Radiation-curable silicone composition

Abstract

The present invention relates to radiation-curable silicone compositions, cured compositions obtained therefrom, and their use as dam and sealing materials in dam and filling applications for electronic components and displays comprising the cured compositions.

Description

[Technical field]

[0001] The present invention relates to radiation-curable silicone compositions, cured compositions obtained therefrom, and their use as dam and seal materials in dam and filling applications for electronic components and displays comprising the cured compositions. [Background technology]

[0002] Generally, in crosslinking silicone compositions, the crosslinking process is carried out by a hydrosilylation reaction, which can be catalyzed, for example, by platinum or another metal of the platinum group, in which an aliphatically unsaturated group reacts with a silicon-bonded hydrogen;

[0003] Typically such compositions contain a Si-alkenyl as component A1), a polyorganohydrogensiloxane with SiH bonds as component B), a catalyst as component C) and additional additives such as fillers as component D).

[0004] For example, U.S. Patent Publication US2018 / 0314352A discloses a one-component silicone material containing no acrylic acid units, which comprises a polysiloxane containing at least two alkenyl groups, a polyhydroxysiloxane having an average of at least two SiH groups per molecule, a silicone resin, a filler, and a photoactive platinum catalyst.

[0005] The cured composition has a variety of different applications. For example, it can be used as a dam material. An example of such a dam material application is described, for example, in International Publication WO2018 / 208348, in which a dam material is provided on the periphery of a first substrate, then another fluid silicone is introduced onto the first substrate, and a second substrate is placed on top of the assembly, whereby the fluid silicone is captured between the two substrates.

[0006] It is also possible to inject fluid silicone in situations where a first and second substrate are positioned one above the other and have a gap between them due to the presence of a dam material.

[0007] The cured compositions are used, for example, in displays, fill and dam applications or for (micro)electronics. Summary of the Invention

[0008] technical challenges When such a cured composition is used as a dam material, the dam material is somewhat flowable until it cures; that is, after the dam material is applied, its height decreases and its width increases due to its flowability between application and curing. This can be detrimental because the decrease in height brings the first and second substrates closer together and the dam material has a larger width. It is desirable to obtain a composition with a good aspect ratio, where aspect ratio refers to the ratio between the height and width of the cured composition.

[0009] When the cured composition is used in a position where it is visible to people, it is often desirable that the cured composition is highly transparent and / or does not have any coloration; i.e., the cured composition should not be "invisible" to people. The cured composition deteriorates over time; this deterioration is highly dependent on the actual environment of the composition. Such deterioration is manifested, for example, by a decrease in transparency and / or a change in color. Even if such changes do not affect other parameters of the composition, they are still undesirable when the cured composition is in a position where it is visible to people. In general, it is desirable to obtain a cured composition with high stability; i.e., a cured composition that does not change in transparency and / or color and / or other changes in visibility even under harsh environments. Preferably, the cured composition should meet these conditions over time at room temperature and / or at high temperature and / or at high temperature and humidity.

[0010] These technical challenges are not adequately addressed and / or resolved by the current state of the art.

[0011] Problem solving means The radiation-curable silicone composition according to the present invention comprises: A1) having at least one alkenyl group, preferably two alkenyl groups, at 20° C. and a shear rate of D=10 s -1 at least one polyorganosiloxane having a viscosity at up to 500 Pa.s; A2) at least one linear polydiorganosiloxane having a complex viscosity of at least 1000 Pa.s, preferably at least 2500 Pa.s, more preferably at least 5000 Pa.s, measured in oscillatory mode at 20° C., selected from the group consisting of linear polydiorganosiloxanes having no alkenyl groups and linear polydiorganosiloxanes having at least one alkenyl group bonded to a silicon atom; B) at least one polyorganohydrogensiloxane having at least one SiH group, preferably at least two SiH groups; and C) at least one radiation-activated catalyst; D) optionally containing one or more accessory ingredients.

[0012] Unless otherwise stated, the viscosities mentioned in this application are determined according to DIN 53019, generally at a shear rate of D = 10 s -1 Complex viscosity is measured at 20 °C with a 1% deformation in oscillatory mode at 1 Hz according to known procedures at 20 °C unless otherwise stated (see for example: https: / / www.tracomme.ch / wordpress / wp-content / uploads / 2018 / 07 / V279-e-iQ-Performing-rheological-tests-in-oscillation-with-the-HAAKE-Viscotester-iQ.pdf). The specified viscosity ranges are intended to include both endpoints.

[0013] Complex viscosity is a frequency dependent viscosity function that is determined by applying a harmonic oscillatory shear stress (see http: / / www1.lsbu.ac.uk / water / rheology.html). When an oscillatory force is applied to a material, the rate of shear strain lags behind the resulting force change by a phase angle φ. This means that φ is zero for an ideal elastic gel and 90° for an ideal viscous liquid. Complex viscosity is defined as: Complex Viscosity = Viscosity - i * Elastic modulus; where "i" denotes the imaginary unit (i 2 =-1); tan(φ) = elastic modulus / viscosity; where φ is the phase angle. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Ingredient A1) The composition of the present invention comprises at least one polyorganosiloxane having at least one, preferably two, unsaturated hydrocarbyl residues (component A1)). Component A1) may comprise one or more polyorganosiloxanes having an average of at least two alkenyl groups. Suitable components A1) can be described by the general formula (Ia): [M a D b T c Q d Z e ] m (Ia) where the subscripts in formula (Ia) represent the ratios of the siloxy units M, D, T and Q, which can be distributed in blocks or randomly in the polysiloxane, each siloxane unit in the polysiloxane can be the same or different, and a=0~10 b=0~2000 c=0~50 d=0~1 e=0~300 m=1~1000 a, b, c, d and m are the viscosity of component A1) at 20°C of 500 Pa.s (shear rate D = 10 s at 20°C). -1) is a value that is less than

[0015] The viscosity of component A1) refers to the viscosity of a single component A1) or of a mixture of component A1). In formula (Ia): M=RSiO 1 / 2 , or M * D=R2SiO 2 / 2 , or D * T=RSiO 3 / 2 , or T * Q = SiO 4 / 2 , The divalent Z is a linking group between the siloxy groups. However, M * , D * or T * and wherein at least one group selected from wherein each R may be the same or different and is selected from optionally substituted alkyl of up to 30 carbon atoms, optionally substituted aryl of up to 30 carbon atoms, poly(C2-C4) alkylene ether with up to 1000 alkyleneoxy units, the group R being free of aliphatic unsaturation, and Here, M * =R 1 p0 R 3~p0 SiO 1 / 2 , D * =R 1 q0 R 2~q0 SiO 2 / 2 , T * =R 1 SiO 3 / 2 , where p0=1 to 3, preferably 1; q0=1~2, and Z is as defined below.

[0016] R is preferably normal, iso, or tertiary alkyl, alkoxyalkyl, C5-C 30 Cyclic alkyl, or C6-C 30aryl, alkylaryl, which groups may be further substituted by one or more O, N, S or F atoms, or a poly(C2-C4) alkylene ether with up to 500 alkyleneoxy units, and the group R is free of aliphatic unsaturation.

[0017] Examples of suitable monovalent hydrocarbon radicals include, preferably, CH3-, CH3CH2-, (CH3)2CH-, CH8H 17 - and C 10 H 21 -, as well as alicyclic radicals such as cyclohexyl, aryl radicals such as phenyl, tolyl, xylyl, and aralkyl radicals such as benzyl and 2-phenylethyl. Preferred monovalent hydrocarbon radicals are of the formula C n F 2n+1 CH2CH2-, where, for example, CF3CH2CH2-, C4F9CH2CH2-, C6F 13 CH2CH2-, C2F5-O (CF2-CF2-O) 1~10 CF2-, F[CF(CF3)-CF2-O] 1~5 -(CF2) 0~2 Such as -, C3F7-OCF(CF3)-, and C3F7-OCF(CF3)-CF2-OCF(CF3)-, where n has a value of 1 to 10. Preferred groups for R are methyl, phenyl, and 3,3,3-trifluoropropyl.

[0018] In formula (Ia), the subscript denotes the number average molecular weight M n Average degree of polymerization P based on n Represents.

[0019] R 1 is selected from unsaturated groups containing C=C-groups (alkenyl groups), such as: normal, iso, tertiary or cyclic alkenyl, C6-C 30 Cycloalkenyl, C8-C 30alkenylaryl, cycloalkenylalkyl, vinyl, allyl, methallyl, 3-butenyl, 5-hexenyl, 7-octenyl, ethylidene-norbornyl, styryl, vinylphenylethyl, norbornenyl-ethyl, limonenyl, optionally substituted with one or more O or F atoms, or C≡C-group-containing radicals (alkynyl radicals), optionally containing one or more O or F atoms.

[0020] The alkenyl radicals are preferably attached to a terminal silicon atom and, due to the ready availability of the alpha and omega dienes used to prepare alkenyl siloxanes, the olefin functionality is at the alkenyl end of the higher alkenyl radical.

[0021] R 1 Preferred groups are vinyl, 5-hexenyl, cyclohexenyl, limonyl, styryl, vinylphenylethyl.

[0022] Z includes, for example, divalent aliphatic or aromatic groups, normal, iso, tertiary or cycloalkylene, arylene or alkylenearyl groups of up to 14 carbon atoms. Z forms a linking element between two siloxy units. The content of Z groups does not exceed 30 mole % of the total siloxy units, preferably does not exceed 20 mole %. Preferably, Z is absent. Preferred examples of suitable divalent hydrocarbon groups Z are preferably -CH2-, -CH2CH2-, -CH2(CH3)CH-, -(CH2)4-, -CH2CH(CH3)CH2-, -(CH2)6-, -(CH2)8- and -(CH2) 18 any alkylene residue such as -; cycloalkylene radicals such as cyclohexylene; arylene radicals such as phenylene, xylene and combinations of hydrocarbon radicals such as benzylene, i.e. -CH2CH2-C6H4-CH2CH2-, -C6H4CH2-. Preferred groups are alpha omega-ethylene, alpha omega-hexylene or 1,4-phenylene.

[0023] Further examples of Z groups include divalent halohydrocarbon radicals; for example, any divalent hydrocarbon group in which one or more hydrogen atoms have been replaced by a halogen, such as fluorine, chlorine, or bromine. Preferred divalent halohydrocarbon residues are of the formula -CH2CH2(CF2), such as, for example, -CH2CH2CF2CH2CH2-. 1~10 Other examples of suitable divalent hydrocarbon ether radicals and halohydrocarbon ether radicals having CH2CH2- include -CH2CH2OCH2CH2-, -C6H4-O-C6H4-, -CH2CH2CF2OCF2CH2CH2-, and -CH2CH2OCH2CH2CH2-.

[0024] In one embodiment, the radiation-curable silicone composition according to the present invention comprises at least one linear polydiorganosiloxane A1) which has at least one alkenyl group on its terminal siloxy groups and no alkenyl groups on its non-terminal siloxy groups.

[0025] In another embodiment of the radiation-curable silicone composition according to the invention, component A1) is preferably at least one linear polydiorganosiloxane of formula (Ia1), [ka] wherein each R is independently selected from a saturated or aromatic organic group; 1 is independently selected from alkenyl groups, and x is ≧0.

[0026] In one embodiment of the invention, the variable x introduced with respect to structural formula (Ia1) above is between 10 and 2000, preferably between 10 and 1000. These ranges are intended to include both end points. The variable x is an average value and can be determined by gel filtration chromatography using polystyrene standards or 1 The number average molecular weight M of any of the polydiorganosiloxanes of formula (Ia1) as determined using H NMR. n It is calculated from:

[0027] Further preferred structures of the alkenyl-terminated polydiorganosiloxanes A1) include: ViMe2SiO(Me2SiO) 10~2000 SiMe2Vi (1a) ViPhMeSiO(Me2SiO) 10~2000 SiMePhVi (1b) ViMe2SiO(Me2SiO) 10~1000 SiMe2Vi (1c) ViMe2SiO(Me2SiO) 10~200 SiMe2Vi (1d) where Vi is a vinyl group, Me is a methyl group, and Ph is a phenyl group. Particularly preferred are linear polydiorganosiloxanes of formula (1a) with x ranging from 10 to 2000, and even more specifically preferred are structures of formula (1c) with x ranging from 10 to 1000. These ranges are intended to include both endpoints.

[0028] It is also possible to use as component A1) resinous polyorganosiloxanes of the formula: {[Q][R 10 O 1 / 2 ] n [M] 0.01~10 [T] 0~50、好ましくは0 [D] 0~1000、好ましくは0} m (Ia2) During the ceremony Q, T, M, and D are as defined above; n=0 to 3, preferably n=0; m is as defined above, R 10 is hydrogen, C1-C such as methyl, ethyl, n-propyl, isopropyl, n-, iso-, and tert-butyl. 25 Alkyl, alkanoyl such as acyl, aryl, -N=CHR such as butanone oxime, alkenyl such as propenyl, provided that M * , D * and T *The most preferred resinous polyorganosiloxanes applied as component A1) contain Q units and M * It has a formula consisting of units, for example: {[Q][M * ] 0.01~10、好ましくは1~10} m (Ia3) Q, M in the formula * and m is as defined above, and m is preferably 1 to 20.

[0029] One preferred embodiment of compound (Ia3) is, for example, represented by the formula [(MeR 1 SiO 0.5 ) k SiO 4 / 2 ] 1~1000 where the subscript k is from 0.3 to 4. Such resinous molecules can contain a significant concentration of up to 10 mol % SiOH- and / or (C1-C6)alkoxySi groups relative to the silicon atoms.

[0030] Particularly preferred resinous polyorganosiloxanes A1) are e.g. Q(M * )4. M2D 10~30 T * 10~30 , M2D * 10~30 T 10~30 and [M * 1~4 Q] 1~40 Contains:

[0031] Component A1) preferably has a viscosity of 0.1 to 500 Pa.s at 20° C. (shear rate D=10 s -1 The viscosity is measured at 100°C.

[0032] The Si-alkenyl or alkenyl content of the alkenyl-terminated polydiorganosiloxanes A1) having formula Ia1) is preferably at least 0.0075 mmol / g and preferably at most 0.8 mmol / g, more preferably at least 0.01 mmol / g and preferably at most 0.7 mmol / g, even more preferably at least 0.010 mmol / g and preferably at most 0.5 mmol / g (mmol of alkenyl bonded to Si per gram of A1).

[0033] The alkenyl content of component A1) is 1 It can be determined by H NMR, see A.L. Smith (Ed.): "Analytical Chemistry of Silicones", J. Wiley & Sons, Inc., 1991, Vol. 112, p. 356 et seq., "Chemical Analysis", J.D. Winefordner (Ed.).

[0034] Component A1) can be used as a single component of one Si alkenyl-containing polysiloxane or as a mixture of at least two thereof.

[0035] In one embodiment of the invention, the radiation-curable silicone composition comprises at least 50 wt. %, preferably at least 60 wt. %, more preferably at least 65 wt. % of component A1), based on the total weight of the composition.

[0036] In one embodiment of the invention, the radiation-curable silicone composition comprises less than 95 wt. %, preferably less than 90 wt. %, more preferably less than 85 wt. % of component A1), based on the total weight of the composition.

[0037] In one embodiment, component A1) is mixed at 20° C. and 10 s -1 at least one polydiorganosiloxane A11) having a viscosity at a shear rate D of from 5 to 300 Pa.s, preferably from 10 to 200 Pa.s, more preferably from 20 to 150 Pa.s.

[0038] In one embodiment of the present invention, the variable x introduced in connection with structural formula (Ia1) above is for the A11) moiety 200 to 2000, preferably 500 to 1200. These ranges are intended to include both endpoints.

[0039] The Si-alkenyl or alkenyl content of the alkenyl-terminated polydiorganosiloxanes A11) having formula Ia1) is preferably at least 0.0075 mmol / g and preferably at most 0.075 mmol / g, more preferably at least 0.01 mmol / g and preferably at most 0.05 mmol / g, even more preferably at least 0.010 mmol / g and preferably at most 0.04 mmol / g (mmol of alkenyl bonded to Si per gram of A11).

[0040] In one embodiment of the invention, the radiation-curable silicone composition comprises at least 50 wt.%, preferably at least 55 wt.%, and more preferably at least 60 wt.% of A11) component, based on the total weight of the composition.

[0041] In one embodiment of the invention, the radiation-curable silicone composition comprises less than 95 wt.%, preferably less than 90 wt.%, and more preferably less than 85 wt.% of component A11), based on the total weight of the composition.

[0042] In another embodiment of the present invention, component A1) is -1 The composition further comprises at least one polydiorganosiloxane A12) having a viscosity at 200° C. of less than 5 Pa.s, preferably from 0.1 to 3 Pa.s, more preferably from 0.2 to 2 Pa.s.

[0043] The Si-alkenyl or alkenyl content of the alkenyl-terminated polydiorganosiloxanes A12) having formula Ia1) is preferably at least 0.1 mmol / g and preferably at most 0.8 mmol / g, more preferably at least 0.125 mmol / g and preferably at most 0.6 mmol / g, even more preferably at least 0.15 mmol / g and preferably at most 0.5 mmol / g (mmol of alkenyl bonded to Si per gram of A12).

[0044] In one embodiment of the invention, the radiation-curable silicone composition comprises from ≧0 to less than 5 wt. %, preferably less than 3 wt. %, more preferably less than 2 wt. % of component A12), based on the total weight of the composition.

[0045] In a preferred embodiment, component A1) comprises a combination of at least one polydiorganosiloxane A11) and at least one polydiorganosiloxane A12), where polydiorganosiloxanes A11) and A12) are as defined above.

[0046] Ingredient A2) The radiation-curable silicone composition according to the invention comprises at least one linear polydiorganosiloxane A2) having a complex viscosity, measured in oscillatory mode at 20° C., of at least 1000 Pa.s and: A2-1) linear polydiorganosiloxanes that do not have functional alkenyl groups; and A2-2) is selected from the group of linear polydiorganosiloxanes having at least one alkenyl group bonded to a silicon atom. The complex viscosity is as defined above.

[0047] The complex viscosity of A2) is at least 1000 Pa.s at 20° C., preferably at least 2500 Pa.s at 20° C., and more preferably at least 5000 Pa.s at 20° C., in the above mentioned vibration modes. In one embodiment of the invention, the complex viscosity of A2) is less than or equal to 25000 Pa.s at 20° C., preferably less than or equal to 15000 Pa.s at 20° C., and more preferably less than or equal to 10000 Pa.s at 20° C., in the above mentioned vibration modes.

[0048] According to one embodiment of the radiation-curable silicone composition according to the invention, component A2) is at least one polydiorganosiloxane of formula (Ib), [ka] In the formula, R and R 1 is as defined above; R 2 is R or R 1 and y≧0, z≧0, the sum y+z being such that the complex viscosity, as defined above, is at least 1000 Pa.s, preferably at least 2500 Pa.s, and more preferably at least 5000 Pa.s, measured at 20° C. in an oscillatory mode as described above.

[0049] In one embodiment, the complex viscosity of the compound according to formula (Ib) is less than or equal to 25000 Pa.s at 20°C in the above mentioned vibrational modes as described above, preferably less than or equal to 15000 Pa.s at 20°C, and more preferably less than 10000 Pa.s at 20°C.

[0050] In one embodiment of the invention, the variable y introduced in connection with structural formula (Ib) above is between 2000 and 10000, preferably between 3000 and 8000. These ranges are intended to include both end points. The variable y is an average value and can be determined by gel filtration chromatography using polystyrene standards or 1The number average molecular weight M of any of the polydiorganosiloxanes of formula (Ib) as determined using H NMR. n It is calculated from:

[0051] In one embodiment of the invention, the variable z introduced in connection with structural formula (Ib) above is from 0 to 350, preferably from 0 to 250, more preferably from 0 to 50. These ranges are intended to include both end points. The variable z is an average value and can be determined by gel filtration chromatography using polystyrene standards or 1 The number average molecular weight M of any of the polydiorganosiloxanes of formula (Ib) as determined using H NMR. n It is calculated from:

[0052] In one embodiment of the radiation-curable silicone composition according to the present invention, component A2) is component A2-1). Component A2-1) is a linear polydiorganosiloxane of formula (Ib), where R 2 =R and z=0. Preferably, in the A2-1) component, R 2 and R is methyl and y is preferably 3000 to 8000.

[0053] In another embodiment of the radiation-curable silicone composition according to the present invention, component A2) is component A2-2). Component A2-2) is a linear polydiorganosiloxane of formula (Ib), in which at least one, and preferably one R of each terminal siloxy group is 2 is R 1 i.e. at least one, and preferably one R of each terminal siloxy group 2 is selected from an alkenyl group. In this A2-2) component, at least one R 2 =R 1 is preferably a vinyl group, y is preferably from 3000 to 8000, R is preferably methyl, and z=0.

[0054] In one embodiment of the present invention, the alkenyl content of compound A2-2) of formula (Ib) is at least 0.002 mmol / g and at most 5 mmol / g, more preferably at least 0.0025 mmol / g and preferably at most 3 mmol / g, even more preferably at least 0.004 mmol / g and preferably at most 2 mmol / g. These values ​​indicate the amount of alkenyl groups (in mmol) in compound A2-2) per mass (in grams) of compound A2-2). Preferably, the alkenyl groups in compound A2-2) are vinyl groups.

[0055] In another embodiment of the radiation-curable silicone composition according to the invention, component A2) is a linear polydiorganosiloxane A2-2) component of formula (Ib), in which at least one, and preferably one R of each terminal siloxy group is 2 is R 1 i.e. at least one, and preferably one R of each terminal siloxy group 2 is selected from an alkenyl group, y is 3000 to 8000, and z ≧ 1. In this A2-2) component, at least one R 2 =R 1 is preferably a vinyl group, y is preferably from 3000 to 8000, and z is preferably from 1 to 250, more preferably from 0 to 50.

[0056] In one embodiment according to the invention, component A2) of the radiation-curable silicone composition according to the invention is a linear polydiorganosiloxane component A2-2) of formula (Ib), in which one R of each terminal siloxy group 2 is R 1 = vinyl, R is methyl, y is preferably 3000 to 8000, and z is preferably 1 to 250, more preferably 0 to 50.

[0057] In a further embodiment of the radiation-curable silicone composition according to the invention, component A2) is a component A2-2) of a linear polydiorganosiloxane of formula (Ib), in which each R 2 is R; R is independently selected from alkyl groups, preferably R 2 =R is methyl, y is preferably from 3000 to 8000, and z > 1.

[0058] In a further preferred embodiment of the radiation-curable silicone composition according to the invention, component A2) is a linear polydiorganosiloxane component A2-2) of formula (Ib), in which each R 2 is R; R is independently selected from alkyl groups, preferably R 2 =R is methyl, y is 3000 to 8000, and z is preferably 1 to 250, more preferably 0 to 50.

[0059] In one embodiment of the radiation-curable silicone composition according to the invention, component A2) is a linear polydiorganosiloxane A2-2) of formula (Ib), in which at least one alkenyl group is bonded to a silicon atom, which compound has a complex viscosity of at least 1000 Pa.s and a Si-alkenyl or alkenyl content of preferably at least 0.002 mmol / g, and preferably at most 5 mmol / g, more preferably at least 0.0025 mmol / g, and preferably at most 3 mmol / g, even more preferably at least 0.004 mmol / g, and preferably at most 2 mmol / g (mmol of alkenyl bonded to Si per gram of A2-2).

[0060] In a preferred embodiment of the present invention, component A2) has a complex viscosity at 20° C. of at least 1000 Pa.s, more preferably this viscosity is in the range of from 2500 to 25000 Pa.s, and even more preferably in the range of from 5000 to 15000 Pa.s.

[0061] In a further embodiment of the invention, when A2) is a mixture of A2-1) and A2-2), the complex viscosity is the complex viscosity of this mixture.

[0062] In one embodiment of the invention, the radiation-curable silicone composition comprises at least 5 wt.-%, preferably at least 8 wt.-%, more preferably more than 10 wt.-%, more preferably at least 12 wt.-%, and even more preferably at least 15 wt.-%, of component A2), based on the total weight of the composition.

[0063] In one embodiment of the invention, the radiation-curable silicone composition comprises up to 50 wt. %, preferably up to 40 wt. %, more preferably up to 35 wt. %, and even more preferably up to 30 wt. % of component A2), based on the total weight of the composition.

[0064] Component B) The radiation-curable silicone composition according to the present invention comprises at least one polyorganohydrogensiloxane (ingredient B)) having at least one SiH group, preferably two SiH groups.

[0065] In one embodiment of the present invention, component B) is selected from one or more polyorganohydrogensiloxanes of general formula (IIa): [M 1 a1 D 1 b1 T 1 c1 Q 1 d1 Z e1 ] m1 (IIa) During the ceremony: M 1 =R3SiO 1 / 2 , and / or M ** D 1 =R2SiO 2 / 2 , and / or D. ** T 1 =RSiO 3 / 2, and / or T ** Q 1 =SiO 4 / 2 , Here, M ** =HR2SiO 1 / 2 , D ** =HRSiO 2 / 2 , T ** =HSiO 3 / 2 Z is as defined above, and R is defined above as a1 is 0.01 to 10, preferably a1 is 2 to 5, more preferably a1 is 2; b1 is 0 to 1000, preferably b1 is 10 to 500; c1 is 0 to 50, preferably c1 is 0; d1 is 0 to 5, preferably d1 is 0; e1 is 0 to 3, preferably e1 is 0; m1 is 1 to 1000, preferably m1 is 1 to 500, more preferably m1 is 1; However, M ** , D ** or T ** There is at least one group selected from:

[0066] Preferably, component B) is selected from polyorganohydrogensiloxanes (or SiH-containing polysiloxanes) having only hydrocarbyl groups as organic residue R as defined above, more preferably only alkyl and aryl groups, even more preferably only methyl or phenyl groups, and most preferably only methyl groups.

[0067] Preferably, the SiH-containing polysiloxane B) has at least 10, preferably at least 15, more preferably at least 20, even more preferably at least 25, and most preferably at least 30 silicon atoms.

[0068] M present in the molecule 1 Unit, D 1 Unit, T 1 Units and Q 1The range of units can encompass almost any value representing a liquid to solid resin. Optionally, these siloxanes can contain additional trace amounts of C1-C6 alkoxy or Si hydroxy groups derived from the synthesis.

[0069] It is also possible to use as component B) resinous polyorganohydrogensiloxanes of the following formula: {[Q 1 ][R 10 O 1 / 2 ] n1 [M 1 ] 0.01~10 [T 1 ] 0~50、好ましくは0 [D 1 ] 0~1000、好ましくは0} m1 (IIb) During the ceremony Q 1 , T 1 , M 1 , D 1 is as defined above, n1=0 to 3, preferably n1=0; m1 is defined above as R 10 is hydrogen, C1-C such as methyl, ethyl, n-propyl, isopropyl, n-, iso- and tert-butyl. 25 alkyl, alkanoyl such as acyl, aryl, -N=CHR such as butanone oxime, alkenyl such as propenyl; However, M ** , D ** and T ** There is at least one group selected from:

[0070] The most preferred resinous polyorganohydrogensiloxanes applied as component B) are 1 Units and M ** It has a formula consisting of units, e.g. {[Q 1 ][M ** ] 0.01~10、好ましくは1~10} m1 (IIc) Q in the formula1 , M ** and m1 are as defined above, and m1 is preferably 1 to 20, more preferably m1=1.

[0071] One preferred embodiment of compound (IIc) is, for example, represented by the formula [(MeHSiO 0.5 ) k SiO 4 / 2 ] 1~1000 where the subscript k is from 0.3 to 4. Such resinous molecules can contain a significant concentration of up to 10 mol % SiOH- and / or (C1-C6)alkoxySi groups relative to the silicon atoms.

[0072] Particularly preferred resinous polyorganohydrogensiloxanes B) are, for example, Q 1 (M ** )4. M 1 2D 1 10~30 T ** 10~30 , M 1 2D ** 10~30 T 1 10~30 , and [M ** 1~4 Q 1 ] 1~40 Contains:

[0073] Component B) preferably has a viscosity of from 2 to 2000 mPa.s, preferably from 1 to 1000 mPa.s, even more preferably from 2 to 100 mPa.s (at 20° C. and a shear rate D=10 s -1 The viscosity is measured at 100°C.

[0074] The SiH content of polyorganohydrogensiloxane B) is preferably at least 0.1 mmol / g, more preferably at least 0.2 mmol / g, and preferably at most 20 mmol / g, more preferably at most 18 mmol / g, even more preferably from 0.1 to 17 mmol / g, and most preferably from 0.2 to 16 mmol / g (mmoles of SiH per gram of component B).

[0075] Component B) can be used as a single component of one SiH-containing polysiloxane or as a mixture of at least two thereof.

[0076] If an increase in the curing rate is required, HMe2SiO 0.5 It is preferred to use some organopolysiloxanes B) having - units or homo-MeHSiO- polymers to adjust the cure speed to shorter times.

[0077] If an even further increase in the cure rate is required, this can be achieved, for example, by increasing the molar ratio of SiH to SiAlkenyl or by increasing the amount of catalyst C).

[0078] In another embodiment of the invention, component B) is a linear polyorganohydrogensiloxane, preferably one having SiH groups on its non-terminal siloxy units, e.g. [ka] wherein R is as defined above, and R 3 is selected from R and H, and p≧0 and q≧1.

[0079] In one embodiment, component B) of formula (IId) has at least 1, more preferably at least 3, and in some cases even more than 15, and even more than 18, SiH groups per molecule.

[0080] In one embodiment, component B) can be used as a mixture of at least one SiH containing polysiloxane of formula (IIc) and at least one SiH containing polysiloxane of formula (IId).

[0081] Component C) The radiation-curable silicone composition according to the present invention comprises at least one radiation-activated catalyst (ingredient C)).

[0082] The catalyst component C) for the hydrosilylation reaction of the composition of the present invention is a compound that promotes the reaction of the silicon-bonded hydrogen atoms of component B) with the silicon-bonded olefinic hydrocarbon substituents of component A). The metal or organometallic compound is generally based on a platinum group metal. Without wishing to be bound by theory, it is believed that catalyst C) contains sigma and pi-bonded carbon ligands, as well as ligands having S, N, or P atoms, complexes of these metals with metal colloids or metal salts. The catalyst can be present on a support such as silica gel or powdered charcoal carrying the metal or a compound or complex of the metal. Preferably, the metal of component C) is any platinum complex compound. Typical platinum-containing catalyst components in the polyorganosiloxane composition of the present invention are platinum(0), (II), or (IV) compounds in any form capable of forming complexes.

[0083] The amount of platinum-containing catalyst component used in the composition of the present invention is not narrowly limited, so long as it is sufficient to accelerate the hydrosilylation between A) and B) at the desired temperature within the required time in the presence of all other components of the composition of the present invention. The exact amount of this catalyst component required depends on the specific catalyst, the amount of other inhibitory compounds, and the ratio of SiH to olefin (Si-bonded), and is not easily predictable. However, for platinum catalyst, the amount can be as small as possible for cost reasons. Preferably, more than 1 part by weight of platinum should be added per million parts by weight of organosiloxane components A1) and B) to ensure cure in the presence of trace amounts of other unidentified inhibitors. For the composition of the present invention, the amount of platinum-containing catalyst component applied is preferably sufficient to provide 1 to 400 ppm, preferably 2 to 200 ppm, more preferably 4 to 100 ppm, by weight of platinum per weight of polyorganosiloxane components A) plus B). According to one embodiment, said amount is at most 20 ppm, more preferably at most 10 ppm, and more preferably at most 8 ppm.

[0084] Component C) is preferably selected from the group of organometallic compounds, salts or metals capable of catalyzing hydrosilylation, as taught in U.S. Pat. Nos. 3,159,601; 3,159,662; 3,419,593; 3,715,334; 3,775,452, and 3,814,730, where the metal is selected from the group of Ni, Ir, Rh, Ru, Os, Pd and Pt compounds.

[0085] Preferably, the transition metal catalyst C) is selected from hydrosilylation catalysts comprising at least one metal selected from the group consisting of platinum, rhodium, palladium, ruthenium and iridium, preferably platinum.

[0086] The photoactivatable catalyst is preferably selected among organometallic compounds, i.e. it comprises a carbon-containing ligand or a salt thereof. In a preferred embodiment, the photoactivatable catalyst C) comprises a metal-carbon bond, and contains a sigma bond and a pi bond. Preferably, the photoactivatable catalyst C) is an organometallic complex compound having at least one metal-carbon sigma bond, even more preferably a platinum complex compound, preferably having one or more sigma-bonded alkyl and / or aryl groups, preferably alkyl groups or alkyl groups. Sigma-bonded ligands include in particular sigma-bonded organic groups, preferably sigma-bonded C1-C6 alkyl, more preferably sigma-bonded methyl groups, sigma-bonded aryl groups, e.g. phenyl groups, sigma-bonded alkyl or aryl groups substituted with Si and O, e.g. trisorganosilylalkyl groups, sigma-bonded silyl groups, e.g. trialkylsilyl groups. Most preferred photoactivatable catalysts include η-organosilyl groups with sigma-bonded ligands, preferably sigma-bonded alkyl ligands. 5 - (optionally substituted) cyclopentadienyl platinum complexes.

[0087] Examples of photoactivatable catalysts include η-diolefin-sigma-aryl platinum complexes as disclosed in U.S. Pat. No. 4,530,879, EP 122008, EP 146307 (corresponding to U.S. Pat. No. 4,510,094 and the prior art documents cited therein), or U.S. Patent Publication No. US 2003 / 0199603, and platinum compounds whose reactivity can be controlled using azodicarboxylates or by using diketonates as disclosed in U.S. Pat. No. 4,640,939.

[0088] Further usable photoactivatable platinum compounds are those selected from the group having ligands selected from diketones, such as benzoylacetone or acetylenedicarboxylic acid esters, and platinum catalysts embedded in photodegradable organic resins.Other platinum catalysts are described, by way of example, in U.S. Pat. No. 3,715,334 or U.S. Pat. No. 3,419,593, European Patent Publication 1672031, and Lewis, Colborn, Grade, Bryant, Sumpter and Scott, Organometallics 1995, 14, 2202-2213, all of which are incorporated herein by reference.

[0089] Photoactivatable catalysts can also be formed in situ in the molded silicone composition by using Pt(0) olefin complexes and adding appropriate photoactivatable ligands to them. However, the photoactivatable catalysts that can be used in the present application are not limited to the above examples.

[0090] In one embodiment of the invention, the radiation-activated catalyst C) is selected from organometallic platinum compounds, preferably from optionally substituted cyclopentadienyl platinum compounds, preferably (η 5 -cyclopentadienyl)-trimethylplatinum complexes and (η 5 -cyclopentadienyl)-triphenylplatinum complexes, most preferably component C) is (methylcyclopentadienyl)-trimethylplatinum(IV).

[0091] The photoactivatable catalyst can be used as is or supported on a support.

[0092] Component D)

[0093] The radiation-curable silicone composition according to the present invention optionally contains one or more auxiliary components (component D)).

[0094] In one embodiment of the invention, the radiation curable silicone composition comprises less than 3 wt % adhesion promoter, preferably less than 1 wt % adhesion promoter, more preferably 0 to 0.1 wt % adhesion promoter.

[0095] The curable polyorganosiloxane composition optionally contains at least one adhesion promoter (D), as defined in the following excerpt from US Pat. No. 9,991,406: "(Component D) is preferably (D1): at least one organosiloxane containing at least one alkoxysilyl group; (D2): at least one organosilane containing at least one alkoxysilyl group; (D3): at least one aromatic organic compound having at least two aromatic moieties and at least one group reactive in hydrosilylation At least one of the following is selected:

[0096] Component (D1) is preferably RHSiO 2 / 2 and R 5 (R)SiO 2 / 2 wherein R is as defined above and may be the same or different, and R 5 is selected from the group consisting of unsaturated aliphatic groups of up to 14 carbon atoms, epoxy group-containing aliphatic groups of up to 14 carbon atoms, cyanurate-containing groups, and isocyanurate-containing groups; and Further comprising at least one unit of formula (3): -O 2 / 2 (R)Si-R 4 -SiR d (OR 3 ) 3-d (3) During the ceremony R is as defined above and may be the same or different; R 3are selected from H (hydrogen) and alkyl radicals having 1 to 6 carbon atoms, which may be the same or different, R 4 is a difunctional optionally substituted hydrocarbyl radical of up to 15 carbon atoms, which may contain one or more heteroatoms selected from O, N and S atoms, bonded to a silicon atom via a Si-C- bond, and d is from 0 to 2.

[0097] Examples of component (D1) include compounds of formulae (3a-3d): [ka] R 11 is R or R 5 , where R, R 3 , R 4 and R 5 are as defined above and may be the same or different, s1=0 to 6, preferably 1 t1=0 to 6, preferably 1 or 2 s1+t1=2 to 6, preferably 2 or 3 However, the compound contains at least one group -(OSi(R)H)- or -(OSi(R)(R 11 )- is present, preferably of the formula: [ka] wherein R, R 3 , R 4 and R 11 is as defined above, and ring positional isomers thereof, the formula: [ka] and ring positional isomers thereof.

[0098] Furthermore, the formula: [ka] is a compound of the formula: R, R 3 , R 4 , R 5 is as defined above, s=0 to 10, preferably =0 to 5 t=0 to 50, preferably =2 to 30 u=1 to 10, preferably =1 s+t+u=≦70 However, the compound contains at least one group -(OSi(R)H)- or -(OSi(R)(R 5 These compounds may contain some amount of Q or T branching groups replacing D units.

[0099] R 5 is selected, for example, from: [ka]

[0100] Component (D2) is preferably selected from compounds of formula (4): X-(CR 6 2) eY-(CH2) e SiR d (OR 3 ) 3-d (4) During the ceremony X is selected from the group consisting of halogens, pseudohalogens, unsaturated aliphatic groups of up to 14 carbon atoms, epoxy-containing aliphatic groups of up to 14 carbon atoms, cyanurate-containing groups, and isocyanurate-containing groups; Y is selected from the group consisting of a single bond, a heteroatom group selected from -COO-, -O-, -S-, -CONH-, and -HN-CO-NH-; R 6 is selected from hydrogen and R as defined above; e is 0, 1, 2, 3, 4, 5, 6, 7, or 8, which may be the same or different; R is as defined above and may be the same or different; R 3are as defined above and may be the same or different, d is 0, 1, or 2.

[0101] Preferred examples of component (D2) include: [ka] [ka] [ka] [ka] where R and d are as defined above.

[0102] Apart from acting as an adhesion promoter, component (D2) can additionally act as an in-situ surface treatment for the filler (E). In order to obtain good adhesion properties at low cost, it is preferred to use a mixture of silanes of component (D2).

[0103] Component (D3) is preferably selected from compounds of formula (3i): [ka] During the ceremony r is 0 or 1, R 7 are groups which may be the same or different and are the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, an alkenylcarbonyloxy group and an aryl group, and formula-E f -Si(OR) 3-d R d where R may be the same or different and d is as defined above. A group of the formula -O-Si(R)2R1, where R and R1 are as defined above, formula-E f the group -Si(R)H, where R is as defined above; where E is a divalent organic group having up to 8 carbon atoms and 0 to 3 heteroatom groups selected from -O-, -NH-, C=O, and -C(=O)O-; f is 0 or 1, and Z is a group: [ka] is selected from, where R 8 is selected from the group consisting of a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl, aryl, alkenyl and alkynyl group; and g is a positive number of at least 2, Here, R 7 and R 8 At least one group selected from is reactive in hydrosilylation.

[0104] Preferred components (D3) include: [ka] [ka] [ka] [ka] [ka] Zr, R in the formula 7 , R 3 , R and d are as defined above."

[0105] Component D4) The curable polyorganosiloxane compositions of the present invention may contain one or more reinforcing fillers, optionally surface-modified. 2 / g or larger BET specific surface area.

[0106] In general, such fillers should be transparent and have high light transmission, if the curable polyorganosiloxane composition is to be cured by irradiation. Fillers include, by way of example, all particulate fillers, i.e. fillers having a particle size smaller than 100 μm, i.e. preferably composed of such particles. They can be silicides, carbides, nitrides, oxides or mineral fillers such as silica. Such fillers are preferably known as reinforcing silicas, which allow the production of elastomers with sufficient transparency for irradiation. Preference is given to reinforcing silicas, which improve the physical properties of the cured encapsulant after crosslinking, in particular those which increase its strength. Examples include reinforcing silicas having a BET specific surface area of ​​50 to 400 m 2 / g of fumed or precipitated silica. Preferably, these fillers are surface hydrophobized. If component D4) is used, its content is 1 to 100 parts by weight, preferably 0 to 70 parts by weight, even more preferably 0 to 50 parts by weight, even more preferably 5 to 45 parts by weight, based on 100 parts by weight of components A) and B).

[0107] BET specific surface area is 50m 2 Fillers exceeding 200 m / g allow the production of silicone elastomers with improved physical properties. From the standpoint of strength and transparency, fumed silica is preferred, and even more preferred silicas are, for example, 200 m 2 Aerosil with a BET specific surface area of ​​more than 1 / g 登録商標 200, 300, HDK 登録商標 N20 or T30, Cab-O-Sil 登録商標MS7 or HS5. As the BET surface area increases, so does the transparency of the silicone mixtures in which these materials are included. Examples of trade names for materials known as precipitated or precipitated silicas include Vulkasil 登録商標 VN3, or FK160 from Evonik (formerly Degussa), or Nipsil from Nippon Silica Industries 登録商標 LP and others.

[0108] BET specific surface area is 50m 2 / g or greater, preferably at least 150m 2 It is preferred to use a silica filler having a BET specific surface area of ​​100 / g. Such compositions are sufficiently transparent to allow light activation if desired.

[0109] The filler D4) may be subjected to any suitable conventional surface treatment with a suitable surface treatment agent, such as hydrophobization with a suitable hydrophobizing agent, dispersion treatment with a suitable dispersing agent, which affects the interaction of the filler with the silicone polymer, for example, affects the thickening action. The surface treatment of the filler is preferably hydrophobization with silanes or siloxanes. This can be carried out in situ by adding water, for example by adding silazanes such as hexamethyldisilazane and / or 1,3-divinyltetramethyldisilazane, and "in situ" hydrophobization is preferred. This can also be carried out with other conventional filler treatment agents and polyorganosiloxane diols with a chain length of 2 to 50 and carrying unsaturated organic radicals, with the purpose of providing reactive sites for the crosslinking reaction.

[0110] Examples of commercially available silicas that have been pre-hydrophobized with various silanes include: Aerosil 登録商標 R972, R974, R976, or R812, or for example HDK 登録商標 Trade names for materials known as hydrophobized precipitated silica or precipitated silica include, for example, Sipernat® from Evonik (formerly Degussa). 登録商標D10 or D15. The rheological properties, i.e. the technological processing properties of the uncured silicone rubber mixtures, can be influenced by the choice of the type of filler, its content and the nature of the hydrophobization.

[0111] Other fillers may be selected from TiO2, nano-TiO2, optical brighteners (such as Tinopal OB) and nano-silica. Silicon dioxide nanoparticles are also known as silica nanoparticles or nano-silica, and have stability, low toxicity and the ability to be functionalized with a range of molecules and polymers. Nano-silica particles are divided into P-type and S-type according to their structure. P-type particles are characterized by a large number of nanopores, have a pore ratio of 0.61 ml / g, and show a higher UV reflectance compared to S-type; the latter also has a relatively smaller surface area. When the filler is nano-silica and is included in the silicone composition according to the present invention, the cured silicone composition will have good transparency for UV curing.

[0112] In one embodiment of the invention, the radiation curable silicone composition contains less than 10% by weight of reinforcing filler, preferably less than 3% reinforcing filler, and more preferably no filler.

[0113] Non-reinforced filler D5): Filler or extender (BET specific surface area <50m 2 Examples of materials that act as a reinforcing filler (Rb / g) are known as non-reinforcing fillers. They include, for example, quartz powder, diatomaceous earth, cristobalite powder, mica, aluminum oxide, and aluminum hydroxide. 2 / g of titanium dioxide or iron oxide, zinc oxide, chalk, or carbon black can also be used as heat stabilizers. These fillers are available under various trade names, e.g. Sicron 登録商標 , Min-U-Sil 登録商標 , Dicalite 登録商標 , Crystallite 登録商標 The BET specific surface area is 50m 2Materials known as inert fillers or extenders, less than 100 μm / g, when used in silicone rubber, advantageously do not contain particles larger than 100 μm (<0.005 wt.%), so that further processing does not cause problems during downstream processing, e.g. passing through sieves or nozzles, or so that the mechanical properties of the manufactured article are not adversely affected.

[0114] Among the opacifying fillers there are also in particular opaque, in particular inorganic, pigments or carbon black. The use of these opacifying fillers is only preferred if pigmentation is required or if a physical function such as thermal or electrical conductivity is required. The use of opaque, non-transparent fillers requires a change in the normal sequence of the activation and shaping steps in the process. Usually, if no filler or a transparent filler is used, the photoactivation through irradiation is carried out after the last shaping process. If an opaque, non-transparent filler is used that inhibits the photoactivation of the photoactivatable catalyst, the photoactivation step is carried out before the opaque, non-transparent filler is mixed in and the mixture is shaped.

[0115] The ratio between the different ingredients In one embodiment of the invention, the radiation-curable silicone composition comprises 50 to 95 parts by weight of A1) and 5 to 50 parts by weight of A2), preferably 60 to 90 parts by weight of A1) and 10 to 40 parts by weight of A2), more preferably 65 to 85 parts by weight of A1) and 15 to 30 parts by weight of A2), based on 100 parts by weight of the total of A1) and A2).

[0116] In one embodiment of the invention, the radiation-curable silicone composition contains 50 to 95 parts by weight of A11) and 5 to 50 parts by weight of A2-2), preferably 60 to 90 parts by weight of A11) and 10 to 40 parts by weight of A2), more preferably 65 to 85 parts by weight of A11) and 15 to 30 parts by weight of A2), based on 100 parts by weight of the total of A11) and A2-2).

[0117] In one embodiment of the present invention, the radiation-curable silicone composition comprises, based on 100 parts by weight of the total of A11) and A2), 0 to 5 parts by weight of component A12), 0.01 to 20 parts by weight of component B), 1 to 100 ppm of component C), and Contains 0 to 10 parts by weight of component D).

[0118] Properties of the Curable Silicone Composition of the Invention In one embodiment of the present invention, the radiation-curable silicone composition is -1 At a shear rate D of at least 150 Pa.s, preferably at least 175 Pa.s, more preferably at least 200 Pa.s, the viscosity being measured using a plate / plate rheology method.

[0119] In one embodiment of the present invention, the radiation-curable silicone composition is -1 At a shear rate D of 1000 MPa, the viscosity is 700 Pa.s.

[0120] In one embodiment of the present invention, the radiation-curable silicone composition is -1 At a shear rate D of at least 150 Pa.s, preferably at least 175 Pa.s, more preferably at least 200 Pa.s, and up to 700 Pa.s. In a preferred embodiment, the radiation-curable silicone composition has a viscosity of at least 10 s at 20° C. -1 At a shear rate D of 300 to 400 Pa.s.

[0121] In one embodiment of the invention, the radiation curable silicone composition comprises less than 10% by weight of resinous polyorganosiloxanes having at least one siloxy group selected from T and Q groups, preferably comprises less than 1% by weight of such resinous polyorganosiloxanes, and more preferably comprises no such resinous polyorganosiloxanes, where the T and Q groups are defined as follows: M=RSiO1 / 2 , or M * D=R2SiO 2 / 2 , or D * T=RSiO 3 / 2 , or T * Q = SiO 4 / 2

[0122] In one embodiment, the radiation curable silicone composition is a ready-to-use one-component system.

[0123] The wavelength used to cure the curable silicone composition of the present invention is not narrowly limited, as long as it is capable of curing the composition within a reasonable time frame.In one embodiment of the present invention, the cured composition is obtained by radiation curing, preferably UV curing.In another embodiment according to the present invention, the wavelength used for curing is in the UV range, for example between 100nm and 500nm.

[0124] Cured Properties of the Curable Silicone Composition of the Invention In one embodiment of the invention, the cured composition provides an aspect ratio of at least 0.5. The aspect ratio refers to the ratio of the height to the width of the UV-cured composition. The width and height are determined, for example, using a Keyence digital microscope. Below this value of 0.5 for the aspect ratio of the radiation-cured composition, some air bubbles may occur or some flow of other liquid compositions may occur. Preferably, the aspect ratio is at least 0.6, more preferably at least 0.65, and even more preferably at least 0.75.

[0125] In one embodiment of the invention, the radiation curable silicone composition has, after curing, a hardness defined within the soft range as measured by penetration up to 75×0.1 mm using a ¼ cone, up to a Shore 00 hardness of 70 (penetration measured according to DIN ISO 2137 and Shore 00 hardness measured according to ASTM D2240-02b).

[0126] In one embodiment of the invention, the radiation curable silicone composition after curing has a transparency of ≥ 65%, preferably ≥ 75%, more preferably ≥ 85%, and even more preferably ≥ 90%, as measured by ASTM D1003 using a BYK haze meter haze-gard-dual.

[0127] In one embodiment of the invention, the radiation curable silicone composition, after curing, has a Yellowness Index (YI) of ≦10, more preferably ≦5, more preferably ≦1. Yellowness Index (YI) is measured according to ASTM E313 using a Konica Minolta CM3600D instrument.

[0128] The radiation curable silicone compositions of the present invention are used, for example, as dam and seal materials in display applications (optical bonding).

[0129] The radiation-curable silicone composition of the present invention is used, for example, in displays.

[0130] The present invention also relates to displays that include the cured silicone composition.

[0131] Working Example To evaluate which compositions would result in a dam material with the desired aspect ratio after curing, the nine compositions shown in the table below were prepared at room temperature (25°C). Each composition was applied in a line onto the substrate using a Nordson XYZ bench robot with a 30cc syringe at 5.34 bar from a 1.6mm nozzle at a discharge speed of 10mm / s. The compositions were then applied using a Panacol metal halide lamp UV H255 at 2 to 4 J / cm. 2 The silicone composition was cured by applying energy of 1000 .mu.m to the silicone composition.

[0132] The ingredients listed in Table 1 below are as follows: Ingredient A11) is heated at 20°C for 10s. -1The viscosity of the composition is either a linear vinyl-terminated dimethylpolysiloxane having a viscosity of 65 Pa.s at a shear rate D of 100 MPa or a linear vinyl-terminated siloxane having a viscosity of 165 Pa.s. Component A2-2a) is a linear vinyl terminated dimethyl-co-(methyl(vinyl)polysiloxane having a complex viscosity of 6000 Pa.s at 20° C. in the oscillatory mode. Component B) is heated at 20°C for 10 seconds. -1 A linear polydimethyl-co-methylhydrogensiloxane (SiH polysiloxane) crosslinker B) having a viscosity of 40 mPa.s at a shear rate D of 100 .mu.m. UV catalyst C1) is 20℃ for 10s. -1 The composition consists of 500 ppm of a UV catalyst, namely (methylcyclopentadiene)trimethylplatinum or TMMCpPt(IV), in a vinyl terminated polydimethylsiloxane A11) having a viscosity of 10 Pa.s at a shear rate D of 100 rpm. UV catalyst premix C2) is heated at 20℃ for 10s. -1 The mixture is 1 g of TMMCpPt(IV) in 99 g of linear vinyl-terminated polydimethylsiloxane A12) having a viscosity of 1 Pa.s at a shear rate D of 100 s.

[0133] The above components are mixed to obtain a radiation-curable silicone composition according to the present invention in which the ratio of component A11) (having vinyl ends and vinyl groups in the chain as pendant groups) to vinyl polydiorganosiloxane A2-2a) is within the range of 86:13 to 60:35, and the composition has a viscosity (shear rate of 10 s at 20° C.) required for application to a dam for a display with the expected fluidity. -1 at greater than 180 Pa.s) and aspect ratios of greater than about 0.5 are obtained (Table 1).

[0134] [Table 1]

[0135] Different compounds A2-1), A2-2a) to A2-2d) were tested in the following radiation-curable silicone compositions according to the invention, cured under the conditions described above and set out in Table 2 below (parts by weight).

[0136] [Table 2]

[0137] In Table 2 above, "Initial Hardness" refers to the hardness measured exactly 2 minutes after irradiation. "Final Hardness" refers to the hardness measured after 1 day; i.e., the point at which the hardness becomes constant.

[0138] Surprisingly, the inventors have found that different types of linear polydiorganosiloxanes A2-1) or A2-2a) to A2-2c) having a complex viscosity of 6000 Pa.s at 20°C and in vibration mode, or A2-2d having a complex viscosity of 3000 Pa.s, at 25% by weight in the radiation curable silicone composition according to the invention, produce dams with an aspect ratio of more than 0.5. Although Example 14 according to the invention shows some haze, for applications such as electronic component sealing applications, the silicone composition according to the invention can still be used, since for this type of application a high level of transparency is not required.

[0139] In the following examples, from Example 15-1 to Example 15-6, different amounts of UV catalyst C2) were used. The amount in ppm is related to the platinum metal content and ranges from 6 to 20 ppm platinum (Table 3).

[0140] [Table 3]

[0141] The radiation-curable silicone composition according to the invention according to Table 3 is used as a ready-to-use one-component package for dams and then 3 J / cm 2The viscosity of the radiation-curable silicone compositions according to the invention (as a ready-to-use one-component package), the aspect ratio of their cured products, and their hardness measurements can be found in Table 4.

[0142] [Table 4]

[0143] From Table 4, it can be seen that the concentration change of additives such as UV-activated catalyst C2) and SiH crosslinker B) in the silicone composition of the present invention in Example 15-1 to Example 15-6 affects the hardness of the UV-cured silicone composition used in the dam according to the present invention. After being applied to the dam and cured, the silicone compositions of the present invention all have a transparency of more than about 90% and low yellowness (less than 0.4). These properties are very useful for application in displays.

[0144] Different silicone compositions of the present invention, Examples 15-1 to 15-6, were left at different temperatures from room temperature (25° C.) to 40° C. or 100° C., and at 85° C. / relative humidity 85% (rH) for 1000 hours. The transmittance (%) and yellowness index (YI) after 1000 hours were measured, and the results are shown in Tables 5a and 5b, respectively.

[0145] [Table 5a] [Table 5b]

[0146] Although the radiation curable silicone compositions of the present invention of Examples 15-1 to 15-6 show a slight increase in yellowness YI with increasing temperature or in the presence of 85% relative humidity, the stability test results for these one-component addition and radiation curable silicone compositions of the present invention show that they can be used for a long time without losing properties. As expected, the radiation curable silicone compositions of the present invention of Examples 15-5 and 15-6 show the largest increase in YI under the above conditions. This is presumably due to the high amount of Pt metal contained in the UV catalyst C2), i.e., 20 ppm used in these examples. The preferred concentration of Pt used would be less than 20 ppm, preferably less than 15 ppm, more preferably less than 10 ppm or less than 10 ppm.

[0147] To test the compatibility of the radiation curable silicone composition of the present invention with liquid optically clear adhesive (LOCA) materials used in displays, Momentive's InvisiSil 登録商標 The following experiments were carried out for each of Examples 15-1 to 15-6 of the radiation-curable silicone composition of the present invention using SN3001 (a two-component, high-elongation silicone gel used in optical bonding applications that goes from a soft, tacky gel to a touch-dry state in about 30 minutes at room temperature with the addition of a curing agent). A dam using one of these compositions of the present invention is first UV-cured. For example, the composition of Example 15-1 is dispensed onto glass at a thickness of about 1 mm, and then exposed to a Panacol metal halide lamp UV H255 (3 J / cm 2 ) and UV cured. The product used as the LOCA material is InvisiSil 登録商標 SN3001 was applied to the top side and covered with a second layer of glass. The sample stack was left at room temperature for one day. The samples were analyzed after aging (1000 hours at different temperatures: room temperature (25°C), 40°C, 100°C or 85°C / 85% relative humidity) to determine if a dam was visible if a LOCA was present (see Table 6 below, with the ranking as follows: visible (-) or not visible (++)). [Table 6]

[0148] The radiation curable silicone compositions according to the present invention of Examples 15-1 and 15-2 are invisible and suitable for display applications (optical coupling). When high Pt catalyst content was used as in Examples 15-5 and 15-6, the rings of the dams prepared for testing were InvisiSil 登録商標 Visible after encapsulation with SN3001 product. These two other compositions are more suitable for applications where invisibility of the dam material is not required, such as sealants, electronic components / components around which the dam is applied, boards, etc.

[0149] Embodiment 1. A radiation curable silicone composition comprising: A1) having at least one alkenyl group, preferably two alkenyl groups, at 20° C. and a shear rate of D=10 s -1 at least one polyorganosiloxane having a viscosity of up to 500 Pa.s at A2) at least one linear polydiorganosiloxane having a complex viscosity of at least 1000 Pa.s, preferably at least 2500 Pa.s, more preferably at least 5000 Pa.s (measured in oscillatory mode at 20° C.) and selected from the following group: Linear polydiorganosiloxanes A2-1) that do not contain alkenyl groups, and Linear polydiorganosiloxanes A2-2) having at least one alkenyl group bonded to a silicon atom B) at least one polyorganohydrogensiloxane having at least one SiH group, preferably at least two SiH groups, and C) at least one radiation-activated catalyst; D) A radiation-curable silicone composition, optionally including one or more accessory ingredients.

[0150] 2.A1) is at least one linear polydiorganosiloxane of formula (Ia1), [ka] wherein each R is independently selected from a saturated or aromatic organic group; 1 is independently selected from alkenyl groups, and x is ≧0.

[0151] 3. A2) is at least one linear polydiorganosiloxane of formula (Ib), [ka] In the formula, R and R 1 is as defined above; R 2 is R or R 1 wherein y≧0 and z≧0. Component A2) is a linear polydiorganosiloxane, in which at least one, preferably at least two R 2 is R 1 and preferably R 2 =R 1 The radiation-curable silicone composition according to any of the previous embodiments, wherein is vinyl.

[0152] 4. A radiation-curable silicone composition according to any of the previous embodiments, wherein component A1) comprises at least one polydiorganosiloxane A11) having a viscosity at 20° C. of 5 to 300 Pa·s, preferably 10 to 200 Pa·s, more preferably 20 to 150 Pa·s.

[0153] 5. A radiation-curable silicone composition according to any of the previous embodiments, wherein component A1) comprises at least one polydiorganosiloxane A12) having a viscosity at 20° C. of less than 5 Pa·s, preferably from 0.1 to 3 Pa·s, more preferably from 0.2 to 2 Pa·s.

[0154] 6. A radiation-curable silicone composition according to any of the previous embodiments, wherein component A1) comprises at least one polydiorganosiloxane A11) and at least one polydiorganosiloxane A12).

[0155] 7. A radiation curable silicone composition according to any of the previous embodiments, wherein component A2) has a complex viscosity of at least 1000 Pa.s at 20°C and in vibration mode, the complex viscosity preferably being in the range of from 1000 to 15000 Pa.s, preferably from 2500 to 10000 Pa.s, more preferably from 3000 to 8000 Pa.s.

[0156] 8. The silicone composition is heated at 20°C and 10s -1 The radiation-curable silicone composition according to any of the previous embodiments, having a viscosity at a shear rate D of at least 150 Pa.s, preferably at least 175 Pa.s, more preferably at least 200 Pa.s.

[0157] 9. The silicone composition is heated at 20°C and 10s -1 The radiation-curable silicone composition according to any of the previous embodiments, having a viscosity of up to 700 Pa.s at a shear rate D of 1000 .mu.m.

[0158] 10. A radiation-curable silicone composition according to any one of embodiments 2 to 10, wherein component A11) is formula Ia) in which the value of x is from 200 to 2000, preferably from 500 to 1200.

[0159] 11. A radiation-curable silicone composition according to any one of embodiments 3 to 11, wherein component A2) is in formula Ib) where the value of y is from 2500 to 10000, preferably from 3000 to 8000.

[0160] 12. A radiation-curable silicone composition according to any one of embodiments 3 to 12, wherein component A2) is of formula Ib) in which the value of z is from 0 to 350, preferably from 0 to 250, more preferably from 0 to 50.

[0161] 13. A radiation-curable silicone composition according to any of the previous embodiments, comprising at least 5 wt.-%, preferably at least 8 wt.-%, more preferably at least 12 wt.-%, and even more preferably at least 15 wt.-% of component A2), based on the total weight of the composition.

[0162] 14. A radiation-curable silicone composition according to any one of embodiments 5 to 14, comprising at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight of component A11), based on the total weight of the composition.

[0163] 15. A radiation-curable silicone composition according to any one of embodiments 6 to 15, comprising from ≥0 to less than 5 wt.-%, preferably less than 3 wt.-%, more preferably less than 2 wt.-%, of component A12), based on the total weight of the composition.

[0164] 16. A radiation-curable silicone composition according to any one of embodiments 5 to 16, comprising 50 to 95 parts by weight of A11) and 5 to 50 parts by weight of A2), preferably 60 to 90 parts by weight of A11) and 10 to 40 parts by weight of A2), more preferably 70 to 85 parts by weight of A11) and 15 to 35 parts by weight of A2), based on 100 parts by weight of the total of A11) and A2).

[0165] 17. Based on 100 parts by weight of the sum of A11) and A2): 0 to 5 parts by weight of component A12), 0.01 to 20 parts by weight of component B), 1 to 100 ppm of component C) based on A and B), and 18. The radiation-curable silicone composition according to any one of embodiments 6 to 17, comprising from 0 to 10 parts by weight of at least one component D).

[0166] A radiation curable silicone composition according to any of the previous embodiments, comprising less than 18.3 wt.% filler, preferably less than 1% filler, and more preferably no filler.

[0167] 19. T group (or RSiO3 / 2 ) and Q group (or SiO 4 / 2 %, preferably less than 1 wt. % of said resinous polyorganosiloxanes, and more preferably no said resinous polyorganosiloxanes.

[0168] 20. A radiation-curable silicone composition according to any of the previous embodiments, wherein the radiation-activated catalyst C) is selected from organometallic platinum compounds, preferably optionally substituted cyclopentadienyl platinum compounds, most preferably component C) is trimethyl(methylcyclopentadienyl)platinum(IV).

[0169] 21. Component B) is selected from linear polyorganohydrogensiloxanes, preferably linear polyorganohydrogensiloxanes having SiH groups on their non-terminal siloxy units, such as [ka] where R is as defined above and R 3 A radiation-curable silicone composition according to any of the previous embodiments, wherein is selected from R and H, and p≧0 and q≧1.

[0170] 22. A radiation-curable silicone composition according to any of the previous embodiments, wherein component D) is selected from the group of reinforcing fillers, non-reinforcing fillers, and the like, and mixtures thereof, preferably a non-reinforcing filler.

[0171] 23. A cured composition produced by curing a silicone composition according to any of the previous embodiments with UV light at a wavelength selected from 100 to 500 nm.

[0172] 24. The hardened composition according to embodiment 23, having an aspect ratio (=height / width) of at least 0.5.

[0173] 25. A cured composition obtained by radiation curing of a silicone composition according to any of the previous embodiments.

[0174] 26. The cured composition according to embodiment 24 or 25, having a Shore hardness penetration of 35 to 70 and a Shore hardness 00 of 5 to 70 (Shore hardness penetration is measured according to standard DIN ISO 2137, Shore hardness 00 is measured according to ASTM D2240-02b).

[0175] 27. The cured composition according to embodiment 24, having a transparency of ≧65%.

[0176] 28. Use of a silicone composition according to any of the previous embodiments as a dam and seal material in optical bonds in electronic components.

[0177] 29. A display or sealant comprising a cured silicone composition according to embodiment 24 or 25.

Claims

1. 1. A radiation-curable silicone composition comprising: A1) having at least one alkenyl group, preferably two alkenyl groups, at 20°C and a shear rate D = 10 s －１ at least one polyorganosiloxane having a viscosity of up to 500 Pa.s at A2) at least one linear polydiorganosiloxane having a complex viscosity of at least 1000 Pa.s, preferably at least 2500 Pa.s, more preferably at least 5000 Pa.s (measured in oscillatory mode at 20°C) and selected from the following group: Alkenyl-free linear polydiorganosiloxanes A2-1), and Linear polydiorganosiloxanes A2-2) having at least one alkenyl group bonded to a silicon atom B) at least one polyorganohydrogensiloxane having at least one SiH group, preferably at least two SiH groups, and C) at least one radiation-activated catalyst; D) A radiation-curable silicone composition, optionally containing one or more auxiliary ingredients.

2. A1) is at least one linear polydiorganosiloxane of formula (Ia1), 【Chemical 23】 wherein each R is independently selected from saturated or aromatic organic groups, and each R １ 2. The radiation-curable silicone composition according to claim 1, wherein is independently selected from alkenyl groups and x is ≥ 0.

3. A2) is at least one linear polydiorganosiloxane of formula (Ib): 【Chemistry 24】 wherein R and R １ is as defined above; R ２ is R or R １ 2. The radiation-curable silicone composition according to claim 1, wherein y is ≧0 and z is ≧0.

4. Component A2) is a linear polydiorganosiloxane, in which at least one, preferably at least two R ２ is R １ and preferably R ２ =R １ The radiation-curable silicone composition according to claim 1 , wherein is vinyl.

5. 2. The radiation-curable silicone composition according to claim 1, wherein component A1) comprises at least one polydiorganosiloxane A11) having a viscosity at 20°C of from 5 to 300 Pa·s, preferably from 10 to 200 Pa·s, more preferably from 20 to 150 Pa·s.

6. 2. The radiation-curable silicone composition according to claim 1, wherein component A1) comprises at least one polydiorganosiloxane A12) having a viscosity at 20°C of less than 5 Pa·s, preferably from 0.1 to 3 Pa·s, more preferably from 0.2 to 2 Pa·s.

7. 2. The radiation-curable silicone composition according to claim 1, wherein component A1) comprises at least one polydiorganosiloxane A11) and at least one polydiorganosiloxane A12).

8. 2. A radiation-curable silicone composition according to claim 1, wherein component A2) has a complex viscosity of at least 1000 Pa.s at 20°C and in vibration mode, the complex viscosity preferably being in the range of from 1000 to 15000 Pa.s, preferably from 2500 to 10000 Pa.s, more preferably from 3000 to 8000 Pa.s.

9. The silicone composition was －１ and / or has a viscosity at a shear rate D of at least 150 Pa.s, preferably at least 175 Pa.s, more preferably at least 200 Pa.s at 20°C and 10 s －１ 2. The radiation-curable silicone composition according to claim 1, having a viscosity of up to 700 Pa.s at a shear rate D of 1000 Pa.s.

10. 6. A radiation-curable silicone composition according to claim 5, wherein component A11) has formula Ia) in which the value of x is from 200 to 2000, preferably from 500 to 1200.

11. 4. A radiation-curable silicone composition according to claim 3, wherein component A2) has formula Ib) in which the value of y is from 2500 to 10000, preferably from 3000 to 8000, and the value of z is from 0 to 350, preferably from 0 to 250, more preferably from 0 to 50.

12. Component B) is selected from linear polyorganohydrogensiloxanes, preferably linear polyorganohydrogensiloxanes having SiH groups on their non-terminal siloxy units, such as: 【Chemistry 25】 where R is as defined above and R ３ 2. The radiation-curable silicone composition according to claim 1, wherein is selected from R and H, and p≧0 and q≧1.

13. A cured composition prepared by curing a silicone composition according to any one of claims 1 to 12 with UV light at a wavelength selected from 100 to 500 nm.

14. 13. Use of a silicone composition according to any of claims 1 to 12 as a dam and seal material in optical bonding of electronic components.

15. A display or sealant comprising the cured silicone composition according to claim 13.

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