TWI323735B - A silicone compound and application thereof - Google Patents

Description

1323735 IX. Description of the Invention: [Technical Field] The present invention relates to an anthrone compound and a composition thereof, which are applied to a substrate, an adhesive, an optical waveguide, a lens, and a security in an electronic/optoelectronic/optical element. The composition such as vine film and encapsulating material has good transparency, low linear expansion coefficient 'high hardness and high heat resistance', and is particularly suitable for the package of light-emitting diodes (LEDs). [Prior Art] In response to the demand for light/small electronic/optoelectronic/optical products, many research efforts have been made to improve the technical development of thermal and transmissive components in such products. Taking LED packaging materials as an example, from the point of view of practical application, high-power LED components with simple installation and relatively small volume will replace traditional low-power LED components in most lighting applications. In order to meet the needs of lighting, it is necessary to concentrate the light energy of many LEDs to meet the design requirements of lighting. The disadvantage is that the wiring is complicated and the heat dissipation is not easy. In order to balance the current-voltage relationship between the LEDs, it is necessary to design a complicated power supply. In contrast, high-power LED components are much larger than the sum of low-power lED components. The power supply circuit is relatively simple, the heat dissipation structure is perfect, and the physical characteristics are stable. Therefore, the power of high-power LED components replaces the low-power LED components into semiconductors. Lighting components are an inevitable trend. For the packaging method of high-power LED components, it is not easy to apply the traditional low-power method and packaging materials, large dissipated power, large heat, high light efficiency 5 P02940051TW (the case number 〇5P〇5 i8) 1323735 = see Some packaging materials, packaging equipment and packaging processes have proposed higher epoxy resin packaging materials with epoxy resin as the mainstream, electrical properties, physical properties, metal adhesion but generally used for high-power led or partial white light Led element r is prone to yellowing deterioration when it encounters high heat or uv, affecting the component, and is replaced by the lithene resin which is better in heat and uv, but the difference is too large, the expansion coefficient is too large, the hardness is poor, etc. U.S. Patent No. 6,632,892, wherein the coffee encapsulating material composition takes the structure of the two t structures as (4) the compound 'since the hardness of the compound is low, the servant character π ·+, and the coefficient of linear expansion is large, when the temperature changes, The

Seal 2: The change is big.曰Patent No. JP61_127723, wherein the [the ketone-based compound of the ED has low polarity and surface energy, is incompatible with the inter-resin, is not easy to mix, and is necessary to increase it? Firstly, it has been upgraded; therefore, it is difficult to improve the above-mentioned conventional packaging materials: I Ming developed a compound and its composition to improve the defects of the resin and epoxy resin, and both The advantages are really necessary. [Invention] In view of the continuous advancement of science and technology and living functions, the demand for electronic, optoelectronic and optical products is light and thin, so the heat resistance standards of electronic, optoelectronic and optical components continue to increase, while the photoelectric and optical components are at high temperatures. Or under UV irradiation conditions, the light transmittance is also required to maintain a certain level. The object of the present invention is to provide an anthrone compound which is a Siic-containing compound having a Si-H functional group at the end of a molecular chain or a side chain (silic) 〇ne) is a main structure with an unsaturated functional group and two epoxy functional groups of isocyanurate ^ P02940051TW (Our Office No. 05P0518) 6 1323735 (isocyanurate) compound to obtain an epoxy functional group An amine compound which is a colorless, transparent liquid. σ Another object of the present invention is to provide a composition having optical and/or thermosetting properties, a substrate, an adhesive, an optical waveguide, a lens, a protective film, a packaging material, and the like applied to an electronic/optoelectronic/optical element. The composition has good transparency, low coefficient of linear expansion, high hardness and high heat resistance after hardening, and is particularly suitable for packaging of light-emitting diodes (LEDs).

In order to achieve the above object, the present invention provides an anthrone compound having a chemical formula as shown in (I):

I

fi—0jSi—oj-Si—r5 B R2 m (i);

Wherein m and n are 〇 or a positive integer, but m and n are not 0 at the same time; !^, R2, R3, Κ·4, R5, A and B are independently nitrogen, halogen, and unsubstituted Ci~C6 a straight or branched alkyl, cycloalkyl or alkoxy group, substituted with dentate (^~(: 6 straight or branched alkyl, cycloalkyl or alkoxy, un An aromatic group substituted or substituted with dentate, a heteroaryl group which is unsubstituted or substituted with a halogen or a substituent represented by the formula (H)

Wherein R6 is independently hydrogen, halogen, unsubstituted (^~(:6 straight chain or 7 P02940051TW (Oh. 05P0518) branched alkyl, cycloalkyl or alkoxy, substituted by halogen (^~(^ is a straight or branched chain, cyclohexyl or decyloxy, unsubstituted or halogen-substituted aromatic group, unsubstituted or heteroaryl substituted with dentate; R7 is independently Unsubstituted c〇~c6 linear or branched alkyl, cycloalkyl or alkoxy, linear or branched alkyl, cycloalkyl or An alkoxy group, an unsubstituted or halogen-substituted aryl group, an unsubstituted or halogen-substituted heteroaryl group or a carboxyl group. At least one of A and B of the above formula (I) is a substituent represented by the above formula (II). The present invention further provides a composition having light and heat hardening properties, comprising: 100 parts by weight of the aforementioned anthrone compound; and a reaction triggering agent. In a preferred embodiment of the present invention, the foregoing light and The composition of the thermosetting property may further comprise from 0.1 to 9900 parts by weight of the epoxy compound. In a preferred embodiment, the composition having optical and thermosetting properties may further comprise an additive, wherein the additive is a surfactant (for example, an antifoaming agent, a flat agent), a dye, a plasticizer, a thermal stabilizer, a UV stabilizer, a refractive index regulator, a adhesion imparting agent, a solvent, an epoxy resin other than the chemical formula (I), or a mixture thereof. A preferred embodiment of the present invention, wherein the reaction accelerator is a thermal hardener, Containing amine compounds, acid compounds, phenolic compounds, alcohol compounds, acid anhydride compounds, guanamine compounds, thiol compounds, boron trifluoride amine complexes, urethane compounds, isocyanurate A compound or a mixture thereof. Another preferred embodiment of the present invention, wherein the reaction triggering agent is a photohardening initiator, which comprises an aromatic hydrocarbon aryldiazonium salt, a diaryl hydrocarbon iodide salt P02940051TW (Our Office No. 05P0518) g 1323735 (diaryliodonium salts), triaryl sulphonium salts, triaryl sulfonate (triarylphosphonium salts), triarylselenonium salts, dialkylphenacylsulphonium salts, disulfo-4-alkylbenzene sulfides (dialkyl-4) -hydroxyphenylsulphonium salts), sulphonic acid esters, silanol-aluminium complexes, ferroceneium salts or mixtures thereof. 1 Another preferred embodiment of the present invention, wherein the reaction stimulating agent is capable of adding a catalyst-promoting reaction, wherein the catalyst comprises an amine compound, an imidazole, an aromatic aryl or an alkane phosphorus. (alkyl phosphonium) compound, tetrabutyl ammonium bromide, 2-methyl-4-imidazole, triphenyl phosphine, benzo Benzyldimethylamine, triethanolamine or a mixture thereof. P The present invention provides an anthrone compound and a composition having photohardening properties, which are formulated into a thermosetting and/or photohardening composition by using a chelating oxygen group, which has enhanced hardness, increased glass transition temperature, The advantage of lowering the coefficient of linear expansion is 'to improve the heat resistance and weather resistance of the composition by introducing an isocyanurate group. The method of the present invention has better processability than the prior art. And light transmission, effectively improving the lack of drawbacks and drawbacks of the prior art 'its application materials for optical / optoelectronic products. [Embodiment] The present invention provides a fluorenone compound, and a composition containing the compound having a hardening property of heat/light P02940051TW, No. 5P〇518) 9 1323735, which can be applied to electronic/photoelectric/ The substrate, the adhesive, the optical waveguide, the lens, the protective film, the encapsulating material and the like in the optical element are particularly suitable for a light emitting diode (LED) package. This composition has good transparency after hardening 'low linear expansion coefficient, high hardness and high heat resistance. The composition containing the above-mentioned alkaloid compound contains: (A) an anthrone compound: the anthrone compound is a main structure having a Si-H functional group-containing ketone compound at the end of the molecular chain or a side chain, and Reaction of an unsaturated functional group with two epoxy functional isocyanurate compounds (see the following chemical formula (m)), by reaction of an unsaturated functional group with a si-H functional group After the knot, 1 obtain an anthrone compound having an epoxy functional group (see chemical formula; and a reaction accelerator: a thermal hardener, or a photohardening initiator).

(ΙΠ) The following is a description of the invention and the features of the present invention. The present invention is not intended to be a detailed description of the present invention. And in the range 'When it can be used as a variety of examples P02940051TW body number is still 1323735 眚 Example 1: ketone compound 1 preparation of 1-propanyl-3,5-epoxyglyceryl ether isocyanuric acid Ester, a little pt catalyst, Si-H functional group-containing oxalyl compound k (Si-H concentration 0.694 (10 2 mol/g) 'viscosity 15~20 cps) and solvent toluene (toluene) placed in a single-mouth reaction bottle The reaction was refluxed at 110 ° C for 4 hours, and FT-IR was sampled to confirm that the Si-H functional group peak disappeared at 2140 cm·1, and then concentrated under reduced pressure to obtain the oleanone compound 1, as shown in the following Table 1. Soil rotation example 1: Anthraquinone compound 2 is prepared in the same manner as in the first embodiment, using the prior art Allyl glycidyl ether plus a little Pt catalyst, Si-H functional group嗣Compound h (Si-H concentration 0.694 (10 2 mol / g) 'viscosity 15~20cps) and solvent toluene, placed in a single-mouth reaction flask, reflux reaction at 110 ° C, continuous reaction for 4 hours 'sampling FT-IR It was confirmed that the Si-H functional group peak 2140 cm-i disappeared, and then concentrated under reduced pressure to obtain the oleanone compound 2 as an experimental control group of the composition of the present invention, as shown in the following Table 1. f Example 2: Preparation of anthrone compound 3 1-propyl-3,5-epoxyglyceryl isocyanuric acid g, a little pt catalyst, Si-H functional group-containing oxalate compound side (Si -H concentration 〇.528 (10·2 mol/g) 'viscosity 10~13 cps) and solvent toluene, placed in a single-mouth reaction flask, refluxing at 110 ° C 'continuous reaction for 4 hours, sampling FT_IR, determining Si- The H functional base peak 2140CHT1 disappeared and then concentrated under reduced pressure to give the oxazolone compound 3' as shown in the following Table 1. 11 P02940051TW (Our Office Case 05P0518) 1323735

Table 1. Synthetic components and properties of the compound. Table 8 Compound 1 Compound 2 Compound 3 SiH-containing compound Mengnet compound anthrone compound Si-H Concentration 〇.694 (10·2 mol/g), viscosity 15~20cps 10 10 oxalate compound side: Si-H concentration 0·528 (10·2 mol/g), viscosity 10~13cps 10 Compound containing C=C and epoxy functional group 1-propenyl-3,5-epoxyglycerol L-allyl-3,5-diglycidyl-isocyanurate 19.5 18 Allyl glycidyl ether - 8.3 - solvent toluene 30 13.3 14 modified epoxy Quantities (EEW) 248 244 282 Thermal loss temperature 7d (weight loss 5%) 340 254 356 Note: The thermal decomposition temperature is obtained by thermogravimetric analysis (TGA). By 20. (: heating up to 850t, heating rate 20 °C / min, in air atmosphere. Comparing the thermal inferior temperature of the fluorenone compounds 1, 2 and 3, the fluorenone compounds 1 and 3 are higher than the fluorenone compound 2 (control group) 86 °c and 102. 〇. It is known that the ketone compound modified with 1-propenyl-3,5-epoxyglyceryl ether isocyanurate has heat resistance higher than that of general allyl glycidyl ether. The modifier is excellent. Example 3: The oxime compound containing the oleanone compound 1 and the epoxy resin: bisphen 〇 1A diglycidyl ether (EPON 828), Different weight ratios 1/1〇, 1/5, 12 P02940051TW (Our Case No. 05P0518) 1323735 1/1, 5/1, 10Π mixed, plus the same equivalent number of anhydride compounds: methylhexahydrophthalic anhydride , MeHHPA) and 0.1 wt% of the catalyst: tetrabutyl ammonium bromide (TBAB) is uniformly mixed, and the composition is shown in Table 2. Example 4: Composition containing the compound of the linalone 1 Three mixing steps, anthrone compound 1 and epoxy resin hydrogenated bisph Enol A diglycidyl ether (HBPA) 'According to different weight ratios of 1/10, 1/5, 1/1, 5/1, 10/1, plus the same equivalent number of anhydride compounds: mercapto hexahydrophthalic anhydride (MeHHPA) It is uniformly mixed with 0.1 wt% catalyst: tetrabutylammonium bromide (TBAB), and the composition is shown in Table 2. Example 5: The composition containing the mash compound 3 will be 0.9 g of the compound 3. 0.1 g epoxy resin EpoxyCyclohexylPOSS® (EP0408, Hybrid Plastics), 0.05 g photoinitiator UVI-6976 (Dow Chemical), mixed with a small amount of solvent, spin coated on glass, exposed to 500 mJ/cm2 with a UV exposure machine, then After baking at 150 ° C for 1 hr, the glass transition temperature rg of the cured product was measured to be 138 ° C. Comparative Example 2: Mixing procedure of the composition containing the ketone compound 2 and the above Example 3, the fluorenone compound 2 and the ring Oxygenated resin bisphenol A diglycidyl ether (HBPA), mixed in different weight ratios of 1/10, 1/5, 1/1, 5/1, 10/1, plus the same equivalent number of anhydride compounds: methyl hexahydrophthalic anhydride (MeHHPA) is uniformly mixed with 0.1 wt% catalyst: tetrabutylammonium bromide (TBAB), as shown in Table 2. Table 2. Composition Composition Table P02940051TW (Originary Case No. 05P0518) 1323735 Mixing System No. Example Example 3 bisphenol A diglycidyl ether (EPON 828) Example 4: hydrogenated bisphenol A diglycidyl ether (HBPA) Comparative Example 2: hydrogenated bisphenol A diglycidyl ether (HBPA):; f. Example 6: Comparison of physical properties of the compound of the present invention. Each of Examples 3, 4 and Comparative Example 2 The mixed composition was cured by heat treatment at 1203 ° C for 2 hours and 150 ° C for 2 hours. The hardness, glass transition temperature (rg), coefficient of linear expansion (CTE), and light transmittance of the cured product were as shown in the first figure. As shown in the fourth figure. It can be seen from the first figure that the addition of the anthrone compound 1 does not reduce the hardness in the composition formulation. When the proportion of the addition of the ketone compound 2 is increased, the hardness of the hardened composition tends to decrease. It can be seen from the second figure that the addition of the linaloxone compound 1 can increase the glass transition temperature, especially when the silicone/epoxy=l:1 is used, and the effect is 135 °C. The hardening composition series of the anthrone compound 2 has a glass transition temperature of only about 7 (TC). It can be seen from the third figure that the addition of the anthrone compound 1 maintains a very small coefficient of linear expansion, less than 80 ppm/° C. When the proportion of the addition of the ketone compound 2 is increased, the coefficient of linear expansion of the hardened composition tends to increase greatly. From the fourth figure, it is known that the composition of the hardened composition (silicone/epoxy=l:5 in Examples 3 and 4), visible light In the wavelength (400 to 700 nm) region, the light transmittance is more than 80% or more, so that the composition of the present invention is transparent to 14 P02940051TW (the case number 〇5P〇518). The object, and one::兮: The car father in the prior art 'the present invention - the ketone ketone compound has a better: 1 compound of the composition with thermal / photohardening properties, and the drawbacks, so that the lack of knowledge of the technology Application materials for optical/optoelectronic products. Other implementations are too detailed. The method of implementation has been described in detail in the foregoing embodiments, and any person who is infected can follow the instructions of the present invention without departing from the following: Need for internal vision The present invention is also included in the patent application of the present invention. The present invention is disclosed in the preferred embodiments as described above, but it is not intended to be used in conjunction with A, without departing from the invention. In the spirit and the dry circumference, it can be long-lasting; Ding Wei, change and retouch, therefore, the Bianbianwei of the present invention is subject to the definition of the patent application scope attached. [Simple description of the schema] It is the relationship between the hardness of the invention and the composition of the silicone/epoxy compound. The first figure is the relationship between the glass transition temperature and the composition of the silicone/epoxy compound of the present invention. The second figure is the linear expansion coefficient of the invention and the silicone/epoxy The composition diagram of the compound composition. The fourth figure is the result of the transmittance of the composition of the third and fourth embodiments of the present invention. [Comparative description of the main components and symbols] P0294〇051TW (the case number Q5P0518) 15

Claims (1)

1323735 X. Patent application scope: An anthrone compound which is represented by the following chemical formula (I): Ri R3 R4 (I); wherein m and η are 0 or a positive integer, but m and η are not 0 at the same time; Ri, R2, R3, R4, R5, Α and Β are independently nitrogen and unruled Or a branched alkyl group, a halogen-substituted C 1-6C6 linear or branched alkyl group or a substituent as shown in the following chemical formula (II) (II); wherein R6 is independently hydrogen, unsubstituted (^~(^ straight or branched alkyl, halogen-substituted Q~C6 straight or branched); R7 Is a linear or branched alkyl group which is independently a linear or branched alkyl group of CQ~C6 which is unsubstituted, and C?~C6 which is substituted by halogen; at least one of A and B of the above formula (I) a substituent represented by the formula (II); and the compound of the formula (I) is represented by the following formula (III): P02940051TW (Case No. 05P0518) 17 ===== The straight chain of the unsubstituted Cl~Q or the branched chain H is replaced by a straight chain of the q~C6 or the green chain of the money chain, which is an unsubstituted Q~Q straight bond or a branched 妓Self-priming CW: A linear or branched alkyl group, Xi (4) (4) t The aforementioned (IV) functional group and not shown by the chemical formula (Π) The substitution (III) shown in formula (II); wherein the 'r6 series is independently hydrogen, π heart ^ substituted (4) the viscosity of the compound is 1G~2GePs, and its Si-H / Chen is 0.528~0.694 (10- 2 _i/g). The private Hi has a composition of the compound of the compound of the first aspect of the patent application, which comprises: an anthrone compound; and 100 parts by weight of the patent application range 1st reaction accelerator. 3. If you apply for the product described in item (4), item 2, you may further include 10 to 1000 parts by weight of epoxy compound. 4. The above-mentioned reaction accelerator is a thermal hardener as claimed in the second aspect of the patent application. a 5. If applying for the & compound described in item 4 of the full-time division, the aforementioned heat P02940051TW (Our Office No. 05P0518) 18 1323735 The hardener contains an amine compound, an acid compound, a phenol compound, an alcohol compound, and an acid. An anhydrate compound, a guanamine compound, a thiol compound, a boron trifluoride amine complex, a urea urethane compound, and an isocyanunate compound or a mixture thereof. 6. The composition of claim 2, wherein the aforementioned anti-initiator is a photohardening initiator. 7. The composition of claim 6, wherein the photohardening initiator comprises: aryldiazonium • salts, diaryliodonium salts, and tri-aromatics. Triaryl sulphonium salts, triarylphosphonium salts, triarylselenonium salts, dialkyl phenyl sulphate ammonium salts. (dialkylphenacylsulphonium salts ), dialkyl-4-hydroxyphenylsulphonium salts, sulphonic acid esters, silanol-aluminium complexes And ferrocenium salts or mixtures thereof. 8. The composition of claim 2, wherein the reaction triggering agent further comprises a catalyst. 9. The composition of claim 8, wherein the catalyst comprises: an amine compound, an imidazole, an aromatic aryl or an alkyl phosphonium compound, Tetrabutyl ammonium bromide, 2-methyl-4-imidazole, triphenyl phosphine, benzyldimethylamine ), triethanolamine or a mixture thereof. P02940051TW (Our Office Case 05P0518) 19