 units is 100 mol% PhSi0, with the methoxy and hydroxy groups distributed to the specified structural units, weighed and stirred at 60 ° C until the phenylsilicone has completely dissolved in phenyltriethoxysilane.

160 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane [(CH ₂ CHCH) Me ₂ Si] ₂ O (186 g / mol = weighed 0.86 mol) and 580 g of water are then added to this solution and stir well.

48 g of methyldichlorosilane Me (H) SiCl ₂ (115 g / mol, initial weight = 0.42 mol) are metered into this mixture over the course of 18 minutes at room temperature at about 23 ° C. After 18 minutes, the temperature of the mixture has increased to 53 ° C.

The mixture is heated for 30 minutes at reflux (temperature of the mixture 84 ° C) and receives a whitish cloudy mixture.

395 ml of distillate are then distilled off and the mixture is cooled to below 80 ° C. before 1000 g of toluene are added and the mixture is stirred for 15 minutes. stir. Stop the stirrer, allow to settle for 30 minutes and then separate the water phase.

 1300 g of demineralized water, 200 g of common salt and 100 g of toluene are added to the organic phase, the mixture is stirred for 20 minutes and the phases are allowed to separate for 30 minutes. The water phase is separated off. The residual HC1 content in the organic phase is 3.5 ppm.

The organic phase is concentrated by distilling off 886 g of toluene.

 It is cooled to below 60 ° C and then 33 g filter aid Seitz EF added, stirred for 15 minutes and filtered at room temperature with a pressure filter chute over a Seitz K 100 filter plate.

 This gives 1170.7 g of clear colorless filtrate having a solids content of 81.1 wt .-% (determined by Ausheitzen of 1 g of substance at 200 ° C for 30 minutes).

 According to SEC (eluent THF), the product has a molecular weight of Mw = 3400 g / mol and Mn = 1600 g / mol.

 The silanol content is only approximate in λ-MR due to signal overlays and is about 5500 ppm. The vinyl content is 1.59 mmol / g, the silicon-bonded hydrogen content 0.37 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

Me (H) Si0 _2/2 : 5.1%

Ph (OR) ₂ Si0 _1/2 : 1.5%

Ph (OR) Si0 _2/2 : 33.3%

PhSi0 _3/2: 40.7%

where R is mainly ethyl, as well as hydrogen.

Example 6:

588 g of phenyltriethoxysilane PhSi (EtO) ₃ (240 g / mol => weight 2.45 mol), 90 g, 3-divinyl-1,1,3,3-tetramethyldisiloxane are introduced into a 4 l 4-necked round-bottomed glass-bottomed flask [(CH ₂ = CH) Me ₂ Si] ₂ O (186 g / mol => weight 0.48 mol), 27 g 1,1,3,3- Weighed and mixed tetramethyldisiloxane [(H) Me ₂ Si] ₂ 0 (134 g / mol => weight 0.20 mol) and 290 g of water.

 2.3 g of 20% strength by weight aqueous hydrochloric acid solution are added to this mixture and the mixture is then heated to 85.degree. The reaction starts at 84 ° C. The product mixture becomes clear and homogeneous. It is heated for 30 minutes at reflux (bottom temperature 87 ° C), whereby the product mixture turns cloudy milky white. Subsequently, 315 g are distilled off, wherein the sump temperature rises to 90 ° C and the head temperature to 84 ° C.

The further treatment is carried out analogously to Example 4, wherein in each case half the amounts of toluene and water are used.

This gives 477 g of clear colorless filtrate having a solids content of 73.7 g (determined by Ausheitzen of 1 g of substance at 200 ° C for 30 minutes.

 According to SEC (eluent THF), the product has a molecular weight of Mw = 1300 g / mol and Mn = 1100 g / mol.

The silanol content is only approximate in ¹ H-NMR due to signal overlays and is about 18800 ppm. The vinyl content is 1.79 mmol / g, the silicon-bonded hydrogen content 0.60 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

Me ₂ (H) Si0 _1/2 : 7.7%

Ph (OR) ₂ Si0 _1/2 : 0.2%

Ph (OR) Si0 _2/2 : 31.5%

PhSi0 _3/2 : 37.0%

where R is mainly ethyl, as well as hydrogen.

EXAMPLE 7 16116 g of water, 12240 g of toluene, 5436 g of ethyl acetate and 3108 g of a short-chain, alpha, omega-silanol-functional phenylmethyl oil having the average composition: HO-Si (Me) (Ph) are introduced into a 60 1 glass stirrer. [O-Si (Me) (Ph)] ₄ OSi (Me) (Ph) OH, which is a total of 6 Silicon repeating units, each of which is substituted with a phenyl and a methyl group and of which the two terminal silicon atoms each carry a hydroxyl function and which has an average molecular weight of Mw = 800 g / mol at Mn = 700 g / mol, and a Viscosity of 503 mPas at 25 ° C and atmospheric pressure of 1013 mbar.

7770 g of phenyltrichlorosilane (211.5 g / mol = weighed 36.7 mol), 1800 g vinyldimethylchlorosilane (120.5 g / mol => weight 14.9 mol) and 1822.5 g of methyldichlorosilane (115 g / mol => weighing

15.8 mol) are mixed together and added to the original within 5 hours. The temperature rises from 25.7 ° C to 48.7 ° C. The mixture is stirred for 45 minutes after completion of the addition, then heated for 1 hour at reflux (bottom temperature 83 ° C) and then the stirrer from. After 45 minutes of phase separation, the water phase is separated off.

 For neutral washing, 12 kg of deionized water are added to the organic phase, stirred for 30 minutes and allowed to separate for 30 minutes. The water phase is separated off. This washing process is carried out a total of three times in the same manner until the residual HCl content in the organic phase is 3 ppm.

The mixture is then distilled off at atmospheric pressure up to a temperature of 124 ° C., giving 9543 g of distillate and 14,125 g of bottom residue.

From the residue, a sample of 1383.5 g is taken, which is distilled off on a rotary evaporator at an oil bath temperature of 160 ° C and a reduced pressure of 20 mbar for 1 hour. This gives 962.1 g of a 69.6 wt .-% product solution, which is filtered hot on a Seitz K 100 filter plate with Seitz filter aid FF. The resulting filtrate is clear and colorless. It has a Brookfield viscosity of 2870 mPas.

According to SEC (eluent THF), the product has a molecular weight of Mw = 2400 g / mol and Mn = 1300 g / mol. The silanol content is only approximate in ¹ H-NMR due to signal overlays and is about 10052 ppm. The vinyl content is 1.30 mmol / g, the silicon-bonded hydrogen content 1.44 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

(CH ₂ = CH) Me ₂ Si0 _1/2 : 15.2%

Me (H) Si0 _2/2: 15.4%

Ph (Me) Si0 _2/2: 27.3% (includes Ph (Me) (RO) SIOI _{/ 2} with a)

Ph (OR) Si0 _2/2 : 15.5%

PhSi0 _3/2: 26.2%

where R is mainly ethyl, as well as hydrogen. EXAMPLE 8 Into a 4 l 4-necked round-bottomed glass-bottomed flask, 135.0 g of methyldichlorosilane (CH ₃ ) Si (H) Cl ₂ (115 g / mol => weight 1.17 mol), 518.0 g of phenyltrichlorosilane PhSiCl ₃ ( 211.5 g / mol => weight 2.45 mol) and 133.4 g of vinyldimethylchlorosilane (CH ₂ = CH) Me ₂ SiCl (120.5 g / mol = weighed 1.11 mol) weighed out together with 816 g of toluene and mixed.

 To this template, 185 g of ethanol are added uniformly within 40 minutes, the temperature of the reaction mixture drops to 16 ° C. The mixture is stirred for 15 minutes and then 125.8 g of a short-chain, alpha, omega-silanol-functional phenylmethyl oil are introduced, which has the average composition: HO-Si (Me) (Ph) [O-Si (Me) (Ph)] OSi (Me) (Ph) OH, which thus comprises a total of 6 silicon repeating units, each of which is substituted by a phenyl and a methyl group and of which the two terminal silicon atoms each carry a hydroxyl function and which has an average molecular weight of Mw = 800 g / mol Mn = 700 g / mol, and has a viscosity of 503 mPas at 25 ° C and atmospheric pressure of 1013 mbar.

Then 250 g of deionised water are added within 2 hours. At the beginning, dosing is very slow to avoid excessive hydrochloric acid gas evolution. The incoming The action is exothermic and controlled by the water addition procedure so that the temperature rises to about 40 ° C. The mixture is stirred after completion of addition of water for 10 minutes at the then given temperature and then heated to reflux (about 83 ° C temperature in the reaction mixture). After refluxing for two hours, 176.4 g of toluene and 175 g of demineralized water are added without prior cooling, stirring is continued for 10 minutes and the stirrer is then switched off. The phases are allowed to separate within 40 minutes without stirring. The lower hydrochloric acid aqueous phase is separated off. Then 500 g of deionized water are added, stirred for 10 minutes, 45 minutes without stirring separate phases and the water phase separated again. The HCl content in the organic phase is less than 7 ppm. The organic phase is concentrated on a rotary evaporator at 150 ° C oil bath temperature and 10 mbar reduced pressure for 30 minutes, and then increases the pressure of 10 to 20 mbar and the oil bath temperature of 150 ° C to 160 ° C. It is distilled for a further 3 hours and receives a colorless liquid product having a viscosity of 2600 mPas.

After SEC, Mw = 2600 and Mn = 1200.

The silanol content, which can only be estimated from signal overlays, is about 10030 ppm. The vinyl content is 0.95 mmol / g, the content of silicon-bonded hydrogen 1.02 mmol / g. According to ²⁹ Si NMR, the molar composition is:

Me (H) Si0 _2/2: 12.0%

Ph (Me) Si0 _2/2: 41.9% (includes Ph (Me) (RO) SIOI _{/ 2} with a)

Ph (OR) ₂ Si0 _1/2 : 0.8%

Ph (OR) Si0 _2/2: 14.4%

PhSi0 _3/2: 19.7%

where R is mainly ethyl, as well as hydrogen. Example 9 Into a 4 l 4 necked round bottomed glass flask, weigh 1074.4 g of water, 816 g of toluene and 362.4 g of ethyl acetate and mix. To this template, a mixture of 106.7 g dimethylchlorosilane (CH _{3) 2} Si (H) Cl (94.5 g / mol => Weigh 1.13 mol), 518.0 g phenyltrichlorosilane PhSiCl ₃ (211.5 g / mol => weighed 2.45 mol) and 137.4 g vinyldimethylchlorosilane

(CH ₂ = CH) Me ₂ SiCl (120.5 g / mol => initial weight 1.14 mol) added uniformly within 3 hours. The exotherm of the reaction leads to a temperature increase of not more than 47 ° C. Stir for 30 minutes and then settle for 30 minutes without stirring, so that the phases can separate. The hydrochloric water phase is then separated off. 800 g of demineralized water (deionized water) are added to the organic phase, stirred for 20 minutes and then allowed to stand for 20 minutes without stirring, so that the phases can separate. The water phase is separated off and the organic phase is washed twice in the same way. Following the last wash, the organic phase is concentrated on a rotary evaporator at 160 ° C oil bath temperature and 20 mbar vacuum for 4.5 hours.

The residue is filtered through a hot water-heated pressure filter chute over a Seitz K 100 filter plate with Seitz filter aid FF.

 This gives 360 g of a clear colorless product having a viscosity of 16 320 mPas (Brookfield).

By size exclusion chromatography (SEC) is determined in THF as eluent Mw = 6800 g / mol and Mn = 1600 g / mol. The product has the following molar composition according to ²⁹ Si-NMR spectrum:

(CH ₂ = CH) Me ₂ SiO 2/2: 10.5%

Me ₂ (H) Si0 _2/2 : 20.5%

Ph (OR) ₂ Si0 _1/2 : 1.1%

Ph (OR) Si0 _2/2 : 25.4%

PhSi0 _3/2 : 42.5% where R is mainly ethyl, as well as hydrogen.

The silanol content can only be approximately estimated from signal overlays and is estimated to be about 6674 ppm from the ¹ H NMR spectrum. The content of vinyl groups is 0.95 mmol / g according to ^X H-NMR, and the content of silicon-bonded hydrogen is 1.29 mmol / g. Example 10:

325.3 g of phenyltriethoxysilane PhSi (EtO) ₃ (240 g / mol => initial weight 1.36 mol), 325.3 g of a phenylsilicone resin solid at 23 ° C. and atmospheric pressure of 1013 mbar are carried in a 4 l necked glass round bottom flask a molecular weight average Mw of 2,900 g / mol (number average Mn = 1,500) and a glass transition temperature of Tg = 52 ° C, containing 5.5% by weight of silicon-bonded hydroxy groups and 3.3% by weight of silicon-bonded ethoxy groups; mol% PhSi0 is _3/2 units, wherein the ethoxy and hydroxy groups distributed to the specified structural units, weighed and stirred at 60 ° C until the phenylsilicone has dissolved in phenyltriethoxysilane.

 260 g of a linear alpha, omega-silanol-functional phenylmethyl oil having the average composition: HO-Si (Me) (Ph) [O] are added to this solution.

Si (Me) (Ph)] ₁₄ OSi (Me) (Ph) OH, which thus comprises a total of 16 silicon repeating units, each of which is substituted by a phenyl and a methyl group and of which the two terminal silicon atoms each have a hydroxyl function and which has an average molecular weight of Mw = 2200 g / mol at Mn = 1000 g / mol, and has a viscosity of 1103 mPas at 25 ° C and atmospheric pressure of 1013 mbar, added and mixed. 129 g of 1, 3-divinyl-1,1,3,3-tetramethyldisiloxane are successively added first to the preparation thus obtained

[(CH ₂ = CH) Me ₂ Si] ₂ O (186 g / mol => weight 0.69 mol) and then 321 g of water added. 130.7 g of vinyldimethylchlorosilane (CH ₂ = CH) Me ₂ SiCl (120.5 g / mol = weighed 1.38 mol) are metered into the resulting preparation while stirring. The dosing time is 46 minutes, the temperature rises during dosing due to the heat of reaction from 22.3 ° C to 41 ° C, without being heated from the outside. After completion of the dosing is heated to reflux (bottom temperature 85 ° C) and held for 30 minutes at reflux.

 Subsequently, 190 ml of distillate are removed. The temperature of the agitator rises to 92 ° C, the head temperature to 84 ° C. It is cooled to below 80 ° C, 533 ml of toluene, mixed for 15 minutes, then the stirrer and waiting for 30 minutes without stirring, before separating the water phase. At the time of phase separation, the temperature of the mixture is still 50 ° C due to slight Zuheitzen from the outside.

 To wash the organic phase, 540 ml of DI water and 100 g of sodium chloride (sodium chloride) are added, stirred for 15 minutes and then the stirrer is switched off. After 30 minutes of phase separation without stirring, the phases are separated. The HCl content of the organic phase is 3 ppm. 200 ml of the solution are separated for stability analysis. The mixture turns out to be stable. This amount is no longer considered in the further work-up.

 Distilled from the organic phase, 420 ml of distillate, cooled to below 60 ° C and filtered off the warm solution then with a pressure filter chute on a Seitz K 100 filter plate with Seitz filter aid FF from. The resulting 672.9 g of filtrate are clear and colorless. The solids content is determined to be 87.9% by weight (1 g of substance was heated to 200 ° C. for half an hour and the residue was determined gravimetrically).

According to SEC (eluent THF), the product has a molecular weight of Mw = 2600 g / mol and Mn = 1200 g / mol. The silanol content is only approximate in ¹ H-NMR due to signal overlays and is about 2200 ppm. The vinyl content is 1.17 mmol / g, the silicon-bonded hydrogen content 0.92 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

(CH ₂ == CH) Me ₂ Si0 _1/2 : 14, 8%

Me ₂ (H) Si0 _1/2 : 11.7%

Ph (Me) Si0 _2/2: 27.2% (includes Ph (Me) (RO) SIOI / ₂ with a)

Ph (OR) Si0 _2/2 : 18.2%

PhSi0 _3/2 : 26.5%

where R is mainly ethyl, as well as hydrogen. Example 11: Procedure as in Example 12 with the difference that instead of the linear phenylmethylpolysiloxane having an average of 16 repeating units, a short-chain, alpha, omega-silanol-functional phenylmethyl oil having the average composition is used: HO-Si (Me) (Ph) [O] Si (Me) (Ph) ₄ OSi (Me) (Ph) OH, that is a total of 6

Silicon repeating units, each of which is substituted with a phenyl and a methyl group and of which the two terminal silicon atoms each carry a hydroxyl function and which has an average molecular weight of Mw = 800 g / mol at Mn = 700 g / mol, and a Viscosity of 503 mPas at 25 ° C and atmospheric pressure of 1013 mbar.

This gives 952 g of a clear colorless product.

The solids content is determined to be 89.2% by weight (1 g of the substance was heated to 200 ° C. for half an hour and the residue was determined gravimetrically).

According to SEC (eluent THF), the product has a molecular weight of Mw = 1800 g / mol and Mn = 1100 g / mol. The silanol content is in the ^{"" "H-NMR} due to overlapping signals only approximate and is about 10100 ppm. The vinyl content is 1.30 mmol / g, the content of silicon-bonded hydrogen 1 14 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

(CH ₂ = CH) Me ₂ Si0 _1/2 : 15.5%

Me ₂ (H) Si0 _1/2 : 13.4%

Ph (Me) Si0 _2/2 : 25.1% (includes Ph (Me) (RO) Si0 _1/2 )

Ph (OR) ₂ Si0 _{1 2} : 1.0%

Ph (OR) Si0 _2/2 : 15.5%

PhSi0 _3/2 : 29.5%

where R is mainly ethyl, as well as hydrogen.

Examples of silicone resin compositions:

By way of illustration, by no means by way of limitation, examples of preparations of the invention are given below. In these examples, all parts or percentages are by weight unless otherwise specified. Furthermore, all indications of refractive indices refer to a temperature of 25 ° C. The Shore hardnesses A and D were determined according to DIN 53505 -A- 87. The transmission was measured as indicated at the beginning. The solids content of the toluene resin solutions was calculated by means of the ¹ H-NMR spectrum.

Formulation Example 1 Preparation with Resin According to Example 1

There are 60.0 g of the resin described in Example 1, 40.0 g of a linear siloxane copolymer which has an average of 60 phenylmethylsiloxane units, 12 dimethylsiloxane units and 2 dimethylvinylsiloxane end groups according to the ²⁹ Si NMR spectrum and 5.0 g of 1, 4-bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a platinum (0) / sym. Tetramethyldivinyldisiloxan- Complex (Karstedt catalyst) containing 20% by weight of platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5290.

The resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for molding first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.

 After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 21 Shore D. The transmission was 98.5% at 550 nm. Preparation Example 2 Preparation with Resin According to Example 2

There are 60.0 g of the resin described in Example 2, 40.0 g of a linear siloxane copolymer which has an average of 60 phenylmethylsiloxane units, 12 dimethylsiloxane units and 2 dimethylvinylsiloxane end groups according to the ²⁹ Si NMR spectrum and 1.6 g of 1, 4-bis (dimethylsilyl) benzene and 0.026 g of an 80

% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a platinum (0) / sym. Tetramethyldivinyldisiloxan complex (Karstedt catalyst) containing 20 wt .-% of platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5215.

 The resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.

After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 15 Shore D. The transmission was at 97.9% at 550 nm. Preparation Example 3 Preparation with Resin According to Example 3

There are obtained 76.48 g (solid content: 60 g) of a 78.45% toluene solution of the resin described in Example 3, 40.0 g of a linear siloxane copolymer which according to the ²⁹ Si NMR spectrum shows an average of 60 phenylmethylsiloxane units, Has 12 dimethylsiloxane units and 2 dimethylvinylsiloxane end groups and 10.0 g of 1,4-bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a platinum (0) / sym. Tetramethyldivinyldisiloxan complex (Karstedt catalyst) containing 20 wt .-% of platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5353.

The resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.

After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 26 Shore D. The transmittance at 550 nm was 97.2%.

Preparation Example 4 Preparation with Resin According to Example 4 75.2 g (solids content: 60 g) of a 79.8% strength toluene solution of the resin described in Example 4, 40.0 g of a linear siloxane copolymer which, according to ²⁹ Si NMR spectrum has an average of 60 phenylmethylsiloxane units, 12 dimethylsiloxane units and 2 dimethylvinylsiloxane end groups and 10.8 g of 1, 4-bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0 , 0026 g of a platinum (0) / sym. Tetramethyldivinyldisiloxan complex (Karstedt catalyst) containing 20 wt .-% of platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5273. The resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.

 After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 14 Shore D. The transmission was at 550 nm at 98.4%.

Preparation Example 5 Preparation with Resin According to Example 5

There are 73.2 g (solids content: 60 g) of an 82% toluene solution of the resin described in Example 5, 40.0 g of a linear Siloxancopolymers, which according to ²⁹ Si NMR spectrum on average 60 Phenylmethylsiloxaneinheiten, 12 Dimethylsilo - xaneinheiten and 2 dimethylvinylsiloxane end groups has and 7.6 g of 1, 4 -Bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a platinum (0) / sym. Tetramethyldivinyldisiloxan-

Complex (Karstedt catalyst) containing 20% by weight of platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5353.

The resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for molding first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.

After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 21 Shore D. The transmission was at 97.9% at 550 nm. Preparation Example 6 Preparation with Resin According to Example 6

75.5 g (solids content: 60 g) of a 79.5% strength toluene solution of the resin described in Example 6, 40.0 g of a linear siloxane copolymer which, according to the ²⁹ Si NMR spectrum, contains an average of 60 phenylmethylsiloxane units, Has 12 dimethylsiloxane units and 2 dimethylvinylsiloxane end groups and 7.6 g of 1, -Bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a platinum (0) / sym , Tetramethyldivinyldisiloxan complex (Karstedt catalyst) containing 20 wt .-% of platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5292.

The resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.

After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 37 Shore D. The transmission was 98.1% at 550 nm.

Formulation Example 7 Preparation with Resin According to Example 7 100.0 g of the liquid resin described in Example 7 and 5.0 g of 1,4-bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a platinum (0) / sym. Tetramethyldivinyldisiloxan complex (Karstedt catalyst) containing 20 wt .-% of platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5290.

The mixture thus obtained is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth, and the closed stainless steel mold for molding is initially for 15 minutes at 165 ° C and a pressure of 5.45 MPa in vulcanised in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.

 After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 21 Shore D. The transmission was 98.3% at 550 nm.

Formulation Example 8 Preparation with Resin According to Example 8

There are 100.0 g of the liquid resin described in Example 8 and 1.0 g of 1, -bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a platinum (0). / sym. Tetramethyldivinyldisiloxan complex (Karstedt catalyst) containing 20 wt -.% Platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5292.

 The resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.

 After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 17 Shore D. The transmission was 98.0% at 550 nm.

Preparation Example 9 Preparation with Resin According to Example 9

There are 60 g of the liquid resin described in Example 9, 40.0 g of a linear siloxane copolymer which has an average of 60 phenylmethylsiloxane units, 12 dimethylsiloxane units and 2 dimethylvinylsiloxane end groups according to ²⁹ Si-NMR spectrum and 2.0 g of 1, -bis (dimethylsilyl ) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a platinum (0) / sym. Tetramethyldivinyldi- siloxane complex (Karstedt catalyst) containing 20 wt .-% platinum, calculated as elemental metal, homogeneously mixed. The preparation had a refractive index of

1.5241.

 The resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for molding first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.

 After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 10 Shore D. The transmission was 98.3% at 550 nm. Preparation Example 10 Preparation with Resin According to Example 10

There are 65.4 g (solids content: 60 g) of a 91.7% strength toluene solution of the resin described in Example 10, 40.0 g of a linear siloxane copolymer which according to the ²⁹ Si NMR spectrum has an average of 60 phenylmethylsiloxane units, 12 dimethylsiloxane units and 2 dimethylvinylsiloxane end groups and 2.2 g of 1, -Bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a Plati (0) / sym , Tetramethyldivinyldisiloxan complex (Karstedt catalyst) containing 20 wt .-% of platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5289.

The resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet. After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 18 Shore D. The transmission was 98.2% at 550 nm. Preparation Example 11 Preparation with Resin According to Example 11

There are 65.9 g (solids content: 60 g) of a 91.0% strength toluene solution of the resin described in Example 11, 40.0 g of a linear siloxane copolymer which according to the ²⁹ Si NMR spectrum has an average of 60 phenylmethylsiloxane units, Has 12 dimethylsiloxane units and 2 dimethylvinylsiloxane end groups and 2.0 g of 1,4-bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a platinum (0) / sym. Tetramethyldivinyldisiloxan complex (Karstedt catalyst) containing 20 wt .-% of platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5280.

The resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.

 After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 15 Shore D. The transmission was at 97.8% at 550 nm.

Claims

claims 1. Addition-crosslinking silicone resin compositions containing A) at least one branched, self-crosslinking organopolysiloxane of the general formula (I)

(RR ⁵ Si0 _{2/2) D} (R ^e Si0 _3/2) T (Si0 _{4/2) Q} (I), wherein R ¹ to R ⁶ independently of one another, monovalent, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, an OH group or a hydrogen atom,  -M, D, T, and Q is a number from 0 to <1,  mean, with the proviso that M + D + T + Q = 1 and Q + T> 0, and with the proviso that one molecule A) is selected as R ¹ to R ^s  at least two alkenyl groups,  - At least two hydrogen atoms, and - At least one aryl group contains wherein the molar ratio of the silicon-bonded alkenyl group-carrying repeating units to the silicon-bonded hydrogen atom-carrying repeating units is at least 0.75; and  wherein the mole fraction of the at least one aryl group-carrying silicon atoms to the total number of silicon atoms is at least 30%; and wherein the molar fraction of the alkyl groups in the total number of silicon-bonded radicals is at most 70%, B) at least 0.1 parts, based on 100 parts A) of at least one Si-H coupler, which contains at least 2 Si-H molecules per molecule Contains bonds and is selected from the following groups: a) organohydrogensilanes of the general formula (II)

in which R ⁷ and R ⁹ independently of one another, monovalent, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, where R ⁷ and R ^{9 are} not an alkenyl group, no OH group and no hydrogen atom,  -H is a hydrogen atom, R ^{8 is} a Cl to C36 hydrocarbylene group which may be interrupted by heteroatoms and such radicals R are always bonded to the silicon atoms with a carbon-silicon bond, or an oxygen atom,  mean,  -g and j can be 0, 1, 2 and 3, -h and i can be 1, 2 and 3,  and g + h = 3 and i + j = 3 are each satisfied, b) organohydrogensiloxanes of the formula (III) [R ¹⁰ _k (H) isio _{1/2] 4} Si (III) wherein R ¹⁰ independently represent monovalent, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, where R ¹⁰ does not denote an alkenyl group, no OH group and no hydrogen atom, -H is a hydrogen atom means  C and 1 have the values 0, 1, 2 and 3, and k + l = 3 is satisfied, C) a sufficient amount of at least one of the addition of Si-bonded hydrogen to aliphatic double bonds promoting catalyst, wherein in the addition-crosslinking silicone resin composition the molar ratio of silicon-bonded alkenyl groups to silicon-bonded hydrogen atoms is between 0.5: 1 and 2: 1. 2. Addition-crosslinking silicone resin compositions according to claim 1 which additionally contains at least one flexiopolymer D) of the general formula (IV), (R ^{1: L} wR ¹² x * SiO _2/2 ) " _* (R ¹¹ _y R ¹² _z Si0 _2/2 ) _{D *} (R ¹³ Si0 _3/2 ) _T * (IV), where R ¹¹ and R ¹² and R ^{13 are} independently, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, and no hydrogen atom; -w and x * each a number 0, 1, 2 or 3, with w + x * = 3; -y and z are each a number 0, 1, 2 or 3, with y + z = 2; -M *, D *, and T * represent a number from 0 to <1, with M * + D * + T * = 1, with the proviso that per molecule D) at least two alkenyl groups as R ¹¹ , and at least one aryl group as R ¹² or R ¹³ is included. 3. Process for the preparation of the addition-crosslinking silicone resin composition according to claim 1 or 2, characterized characterized in that the components A), B) and C or A), B), C) and D) are mixed. 4. Use of the addition-crosslinking silicone resin composition according to claim 1 or 2 as potting compounds in electrical and electronic applications. 5. Use of the addition-crosslinking silicone resin composition according to claim 1 or 2 as potting compounds for the production of LEDs.