Condensation-curable resin composition, cured product, molded body, and semiconductor device

Abstract

To provide a condensation-curable resin composition capable of yielding a molded body resistant to embrittlement and coloring.SOLUTION: A condensation-curable resin composition comprises: (A) an organosilicon compound having a structural unit represented by the following formula (i) and a siloxane structural unit, having a SiOH group at both ends of the molecular chain, and having a weight average molecular weight of 10,000 or more and 10,000,000 or less; and (B) an organometallic compound having three or more condensation-reactive groups.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a condensation-curing type resin composition, a cured product, a molded article, and a semiconductor device.

Background Art

[0002] Optical semiconductor devices including optical semiconductor elements such as light-emitting diodes (LEDs) have been put into practical use in various lighting devices, electro-optical display boards, traffic signals, backlights of liquid crystal display devices, LED displays, and the like. In these optical semiconductor devices, it is common for the optical semiconductor element to be encapsulated with a transparent encapsulant. In recent years, in the optical semiconductor industry, demands such as higher output power, smaller and thinner packages have been progressing, and the heat density per unit volume has a tendency to increase. For this reason, problems such as yellowing and embrittlement of the encapsulant have become serious. The same is true for semiconductor devices other than optical semiconductor devices.

[0003] Silicone resins have come to be widely used as encapsulants to replace epoxy resins because of their high heat resistance. These resins are also used as forming materials for light reflection walls, wavelength conversion layers, etc. in optical semiconductor devices. As curable compositions using silicone resins, there are those of a type in which an Si-C bond is formed and cured by a hydrosilylation reaction between a hydrosilyl group and a vinyl group, etc., and those of a type in which an Si-O bond is formed and cured by a condensation reaction between a silanol group (SiOH group) and an alkoxysilyl group, etc. In the case of the type cured by a hydrosilylation reaction, since the Si-C bond formed during curing has a lower bond energy than the Si-O bond, when the temperature reaches 200°C or higher, the Si-C bond is cleaved and the formation of the Si-O bond proceeds. For this reason, encapsulants of the type cured by a hydrosilylation reaction become hard and brittle and are likely to crack at temperatures of 200°C or higher. On the other hand, as encapsulants cured by a condensation reaction between a silanol group and an alkoxysilyl group, etc., Patent Documents 1 and 2 describe encapsulants containing a polydimethylsiloxane having silanol groups at both ends and a narrow molecular weight distribution, and an alkoxysilane, etc. In Patent Documents 1 and 2, it is shown that the obtained cured product had a low weight loss rate and no cracks occurred in the heat resistance evaluation test.

[0004] Also, siloxane polymers containing a silsesquioxane structure are known to have excellent heat resistance. Patent Document 3 describes a crosslinkable composition containing such a siloxane polymer.

[0005] On the other hand, glass plates and sintered plates themselves generally have higher heat resistance than resins. Therefore, in the wavelength conversion layer, etc. in an optical semiconductor device that is particularly susceptible to the influence of thermal degradation, a glass plate in which a phosphor is dispersed or a sintered plate of a phosphor may be used instead of a resin (see Patent Documents 4 and 5).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[0007] Sealants using polydimethylsiloxane as described in Patent Documents 1 and 2 do not have sufficient long-term reliability for heat resistance, such as embrittlement and coloring when exposed to high temperatures for a long period exceeding 1,000 hours. On the other hand, in Patent Document 3, only a crosslinkable composition that cures by a hydrosilylation reaction is implemented, and a cured product of such a crosslinkable composition is concerned about the occurrence of cracks and the like in a high-temperature environment as described above. Further, in Patent Document 3, although a result showing little mass reduction due to thermal decomposition even under heating is shown regarding heat resistance, crack resistance, color resistance, etc. required for a sealant of a semiconductor element and the like are not considered. Further, when using a glass plate or a sintered plate, the cost becomes high due to difficulties in molding, and an adhesive is required to attach these, and ultimately, the heat resistance of the resin as the adhesive becomes a problem.

[0008] The present invention has been made based on the above circumstances, and an object thereof is to provide a condensation-curing type resin composition and a cured product capable of obtaining a molded body that is less likely to embrittle and color even when exposed to high temperatures for a long period, and a molded body and a semiconductor device using these. [Means for Solving the Problems

[0009] The invention made to solve the above problems is a condensation-curing type resin composition (α) containing (A) an organosilicon compound having a structural unit (i) represented by the following formula (i) and a structural unit (ii) represented by the following formula (ii), with SiOH groups present at both ends of the molecular chain and having a weight average molecular weight of 10,000 or more and 10,000,000 or less, and (B) an organometallic compound having three or more condensation-reactive groups. [Chemical formula] (In formula (i), R 1 is independently a hydrocarbon group having 1 to 8 carbon atoms. In formula (ii), R 2 is independently a hydrocarbon group having 1 to 8 carbon atoms.)

[0010] In the above (A) organosilicon compound, it is preferable that the degree of polymerization of the structural unit (i) is 10 or more and 10,000 or less, and the degree of polymerization of the structural unit (ii) is 1 or more and 10,000 or less.

[0011] It is preferable that the above (A) organosilicon compound is represented by the following formula (1). [Chemical formula] (In formula (1), R 1 is independently a hydrocarbon group having 1 to 8 carbon atoms. R 2 is independently a hydrocarbon group having 1 to 8 carbon atoms. m is a numerical value satisfying a weight average molecular weight of 10,000 or more and 10,000,000 or less. n is an average value satisfying 1 to 30.)

[0012] It is preferable that the above (B) organometallic compound is represented by the following formula (2). [Chemical formula] (In formula (2), R 3 is independently an alkyl group having 1 to 4 carbon atoms. q is an average value satisfying 1 to 100.)

[0013] It is preferable that the condensation-curing type resin composition (α) further contains (C) a condensation catalyst.

[0014] It is preferable that the condensation-curing type resin composition (α) further contains (D) a solvent.

[0015] It is preferable that the condensation-curing type resin composition (α) further contains (E) a phosphor, (F) a white pigment, or (G) an inorganic oxide (excluding components corresponding to (E) the phosphor or (F) the white pigment).

[0016] It is preferable that the content of the above (E) phosphor is 1 part by mass or more and 80 parts by mass or less with respect to 100 parts by mass in total of the above (A) organosilicon compound and (B) organometallic compound.

[0017] It is preferable that the above (F) white pigment is titanium oxide, and the content of the above (F) white pigment is 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass in total of the above (A) organosilicon compound and (B) organometallic compound.

[0018] Another invention made to solve the above problems is a condensation-curing type resin composition containing an organosilicon compound, wherein when the cured product obtained under the following thermosetting conditions is heated at 250 ° C for 504 hours in an air atmosphere, and the following tensile test and the following light transmittance measurement of the cured product are performed before and after the heating, the ratio (Eb / Ea) of the elongation at break (Eb) after the heating to the elongation at break (Ea) before the heating is 0.1 or more, the ratio (Sb / Sa) of the breaking stress (Sb) after the heating to the breaking stress (Sa) before the heating is 0.5 or more and less than 10, and the ratio (Tb / Ta) of the light transmittance (Tb) after the heating to the light transmittance (Ta) before the heating is 0.9 or more, which is a condensation-curing type resin composition (β). (Thermosetting conditions) Heating continuously in this order at 70 ° C for 30 minutes, 100 ° C for 1 hour, and 200 ° C for 2 hours in an air atmosphere (Tensile test) A strip-shaped test piece with a length of 50 mm, a width of 5 mm, and a thickness of 0.2 mm was produced, and the test was carried out on this test piece at a temperature of 25°C and a tensile speed of 5 mm / min. (Measurement of light transmittance) For a test piece that is a cured product with a thickness of 0.1 mm, the transmittance of light with a wavelength of 350 nm was measured.

[0019] Another invention made to solve the above problems is a cured product obtained by curing the condensation-curing type resin composition (α) or the condensation-curing type resin composition (β).

[0020] Another invention made to solve the above problems is a molded article obtained from the condensation-curing type resin composition (α), the condensation-curing type resin composition (β), or the cured product.

[0021] Another invention made to solve the above problems is a semiconductor device including a semiconductor element and the molded article that seals the semiconductor element.

Effect of the Invention

[0022] According to the present invention, it is possible to provide a condensation-curing type resin composition and a cured product capable of obtaining a molded article that is less likely to be embrittled and colored even when exposed to high temperatures for a long time, and a molded article and a semiconductor device using these.

Embodiments for Carrying Out the Invention

[0023] Hereinafter, a condensation-curing type resin composition, a cured product, a molded article, and a semiconductor device according to an embodiment of the present invention will be described in detail.

[0024] <Condensation-curing type resin composition (α)> The condensation-curing resin composition (α) according to an embodiment of the present invention contains (A) an organosilicon compound and (B) an organometallic compound. The condensation-curing resin composition (α) can further contain, as suitable components, (C) a condensation catalyst, (D) a solvent, (E) a phosphor, (F) a white pigment, and (G) an inorganic oxide (excluding (E) the phosphor and (F) the white pigment). The condensation-curing resin composition (α) may further contain other components. Further, the condensation-curing resin composition (α) includes those formed by mixing two or three or more thereof, those used by mixing, and those before mixing. That is, the condensation-curing resin composition (α) may be a composition such as a two-component type or a three-component type. Each of the components such as (A) to (F) can be used alone or as a mixture of two or more. Hereinafter, each component constituting the condensation-curing resin composition (α) will be described in detail.

[0025] ((A) Organosilicon compound) (A) The organosilicon compound contains a structural unit (i) and a structural unit (ii). Further, SiOH groups are present at both ends of the molecular chain of the (A) organosilicon compound. The condensation-curing resin composition (α) is a condensation-curing composition containing an (A) organosilicon compound having a structural unit (i) having a double-decker type silsesquioxane structure and a structural unit (ii) having a siloxane structure. When the condensation-curing resin composition (α) is thermally cured, a molded article that is hardly embrittled and colored even when exposed to a high temperature for a long time can be obtained. Specifically, the molded article obtained by curing the condensation-curing resin composition is excellent in crack resistance under a high temperature environment, and thermal deterioration such as mechanical strength hardly occurs. Further, the obtained molded article is also excellent in color resistance under a high temperature environment, and thermal deterioration of translucency hardly occurs.

[0026] (Structural unit (i)) The structural unit (i) is represented by the following formula (i).

[0027] [Chemical formula]

[0028] In formula (i), R 1 is, independently of one another, a hydrocarbon group having 1 to 8 carbon atoms.

[0029] Examples of the hydrocarbon group represented by R 1 include aliphatic chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Examples of aliphatic chain hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group, alkenyl groups such as vinyl group, propenyl group, and alkynyl groups such as ethynyl group, propynyl group and the like. Examples of alicyclic hydrocarbon groups include, for example, cyclopropyl group, cyclobutyl group, cyclohexyl group, cyclohexenyl group and the like. Examples of aromatic hydrocarbon groups include phenyl group, tolyl group and the like.

[0030] Examples of the upper limit of the carbon number of R 1 are preferably 5, more preferably 3. As R 1 , an aliphatic chain hydrocarbon group is preferable, an alkyl group is more preferable, and a methyl group is even more preferable. When R 1 is these groups, the optical performance and ease of synthesis are better.

[0031] (A) The lower limit of the degree of polymerization of the structural unit (i) in the organosilicon compound, that is, the double-decker type silsesquioxane structural unit, is preferably 10, more preferably 15, and even more preferably 40. The upper limit of this degree of polymerization is preferably 8,000, more preferably 5,000, and even more preferably 1,000, 500 or 200. The degree of polymerization refers to the average number of the structural units contained in one molecule.

[0032] (Structural unit (ii)) The structural unit (ii) is represented by the following formula (ii).

[0033] [Chemical formula]

[0034] In formula (ii), R 2Each is independently a hydrocarbon group having 1 to 8 carbon atoms.

[0035] R 2 Examples of the hydrocarbon group represented by R 1 are the same as those exemplified for the hydrocarbon group represented by R 2 The upper limit of the carbon number of R 2 is preferably 5, more preferably 3. As R 2 an aliphatic chain hydrocarbon group is preferable, an alkyl group is more preferable, and a methyl group is even more preferable. When R

[0036] is these groups, the optical performance and ease of synthesis become better.

[0036] (A) In the organosilicon compound, the lower limit of the degree of polymerization of the structural unit (ii), that is, the siloxane structural unit, is preferably 1, more preferably 10, and even more preferably 50. Further, the upper limit of this degree of polymerization is preferably 10,000, more preferably 2,000, and even more preferably 1,000 or 500.

[0037] (A) In the organosilicon compound, it is preferable that a polysiloxane chain formed by linking a plurality of structural units (ii) is formed. The (A) organosilicon compound may have one or a plurality of the above polysiloxane chains in one molecule. The degree of polymerization of the structural unit (ii) in the above polysiloxane chain is, for example, 1 or more and 30 or less. The lower limit of this degree of polymerization is preferably 2, more preferably 3. On the other hand, the upper limit of this degree of polymerization is preferably 15, more preferably 10, and even more preferably 6. That is, the above polysiloxane chain is formed by, for example, an average of 1 or more and 30 or less structural units (ii). When the degree of polymerization of the structural unit (ii) in the above polysiloxane chain is within the above range, the balance between the performance by the structural unit (i) having a silsesquioxane structure and the performance by the structural unit (ii) having a siloxane structure is optimized, and the heat resistance of the obtained molded body and the like are further enhanced.

[0038] (A) Organosilicon compounds usually have a linear molecular chain structure. In (A) organosilicon compounds, SiOH groups (silanol groups) are present at both ends of this molecular chain respectively. The SiOH group is a group formed by the bonding of a silicon atom (Si) with a hydroxy group (OH). In this specification, the SiOH group and the silanol group are synonymous, and the SiOH group is also referred to as the silanol group. The silicon atom in the silanol group has four bonds, and one of them is bonded to the hydroxy group. The atoms or groups to which the other three bonds of this silicon atom are bonded are not particularly limited. Also, the silanol groups at both ends of the molecular chain may overlap with a part of structural unit (i) and structural unit (ii).

[0039] (A) The arrangement of structural units such as structural unit (i) and structural unit (ii) in the organosilicon compound is not particularly limited. Also, the orientation of structural unit (i) and structural unit (ii) is not limited either. (A) The organosilicon compound may have a structure in which a hydrogen atom or a hydroxy group is bonded to both ends of a polymer chain formed from one or more structural units (i) and one or more structural units (ii) respectively. When the outermost atom of the polymer chain composed of structural unit (i) and structural unit (ii) is a silicon atom, a silanol group is formed by the bonding of a hydroxy group to the outermost silicon atom. On the other hand, when the outermost atom of the above polymer chain is an oxygen atom in siloxane, a silanol group is formed by the bonding of a hydrogen atom to the outermost oxygen atom. Also, the structural units located at both ends of the above polymer chain are preferably structural unit (ii).

[0040] (A) As a preferred form of the organosilicon compound, there can be mentioned a polymer in which a hydrogen atom or a hydroxy group is bonded to both ends of a polymer chain formed by the repetition of a polysiloxane chain in which one structural unit (i) and a plurality of structural units (ii) are linked. More specifically, (A) the organosilicon compound preferably has a repeating structure of each structural unit as shown by the compound represented by formula (1) described later.

[0041] (A) The organosilicon compound may further have other structural units in addition to structural unit (i) and structural unit (ii). However, it is preferable that the other structural units do not contain vinyl groups or other crosslinkable groups. The crosslinkable group refers to a group capable of a crosslinking reaction, and examples thereof include vinyl groups and hydrosilyl groups. (A) The organosilicon compound preferably has a structure having crosslinkable groups only at both ends. As the number (average value) of crosslinkable groups possessed by (A) the organosilicon compound, 5 or less is preferable, 3 or less is more preferable, and 2 is particularly preferable. Further, the content ratio of the above other structural units in all the structural units of (A) the organosilicon compound is preferably 10 mol% or less, and more preferably 1 mol% or less.

[0042] (A) The lower limit of the weight average molecular weight of the organosilicon compound is 10,000, preferably 15,000, and more preferably 20,000. The upper limit of this weight average molecular weight is 10,000,000, preferably 1,000,000, and more preferably 300,000. When the weight average molecular weight of (A) the organosilicon compound is within the above range, the obtained molded body can exhibit high heat resistance and the like.

[0043] (A) The organosilicon compound is preferably represented by the following formula (1).

[0044]

Chemical formula

[0045] In formula (1), R 1 are each independently a hydrocarbon group having 1 to 8 carbon atoms. R 2 are each independently a hydrocarbon group having 1 to 8 carbon atoms. m is a numerical value satisfying a weight average molecular weight of 10,000 or more and 10,000,000 or less. n is an average value satisfying 1 to 30.

[0046] Specific examples and preferred examples of the hydrocarbon groups represented by R 1 and R 2 in formula (1) are the same as those of R 1and R 2 is the same as the hydrocarbon group represented by

[0047] The above m is a numerical value satisfying a weight average molecular weight of 10,000 or more and 10,000,000 or less. Specifically, the lower limit of the above m is, for example, 5, preferably 10, more preferably 15, and even more preferably 40. Further, the upper limit of this m is, for example, 8,000, preferably 5,000, and even more preferably 1,000, 500 or 200.

[0048] The lower limit of the above n is 1, preferably 2, and more preferably 3. Further, the upper limit of this n is 30, preferably 15, more preferably 10, and even more preferably 6. When n is within the above range, the balance between the performance by the structural unit (i) having a silsesquioxane structure and the performance by the structural unit (ii) having a siloxane structure is optimized, and the heat resistance and the like of the obtained molded body are further enhanced.

[0049] It can be said that m in the formula (1) represents the degree of polymerization of the above structural unit (i) in the (A) organosilicon compound. It can be said that n represents the average number (degree of polymerization of the polysiloxane chain) of the above structural unit (ii) in the polysiloxane chain formed by the continuous arrangement of the above structural unit (ii). Further, it can be said that substantially mn + n is equal to the degree of polymerization of the structural unit (ii) in the (A) organosilicon compound.

[0050] The specific structure of the (A) organosilicon compound represented by the above formula (1) is as follows when the structural unit (i) is X, the structural unit (ii) is Y, m = 2, and n = 5. However, since m and n are average values, even in one molecule, the number of consecutive arrangements of Y (structural unit (ii)), that is, the average number of structural unit (ii) in the polysiloxane chain may be different.

[0051] [Chemical formula]

[0052] As the lower limit of the content of the organosilicon compound (A) with respect to 100 parts by mass in total of the organosilicon compound (A) and the organometallic compound (B) in the condensation-curing type resin composition (α), 80 parts by mass is preferable, 90 parts by mass is more preferable, 95 parts by mass is still more preferable, and 97 parts by mass is even more preferable. On the other hand, as the upper limit of this content, 99.9 parts by mass is preferable, and 99.5 parts by mass is more preferable.

[0053] <Method for producing (A) organosilicon compound> The method for producing the organosilicon compound (A) is not particularly limited, and examples thereof include a method of subjecting a compound represented by the following formula (2-1) and a compound represented by the following formula (2-2) to equilibrium polymerization in the presence of a catalyst.

[0054]

Chemical formula

[0055] In formula (2-1), R 1 are each independently a hydrocarbon group having 1 to 8 carbon atoms. In formula (2-2), R 2 are each independently a hydrocarbon group having 1 to 8 carbon atoms. p is an integer of 3 to 8.

[0056] Specific examples and preferred examples of R 1 in the above formula (2-1) are the same as R 1 in the above formulas (i) and (1). Specific examples and preferred examples of R 2 in the above formula (2-2) are the same as R 2 in the above formulas (ii) and (1). The above p is preferably an integer of 3 to 6, and more preferably 4. Note that n in the above (1) depends on the value of p, that is, the structure of the compound represented by the above formula (2-2).

[0057] The compound represented by the above formula (2-1) and the compound represented by the above formula (2-2) may be used one by one respectively, or may be used two or more by two or more. The usage ratio of the compound represented by the above formula (2-1) and the compound represented by the above formula (2-2) can be appropriately set according to the degree of polymerization of each structural unit in the target organosilicon compound and the like.

[0058] As the catalyst used in the above method, an acid catalyst is preferred. Examples of the acid catalyst include acid catalysts such as hydrochloric acid, sulfuric acid, fluorosulfuric acid, trifluoromethanesulfonic acid, activated clay, and cation exchange resins such as sulfonic acid-based ion exchange resins. Among these, trifluoromethanesulfonic acid, activated clay, and cation exchange resins are preferred.

[0059] (A) A more specific synthesis method of the organosilicon compound includes, for example, the method described in Synthesis Example 1 of JP-A-2010-116464.

[0060] ((B) Organometallic compound) (B) The organometallic compound is an organometallic compound having three or more condensation-reactive groups. (B) The organometallic compound undergoes a crosslinking reaction with the (A) organosilicon compound.

[0061] Examples of the condensation-reactive group include an alkoxy group, an acetoxy group, an oxime group (-O-N=CR2: R is a hydrocarbon group), a halogen atom, and the like. These condensation-reactive groups are preferably bonded to a metal atom. As the condensation-reactive group, an alkoxy group is preferred. Examples of the alkoxy group include alkoxy groups having an alkyl group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Among these, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.

[0062] (B) Examples of the metal atom included in the organometallic compound include silicon, titanium, aluminum, zirconium, etc., and silicon is preferred. In the present specification, semi-metal atoms such as silicon and germanium are also included in the metal atoms.

[0063] (B) As the organometallic compound, a compound having four or more condensation reactive groups is preferable from the viewpoints of crosslinkability, heat resistance of the resulting molded article, mechanical properties, etc. Further, as the (B) organometallic compound, a compound in which four condensation reactive groups are bonded to a metal atom, a hydrolysis condensate of this compound, and a combination thereof are preferable. The hydrolysis condensate is preferably a linear compound.

[0064] More specifically, preferable examples of the (B) organometallic compound include compounds represented by the following formula (2).

[0065]

Chemical formula

[0066] In formula (2), R 3 each independently represents an alkyl group having 1 to 4 carbon atoms. q is an average value satisfying 1 to 100.

[0067] Examples of the alkyl group represented by the above R 3 include a methyl group, an ethyl group, a propyl group, and a butyl group, with a methyl group and an ethyl group being preferable, and a methyl group being more preferable.

[0068] As the upper limit of q, 10 is preferable. As the lower limit of q, 2 is preferable.

[0069] (B) Among the organometallic compounds, examples of the compounds having three condensation-reactive groups include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, glycidyltrimethoxysilane, mercaptoprimethoxysilane, mercaptopriethoxysilane, aminopropyltriethoxysilane, etc. (B) Among the organometallic compounds, examples of the compounds having four condensation-reactive groups include tetramethoxysilane, tetraethoxysilane, tetraisopropyl titanate, tetranormal butyl titanate, etc. (B) Among the organometallic compounds, examples of the compounds having five or more condensation-reactive groups include partial hydrolysis condensates of the above-mentioned respective compounds.

[0070] (B) Commercially available products of organometallic compounds include MKC Silicate MS57 (trademark), MKC Silicate MS51 (trademark) (tetramethoxysilane pentamer on average), MKC Silicate MS56, MS56S (both trademarks), manufactured by Mitsubishi Chemical Corporation; methyl silicate 51 (tetramethoxysilane tetramer), methyl silicate 53 (tetramethoxysilane heptamer), ethyl silicate 40 (tetraethoxysilane pentamer), ethyl silicate 48 (tetraethoxysilane decamer), etc., manufactured by Colcoat Co., Ltd.

[0071] As the lower limit of the content of the (B) organometallic compound with respect to 100 parts by mass in total of the (A) organosilicon compound and the (B) organometallic compound in the condensation-curing type resin composition (α), 0.1 part by mass is preferable, and 0.5 part by mass is more preferable. On the other hand, as the upper limit of this content, 10 parts by mass is preferable, and 5 parts by mass is more preferable.

[0072] In addition, as for the mixing ratio of the (A) organosilicon compound and the (B) organometallic compound in the condensation-curing resin composition (α), the ratio of the number of moles of the condensation-reactive group of the (B) organometallic compound to the number of moles of the silanol group of the (A) organosilicon compound (condensation-reactive group / silanol group) is preferably a ratio exceeding 1. From the viewpoint of allowing the crosslinking reaction to proceed sufficiently, the above ratio (condensation-reactive group / silanol group) is preferably 1.5 or more, more preferably 2 or more. On the other hand, from the viewpoint of sufficiently containing the (A) organosilicon compound, which is a component capable of exhibiting excellent heat resistance, the above ratio (condensation-reactive group / silanol group) is preferably 15 or less, more preferably 5 or less.

[0073] ((C) Condensation catalyst) (C) The condensation catalyst is not particularly limited as long as it is a catalyst that causes a condensation reaction between the (A) organosilicon compound and the (B) organometallic compound. Examples of such catalysts include tin-based catalysts, titanium-based catalysts, bismuth-based catalysts, etc., with tin-based catalysts and titanium-based catalysts being preferred, and tin-based catalysts being more preferred.

[0074] Examples of tin-based catalysts include organotin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin maleate, dioctyltin maleate, and tin 2-ethylhexanoate.

[0075] When the (B) organometallic compound is an organosilicon compound, organotitanium compounds such as titanium tetra-2-ethylhexoxide, titanium tetra-n-butoxide, and titanium tetraisopropoxide can also be used as suitable catalysts for the (C) condensation catalyst.

[0076] The content of the (C) condensation catalyst with respect to a total of 100 parts by mass of the (A) organosilicon compound and the (B) organometallic compound in the condensation-curing resin composition (α) can be, for example, 10 -7 parts by mass or more and 1 part by mass or less.

[0077] ((D) Solvent) (D) The solvent is preferably a solvent that can dissolve (A) an organosilicon compound, (B) an organometallic compound, etc., and is non-reactive with the contained components.

[0078] Examples of (D) the solvent include aliphatic hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF), dioxane, and propylene glycol monomethyl ether acetate (PGMEA), halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride, and ester solvents such as ethyl acetate and butyl acetate.

[0079] The content of (D) the solvent in the condensation-curing type resin composition (α) is not particularly limited, but for example, 10% by mass or more and 80% by mass or less is preferable, and 20% by mass or more and 60% by mass or less is more preferable.

[0080] ((E) Phosphor) (E) The phosphor is usually dispersed and contained in the condensation-curing type resin composition (α). When the condensation-curing type resin composition (α) further contains (E) the phosphor, the condensation-curing type resin composition (α) can be more preferably used as a sealing material for semiconductor elements, etc., specifically, a forming material for a wavelength conversion layer, etc.

[0081] Examples of (E) the phosphor include inorganic phosphors such as YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors, and organic phosphors such as allylsulfoamide·melamine formaldehyde co-condensation dyes and perylene-based phosphors.

[0082] As the lower limit of the content of the (E) phosphor in the condensation-curing resin composition (α), 1 part by mass is preferable, 10 parts by mass is more preferable, and 30 parts by mass is even more preferable with respect to 100 parts by mass in total of the (A) organosilicon compound and the (B) organometallic compound. On the other hand, as the upper limit of this content, 80 parts by mass is preferable, and 50 parts by mass is more preferable. By setting the content of the (E) phosphor within the above range, while having sufficient heat resistance and the like, the properties (fluorescent properties, wavelength conversion properties, etc.) by the (E) phosphor can be sufficiently exhibited.

[0083] ((F) white pigment) (F) The white pigment is usually dispersed and contained in the condensation-curing resin composition (α). When the condensation-curing resin composition (α) further contains the (F) white pigment, the condensation-curing resin composition (α) can be more preferably used as a forming material for a sealing material of a semiconductor element or the like, specifically, a light reflecting plate or the like. Further, when the condensation-curing resin composition (α) further contains the (F) white pigment, the obtained cured product or molded body is excellent in heat resistance, and the light reflectance is hardly reduced even when exposed to a high temperature for a long period of time.

[0084] Examples of the (F) white pigment include titanium oxide, barium titanate, magnesium oxide, antimony oxide, zirconium oxide, inorganic hollow particles, etc. Among these, titanium oxide is preferable.

[0085] As the lower limit of the content of the (F) white pigment in the condensation-curing resin composition (α), 10 parts by mass is preferable, and 20 parts by mass is more preferable with respect to 100 parts by mass in total of the (A) organosilicon compound and the (B) organometallic compound. On the other hand, as the upper limit of this content, 80 parts by mass is preferable, and 50 parts by mass is more preferable. By setting the content of the (F) white pigment within the above range, while having sufficient heat resistance and the like, the properties (light reflectivity, etc.) by the (F) white pigment can be sufficiently exhibited.

[0086] ((G) inorganic oxide) (G) The inorganic oxide is usually dispersed and contained in the condensation-curing resin composition (α). The (G) inorganic oxide does not include components corresponding to the (E) phosphor or (F) white pigment. Examples of the (G) inorganic oxide include those that function as fillers such as silica and alumina, and those that function as sedimentation inhibitors such as nanosilica. The content of the (G) inorganic oxide in the condensation-curing resin composition (α) is preferably 0.1 part by mass or more and 80 parts by mass or less with respect to a total of 100 parts by mass of the (A) organosilicon compound and the (B) organometallic compound.

[0087] (Other components) The condensation-curing resin composition (α) may contain other components other than the above-described components (A) to (G). Examples of other components include flame retardants, ion adsorbents, antioxidants, curing retardants, curing inhibitors, ultraviolet absorbers, and the like.

[0088] The content of other components other than the above-described components (A) to (G) can be appropriately set according to the use and the like. On the other hand, in some cases, it is preferable that these other components be less. The upper limit of the content of other components other than the above-described components (A) to (G) in the condensation-curing resin composition (α) may preferably be 10% by mass, 1% by mass, or 0.1% by mass. On the other hand, the lower limit of the content of other components other than the above-described components (A) to (G) may be, for example, 0.01% by mass, 0.1% by mass, or 1% by mass.

[0089] (Preparation method) The preparation method of the condensation-curing resin composition (α) is not particularly limited, and it can be prepared by a method such as mixing each component using a known mixer.

[0090] (Use) The condensation-curing resin composition (α) can be suitably used as a sealing material for an optical semiconductor element, a sealing material for other semiconductor elements, a wavelength conversion layer, a light reflecting plate, a buffer material, an insulating film, a sealing material, a forming material for an optical lens, or other adhesives. Among them, since the molded article obtained by curing has excellent crack resistance in a high-temperature environment and is less likely to cause thermal deterioration such as light transmittance and strength, it can be suitably used as a sealing material for semiconductor elements, particularly for optical semiconductor elements. Further, in particular, when the condensation-curing resin composition (α) contains (E) a phosphor, it is suitably used as a forming material for a wavelength conversion layer of a light-emitting device such as an optical semiconductor device. When the condensation-curing resin composition (α) contains (F) a white pigment, it is suitably used as a forming material for a light reflecting plate of a light-emitting device such as an optical semiconductor device.

[0091] <Condensation-curing resin composition (β)> The condensation-curing resin composition (β) according to an embodiment of the present invention is a condensation-curing resin composition containing an organosilicon compound, When the cured product obtained under the following thermosetting conditions is heated at 250°C for 504 hours in an air atmosphere, and the following tensile test and the following light transmittance measurement of the cured product are performed before and after the heating, the ratio (Eb / Ea) of the elongation at break (Eb) after the heating to the elongation at break (Ea) before the heating is 0.1 or more, the ratio (Sb / Sa) of the breaking stress (Sb) after the heating to the breaking stress (Sa) before the heating is 0.5 or more and less than 10, and the ratio (Tb / Ta) of the light transmittance (Tb) after the heating to the light transmittance (Ta) before the heating is 0.9 or more. (Thermosetting conditions) In an air atmosphere, heat continuously in this order at 70°C for 30 minutes, 100°C for 1 hour, and 200°C for 2 hours (Tensile test) Prepare a strip-shaped test piece with a length of 50 mm, a width of 5 mm, and a thickness of 0.2 mm, and perform the test on this test piece at a temperature of 25°C and a tensile speed of 5 mm / min (Measurement of light transmittance) Measure the transmittance of light with a wavelength of 350 nm for a test piece that is a cured product with a thickness of 0.1 mm

[0092] The details of each test and measurement are as described in the examples.

[0093] The lower limit of the ratio (Eb / Ea) of the elongation at break is 0.1, and in some cases, 0.2 or 0.3 is more preferable. As the lower limit of the elongation at break (Ea) before heating, 5% is preferable, and 10% is more preferable. Also, as the upper limit of the elongation at break (Ea) before heating, 300% is preferable. The cured product of the condensation-curing type resin composition (β) maintains a certain degree of elongation at break even when exposed to high temperatures for a long time, and is less likely to embrittle. Note that the upper limit of the ratio (Eb / Ea) of the elongation at break is preferably 2, and more preferably 1.5.

[0094] The lower limit of the ratio (Sb / Sa) of the breaking stress is preferably 0.6, and more preferably 0.8. On the other hand, the upper limit of this ratio (Sb / Sa) is preferably 7, and more preferably 5. The cured product of the condensation-curing type resin composition (β) has a small change in breaking stress even when exposed to high temperatures for a long time. Therefore, according to the condensation-curing type resin composition (β), a molded article that is less likely to embrittle even when exposed to high temperatures for a long time can be obtained.

[0095] The ratio (Tb / Ta) of the light transmittance (Tb) after heating to the light transmittance (Ta) before heating is 0.9 or more, and more preferably 1.0. The cured product of the condensation-curing type resin composition (β) maintains the light transmittance and is less likely to be colored even when exposed to high temperatures for a long time. Note that as the light transmittance (Ta) before heating, 98% or more is preferable, 99% or more is more preferable, and 100% is even more preferable.

[0096] Specific and preferred compositions of the condensation-curing type resin composition (β) can include the compositions of the above-described condensation-curing type resin composition (α). On the other hand, also in the condensation-curing type resin composition (α), it is preferable that the ratio (Eb / Ea) of the elongation at break, the ratio (Sb / Sa) of the breaking stress, and the ratio (Tb / Ta) of the light transmittance (Tb) obtained by the above method are within the above ranges, respectively.

[0097] <Cured Product> The cured product according to one embodiment of the present invention is a cured product obtained by curing the above-described condensation-curing type resin composition (α) or condensation-curing type resin composition (β). The cured product can be obtained by heating the condensation-curing type resin composition (α) or condensation-curing type resin composition (β) by a known method. The heating temperature at this time is, for example, 60 to 250°C, and the heating time can be, for example, 1 to 24 hours. Note that the cured product only needs to be one in which a crosslinking reaction occurs in at least a part of each component in the condensation-curing type resin composition and the fluidity has decreased, and is not limited to one that is completely cured. That is, the cured product includes those having elasticity or viscosity, those that soften or melt by heating, and the like. Since the condensation-curing type resin composition (α) or condensation-curing type resin composition (β) is used for the cured product, embrittlement hardly occurs even when exposed to a high temperature for a long period of time, and a molded article in which embrittlement hardly occurs even when exposed to a high temperature for a long period of time can be obtained. Specifically, the cured product and the molded article obtained from the cured product are excellent in crack resistance in a high-temperature environment, and thermal deterioration such as mechanical strength hardly occurs. Further, the cured product and the molded article obtained from the cured product are also excellent in coloring resistance in a high-temperature environment, and thermal deterioration of translucency hardly occurs.

[0098] The cured product may be a B-stage cured product. The B-stage cured product refers to a semi-cured product. Specifically, the B-stage cured product is preferably solid at 25°C and has a softening point in the range of 100°C or higher and 200°C or lower. The B-stage cured product can be obtained by heating the condensation-curing type resin composition (α) or condensation-curing type resin composition (β) in a temperature range of, for example, 100 to 250°C for 1 to 5 hours.

[0099] The shape of the cured product is not particularly limited, and may be, for example, powdery, granular, plate-like, sheet-like, or the like. Further, it may be formed into a predetermined shape.

[0100] <Molded article> The molded article according to an embodiment of the present invention is a molded article obtained from the condensation-curing resin composition (α), the condensation-curing resin composition (β), or the cured product. Examples of the molded article include encapsulants for semiconductor elements such as optical semiconductor elements, wavelength conversion layers, light reflectors, buffer materials, insulating films, sealing materials, optical lenses, etc. Among these, it is preferably an encapsulant for semiconductor elements, and more preferably an encapsulant for optical semiconductor elements.

[0101] The molded article may be a molded article obtained by curing the above-described condensation-curing resin composition (α) or condensation-curing resin composition (β) into a predetermined shape using a mold or the like, or a molded article obtained by processing the cured product into a predetermined shape. Further included are molded articles obtained by further heat-curing the cured product in a semi-cured state or the like.

[0102] The minimum light transmittance of the molded article in the wavelength range of 350 to 800 nm is preferably 95% or more, and more preferably 99% or more. That is, in the wavelength range of 350 to 800 nm, it is preferable that the lowest transmittance is 95% or 99% or more. When having such a high light transmittance, it becomes more useful as an encapsulant for optical semiconductor elements, etc. The upper limit of this light transmittance is, for example, 99.9%, and it may also be 99%.

[0103] <Semiconductor device> The semiconductor device according to an embodiment of the present invention includes a semiconductor element and the above-described molded article that encapsulates the semiconductor element.

[0104] The above semiconductor element may be an optical semiconductor element or other semiconductor elements. The above optical semiconductor element is not particularly limited. For example, when the optical semiconductor element is an LED, examples include those formed by laminating a semiconductor material on a substrate. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, SiC, etc.

[0105] The semiconductor device is obtained by encapsulating a semiconductor element with the condensation-curing type resin composition or cured product according to an embodiment of the present invention. This encapsulation method can be performed by a known method. When using the condensation-curing type resin composition, for example, (1) a method of previously injecting the condensation-curing type resin composition into a mold frame, immersing a lead frame or the like to which the semiconductor element is fixed therein, and then thermally curing it; (2) a method of injecting the condensation-curing type resin composition into a mold frame into which the semiconductor element is inserted and thermally curing it, etc. can be mentioned. Examples of the method of injecting the condensation-curing type resin composition include transfer molding and injection molding. Further, as other encapsulation methods, for example, a method of attaching the cured product in a semi-cured state onto the semiconductor element and then thermally curing it, etc. can also be mentioned.

[0106] Since the condensation-curing type resin composition or cured product according to an embodiment of the present invention is used as the encapsulant for the semiconductor device, the encapsulant is excellent in crack resistance under a high-temperature environment, and thermal deterioration such as light transmittance and strength hardly occurs. Therefore, the semiconductor device is excellent in long-term durability even if it has high output and high power density. For such reasons, the semiconductor device is preferably an optical semiconductor device. The optical semiconductor device can be used in various lighting devices, electro-optical display boards, signal lights, backlights of liquid crystal display devices, LED displays, etc.

Examples

[0107] The present invention will be described in more detail based on examples. Note that the present invention is not limited by the following examples. Hereinafter, the analysis method of the synthesized organosilicon compound will be shown.

[0108] <Number average molecular weight and weight average molecular weight> Using a high-performance liquid chromatograph system CO-2065plus manufactured by JASCO Corporation, 20 μL of a THF solution with a sample concentration of 1 mass% was used as an analysis sample, and it was measured by the GPC method under the following conditions. The number average molecular weight and weight average molecular weight were determined by converting to polystyrene. Column: Shodex KF804L [manufactured by Showa Denko K.K.](two connected in series) Column temperature: 40℃ Detector: RI Eluent:THF Eluent flow rate: 1.0 mL per minute

[0109] <NMR(核磁気共鳴スペクトル)> 400MH manufactured by JEOL Ltd. Z The NMR measurement apparatus was used, and the measurement sample was dissolved in deuterated acetone (manufactured by Wako Pure Chemical Industries, Ltd.). 1 The average polysiloxane chain length (n in the above formula (1)) introduced into the synthesized organosilicon compound was determined from the integral ratio of 1 H-NMR.

[0110] [Synthesis Example 1] <Synthesis of silsesquioxane derivative (DD-4OH)> A silsesquioxane derivative (DD-4OH) represented by the following formula was synthesized by the method described in Japanese Patent No. 5704168.

[0111] [ka]

[0112] [Synthesis Example 2] <Synthesis of silsesquioxane derivative (DD(Me)-OH)> A silsesquioxane derivative (DD(Me)-OH) represented by the following formula was synthesized by the method described in Japanese Patent No. 4379120. The silsesquioxane derivative (DD-4OH) synthesized in Synthesis Example 1 was used as a raw material.

[0113] [ka]

[0114] [Synthesis Example 3] Synthesis of organosilicon compound (A-1) A 3L flask was equipped with a cooling tube, a mechanical stirrer, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 400 g of a silsesquioxane derivative (DD(Me)-OH), 200 g of octamethylcyclotetrasiloxane (D4) (manufactured by Momentive Performance Materials), 40.8 g of a strongly acidic cation exchange resin (Mitsubishi Chemical Corporation's "RCP-160M" (water content 23.4 mass%) dried before use), 961 g of dehydrated toluene, and 9.6 g of water were placed in the flask. The mixture was refluxed for 1 hour and then aged at 50°C. After completion of the aging, the mixture was cooled to room temperature, and the strongly acidic cation exchange resin was filtered off. The obtained filtrate was washed with water several times. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the obtained crude product was purified by reprecipitation with methanol. The obtained white viscous liquid was vacuum dried at 40°C to obtain 439 g of a white solid. 1 By 1H-NMR and GPC analysis, the obtained white solid was an organosilicon compound represented by the above formula (1), and R in the formula (1) 1 and R 2 were methyl groups, m was 43.6, n was 5.3, the number-average molecular weight Mn was 34,000, the weight-average molecular weight Mw was 68,000, the degree of polymerization of the structural unit (i) was 43.6, and the degree of polymerization of the structural unit (ii) was 230.9. It was confirmed that the compound was an organosilicon compound (A-1).

[0115] [Synthesis Example 4] Synthesis of Organosilicon Compound (A-2) A 300 mL flask was equipped with a condenser, a mechanical stirrer, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 40.0 g of silsesquioxane derivative (DD(Me)-OH), 20.0 g of octamethylcyclotetrasiloxane (D4) (manufactured by Momentive Performance Materials), 8.2 g of strongly acidic cation exchange resin (Mitsubishi Chemical Corporation's "RCP-160M" (water content 23.4 mass%) dried before use), 10.2 g of dehydrated toluene, and 1.0 g of water were placed in the flask. The mixture was refluxed for 1 hour and then aged at 50 °C. After the aging was completed, the mixture was cooled to room temperature, and the strongly acidic cation exchange resin was filtered off. The resulting filtrate was washed with water several times. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the obtained crude product was reprecipitated with methanol for purification. The obtained white viscous liquid was vacuum dried at 40 °C to obtain 43.6 g of a white solid. 1 By 1H-NMR and GPC analysis, the obtained white solid was confirmed to be an organosilicon compound represented by the above formula (1), where R in formula (1) 1 and R 2 are methyl groups, m is 29.2, n is 5.5, the number average molecular weight Mn is 23,000, the weight average molecular weight Mw is 46,000, the degree of polymerization of structural unit (i) is 29.2, and the degree of polymerization of structural unit (ii) is 160.6, which is an organosilicon compound (A-2).

[0116] [Synthesis Example 5] Synthesis of Organosilicon Compound (A-3) A 500 mL flask was equipped with a condenser, a mechanical stirrer, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 100 g of a silsesquioxane derivative (DD(Me)-OH), 50.0 g of octamethylcyclotetrasiloxane (D4) (manufactured by Momentive Performance Materials), 20.4 g of a strongly acidic cation exchange resin (Mitsubishi Chemical Corporation's "RCP-160M" (water content 23.4 mass%) dried before use), 256 g of dehydrated toluene, and 2.4 g of water were placed in the flask. The mixture was refluxed for 1 hour and then aged at 50 °C. After the aging was completed, the mixture was cooled to room temperature, and the strongly acidic cation exchange resin was filtered off. The resulting filtrate was washed with water several times. Then, the solvent and low-boiling components were distilled off from the filtrate, and the obtained crude product was reprecipitated with methanol for purification. The obtained white viscous liquid was vacuum dried at 40 °C to obtain 71.5 g of a white solid. 1 By 1H-NMR and GPC analysis, the obtained white solid was an organosilicon compound represented by the above formula (1), and R in the formula (1) 1 and R 2 were methyl groups, m was 24.6, n was 5.1, the number average molecular weight Mn was 20,000, the weight average molecular weight Mw was 38,000, the degree of polymerization of the structural unit (i) was 24.6, and the degree of polymerization of the structural unit (ii) was 125.4. It was confirmed that the organosilicon compound (A-3) was obtained.

[0117] [Synthesis Example 6] Synthesis of Organosilicon Compound (A-4) A 300 mL flask was equipped with a condenser, a mechanical stirrer, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 48.0 g of a silsesquioxane derivative (DD(Me)-OH), 18.0 g of octamethylcyclotetrasiloxane (D4) (manufactured by Momentive Performance Materials), 9.0 g of a strongly acidic cation exchange resin (dried and used "RCP-160M" (water content 23.4 mass%) manufactured by Mitsubishi Chemical Corporation), 112 g of dehydrated toluene, and 1.0 g of water were placed in the flask. The mixture was refluxed for 1 hour and then aged at 50 °C. After completion of aging, the mixture was cooled to room temperature, and the strongly acidic cation exchange resin was filtered off. The obtained filtrate was washed with water several times. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the obtained crude product was reprecipitated with methanol for purification. The obtained white viscous liquid was vacuum dried at 40 °C to obtain 56.1 g of a white solid. 1 By 1H-NMR and GPC analysis, the obtained white solid was an organosilicon compound represented by the above formula (1), and R in the formula (1) 1 and R 2 were methyl groups, m was 61.5, n was 4.2, the number average molecular weight Mn was 31,000, the weight average molecular weight Mw was 91,000, the degree of polymerization of the structural unit (i) was 61.5, and the degree of polymerization of the structural unit (ii) was 258.4. It was confirmed that the compound was an organosilicon compound (A-4).

[0118] [Synthesis Example 7] Synthesis of Organosilicon Compound (A-5) A 500 mL flask was equipped with a condenser, a mechanical stirrer, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 100 g of a silsesquioxane derivative (DD(Me)-OH), 32.5 g of octamethylcyclotetrasiloxane (D4) (manufactured by Momentive Performance Materials), 18.0 g of a strongly acidic cation exchange resin (dried and used "RCP-160M" (water content 23.4 mass%) manufactured by Mitsubishi Chemical Corporation), 226 g of dehydrated toluene, and 1.8 g of water were placed in the flask. The mixture was refluxed for 1 hour and then aged at 50 °C. After the aging was completed, the mixture was cooled to room temperature, and the strongly acidic cation exchange resin was filtered off. The obtained filtrate was washed with water several times. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the obtained crude product was reprecipitated with methanol for purification. The obtained white viscous liquid was vacuum dried at 40 °C to obtain 108.6 g of a white solid. 1 By 1H-NMR and GPC analysis, the obtained white solid was an organosilicon compound represented by the above formula (1), and R in the formula (1) 1 and R 2 were methyl groups, m was 40.9, n was 3.7, the number average molecular weight Mn was 24,000, the weight average molecular weight Mw was 59,000, the degree of polymerization of the structural unit (i) was 40.9, and the degree of polymerization of the structural unit (ii) was 151.4. It was confirmed that the compound was an organosilicon compound (A-5).

[0119] [Synthesis Example 8] Synthesis of Organosilicon Compound (A-6) A 300 mL flask was equipped with a condenser, a magnetic stirrer, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 50 g of a silsesquioxane derivative (DD(Me)-OH), 18.8 g of octamethylcyclotetrasiloxane (D4) (manufactured by Momentive Performance Materials), 5.6 g of a strongly acidic cation exchange resin (Mitsubishi Chemical Corporation's "RCP-160M" (water content 23.4 mass%) dried before use), 100 g of dehydrated toluene, and 0.6 g of water were placed in the flask. The mixture was refluxed for 1 hour and then aged at 50°C. After the aging was completed, the mixture was cooled to room temperature, and the strongly acidic cation exchange resin was filtered off. The resulting filtrate was washed with water several times. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the obtained crude product was purified by reprecipitation with methanol. The obtained white viscous liquid was vacuum dried at 40°C to obtain 42.8 g of a white solid. 1 By 1H-NMR and GPC analysis, the obtained white solid was an organosilicon compound represented by the above formula (1), and R in the formula (1) 1 and R 2 were methyl groups, m was 78.2, n was 4.6, the number average molecular weight Mn was 31,000, the weight average molecular weight Mw was 118,000, the degree of polymerization of the structural unit (i) was 78.2, and the degree of polymerization of the structural unit (ii) was 359.7. It was confirmed that the organosilicon compound (A-6) was obtained.

[0120] [Synthesis Example 9] Synthesis of Organosilicon Compound (A-7) A 300 mL flask was equipped with a condenser, a magnetic stirrer, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 50 g of a silsesquioxane derivative (DD(Me)-OH), 62.5 g of octamethylcyclotetrasiloxane (D4) (manufactured by Momentive Performance Materials), 5.0 g of a strongly acidic cation exchange resin (dried and used "RCP-160M" (water content 23.4 mass%) manufactured by Mitsubishi Chemical Corporation), 100 g of dehydrated toluene, and 0.5 g of water were placed in the flask. The mixture was refluxed for 1 hour and then aged at 50 °C. After the aging was completed, the mixture was cooled to room temperature, and the strongly acidic cation exchange resin was filtered off. The resulting filtrate was washed with water several times. Then, the solvent and low-boiling components were distilled off from the filtrate, and the obtained crude product was reprecipitated with methanol for purification. The obtained white viscous liquid was vacuum dried at 40 °C to obtain 74.0 g of a white solid. 1 By 1H-NMR and GPC analysis, the obtained white solid was found to be an organosilicon compound represented by the above formula (1), where R 1 and R 2 are methyl groups, m is 26.6, n is 13.7, the number-average molecular weight Mn is 23,000, the weight-average molecular weight Mw is 58,000, the degree of polymerization of structural unit (i) is 26.6, and the degree of polymerization of structural unit (ii) is 363.9, and it was confirmed to be an organosilicon compound (A-7).

[0121] [Synthesis Example 10] Synthesis of Organosilicon Compound (A-8) A 500 mL flask was equipped with a condenser, a magnetic stirrer, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 100 g of a silsesquioxane derivative (DD(Me)-OH), 37.6 g of octamethylcyclotetrasiloxane (D4) (manufactured by Momentive Performance Materials), 10.0 g of a strongly acidic cation exchange resin (Mitsubishi Chemical Corporation's "RCP-160M" (water content 23.4 mass%), dried before use), 200 g of dehydrated toluene, and 1.0 g of water were placed in the flask. The mixture was refluxed for 1 hour and then aged at 50 °C. After completion of the aging, the mixture was cooled to room temperature, and the strongly acidic cation exchange resin was filtered off. The resulting filtrate was washed with water several times. Then, the solvent and low-boiling components were distilled off from the filtrate, and the obtained crude product was reprecipitated with methanol for purification. The obtained white viscous liquid was vacuum dried at 40 °C to obtain 113.0 g of a white solid. 1 By 1H-NMR and GPC analysis, the obtained white solid was an organosilicon compound represented by the above formula (1), and R in the formula (1) 1 and R 2 were methyl groups, m was 57.0, n was 4.6, the number-average molecular weight Mn was 31,000, the weight-average molecular weight Mw was 86,000, the degree of polymerization of the structural unit (i) was 57.0, and the degree of polymerization of the structural unit (ii) was 262.2. It was confirmed that the organosilicon compound (A-8) was obtained.

[0122] [Synthesis Example 11] Synthesis of organosilicon compound (A-9) A 100 mL flask was equipped with a condenser, a mechanical stirrer, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 20 g of silsesquioxane derivative (DD(Me)-OH), 7.5 g of octamethylcyclotetrasiloxane (D4) (manufactured by Momentive Performance Materials), 3.7 g of strongly acidic cation exchange resin (Mitsubishi Chemical Corporation's "RCP-160M" (water content 23.4 mass%) dried before use), 31 g of dehydrated toluene, and 0.4 g of water were placed in the flask. The mixture was refluxed for 1 hour and then aged at 50 °C. After the aging was completed, the mixture was cooled to room temperature, and the strongly acidic cation exchange resin was filtered off. The resulting filtrate was washed with water several times. Then, the solvent and low-boiling components were distilled off from the filtrate, and the obtained crude product was reprecipitated with methanol for purification. The obtained white viscous liquid was vacuum dried at 40 °C to obtain 20.6 g of a white solid. 1 By 1H-NMR and GPC analysis, the obtained white solid was an organosilicon compound represented by the above formula (1), and R in the formula (1) 1 and R 2 were methyl groups, m was 119.0, n was 4.2, the number-average molecular weight Mn was 59,000, the weight-average molecular weight Mw was 176,000, the degree of polymerization of the structural unit (i) was 119.0, and the degree of polymerization of the structural unit (ii) was 499.7. It was confirmed that the compound was an organosilicon compound (A-9).

[0123] [Synthesis Example 12] Synthesis of Organosilicon Compound (A-10) A 500 mL flask was equipped with a condenser, a magnetic stirrer, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 49.9 g of a silsesquioxane derivative (DD(Me)-OH), 18.8 g of octamethylcyclotetrasiloxane (D4) (manufactured by Momentive Performance Materials), 10.1 g of a strongly acidic cation exchange resin (dried and used, “RCP-160M” (water content 23.4 mass%) manufactured by Mitsubishi Chemical Corporation), 250 g of dehydrated toluene, and 0.76 g of water were placed in the flask. The mixture was refluxed for 1 hour and then aged at 50 °C. After the aging was completed, the mixture was cooled to room temperature, and the strongly acidic cation exchange resin was filtered off. The resulting filtrate was washed with water several times. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the obtained crude product was reprecipitated with methanol for purification. The obtained white viscous liquid was vacuum dried at 40 °C to obtain 30.2 g of a white solid. 1 By 1H-NMR and GPC analysis, the obtained white solid was an organosilicon compound represented by the above formula (1), and R in the formula (1) 1 and R 2 were methyl groups, m was 16.3, n was 4.1, the number-average molecular weight Mn was 8,400, the weight-average molecular weight Mw was 24,000, the degree of polymerization of the structural unit (i) was 16.3, and the degree of polymerization of the structural unit (ii) was 66.7. It was confirmed that the compound was an organosilicon compound (A-10).

[0124] Hereinafter, each component used for the preparation of the condensation-curing type resin composition is shown. (A) Organosilicon compound Organosilicon compounds (A-1) to (A-10): Organosilicon compounds (A-1) to (A-10) synthesized in Synthesis Examples 3 to 12 Organosilicon compound (a-1): Polydimethylsiloxane having silanol groups at both ends (number-average molecular weight Mn 27,000, molecular weight distribution index (Mw / Mn) 1.05, “FM-9927” manufactured by JNC Corporation) (B) Organometallic compound Organometallic compound (B-1): A compound in which R in the above formula (2) 3 is a methyl group and q is about 5 (manufactured by Mitsubishi Chemical Corporation, “MKC Silicate MS51”) (C) Condensation catalyst Condensation catalyst (C-1): Dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) (D) Solvent Solvent (D-1): Toluene Solvent (D-2): PGMEA (propylene glycol monomethyl ether acetate) Solvent (D-3): Butyl acetate (E) Phosphor Phosphor (E-1): Silicate phosphor "EY4254" manufactured by INTEMATIX (G) Inorganic oxide Inorganic oxide (G-1): Silica ("DM30S" manufactured by Tokuyama)

[0125] [Examples 1 to 11 and Comparative Example 1] Preparation of condensation-curing resin composition Each component was uniformly mixed at the blending ratios (mass %) shown in Table 1 to prepare each condensation-curing resin composition of Examples 1 to 11 and Comparative Example 1. Table 1 also shows the ratio of the number of moles of the condensation-reactive groups of the (B) organometallic compound to the number of moles of the silanol groups of the (A) organosilicon compound (functional group ratio (SiOMe / SiOH)) in each condensation-curing resin composition.

[0126] (Preparation of molded body A) Each obtained condensation-curing resin composition was applied to a SUS plate (5 mm thick) processed with a fluororesin using an applicator. Then, it was placed in an oven and heated at 70°C for 30 minutes, 100°C for 1 hour, and further at 200°C for 2 hours to obtain a molded body A (crosslinked cured product) with a thickness of about 0.2 mm. The thickness of the obtained molded body A was measured with a digital indicator ("ID-H0530" manufactured by Mitutoyo).

[0127] (Initial performance / Tensile test) Strip-shaped test pieces (length 50 mm × width 5 mm) were prepared using the obtained molded body A. Using these strip-shaped test pieces, a tensile test was conducted at a tensile speed of 5 mm / min and 25°C, and the elongation at break (Ea) and the breaking stress (Sa) were measured. The results are shown in Table 1.

[0128] (Heat resistance test at 250°C / Tensile test) The obtained molded body A was heated in an air atmosphere at 250°C for the predetermined time described in Table 1, and then strip-shaped test pieces (length 50 mm × width 5 mm) were produced from each molded body. Using these strip-shaped test pieces, a tensile test was conducted at a tensile speed of 5 mm / min and 25°C, and the elongation at break and the breaking stress were measured. The results are shown in Table 1. Also, the ratio (Eb / Ea) of the elongation at break (Eb) after heating for 504 hours to the elongation at break (Ea) before heating, and the ratio (Sb / Sa) of the breaking stress (Sb) after heating for 504 hours to the breaking stress (Sa) before heating are shown in Table 1.

[0129] (Production of Molded Body B) Each of the obtained condensation-curing type resin compositions was applied to a slide glass (「S9213」manufactured by Matsunami Glass Industry Co., Ltd., thickness 1.3 mm) using an applicator. Then, it was placed in an oven and heated at 70°C for 30 minutes, 100°C for 1 hour, and further at 200°C for 2 hours to obtain a molded body B (crosslinked cured film) with a thickness of 0.1 mm. The thickness of the obtained molded body B was measured with a micrometer (「BMD-25MX」manufactured by Mitutoyo).

[0130] (Evaluation of Initial Performance / Light Transmittance) For the obtained molded body B, the light transmittance was measured. The light transmittance measurement was performed using an ultraviolet-visible spectrophotometer (「V-650」manufactured by JASCO Corporation). The reference was a slide glass (「S9213」manufactured by Matsunami Glass Industry Co., Ltd., thickness 1.3 mm). The evaluation was marked as 「○」 when the minimum transmittance at wavelengths of 350 to 800 nm was 98% or more, and 「×」 when it was less than that. The results are shown in Table 1.

[0131] (250°C Heat Resistance Test / Crack Resistance Test and Evaluation of Light Transmittance) The obtained molded body B was heated in an air atmosphere at 250°C for the predetermined time described in Table 1. The molded body B during heating was taken out every 168 hours, returned to room temperature, and then the appearance was observed and the time when cracks occurred was recorded. For the molded bodies in which no cracks occurred, the light transmittance was measured. The results are shown in Table 1. In Table 1, "no change" regarding the light transmittance means that for light of any wavelength in the range of 350 to 800 nm, the ratio of the light transmittance after heating to the light transmittance before heating is 0.9 or more. Also, the ratio (Tb / Ta) of the light transmittance (Tb) after heating for 504 hours to the light transmittance (Ta) before heating is also shown in Table 1.

[0132]

Table 1

[0133] As shown in Table 1, all of the condensation-curing type resin compositions of Examples 1 to 6 and 11 that underwent a heat resistance test for 1008 hours had an elongation of 3% or more after heat resistance at 250°C for 1008 hours, were less likely to embrittle, and showed strong crack resistance. Also, in all of the crack tests after the heat resistance test at 250°C, no cracks occurred even after exceeding 1000 hours, and it was confirmed that embrittlement was less likely to occur. Furthermore, the change in light transmittance after the heat resistance test at 250°C was small, and transparency could be maintained. It can be seen that the cured products obtained from the condensation-curing type resin compositions of each example are less likely to embrittle and color even when exposed to high temperatures for a long time, and have the performances such as crack resistance and color resistance under high temperature environments required for semiconductor encapsulants and the like. Note that in Example 8, since the tack (adhesiveness) of the cured product was strong, the initial elongation at break and breaking stress were not measured, and since the cured product became cloudy, the light transmittance was not measured. However, it has been confirmed that the cured product obtained from the condensation-curing type resin composition of Example 8 also has both crack resistance and color resistance under high temperature environments.

[0134] On the other hand, for the condensation-curing type resin composition of Comparative Example 1, cracks occurred due to resin embrittlement after the heat resistance test at 250°C, and it became impossible to measure the tensile test and light transmittance.

[0135] [Example 12] 1 g of the condensation-curing type resin composition obtained in Example 7 was poured into an aluminum cup with a diameter of 3 cm for rheometer measurement. This was cured under the conditions of 80°C for 1 hour, 100°C for 1 hour, 120°C for 1 hour, and 200°C for 1 hour to obtain a sheet-like cured product. Using a rheometer ("MCR302" manufactured by Anton Paar), the rheometer measurement of the cured product was performed under the following conditions. The measurement results are shown in Table 2. Measurement conditions Oscillation angle: 0.1%, Frequency: 1 Hz, Normal force: 0.5 N Measurement temperature: 30 to 250°C, Heating rate: 2 to 2.5°C / min

[0136] [Table 2]

[0137] As shown in Table 2 above, the sheet-like cured product obtained in Example 12 softens by heating, so it can be adhered to a semiconductor chip or the like. Further, such a cured product can also be melt-molded.

[0138] [Example 13] 50.4% by mass of organosilicon compound (A-7), 0.8% by mass of organometallic compound (B-1), 0.03% by mass of condensation catalyst (C-1), 25.2% by mass of solvent (D-2), 22.9% by mass of phosphor (E-1) and 0.8% by mass of inorganic oxide (G-1) were mixed to obtain the condensation-curing type resin composition of Example 13. A frame was provided so that the height was 1 mm on a 3 cm × 3 cm × 2 mm slide glass plate with a release film attached, and the obtained condensation-curing type resin composition was poured into this frame. The composition was cured under the conditions of 80°C for 1 hour, 100°C for 1 hour, 120°C for 1 hour, and 200°C for 1 hour to prepare a cured product (phosphor sheet) with a thickness of about 0.3 mm. The phosphor sheet was cut out and placed on an aluminum substrate. Then, it was heated at 200°C for 10 minutes and cooled to room temperature. The phosphor sheet was adhered to the aluminum substrate without deformation.

[0139] [Examples 14 - 15 and Comparative Example 2] Each component was uniformly mixed at the blending ratios (mass %) shown in Table 3 to prepare the condensation - curing type resin compositions of Examples 14 - 15 and Comparative Example 2. 1 g of each of the condensation - curing type resin compositions obtained in Examples 14 - 15 and Comparative Example 2 was poured into an aluminum cup with a diameter of 3 cm for rheometer measurement. This was cured under the conditions of 80°C for 1 hour, 100°C for 1 hour, 120°C for 1 hour, and 200°C for 1 hour to obtain sheet - like cured products. Using a rheometer (Anton Paar's "MCR302"), rheometer measurements of the cured products were carried out under the following conditions. The measurement results are shown in Table 3. Measurement conditions Oscillation angle: 0.1%, Frequency: 1 Hz, Normal force: 0.5 N Measurement temperature: 30 - 250°C, Heating rate: 2 - 2.5°C / min

[0140]

Table 3

[0141] The cured product of Example 14 was solid at room temperature. The storage modulus at 30°C was 37,000 Pa, and the loss modulus was 1,700 Pa. The storage modulus at 150°C was 6 Pa, and the loss modulus was 92 Pa, indicating viscosity - dominant performance. The storage modulus at 200°C was 5,400 Pa, and the loss modulus was 240 Pa, indicating elasticity - dominant performance. That is, it was found that it melts around 150°C and can be cured and molded around 200°C. The cured product of Example 15 was solid at room temperature. The storage modulus at 30°C was 37,000 Pa, and the loss modulus was 8,000 Pa. The storage modulus at 200°C was 11 Pa, and the loss modulus was 73 Pa, showing viscosity - dominant performance at 200°C. The storage modulus at 250°C was 83 Pa, and the loss modulus was 55 Pa, being elasticity - dominant around 250°C. It was found that it melts around 200°C and can be cured and molded at 250°C or higher. Comparative Example 2 was solid at room temperature, had a storage modulus of 53,300 Pa and a loss modulus of 17,000 Pa at 30°C. When the temperature was raised to 150°C and 200°C, the storage modulus decreased significantly and showed a melting behavior. However, even when the temperature was raised to 250°C, the storage modulus continued to decrease and it was impossible to perform curing molding.

Industrial Applicability

[0142] The condensation-curing type resin composition of the present invention can be suitably used as a sealing material for optical semiconductor elements, a sealing material for other semiconductor elements, a wavelength conversion layer, a light reflecting plate, a buffer material, an insulating film, a sealing material, a forming material for optical lenses, and other adhesives.

Claims

1. (A) an organosilicon compound containing a structural unit (i) represented by the following formula (i) and a structural unit (ii) represented by the following formula (ii), having SiOH groups at both ends of the molecular chain, and having a weight average molecular weight of 15,000 or more and 10,000,000 or less; (B) An organometallic compound having six or more condensation reactive groups, the condensation reactive groups being alkoxy groups, acetoxy groups, oxime groups or halogen atoms. A condensation-curable resin composition comprising: 【Chemistry 1】 (In formula (i), R １ are each independently a hydrocarbon group having 1 to 8 carbon atoms. In formula (ii), R ２ are each independently a hydrocarbon group having 1 to 8 carbon atoms.

2. 2. The condensation-curable resin composition according to claim 1, wherein the degree of polymerization of the structural unit (i) in the organosilicon compound (A) is 10 or more and 8,000 or less, and the degree of polymerization of the structural unit (ii) is 1 or more and 10,000 or less.

3. 3. The condensation-curable resin composition according to claim 1, wherein the organosilicon compound (A) is represented by the following formula (1): 【Chemistry 2】 (In formula (1), R １ are each independently a hydrocarbon group having 1 to 8 carbon atoms. ２ are each independently a hydrocarbon group having 1 to 8 carbon atoms; m is a number satisfying the weight average molecular weight of 15,000 or more and 10,000,000 or less; and n is an average value satisfying the range of 1 to 30.

4. 4. The condensation-curable resin composition according to claim 1, wherein the organometallic compound (B) is represented by the following formula (2): 【Transformation 3】 (In formula (2), R ３ are each independently an alkyl group having 1 to 4 carbon atoms, and q is an average value satisfying the range of 2 to 100.

5. The condensation-curable resin composition according to claim 1 , further comprising (C) a condensation catalyst.

6. The condensation-curable resin composition according to claim 1 , further comprising (D) a solvent.

7. 7. The condensation-curable resin composition according to claim 1, further comprising: (E) a phosphor; (F) a white pigment; or (G) an inorganic oxide (excluding components corresponding to (E) the phosphor or (F) the white pigment).

8. 8. The condensation-curable resin composition according to claim 7, wherein the content of the (E) phosphor is 1 part by mass or more and 80 parts by mass or less per 100 parts by mass of the total of the (A) organosilicon compound and the (B) organometallic compound.

9. the (F) white pigment is titanium oxide, 9. The condensation-curable resin composition according to claim 7, wherein the content of the (F) white pigment is 10 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of the total of the (A) organosilicon compound and the (B) organometallic compound.

10. A condensation-curable resin composition according to any one of claims 1 to 9, A cured product obtained under the following thermal curing conditions was heated in an air atmosphere at 250°C for 504 hours, and the following tensile test and the following light transmittance measurement were performed on the cured product before and after the heating. a ratio (Eb / Ea) of the breaking elongation (Eb) after heating to the breaking elongation (Ea) before heating of 0.1 or more; a ratio (Sb / Sa) of the breaking stress after heating (Sb) to the breaking stress before heating (Sa) of 0.5 or more and less than 10; The condensation-curable resin composition has a ratio (Tb / Ta) of the light transmittance (Tb) after heating to the light transmittance (Ta) before heating of 0.9 or more. (Thermosetting conditions) In an air atmosphere, the sample was heated successively at 70°C for 30 minutes, 100°C for 1 hour, and 200°C for 2 hours in this order. (Tensile test) A rectangular test piece having a length of 50 mm, a width of 5 mm, and a thickness of 0.2 mm was prepared, and the test piece was subjected to a tensile test at a temperature of 25°C and a tensile speed of 5 mm / min. (Light transmittance measurement) The transmittance of light with a wavelength of 350 nm was measured for a test piece of cured material with a thickness of 0.1 mm.

11. A cured product obtained by curing the condensation-curable resin composition according to any one of claims 1 to 10.

12. A molded article obtained from the condensation-curable resin composition according to any one of claims 1 to 10 or the cured product according to claim 11.

13. A semiconductor device comprising: a semiconductor element; and the molded article according to claim 12 that encapsulates the semiconductor element.

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