Polyester-modified silicone resin and silicone composition for sealing materials containing the same

Abstract

The present invention comprises a polyester polyol and a first organopolysiloxane, wherein the first organopolysiloxane comprises an aryl group and an alkoxy group, (R 1 3SiO 1 / 2 ) M units expressed as 1 to 40 mol%, (R 2 SiO 3 / 2 ) T units expressed as 20 to 80 mol%, (R 3 2SiO 2 / 2 The D units represented by ) are 1 to 60 mol%, (SiO 4 / 2 This invention relates to a polyester-modified silicone resin composition containing Q units represented by ) in a content of 10 mol% or less, a polyester-modified silicone resin produced therefrom, and a silicone composition for sealing materials containing the same.

Description

[Technical Field] 【0001】 This application claims priority based on Korean Patent Application No. 10-2023-0073158 dated June 7, 2023, the entirety of which is incorporated herein. 【0002】 The present invention relates to a polyester-modified silicone resin containing M units and T units, which has excellent adhesion and durability, and to a silicone composition for sealing materials containing the same, which has a low aryl group content and minimizes the problem of yellowing, which causes the cured product to change color. [Background technology] 【0003】 Organic resins are widely used in a variety of fields due to their excellent processability, lightweight nature, low cost, and impact resistance. In particular, silicone resins are widely used in various industrial fields due to their excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency. For example, addition-curing silicone compositions, i.e., addition-curing organopolysiloxane compositions, are excellent in terms of rapid curing, inter-curing time, by-product formation, and moldability, and are used in a variety of fields such as optical components (e.g., optical lenses) and / or encapsulants. 【0004】 Such silicone resins can also be modified to improve various physical properties such as heat resistance by converting them to polyester, epoxy resin, etc. In particular, polyester-modified silicone resins have excellent weather resistance and heat resistance, and among modified silicone resins, they show less discoloration due to heat degradation, and are used in a wide range of fields, such as building material coatings, automotive coatings, transport aircraft mufflers, paints, and cooking utensil coatings. Conventional polyester-modified silicone resins are usually produced by a multi-step reaction that includes the steps of: producing a polyester resin with a saturated polybasic acid and a polyhydric alcohol; producing a silicone resin by hydrolysis and / or condensation reaction of the produced polyester resin and silane compounds such as chlorosilane and alkoxysilane; and dehydrating or dealcoholizing the produced silicone resin with a metal catalyst such as titanium. 【0005】 For example, Japanese Registered Patent No. 6947913 (Patent Document 1) discloses a siloxane resin block containing a siloxane unit represented by (i) the formula: R 1 SiO 3 / 2 [wherein, R 1 is a monovalent hydrocarbon group], and selectively contains a siloxane unit represented by the formula: SiO 4 / 2 , and (ii) a siloxane linear block represented by the formula: (R 2 2SiO 2 / 2 ) n [wherein each R 2 is independently a monovalent hydrocarbon group, and n is an integer of at least 5], and (iii) a polysiloxane-polyester block copolymer containing a polyester block. However, like Patent Document 1, the siloxane resin containing the Q unit represented by SiO 4 / 2 has problems such as an excessive increase in the viscosity of the composition containing it, or an increase in the hardness of the produced cured product and a decrease in the refractive index. 【0006】 Therefore, there is a need for research and development of a silicone resin that is excellent in adhesion, excellent in durability, can prevent the problem of yellowing, is excellent in the hardness and transmittance of the produced cured product, and is very suitable as an optical component and / or a sealing material. 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0007】 Therefore, the present invention aims to provide a silicone resin that is excellent in adhesion, excellent in durability, can prevent the problem of yellowing, is excellent in the hardness and transmittance of the produced cured product, and is very suitable as an optical component and / or a sealing material, and a silicone composition for a sealing material containing the same. 【Means for Solving the Problems】 【0008】 The present invention contains a polyester polyol and a first organopolysiloxane, the first organopolysiloxane contains an aryl group and an alkoxy group, and (R1 3SiO 1 / 2 ) M units expressed as 1 to 40 mol%, (R 2 SiO 3 / 2 ) T units expressed as 20 to 80 mol%, (R 3 2SiO 2 / 2 The D units represented by ) are 1 to 60 mol%, (SiO 4 / 2 It contains Q units represented by ) in a content of 10 mol% or less, The aforementioned R 1 These are substituted or unsubstituted alkyl groups, alkoxy groups, or alkenyl groups. The aforementioned R 2 These are substituted or unsubstituted aryl or aralkyl groups, The aforementioned R 3 The present invention provides a polyester-modified silicone resin composition comprising a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group. 【0009】 Furthermore, the present invention is manufactured from the polyester-modified silicone resin composition, The present invention provides a polyester-modified silicone resin having an aryl group content of 50 mol% or less. 【0010】 Furthermore, the present invention is (A) Second organopolysiloxane; (B) Organohydrogenpolysiloxane; (C) The polyester-modified silicone resin; and (D) Silica; A silicone composition comprising, The content of the polyester-modified silicone resin per 100 parts by weight of the silicone composition is between 10 and 45 parts by weight. The present invention provides a silicone composition for sealing materials in which the molar ratio of Si-H bonds to alkenyl groups in the silicone composition is 0.5 to 1.2. [Effects of the Invention] 【0011】 The polyester-modified silicone resin according to the present invention exhibits excellent adhesion to substrates, has a low aryl group content resulting in superior durability and preventing yellowing. Furthermore, cured products produced from compositions containing the silicone resin exhibit excellent hardness and transmittance, making them highly suitable as optical components and / or encapsulants. [Modes for carrying out the invention] 【0012】 The present invention will be described in detail below. 【0013】 In this specification, "viscosity" is measured by a method commonly known in the art, and may be a value measured using, for example, a Brookfield viscometer (LVDV) or a rheometer (MCR301, Anton Paar). 【0014】 Furthermore, the "weight-average molecular weight" and "number-average molecular weight" can be measured by methods well known in the industry, and may be values ​​measured by, for example, GPC (gel permeation chromatography). 【0015】 Furthermore, equivalent or functional group content, such as "aryl group content," can be measured by methods well known in the art, for example, values ​​measured by titration. 【0016】 Furthermore, the units used herein are defined as follows, where R represents a substituted or unsubstituted hydrocarbon group. (R 3 SiO 1 / 2 Unit: M units (R 2 SiO 2 / 2 Unit: D units (RSiO 3 / 2 Unit: T units (SiO 4 / 2 Unit: Q units 【0017】 Polyester-modified silicone resin composition The polyester-modified silicone resin composition according to the present invention comprises a polyester polyol and a first organopolysiloxane. 【0018】 1) Polyester polyol Polyester polyols play a role in enhancing the adhesion of silicone resins by imparting ester groups to them. 【0019】 The polyester polyol may be one that has been directly synthesized by a known method, or a commercially available product may be used. For example, the polyester polyol may be produced by a condensation reaction between a polyol monomer and a carboxyl group-containing monomer. Specifically, the polyester polyol may be produced by a condensation reaction between a polyol monomer and a carboxyl group-containing aliphatic monomer. 【0020】 The polyol monomer can include, for example, one or more selected from the group consisting of 1,4-cyclohexanedimethanol, ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane, triethylolpropane, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, hydroquinone-bis(β-hydroxyethyl) ether, glycerin, pentaerythritol, and 3-methylpentanediol, and preferably contains 1,4-cyclohexanedimethanol. 【0021】 Furthermore, the carboxyl group-containing monomer may include, for example, one or more selected from the group consisting of tetrahydrophthalic anhydride, adipic acid, trimellitic anhydride, terephthalic acid, fumaric acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, succinic anhydride, isophthalic acid, azelaic acid, and maleic anhydride, and preferably may include tetrahydrophthalic anhydride. 【0022】 When the polyester polyol contains 1,4-cyclohexanedimethanol and tetrahydrophthalic anhydride, it is preferable in that the transparency of the resin can be increased. 【0023】 The polyester polyol may have a number-average molecular weight (Mn) of 300 to 10,000 g / mol, or 500 to 5,000 g / mol. When the number-average molecular weight of the polyester polyol is within the above range, it has the effect of appropriately adjusting the viscosity of the resin composition. If the number-average molecular weight of the polyester polyol is below the above range, the viscosity of the resin composition may become too low, and if it exceeds the above range, the viscosity of the resin composition may become too high, becoming solid-like and making resin manufacturing difficult. 【0024】 Furthermore, the polyester polyol may have a hydroxyl value (OHv) of 10 to 500 mgKOH / g, 30 to 300 mgKOH / g, or 100 to 200 mgKOH / g. When the hydroxyl value of the polyester polyol is within the above range, it has the effect of improving the adhesion to the manufactured polyester-modified silicone resin. If the hydroxyl value of the polyester polyol is below the above range, there is a problem of insufficient viscosity of the resin composition due to the small number of hydroxyl groups that react with the alkoxy groups of the organopolysiloxane. If it exceeds the above range, there is a large amount of residual hydroxyl groups in the manufactured polyester-modified silicone resin, which can reduce its storability and cause stickiness. 【0025】 The polyester polyol may have a glass transition temperature (Tg) of 0 to 40°C, 5 to 30°C, or 5 to 15°C. When the glass transition temperature of the polyester polyol is within the above range, the manufactured polyester-modified silicone resin has the effect of having appropriate hardness and being easy to handle. On the other hand, if the glass transition temperature of the polyester polyol is below the above range, the manufactured polyester-modified silicone resin becomes too soft and difficult to handle, and if it exceeds the above range, the manufactured polyester-modified silicone resin becomes too hard and difficult to handle. 【0026】 Furthermore, the polyester polyol may have a refractive index (RI) of 1.45 to 1.65, or 1.49 to 1.55. When the refractive index of the polyester polyol is within the above range, the refractive index of the encapsulant containing it is appropriate and has a suitable effect for application as an encapsulant for optical chips. On the other hand, if the refractive index of the polyester polyol is below the above range, applying a modified silicone resin manufactured from it as an encapsulant results in the encapsulant becoming cloudy due to the difference in refractive index between the optical chip and the encapsulant. If the refractive index exceeds the above range, the refractive index is too high, and applying a modified silicone resin manufactured from it as an encapsulant may result in the encapsulant becoming cloudy, as described above. 【0027】 The polyester polyol resin may have a viscosity at 25°C of 2,000 to 500,000 mPa·s, 3,000 to 300,000 mPa·s, or 3,000 to 10,000 mPa·s. When the viscosity of the polyester polyol at 25°C is within the above range, the manufactured modified silicone resin can have the effect of forming an appropriate handling viscosity. If the viscosity of the polyester polyol at 25°C is below the above range, the viscosity of the resin composition is low and it flows easily, making it difficult to handle. If it exceeds the above range, the fluidity of the resin composition may be insufficient, making it difficult to handle. 【0028】 The polyester-modified silicone resin composition may contain the polyester polyol and organopolysiloxane in a weight ratio of 0.02:1 to 0.3:1. Specifically, the polyester-modified silicone resin composition may contain the polyester polyol and organopolysiloxane in a weight ratio of 0.06:1 to 0.25:1, or 0.08:1 to 0.15:1. When the weight ratio of the polyester polyol and organopolysiloxane is within the above range, the yellowing of the manufactured modified silicone resin is prevented and adhesion is improved. On the other hand, if the weight ratio of the polyester polyol and organopolysiloxane is less than the above range, i.e., if a small amount of polyester polyol is included relative to the weight of organopolysiloxane, the manufactured modified silicone resin may yellow. If the ratio exceeds the above range, i.e., if an excessive amount of polyester polyol is included relative to the weight of organopolysiloxane, the manufactured modified silicone resin may become sticky. 【0029】 2) First organopolysiloxane The first organopolysiloxane plays a role in forming the main chain of the silicone resin. 【0030】 The organopolysiloxane comprises an aryl group and an alkoxy group, (R 1 3SiO 1 / 2 ) M units expressed as 1 to 40 mol%, (R 2 SiO 3 / 2 ) T units expressed as 20 to 80 mol%, (R 3 2SiO 2 / 2 The D units represented by ) are 1 to 60 mol%, (SiO 4 / 2 It contains Q units represented by ) in a content of 10 mol% or less. At this time, the R 1 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkenyl group, preferably C 1-15 alkyl group, C 1-15 Alkoxy group or C 2-10It is an alkenyl group, more preferably a methyl group or a vinyl group, and the three R 1 They are either the same or different from one another. 【0031】 The aforementioned R 2 is a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, preferably C 6-15 The aryl group or C 7-15 It is an aralkyl group, and more preferably a phenyl group. 【0032】 The aforementioned R 3 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group, preferably C 1-15 alkyl group, C 1-15 Alkoxy group, C 6-15 The aryl group of, or C 2-10 It is an alkenyl group, and more preferably a methyl group or a phenyl group, and the two R 3 They are either the same or different from one another. 【0033】 Specifically, the organopolysiloxane is (R 1 3SiO 1 / 2 The M unit represented by (R can be contained in an amount of 10 to 40 mol%, preferably 20 to 40 mol%, and more preferably 25 to 35 mol%. Furthermore, the organopolysiloxane may contain (R 2 SiO 3 / 2 The T units represented by (R) may be present in 20 to 60 mol%, preferably 20 to 50 mol%, and more preferably 20 to 40 mol%. Furthermore, the organopolysiloxane may be (R 3 2SiO 2 / 2 The organopolysiloxane may contain 10 to 50 mol%, preferably 20 to 50 mol%, and more preferably 30 to 50 mol%, of D units represented by (SiO). 4 / 2 The Q units represented by ) may be contained in 5 mol% or less, preferably not at all. 【0034】 The organopolysiloxane is (SiO 4 / 2 If the Q unit, represented by ), is present in 10 mol% or more, problems may occur such as an excessive increase in viscosity or an increase in the hardness of the manufactured cured product and a decrease in the refractive index. 【0035】 More specifically, the organopolysiloxane may be represented by the following chemical formula 1. [C1] (R 1 3SiO 1 / 2 ) a (R 2 SiO 3 / 2 ) b (R 3 2SiO 2 / 2 ) c In chemical formula 1, R 1 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkenyl group, and the three R 1 They are either the same or different from one another. R 2 is a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. R 3 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group, and the two R 3 They are either the same or different from one another. a, b, and c are mole fractions of each unit, and a + b + c equals 1. 【0036】 For example, a may be between 0.01 and 0.4, b may be between 0.2 and 0.8, and c may be between 0.01 and 0.6. 【0037】 R 1 , R 2 , and R 3 Preferred examples for each of these are as described above. 【0038】 In this case, the alkyl group and alkenyl group may be linear or branched. 【0039】 The first organopolysiloxane may have a viscosity at 25°C of 500 to 500,000 mPa·s, 1,000 to 200,000 mPa·s, or 5,000 to 50,000 mPa·s. If the viscosity of the first organopolysiloxane is below the above range, there is a problem that the viscosity of the manufactured polyester-modified silicone resin will be too low, and if it exceeds the above range, the viscosity of the manufactured polyester-modified silicone resin will be too high, which may cause handling problems. 【0040】 Furthermore, the first organopolysiloxane may have an aryl group content of 15 to 70 mol%, 20 to 60 mol%, or 20 to 30 mol%. In this case, the "aryl group" in "aryl group content" may be a phenyl group. When the aryl group content of the organopolysiloxane is within the above range, the encapsulant containing the manufactured polyester-modified silicone resin exhibits a refractive index similar to that of an optical tip, thus maintaining transparency. On the other hand, if the aryl group content of the first organopolysiloxane is below the above range, the refractive index of the encapsulant containing the manufactured polyester-modified silicone resin is too low, which can induce haze. If the content exceeds the above range, the manufactured polyester-modified silicone resin may contain an excessive amount of phenyl groups, causing yellowing. 【0041】 The first organopolysiloxane may contain alkenyl groups. Specifically, the first organopolysiloxane may have an alkenyl group content of 1 to 30 mol%, or 5 to 25 mol%. In this case, the "alkenyl group" in "alkenyl group content" may be a vinyl group. When the alkenyl group content of the first organopolysiloxane is within the above range, the cured product produced has the effect of having appropriate hardness. On the other hand, if the alkenyl group content of the first organopolysiloxane is below the above range, there is a problem that the curing performance of the polyester-modified silicone resin produced will be low, and if it exceeds the above range, the polyester-modified silicone resin produced may become sticky. 【0042】 Furthermore, the degree of polymerization of the first organopolysiloxane may be 5 to 3,000, 5 to 2,000, or 5 to 20. When the degree of polymerization of the first organopolysiloxane is within the above range, the viscosity of the manufactured polyester-modified silicone resin is appropriate and easy to handle. In this case, the degree of polymerization is the number of silicon atoms in one molecule of the first organopolysiloxane. On the other hand, if the degree of polymerization of the first organopolysiloxane is below the above range, the viscosity of the manufactured polyester-modified silicone resin is too low and it is difficult to handle. If it exceeds the above range, the viscosity of the manufactured polyester-modified silicone resin may be too high and it may be difficult to handle. 【0043】 Polyester-modified silicone resin Furthermore, the polyester-modified silicone resin according to the present invention is produced from the aforementioned polyester-modified silicone resin composition and has an aryl group content of 50 mol% or less. 【0044】 Specifically, the content of aryl groups in the polyester-modified silicone resin may be 5 mol% to 50 mol%, 8 mol% to 40 mol%, or 30 mol% to 35 mol%. In this case, the "aryl group" in the "content of aryl groups" may be a phenyl group. 【0045】 It is known that aryl groups in silicone resins induce yellowing, a phenomenon in which the cured product turns yellow at high temperatures. On the other hand, the polyester-modified silicone resin according to the present invention has the advantage of having a low aryl group content, which prevents the aforementioned yellowing phenomenon. Specifically, if the aryl group content in the silicone resin exceeds the aforementioned range, the cured product may discolor at high temperatures, making it unsuitable for use as an optical component and / or encapsulant. 【0046】 The polyester-modified silicone resin may have a viscosity at 60°C of 1,000 to 100,000 mPa·s, 2,000 to 90,000 mPa·s, or 50,000 to 85,000 mPa·s. When the viscosity of the polyester-modified silicone resin at 60°C is within the above range, it has the effect of making it easy to handle the viscosity of the encapsulant containing it appropriately. On the other hand, if the viscosity of the polyester-modified silicone resin at 60°C is below the above range, there is a problem that the viscosity of the encapsulant containing it is too low and it flows too easily, and if it exceeds the above range, the handlingability of the encapsulant containing it may decrease due to its high viscosity. 【0047】 Furthermore, the polyester-modified silicone resin may have a weight-average molecular weight (Mw) of 1,000 to 500,000 g / mol, 2,000 to 150,000 g / mol, or 50,000 to 100,000 g / mol. When the weight-average molecular weight of the polyester-modified silicone resin is within the above range, the viscosity of the encapsulant containing it is appropriate and easy to handle. On the other hand, if the weight-average molecular weight of the polyester-modified silicone resin is below the above range, there is a problem that the encapsulant containing it flows before curing, and if it exceeds the above range, the viscosity of the encapsulant containing it may be high and its handling may be reduced. 【0048】 The polyester-modified silicone resin may contain alkenyl groups. Specifically, the content of alkenyl groups in the polyester-modified silicone resin may be 1 to 30 mol%, 5 to 25 mol%, or 5 to 10 mol%. In this case, the "alkenyl group" in "content of alkenyl groups" may be a vinyl group. When the content of alkenyl groups in the polyester-modified silicone resin is within the above range, the encapsulant containing it has the effect of having appropriate hardness after curing. On the other hand, when the content of alkenyl groups in the polyester-modified silicone resin is below the above range, there is a problem that the curing performance of the encapsulant containing it will be low, and when it exceeds the above range, stickiness may occur in the encapsulant containing it. 【0049】 As described above, the polyester-modified silicone resin according to the present invention exhibits excellent adhesion to substrates, superior durability due to its low aryl group content, and can prevent yellowing. Furthermore, cured products produced from compositions containing the silicone resin exhibit excellent hardness and transmittance, making them highly suitable as optical components and / or encapsulants. 【0050】 Silicone composition for sealing materials Furthermore, the silicone composition for sealing materials according to the present invention comprises (A) a secondary organopolysiloxane; (B) an organohydrogenpolysiloxane; (C) the aforementioned polyester-modified silicone resin; and (D) silica. 【0051】 (A) Second organopolysiloxane The second organopolysiloxane plays a role in imparting elasticity to the manufactured coating film. The second organopolysiloxane may be the same as or different from the first organopolysiloxane, and the description of the first organopolysiloxane can be referenced. 【0052】 The second organopolysiloxane has at least two silicon-bonded alkenyl groups (Si-alkenyl) per molecule. 【0053】 For example, the content of alkenyl groups in the second organopolysiloxane may be 0.1 to 4 mmol / g, or 0.2 to 3 mmol / g. In this case, the "alkenyl group" in the "content of alkenyl groups" may be a vinyl group. Furthermore, the alkenyl group may be a silicon atom-bonded alkenyl group. When the content of alkenyl groups in the second organopolysiloxane is within the above range, the mechanical properties such as hardness and strength of the cured product can be improved. Conversely, when the content of alkenyl groups in the second organopolysiloxane is below the above range, the cured product manufactured using an organopolysiloxane with insufficient alkenyl group content has low strength properties, which may reduce the sealing ability of the cured product. If the content of alkenyl groups in the second organopolysiloxane exceeds the aforementioned range, the crosslinking density of the cured product increases excessively. While this may improve curing performance, the high crosslinking density can lead to an excessive increase in the hardness of the cured product, resulting in a decrease in physical properties such as tensile strength and elongation, and thus a decline in its performance as a sealant. 【0054】 The degree of polymerization of the second organopolysiloxane may be 5 to 3,000, 5 to 2,000, or 6 to 100. When the degree of polymerization of the second organopolysiloxane is within the above range, it has the advantage of being advantageous in increasing the tensile strength of the cured product. In this case, the degree of polymerization is the number of silicon atoms in one molecule of the second organopolysiloxane. On the other hand, if the degree of polymerization of the second organopolysiloxane is below the above range, the crosslinking density of the cured product produced using it may be insufficient, making it difficult to achieve appropriate hardness, and the elasticity may be insufficient, making it difficult to achieve sufficient sealing ability. On the other hand, if the degree of polymerization of the second organopolysiloxane exceeds the above range, the viscosity of the silicone composition may be excessively high, reducing workability. 【0055】 Furthermore, the second organopolysiloxane may have a viscosity at 25°C of 500 to 500,000 mPa·s, 1,000 to 200,000 mPa·s, or 5,000 to 50,000 mPa·s. When the viscosity of the second organopolysiloxane at 25°C is within the above range, the viscosity of the silicone composition is appropriately formed, resulting in excellent injection workability. Conversely, when the viscosity of the second organopolysiloxane at 25°C is below the above range, the viscosity of the silicone composition decreases, which can cause a large amount of flash during injection molding, making it difficult to improve the tensile strength and elongation of the cured product. Conversely, when the viscosity of the second organopolysiloxane at 25°C exceeds the above range, uniform dispersion of silica in the silicone composition becomes difficult, which can reduce storage stability, leading to reduced injection workability or excessive load on manufacturing equipment. 【0056】 (B) Organohydrogenpolysiloxane The organohydrogenpolysiloxane is a substance that crosslinks with the second organopolysiloxane to form a cured product, and can act as a crosslinking agent. 【0057】 The organohydrogenpolysiloxane contains Si-H bonds, and most of the Si-H bonds detected in the silicone composition originate from the organohydrogenpolysiloxane. Specifically, each molecule of the organohydrogenpolysiloxane may contain at least one Si-H bond. On the other hand, the organohydrogenpolysiloxane may not contain an alkenyl group. 【0058】 For example, the organohydrogenpolysiloxane may be represented by the following Chemical Formula 2. [Chemical Formula 2] (R 15 SiO 3 / 2 ) i (R 16 R 17 HSiO 1 / 2 ) j In Chemical Formula 2, R 15 is a substituted or unsubstituted C 1-6 alkyl group or a C 6-15 aryl group, R 16 and R 17 are each independently a substituted or unsubstituted C 1-10 alkyl group, i and j are the molar fractions of each unit, and i + j is 1. 【0059】 For example, i may be from 0.01 to 0.5, and j may be from 0.5 to 0.99. 【0060】 For example, R 15 is a substituted or unsubstituted C 6-12 aryl group, more specifically, a phenyl group, a tolyl group or a xylyl group, preferably a phenyl group. 【0061】 Specifically, R 16 and R 17 are each independently a substituted or unsubstituted C1-6The alkyl group, more specifically a methyl group, an ethyl group, or a butyl group, preferably a methyl group, may be present. In this case, the alkyl group may be linear or branched. 【0062】 The Si-H content in the organohydrogenpolysiloxane may be 0.1 to 4 mmol / g, or 0.2 to 0.3 mmol / g. When the content of hydrogen groups (Si-H) directly bonded to silicon in the organohydrogenpolysiloxane is within the above range, the crosslinking density of the manufactured cured product can be appropriately adjusted, and the physical properties can be easily improved. If the content of hydrogen groups (Si-H) directly bonded to silicon in the organohydrogenpolysiloxane is below the above range, the crosslinking density of the manufactured cured product will be low, and the desired hardness and mechanical strength may not be achieved. If it exceeds the above range, it will be difficult to adjust the crosslinking density of the manufactured cured product, and the elasticity may decrease or the desired mechanical strength may not be achieved. 【0063】 Furthermore, the viscosity of the organohydrogenpolysiloxane at 25°C may be 1 to 50,000 mPa·s, 1 to 30,000 mPa·s, or 1 to 20,000 mPa·s. If the viscosity of the organohydrogenpolysiloxane at 25°C is below the above range, the crosslinking density of the manufactured cured product may increase excessively, leading to a decrease in mechanical properties such as tensile strength and elongation. If it exceeds the above range, the elasticity of the cured product may decrease, resulting in a decrease in sealing durability. 【0064】 On the other hand, the molar ratio of Si-H bonds to alkenyl groups in the silicone composition is 0.5 to 1.2, preferably 0.6 to 1.0, and more preferably 0.7 to 0.9. In this case, the alkenyl groups may be vinyl groups. Furthermore, if the molar ratio of Si-H bonds to alkenyl groups in the silicone composition is less than the above range, it is undesirable because a large amount of unreacted alkenyl groups originating from the second organopolysiloxane remain, increasing the compressive deformation rate of the cured product. If it exceeds the above range, unreacted Si-H groups originating from the organohydrogenpolysiloxane remain, resulting in lower hardness and elasticity of the cured product, which can ultimately reduce the sealing durability. 【0065】 (C) Polyester-modified silicone resin The aforementioned polyester-modified silicone resin improves adhesion to the substrate and minimizes the problem of the cured product yellowing at high temperatures. 【0066】 Furthermore, the content of the polyester-modified silicone resin per 100 parts by weight of the silicone composition may be 10 to 45 parts by weight, preferably 10 to 30 parts by weight. When the content of the polyester-modified silicone resin is within the above range, the cured product produced from the silicone composition containing it has excellent adhesion to the substrate and minimizes yellowing at high temperatures. If the content of the polyester-modified silicone resin is below the above range, the cured product may have insufficient adhesion or yellowing may occur, and if it exceeds the above range, the cured product may become sticky or excessively hard. 【0067】 (D) Silica Silica plays a role in improving the mechanical strength and hardness of cured materials. 【0068】 The silica is not particularly limited, as long as it is generally applicable to silicone compositions, and may be, for example, amorphous or crystalline. 【0069】 Furthermore, the silica may be fumed, wet, dry, aerosolized, or calcined silica. 【0070】 The silica has a BET specific surface area of ​​50 to 400 m². 2 / g, 100 to 400m 2 / g, or 200 to 300m 2 It may be / g. If the BET specific surface area of ​​silica is less than the above range, there is a problem that the improvement in mechanical properties such as hardness and tensile strength of the manufactured cured product, which is the effect of adding silica, is not sufficient. If it exceeds the above range, the dispersion of silica in the composition is not easy, which may result in poor hardness of the manufactured cured product, and problems with storage stability may occur, such as an increase in the viscosity of the composition over time. 【0071】 Furthermore, the silica may have an average particle size of 0.001 to 1 μm, 0.005 to 0.1 μm, or 0.007 to 0.03 μm. If the average particle size of the silica is below the above range, the dispersion time of the silica in the composition will be longer, which may reduce the productivity and storage stability of the composition. If it exceeds the above range, the reinforcing effect of the silica on the cured product will be minimal, making it difficult to achieve physical properties other than the desired hardness. 【0072】 The silica may be present in an amount of 1 to 10 parts by weight, or 3 to 7 parts by weight, per 100 parts by weight of the silicone composition. If the silica content is below the above range, the effect of silica addition on improving the mechanical properties such as hardness and tensile strength of the cured product and its acid resistance will be minimal. If the silica content exceeds the above range, an excessive amount of silica may increase the compressive deformation rate of the cured product or reduce its sealing properties. 【0073】 (E) Additives The aforementioned silicone composition for sealing materials may further contain additives commonly used in the art. In this case, the additives may be, for example, surfactants, catalysts, curing retarders, adhesion promoters, and the like. 【0074】 The viscosity of the silicone composition for sealing material at 25°C may be 15,000 to 22,000 mPa·s, 16,000 to 21,000 mPa·s, or 18,000 to 20,000 mPa·s. 【0075】 Furthermore, the silicone composition for sealing material has a shear rate of 1s -1 Viscosity and shear rate at 25°C measured at 10s -1 The viscosity ratio measured at 25°C may be 1.5:1 to 3.3:1, 2.0:1 to 3.0:1.0, or 2.4:1 to 2.8:1.0. 【0076】 The silicone composition for sealing materials according to the present invention, as described above, exhibits excellent adhesion to substrates, and the cured product produced therefrom has excellent hardness and transmittance, making it highly suitable as an optical component and / or sealing material. 【0077】 cured product The cured product according to the present invention is manufactured by curing the silicone composition for sealing material. 【0078】 The cured material, with an average thickness of 6 mm, may have a hardness of 30 to 40 Shore A, or 30 to 36 Shore A. 【0079】 The cured material, with an average thickness of 1 mm, may have a maximum stress of 3.5 MPa or more, 4.0 MPa or more, or 4.0 to 5.0 MPa. 【0080】 The cured products described above exhibit excellent transparency and hardness, as well as superior adhesion, making them suitable as materials for sensitive fields such as electrical and electronics. 【0081】 The present invention will be described more specifically below through examples. However, these examples are provided only to aid in understanding the present invention, and the scope of the present invention is not limited in any sense to these examples. 【0082】 [Examples] Manufacturing Example 1: Production of Polyester Polyols In a four-necked flask equipped with a thermometer, stirrer, condenser, packed column, and separation tube, 48.4 parts by weight of 1,4-cyclohexanedimethanol (CHDM), 35.8 parts by weight of tetrahydrophthalic anhydride (THPAN), and 0.02 parts by weight of monobutyltin dihydroxychloride as a catalyst were added. The mixture was heated to 180°C under a nitrogen atmosphere and maintained for 2 hours. Subsequently, the mixture was heated from 180°C to 220°C over 3 hours while removing condensation water, and then cooled to 160°C. At 160°C, 2.53 parts by weight of xylene were added, and the mixture was refluxed for 5 hours. After cooling to 100°C, 17.44 parts by weight of xylene were added to produce a polyester polyol. 【0083】 The manufactured polyester polyol had a hydroxyl value (OHv) of 140 mgKOH / g, a viscosity of 4,500 mPa·s at 25°C, a number-average molecular weight (Mn) of 898 g / mol, a glass transition temperature (Tg) of 10°C, and a refractive index (RI) of 1.493. 【0084】 Manufacturing Example 2. Manufacturing of Organopolysiloxane-1 Into a four-necked flask equipped with a thermometer, a stirring device, a condenser, a packed column and a separation tube, 11.4 parts by weight of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 9.6 parts by weight of hexamethyldisiloxane and 17.2 parts by weight of methylphenylcyclosiloxane were placed. After adding 6.6 parts by weight of water, the mixture was stirred. Then, 0.06 parts by weight of trifluoromethane sulfonic acid was added, and 26.7 parts by weight of phenyltrimethoxysilane was introduced over 30 minutes. After raising the temperature to 60 °C, the temperature was maintained for 2 hours. Then, after raising the temperature to 80 °C and maintaining it for 3 hours, for neutralization, 2.0 parts by weight of CaCO3 was added and maintained for 30 minutes, and then cooled to room temperature. Then, for filtration, 26.44 parts by weight of xylene was added and stirred for 30 minutes for dilution. Then, after filtering with a cartridge filter, the filtrate was put into a four-necked flask equipped with a thermometer, a stirring device, a condenser, a packed column and a separation tube, and vacuum distillation was carried out while raising the temperature to 150 °C and maintained for 2 hours, and then cooled to room temperature and filtered with a mesh filter to produce organopolysiloxane-1. 【0085】 The produced organopolysiloxane-1 had a methoxy group content of 2.3 mol%, a vinyl group content of 9.38 mol%, a phenyl group content of 22.3 mol%, and a degree of polymerization of 8. Also, 29 As a result of Si-NMR analysis, SiO 1 / 2 (CH3)3 units (hereinafter referred to as M me ) 13 mol%, SiO 1 / 2 Vi(CH3)2 units (hereinafter referred to as M Vi ) 17.9 mol%, SiO 3 / 2 Ph units (hereinafter referred to as T Ph ) 29.1 mol% and SiO 2 / 2 (CH3)Ph units (hereinafter referred to as D mePhIt contained 40 mol% (assuming this). In this case, Vi is a vinyl group and Ph is a phenyl group. 【0086】 Manufacturing Example 3. Manufacturing of Polyester-Modified Silicone Resin-1 In a four-necked flask equipped with a thermometer, stirrer, condenser, packed column, and separation tube, 10 parts by weight of polyester polyol prepared in Production Example 1, 1100 parts by weight of organopolysiloxane prepared in Production Example 2, and 0.02 parts by weight of tetraisopropyl titanate as a catalyst were placed, and the temperature was raised to 160°C and maintained at 160°C for 5 hours. After cooling to 90°C, 110 parts by weight of xylene, 0.02 parts by weight of potassium hydroxide (KOH), and 2.2 parts by weight of distilled water were added, and the temperature was raised to 150°C and maintained at 1 hour. After that, water and methanol (product) were removed using a Dean-Stark filter. After cooling to 90°C, 2.2 parts by weight of water were added, and the temperature was raised to 150°C and maintained at 1 hour, after which water and methanol were removed in the same manner as above. After cooling to room temperature, 2.2 parts by weight of ethylene chlorohydrin were added for neutralization, and the mixture was stirred for 10 hours. The mixture was then filtered to produce polyester-modified silicone resin-1. 【0087】 The manufactured polyester-modified silicone resin-1 had a methoxy content of 0.2 mol%, a viscosity of 80,000 mPa·s at 60°C, a vinyl group content of 6.55 mol%, a phenyl group content of 32.1 mol%, and a weight-average molecular weight of 80,000 g / mol. 29 Si NMR analysis results showed that SiO 1 / 2 (CH3)3 units 13.4 mol%, SiO 1 / 2 (CH3)2Vi units 13.6 mol%, SiO 2 / 2 (CH3) pH unit 34.5 mol%, SiO 3 / 2 It was composed of 29.1 mol% pH units. In this case, Vi is a vinyl group and Ph is a phenyl group. 【0088】 Manufacturing Example 4. Manufacturing of Polyester-Modified Silicone Resin-2 Instead of organopolysiloxane-1 in manufacturing example 2, organopolysiloxane-2 (M) contains Q units. me 15 mol%, M Vi 15 mol%, T Ph 30 mol%, D mePh 25 mol% and SiO 4 / 2 Polyester-modified silicone resin-2 was produced in the same manner as in Production Example 3, except that it contained 15 mol% of the unit (hereinafter referred to as Q) and had a methoxy group content of 2.2 mol%). 【0089】 The manufactured polyester-modified silicone resin-2 had a methoxy content of 0.22 mol%, a viscosity of 90,000 mPa·s at 60°C, a vinyl group content of 8.0 mol%, a phenyl group content of 22.7 mol%, and a weight-average molecular weight of 150,000 g / mol. 29 Si NMR analysis results showed that SiO 1 / 2 (CH3)3 units 13.6 mol%, SiO 1 / 2 (CH3)2Vi units 14.0 mol%, SiO 2 / 2 (CH3) pH unit 22.7 mol%, SiO 3 / 2 pH unit 27.3 mol% and SiO 4 / 2 It was composed of 13.6 mol% units. In this case, Vi is a vinyl group and Ph is a phenyl group. 【0090】 Manufacturing Example 5. Manufacturing of Polyester-Modified Silicone Resin-3 Instead of organopolysiloxane-1 in Production Example 2, organopolysiloxane-3 (M) has a lower phenyl group content. me 45 mol%, M Vi 18 mol%, T Ph 10 mol% and D mePh Polyester-modified silicone resin-3 was produced in the same manner as in Production Example 3, except that a 27 mol% of the resin was used, with a phenyl group content of 10 mol%). 【0091】 The manufactured polyester-modified silicone resin-3 had a methoxy content of 0.21 mol%, a viscosity of 60,000 mPa·s at 60°C, a vinyl group content of 11.0 mol%, a phenyl group content of 9.1 mol%, and a weight-average molecular weight of 150,000 g / mol. 29 The results of the Si-NMR analysis are shown in Table 4 below. 【0092】 Manufacturing Example 6. Manufacturing of Polyester-Modified Silicone Resin-4 Polyester-modified silicone resin-4 was produced in the same manner as in Production Example 3, except that 5 parts by weight of the polyester polyol produced in Production Example 1 and 1100 parts by weight of the organopolysiloxane produced in Production Example 2 were used. 【0093】 The manufactured polyester-modified silicone resin-4 had a methoxy content of 0.015 mol%, a viscosity of 120,000 mPa·s at 60°C, a vinyl group content of 6.8 mol%, a phenyl group content of 33.6 mol%, and a weight-average molecular weight of 75,000 g / mol. 29 The results of the Si-NMR analysis are shown in Table 4 below. 【0094】 Manufacturing Example 7. Manufacturing of Polyester-Modified Silicone Resin-5 Polyester-modified silicone resin-5 was produced in the same manner as in Production Example 3, except that 30 parts by weight of the polyester polyol produced in Production Example 1 and 1100 parts by weight of the organopolysiloxane produced in Production Example 2 were used. 【0095】 The manufactured polyester-modified silicone resin-5 had a methoxy content of 0.07 mol%, a viscosity of 50,000 mPa·s at 60°C, a vinyl group content of 5.5 mol%, a phenyl group content of 27.2 mol%, and a weight-average molecular weight of 100,000 g / mol. 29 The results of the Si-NMR analysis are shown in Table 4 below. 【0096】 Manufacturing Example 8. Manufacturing of Polyester-Modified Silicone Resin-6 Instead of organopolysiloxane-1 in manufacturing example 2, organopolysiloxane-4 (M) has a high M unit content and does not contain D units. me 35 mol%, M Vi 20 mol% and T Ph Polyester-modified silicone resin-6 was produced using the same method as in Production Example 3, except that 45 mol% was used. 【0097】 The manufactured polyester-modified silicone resin-6 had a methoxy content of 0.22 mol%, a viscosity of 80,000 mPa·s at 60°C, a vinyl group content of 9.18 mol%, a phenyl group content of 20.6 mol%, and a weight-average molecular weight of 150,000 g / mol. 29 The results of the Si-NMR analysis are shown in Table 4 below. 【0098】 Experimental Examples 1 to 16. Production of Silicone Compositions Silicone compositions were prepared by mixing the components in the compositions shown in Tables 1 to 3. 【0099】 [Table 1] [Table 2] [Table 3] 【0100】 In Tables 1 to 3, organopolysiloxanes 1, 2, 3, and 4 are the same as the organopolysiloxanes described in Production Examples 2, 4, 5, and 8, respectively, and polyester-modified silicone resins 1 to 6 are those produced in Production Examples 3 to 8, respectively. 【0101】 The manufacturers, product names, or substance names of each component used in these other experimental examples are shown in Table 4. (B) The viscosity of organohydrogenpolysiloxane at 25°C was measured using a rheometer. 【0102】 [Table 4] 【0103】 Test example: Characterization The physical properties of the silicone compositions used in the experiment and the cured products produced therefrom were measured using the following method, and the results are shown in Table 5. 【0104】 Specifically, the silicone compositions of the examples or comparative examples were cured at a temperature of 190°C for 10 minutes using a mold capable of forming them to a thickness of 1 mm or 60 mm, to produce cured products. 【0105】 (1) Viscosity and thixotropy Anton Paar Rheometer (Model: MCR) 3 Using method 01), the viscosity of the composition was measured at a shear rate of 1 / s or 10 / s at 25°C. Subsequently, the thixotropy was calculated using the following formula. Thixometric index = (Viscosity at shear rate 1 / s) / (Viscosity at shear rate 10 / s) 【0106】 Furthermore, the viscosity values ​​in Table 5 were measured at 25°C. 【0107】 (2)Hardness The hardness of a 6mm thick hardened material was measured at 25°C using a Shore D type hardness tester (KOBUNSHI, ASKER TYPE D from KEIKI). 【0108】 (3) Transmittance The transmittance to light at a wavelength of 450 nm was measured for a 1 mm thick cured material using a spectrophotometer (HITACHI U-3900H). 【0109】 (4) Adhesion strength (maximum stress) A silicone composition was applied between two PCB substrates to a thickness of 10 mm horizontally, 5 mm wide, and 1 mm high, and cured at 150°C for 30 minutes. Then, using a universal material testing instrument (UTM), the adhesive strength was measured by measuring the maximum stress at which the cured silicone material fractured from the PCB substrates by pulling on both sides of the two PCB substrates. 【0110】 (5) Yellowing of the hardened material The silicone composition was cured at 150°C for 30 minutes to a size of 30 mm in width, 30 mm in height, and 2 mm in depth. The degree of discoloration (APHA color) of the cured specimens was measured. 【0111】 (6) Stickiness of the hardened material The silicone composition was cured at 150°C for 30 minutes to a size of 30 mm in width, 30 mm in height, and 2 mm in depth. After that, the surface of the cured object was polished once using a flat cloth, and then visually inspected for scratches or a smooth surface. 【0112】 [Table 5] 【0113】 As shown in Table 5, Experimental Examples 1 to 4 demonstrated that the viscosity and thixotropy of the silicone compositions were appropriate and offered excellent workability. The cured products exhibited appropriate hardness and permeability, as well as excellent adhesive strength, making them suitable for use as encapsulants for electronic and electrical components. 【0114】 On the other hand, Experimental Example 5, which included polyester-modified silicone resin-2 produced using organopolysiloxane-2 containing Q units; Experimental Example 6, which included polyester-modified silicone resin-3 produced using organopolysiloxane-3 with a low phenyl group content; Experimental Example 9, in which the molar ratio of Si-H bonds to alkenyl groups in the silicone composition was less than 0.5; and Experimental Example 12, which included polyester-modified silicone resin-6 produced using organopolysiloxane-4 with a high M unit content, all showed insufficient adhesive strength in the cured products and were unsuitable for use as sealants. 【0115】 Furthermore, in Experimental Example 7, which contained polyester-modified silicone resin in amounts below the standard value, and in Experimental Examples 10 and 11, where a small amount of polyester polyol was used during the production of the polyester-modified silicone resin, and an excessive amount was used, the hardness of the cured product was insufficient. In particular, Experimental Examples 10 and 11 also showed insufficient adhesive strength. 【0116】 Experimental Example 8, which contained an excessive amount of polyester-modified silicone resin, showed insufficient permeability of the cured product. 【0117】 Furthermore, in experimental examples 13 and 14, which did not contain polyester-modified silicone resin, the cured products lacked sufficient hardness and adhesive strength, resulting in yellowing and making them unsuitable as sealing materials. 【0118】 Experimental example 15, which did not contain silica, had insufficient viscosity and thixotropy of the silicone composition, resulting in poor workability. The cured product also lacked hardness and yellowing, making it unsuitable as a sealant.

Claims

[Claim 1] It contains a polyester polyol and a primary organopolysiloxane, The first organopolysiloxane contains an aryl group and an alkoxy group, and contains M units represented by (R １ ３ SiO １／２ ), in a content of 1 to 40 mol%, T units represented by (R ２ SiO ３／２ ), in a content of 20 to 80 mol%, D units represented by (R ３ ２ SiO ２／２ ), in a content of 1 to 60 mol%, and Q units represented by (SiO ４／２ ), in a content of 10 mol% or less. The aforementioned R １ This is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkenyl group. The aforementioned R ２ is a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group, The aforementioned R ３ The polyester-modified silicone resin composition is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group. [Claim 2] The polyester-modified silicone resin composition according to claim 1, comprising the polyester polyol and the first organopolysiloxane in a weight ratio of 0.02:1 to 0.3:

1. [Claim 3] Produced from the polyester-modified silicone resin composition described in claim 1, A polyester-modified silicone resin having an aryl group content of 50 mol% or less. [Claim 4] The polyester-modified silicone resin according to claim 3, wherein the viscosity at 60°C is 1,000 to 100,000 mPa·s and the weight-average molecular weight is 1,000 to 500,000 g / mol. [Claim 5] (A) Second organopolysiloxane; (B) Organohydrogenpolysiloxane; (C) Polyester-modified silicone resin according to claim 3 or claim 4; and (D) Silica; A silicone composition comprising, The content of the polyester-modified silicone resin relative to 100 parts by weight of the silicone composition is 10 to 45 parts by weight. A silicone composition for sealing, wherein the molar ratio of Si-H bonds to alkenyl groups in the silicone composition is 0.5 to 1.2.

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