JP5491159B2 - Silica particle-containing condensation reaction product, resin composition, sealing resin, lens and underfill material - Google Patents

Description

  The present invention relates to a silica particle-containing condensation reaction product obtained by condensation reaction of siloxane and silica while maintaining transparency. The present invention further includes a resin composition containing the silica particle-containing condensation reaction product and giving a cured product having high heat resistance and high light resistance useful for sealing an optical semiconductor element, a sealing resin containing the resin composition, The present invention relates to a lens and an underfill material.

  An optical semiconductor device typified by an LED generally has a structure covered with a transparent sealing resin in order to protect a chip peripheral portion which is a light emitting portion. In addition to the role as a dispersion medium for dispersing the phosphor, the sealing resin plays a role of protecting the light emitting portion from external impacts, moisture in the atmosphere, and the like. The sealing resin is also used as a lens for the purpose of improving the extraction efficiency and controlling light collection.

  Conventionally, an epoxy resin has been mainly used as such a sealing resin. However, in the epoxy resin, the increase in the amount of heat generated with the recent increase in brightness of the LED, and the shortening of the excitation wavelength and the emission wavelength of the phosphor cause yellowing of the sealing resin itself, and cracks occur. The brightness is reduced or the life is shortened.

  As a method for preventing a decrease in luminance and life of the sealing resin, a silicone resin mainly composed of organosiloxane is used. Among these, addition-curing organosiloxane resins using hydrosilylation have high heat resistance and light resistance, and are also used in high-brightness LEDs.

For example, Patent Document 1, a SiO _4/2 structural MQ resin organosiloxane compositions introduced as (and SiO _4/2 component of the tetrafunctional structure consisting of a monofunctional SiO _1/2 component) Have been described. For example, Patent Document 2 reports a composition obtained by mixing an inorganic material with a silicone resin. For example, Patent Document 3 reports a composition in which a silica component having a SiO _4/2 structure and an organosiloxane are mixed and heated to modify the silica surface.

JP 2000-198930 A JP 2008-78521 A JP 2009-120437 A

  However, in the technique of Patent Document 1, since the cured resin is soft, there is a tack property on the surface of the sealing resin, there is a problem such as a decrease in luminance due to adhesion of dust, a change in volume and shape due to thermal expansion during heating is there. On the other hand, in the technique of Patent Document 2, there is a possibility that the hardness of the resin can be improved. However, if sufficient hardness is obtained, the viscosity and thixotropy of the composition are increased, and defoaming when mixing the resin is difficult. become. Further, when the phosphor, which is an inorganic material, is mixed with the composition, the viscosity is further increased. If an inorganic material capable of obtaining sufficient hardness is introduced, there is a problem that thickening or white turbidity of a cured product occurs. In the technique of Patent Document 3, there is a possibility that the viscosity and thixotropy can be improved, but this composition requires an operation for removing unmodified organosiloxane having low heat resistance after modification. If such unreacted siloxane remains in the sealing resin before curing or in the cured product, it becomes a desorbing component, which may cause shrinkage of the sealing resin and cause cracks. Yes, it is not sufficient in terms of hardness. For these reasons, there is a strong demand for a high-hardness sealing resin that is excellent in heat resistance and light resistance and has no tackiness.

  An object of the present invention is to provide a resin composition and a material for the resin composition that give a resin cured product having high hardness, no tackiness, and excellent heat yellowing resistance and light yellowing resistance.

[1] It has at least a structure in which the polysiloxane compound (a) containing a silanol group and the silica particles (b) are condensed,
Obtained by a condensation reaction of a reaction component containing at least the polysiloxane compound (a) and the silica particles (b),
The polysiloxane compound (a) is a polymerization product of a silane compound having one or more groups selected from a hydroxyl group and a hydrolyzable group or a condensate thereof,
The hydrolyzable group is at least one of a halogen atom, an alkoxy group having 1 to 6 carbon atoms and an acetoxy group;
In the polysiloxane compound (a), the hydroxyl group with respect to the total number of bonds forming any of a siloxane bond, a direct bond with the hydroxyl group, and a direct bond with the hydrolyzable group A silica particle-containing condensation reaction product, wherein the silanol group content defined as the ratio of the number of bonds forming direct bonds is 1 to 90 mol%.
[2] The silica particle-containing condensation reaction product according to [1], wherein the polysiloxane compound (a) has an unsaturated hydrocarbon group and / or a SiH group.
[3] The reaction component further includes a silane coupling agent,
The above condensation reaction further causes a condensation product obtained by condensing the polysiloxane compound (a) and the silica particles (b) to further react with a silane coupling agent, or the polysiloxane compound (a) and the silica particles ( The silica particle-containing condensation reaction according to the above [1] or [2], which is performed by simultaneously condensing b) and a silane coupling agent.
[4] The silica particle-containing condensation reaction product according to [3], wherein the polysiloxane compound (a) and / or the silane coupling agent has an unsaturated hydrocarbon group and / or a SiH group.
[5] The silane coupling agent is represented by the following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{Wherein n1 is an integer of 1 to 3, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ¹ is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. A group selected from a group and an acetoxy group, and when there are plural groups, R ¹ and X ¹ may be the same or different}
The silica particle-containing condensation reaction product according to the above [3] or [4], which is a silane compound represented by:
[6] The silica particle-containing condensation reaction product according to any one of [1] to [5], wherein the content of the silica particles (b) in the reaction component is 1% by mass or more and 70% by mass or less.
[7] The silica particle-containing condensation reaction product according to any one of [1] to [6], wherein the silica particles (b) have an average primary particle diameter of 1 nm to 120 nm.
[8] The siloxane bond with respect to the total number of bonds forming the silicon siloxane bond, the direct bond with the hydroxyl group, and the direct bond with the hydrolyzable group of silicon in the polysiloxane compound (a). The condensation reaction product containing silica particles according to any one of the above [1] to [7], wherein the condensation rate defined as a ratio of the number of bonds formed is 5 mol% or more and 95 mol% or less.
[9] The silica particle-containing condensation reaction product according to any one of [1] to [8], wherein the silanol group content is 5 mol% or more and 90 mol% or less.
[10] The silica particle-containing condensation reaction product (A) according to any one of the above [1] to [9] and a hydrosilylation catalyst (B), wherein the silica particle-containing condensation reaction product (A) is not Resin composition containing a saturated hydrocarbon group and / or SiH group, the content of the silica particle-containing condensation reaction product (A) being 20% by mass or more, and containing an unsaturated hydrocarbon group and a SiH group .
[11] A component containing the silica particle-containing condensation reaction product (A) according to any one of [1] to [9], a hydrosilylation catalyst (B), an unsaturated hydrocarbon group and / or a SiH group. A resin composition containing (C), wherein the content of the silica particle-containing condensation reaction product (A) is 20% by mass or more, and contains an unsaturated hydrocarbon group and a SiH group.
[12] The resin composition according to the above [10] or [11], wherein the total unsaturated hydrocarbon group number Z ¹ and the total SiH number Z ² satisfy 0.25 ≦ Z ¹ / Z ² ≦ 2. Resin composition.
[13] A sealing resin comprising the resin composition according to any one of [10] to [12].
[14] A lens formed using a curable composition containing the resin composition according to any one of [10] to [12].
[15] An underfill material comprising the resin composition according to any one of [10] to [12].

  INDUSTRIAL APPLICABILITY The present invention can provide a resin composition and a material for the resin composition that give a resin cured product having high hardness and no tackiness and excellent in heat yellowing resistance and light yellowing resistance.

  Hereinafter, embodiments of the present invention will be described in detail.

[Silica particle-containing condensation reaction product]
One embodiment of the present invention has at least a structure in which a polysiloxane compound (a) containing a silanol group and silica particles (b) are condensed, and the polysiloxane compound (a) and the silica particles ( b) and a polymerization product of a silane compound or a condensate thereof obtained by a condensation reaction of a reaction component containing at least the polysiloxane compound (a) having one or more groups selected from a hydroxyl group and a hydrolyzable group The hydrolyzable group is at least one of a halogen atom, an alkoxy group having 1 to 6 carbon atoms and an acetoxy group, and the silicon in the polysiloxane compound (a) is bonded to the siloxane bond and the hydroxyl group. Ratio of the number of bonds forming a direct bond with the hydroxyl group to the total number of bonds forming either a direct bond or a direct bond with the hydrolyzable group Silanol group content is defined by is 1 to 90% provides a silica particle-containing condensation reaction products.

  The silica particle-containing condensation product of the present invention has at least a structure formed by condensation of the polysiloxane compound (a) and the silica particles (b). The resin formed using the condensation reaction product of the present invention has good heat yellowing resistance and light yellowing resistance, which are characteristics of polysiloxane resins. In the present invention, since the polysiloxane compound (a) and the silica particles (b) are condensed, a resin having high hardness and reduced tackiness can be formed, while a silica particle-containing condensation reaction product is formed. The viscosity and thixotropy of the resin composition to be included can be kept low.

<Polysiloxane compound (a)>
The polysiloxane compound (a) used in the present invention is a polysiloxane compound having a silanol group content defined above of 1 to 90 mol%. The silanol group participates in the condensation reaction with the silica particles (b). The silanol group content is preferably 5 to 90 mol%, more preferably 10 to 90 mol%, still more preferably 10 to 80 mol%, still more preferably 10 to 70 mol%, still more preferably 15 to 70 mol%. The silanol group content is 1 mol% or more from the viewpoint of ease of bonding with the silica particles (b), and 90 mol% or less from the viewpoint of molecular weight control. The silanol group content can be calculated by ²⁹ Si NMR analysis and gas chromatogram analysis.

The polysiloxane compound (a) preferably has an unsaturated hydrocarbon group and / or a SiH group. By having an unsaturated hydrocarbon group and / or a SiH group, there is an advantage that a hardened resin cured product is formed. As the unsaturated hydrocarbon group, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, cyclohexenylethyl group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, Examples thereof include acyclic and cyclic alkenyl groups such as a styrenyl group, araalkenyl groups such as a PhCH═CH— group, and the like. The presence or absence of unsaturated hydrocarbon groups and / or SiH groups can be evaluated by ¹ HNMR analysis, Fourier transform infrared spectroscopy (FT-IR), or the like.

<Synthesis of polysiloxane compound (a)>
The polysiloxane compound (a) is a polymerization product of a silane compound having one or more groups selected from a hydroxyl group and a hydrolyzable group or a condensate thereof. Here, the hydrolyzable group is at least one of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group. Typically, the polysiloxane compound (a) includes, for example, one or more components selected from silane compounds represented by the following general formulas (2), (3), and (4) and condensates thereof. It can be obtained by hydrolysis (but not essential if the component has a silanol group) and condensation.

R ² _n2 R ³ _n3 SiX ² _4-n2-n3 (2)
{Wherein n2 is an integer of 1 to 3, n3 is an integer satisfying 1 ≦ n2 + n3 ≦ 3, R ² is a monovalent organic group containing an unsaturated hydrocarbon, R ³ Is an organic group selected from a saturated hydrocarbon group and an aromatic group, and X ² is a group selected from a hydroxyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group. R ² , R ³ and X ² may be the same or different. }
H _n4 R ⁴ _n5 SiX ³ _4-n4-n5 (3)
{Wherein n4 is an integer of 1 to 3, n5 is an integer satisfying 1 ≦ n4 + n5 ≦ 3, R ⁴ is a monovalent organic group, X ³ is a hydroxyl group, a halogen atom, When R ⁴ and X ³ are a group selected from an alkoxy group having 1 to 6 carbon atoms and an acetoxy group, a plurality of R ⁴ and X ³ may be the same or different. }
R ⁵ _n6 SiX ⁴ _4-n6 (4)
{In the formula, n6 is an integer of 0 to 3, R ⁵ is a monovalent organic group, and X ⁴ is selected from a hydroxyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group. R ⁵ and X ⁴ in the case where a plurality of groups are present may be the same or different. }

R ² in the general formula (2) may contain an unsaturated hydrocarbon group, and specifically includes a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclohexenyl group, and a cyclohexenylethyl group. Group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, styenyl group and other acyclic alkenyl groups, PhCH = CH- group and other araalkenyl groups. Among these, a vinyl group is preferable from the viewpoint of heat resistance and light resistance. The unsaturated hydrocarbon group gives an unsaturated hydrocarbon group in the polysiloxane compound (a) and contributes to the improvement of the hardness of the resin cured product.

R ³ is selected from a saturated hydrocarbon group and an aromatic group, and when there are a plurality of R ^{3 s} , they are independently selected from each other. As R ³ , specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neopentyl group , Cyclopentyl group, n-hexyl group, iso-hexyl group, cyclohexyl group, n-heptyl group, iso-heptyl group, n-octyl group, iso-octyl group, t-octyl group, n-nonyl group, iso-nonyl Group, n-decyl group, iso-decyl group or the like acyclic or cyclic aliphatic hydrocarbon group, benzyl group, phenethyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, etc. And aryl groups such as a phenyl group, a tolyl group, and a xylyl group. Especially, a C1-C10 organic group is preferable from a heat resistant viewpoint, More preferably, they are a methyl group, an ethyl group, and a phenyl group.

R ⁴ and R ⁵ in the general formulas (3) and (4) are each independently a monovalent organic group. Specifically, the unsaturated hydrocarbon groups exemplified for R ^{2 and} R ³ are exemplified. Examples thereof include an organic group containing one or more selected from a saturated hydrocarbon group and an aromatic group. Especially, a C1-C10 organic group is preferable from a heat resistant viewpoint, More preferably, they are a methyl group, an ethyl group, and a phenyl group.

X ² , X ³ and X ⁴ are each independently selected from a hydroxyl group, a halogen atom which is a hydrolyzable substituent, an alkoxy group having 1 to 6 carbon atoms and an acetoxy group. Specifically, for example, a halogen atom such as a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, an n-propyloxy group, an iso-propyloxy group, an n-butyloxy group, a t-butyloxy group, n -Alkoxy groups, such as a hexyloxy group and a cyclohexyloxy group, and an acetoxy group etc. are mentioned. Among these, halogen atoms such as chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, and acetoxy group are preferable because of high reactivity of the condensation reaction during the synthesis of polysiloxane compound (a).

Hereinafter, the production of the polysiloxane compound (a) will be described by taking as an example the case of using the silane compound represented by the general formulas (2), (3) and (4) and / or the condensate thereof. However, the present invention is not limited to this. The polysiloxane compound (a) is preferably produced by adding water to the silane compound and / or the condensate thereof as described above. The amount of water added is represented by X ^{2 of the} silane compound represented by the general formula (2), X ^{3 of the} silane compound represented by the general formula (3), and the general formula (4). A range of 0.1 equivalents to 10 equivalents (molar basis) is preferable with respect to the total number of moles of X ⁴ of the silane compound, and a range of 0.4 equivalents to 8 equivalents is more preferable. When the amount of water added is 0.1 equivalent or more, the molecular weight of the polysiloxane compound (a) increases, and preferably 10 equivalents or less means a solution of the product of the polysiloxane compound (a) obtained by the condensation reaction. It is preferable from the viewpoint of extending the pot life.

  When the polysiloxane compound (a) is produced by a condensation reaction in the presence of a catalyst, it is preferable because the hydrolysis and condensation rates are increased.

  Specifically as a kind of catalyst, an inorganic acid and an organic acid are mentioned as an acid catalyst. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and boric acid. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, benzoic acid, and p-aminobenzoic acid. Examples include acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, citraconic acid, malic acid, glutaric acid and the like.

  These catalysts can be used alone or in combination of two or more. When the amount of the acid catalyst used is an amount that adjusts the pH of the reaction system in the production of the polysiloxane compound (a) to a range of 0.01 to 6.0, the polysiloxane compound (a) It is preferable because the weight average molecular weight can be controlled well.

  The condensation reaction for producing the polysiloxane compound (a) can be performed in an organic solvent. Examples of the organic solvent that can be used for the condensation reaction include alcohols, esters, ketones, ethers, aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, amide compounds, and the like.

  Examples of the alcohols include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, B propylene glycol monopropyl ether, mono-ethers of polyhydric alcohols such as propylene glycol monobutyl ether.

  Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, and γ-butyrolactone. Examples of ketones include acetone, methyl ethyl ketone, methyl isoamyl ketone, and the like.

  In addition to the above monoethers of polyhydric alcohols, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol Examples include polyhydric alcohol ethers obtained by alkyl etherifying all hydroxyl groups of polyhydric alcohols such as dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether, and tetrahydrofuran, 1,4-dioxane, anisole, and the like. .

  Examples of the aliphatic hydrocarbon compound include hexane, heptane, octane, nonane, decane, and the like.

  Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene and the like.

  Examples of the amide compound include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  Among these solvents, alcohol solvents such as methanol, ethanol, isopropanol and butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Ether solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are easily mixed with water, and in the polysiloxane compound (a) during the condensation reaction of the polysiloxane compound (a) and the silica particles (b). It is preferable because the silica particles (b) can be easily dispersed.

  These solvents may be used alone or in combination with a plurality of solvents. Moreover, you may react in a bulk, without using the said solvent.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of manufacturing a polysiloxane compound (a), Preferably it is -50 degreeC or more and 200 degrees C or less, More preferably, it is the range of 0 degreeC or more and 150 degrees C or less. By carrying out the reaction in the above range, the molecular weight of the polysiloxane compound (a) can be well controlled.

  In the present invention, the siloxane bond with respect to the total number of bonds forming the siloxane bond, the direct bond with the hydroxyl group, and the direct bond with the hydrolyzable group of silicon in the polysiloxane compound (a). The condensation rate, defined as the ratio of the number of bonds forming the bond, is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 95 mol% or less, more preferably 20 mol% or more and 90 mol% or less. % Or less, and more preferably 30 mol% or more and 85 mol% or less. The condensation rate is preferably 5 mol% or more from the viewpoint of increasing the molecular weight of the polysiloxane compound (a), and is preferably 5 mol% or more from the ease of condensation between the polysiloxane compound (a) and the silica particles (b). It is preferable that it is 95 mol% or less.

The condensation rate is more typically represented by X ² , X ³ and X ^{4 in} the components represented by the general formulas (2), (3) and (4) used for the production of the polysiloxane compound (a). Of these, the ratio is changed to Si—O—Si bond.

The condensation rate is obtained by removing the solvent from the reaction product liquid containing the polysiloxane compound (a) using a vacuum pump at 50 ° C. or lower, or by synthesizing the polysiloxane compound (a) in a heavy solvent. The obtained reaction product liquid is analyzed by ²⁹ SiNMR, and calculated by confirming M0, M1, D0, D1, D2, T0, T1, T2, T3, Q0, Q1, Q2, Q3, and Q4 components. it can. Of the (SiO _1/2 ) components, a silicon atom having no Si—O—Si bond is represented as an M0 component, and a silicon atom having one Si—O—Si bond is represented as M1. Of the (SiO _2/2 ) component, a silicon atom having no Si—O—Si bond is represented as a D0 component, a silicon atom having one Si—O—Si bond is represented as a D1 component, and Si A silicon atom having two —O—Si bonds is represented as a D2 component. Of the (SiO _3/2 ) component, a silicon atom having no Si—O—Si bond is represented as a T0 component, and a silicon atom having one Si—O—Si bond is represented as a T1 component, and Si A silicon atom having two —O—Si bonds is represented as a T2 component, and a silicon atom having three Si—O—Si bonds is represented as a T3 component. Of the (SiO _4/2 ) component, a silicon atom having no Si—O—Si bond is represented as a Q0 component, and a silicon atom having one Si—O—Si bond is represented as a Q1 component, and Si A silicon atom having two -O-Si bonds is represented as a Q2 component, a silicon atom having three Si-O-Si bonds is represented as a Q3 component, and silicon having four Si-O-Si bonds An atom is represented as a Q4 component.

The condensation rate of the polysiloxane compound (a) can be calculated as follows from the area ratio of each silicon peak of ²⁹ SiNMR.
For example, the peak area of the D1 component is represented as (D1).
Condensed silicon area:
{(M1) + (D1) + (D2) × 2 + (T1) + (T2) × 2 + (T3) × 3 + (Q1) + (Q2) × 2 + (Q3) × 3 + (Q4) × 4}
Total silicon area:
{(M0) + (M1)} + {(D0) + (D1) + (D2)} × 2 + {(T0) + (T1) + (T2) + (T3)} × 3 + {(Q0) + ( Q1) + (Q2) + (Q3) + (Q4)} × 4
Polysiloxane compound (a) condensation rate = (condensed silicon area) / (total silicon area) × 100

When the reaction solution containing the polysiloxane compound (a) obtained in the synthesis of the polysiloxane compound (a) is analyzed by gas chromatogram, X ² , X ³ and X ⁴ released by hydrolysis may be detected. it can. The mass of the liberated hydrolyzing group can be calculated, for example, by drawing a calibration curve for each component. Free hydrolyzable groups calculated by taking into account the total number of moles of X ² , X ³ and X ⁴ before the reaction (M ¹ ) [mol] and the amount of the reaction solution containing the polysiloxane compound (a). Assuming that the total amount of (M ² ) [mol] is, the hydrolysis rate can be calculated as follows.
Hydrolysis rate = (M ² ) / (M ¹ ) × 100
The silanol group content can be calculated as follows from the condensation rate and hydrolysis rate of the polysiloxane compound (a).
Silanol group content = (hydrolysis rate)-(condensation rate of polysiloxane compound (a))

  The hydrolysis rate is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, further preferably 40 to 100 mol%, and most preferably 50 to 100 mol%. The hydrolysis rate is preferably 10 mol% or more from the viewpoint of satisfactorily supplying silanol groups for the condensation reaction.

<Silica particles (b)>
Examples of the silica particles (b) used in the present invention include fumed silica and colloidal silica.

  The fumed silica can be obtained by reacting a compound containing a silicon atom with oxygen and hydrogen in a gas phase. Examples of the silicon compound used as a raw material include silicon halide (for example, silicon chloride).

  Colloidal silica can be synthesized by a sol-gel method in which a raw material compound is hydrolyzed and condensed. Examples of the raw material compound for colloidal silica include alkoxy silicon (for example, tetraethoxysilane) and halogenated silane compounds (for example, diphenyldichlorosilane). Especially, since it is preferable that there are few impurities, such as a metal and a halogen, the colloidal silica obtained from alkoxy silicon is more preferable.

The silica particle-containing condensation reaction product of the present invention is obtained by a condensation reaction of a reaction component containing at least the polysiloxane compound (a) and the silica particles (b). Here, the reaction component means a component that forms a condensation structure in the silica particle-containing condensation reaction product. The content of the silica particles (b) in the reaction component is preferably 1% by mass or more and 70% by mass or less. The content is preferably 1% by mass or more from the viewpoint of improving the hardness of the cured film, and preferably 70% by mass or less from the viewpoint of the viscosity of the condensation reaction product. The content is more preferably 5% by mass or more and 60% by mass or less, and further preferably 10% by mass or more and 50% by mass or less. The silica particle content in the reaction component can be calculated from, for example, the raw materials used in the reaction and ²⁹ Si NMR measurement. The D component, T component, Q component, and silica particles used in the reaction are calculated from the raw materials used. For the M component, the abundance ratio of the M component in the silica particle-containing condensation reaction product is determined from the area ratio of ²⁹ SiNMR measurement. Can be calculated. It is possible to calculate the silica particle content in the reaction component, assuming that all the bonds possessed by the M component, D component, T component, and Q component in the silica particle-containing condensation reaction product have been used for Si—O—Si bonds. It can also be calculated by adding an internal standard and measuring ²⁹ Si NMR.

  The average primary particle diameter of the silica particles is preferably 1 nm or more and 120 nm or less, and more preferably 1 nm or more and 40 nm or less. When the average primary particle system is 1 nm or more, it is preferable because the hardness is improved, and when it is 120 nm or less, it is preferable because the transparency of the cured product is 300 nm or less.

  The average secondary particle diameter of the silica particles is preferably 2 nm or more and 250 nm or less, and more preferably 2 nm or more and 80 nm or less. When the average secondary particle diameter is 2 nm or more, it is preferable because the hardness is improved, and when it is 250 nm or less, it is preferable because the transparency of the cured product is 300 nm or less.

  The average primary particle diameter is a value obtained by calculation from the specific surface area of BET, and the average secondary particle diameter is a value measured by a dynamic light scattering photometer.

  The shape of the silica particles (b) can be spherical, rod-shaped, plate-shaped or fibrous, or a shape in which two or more of these are combined, but is preferably spherical. The term “spherical” as used herein includes not only true spheres but also cases where the shape is substantially spherical, such as a spheroid or oval.

The specific surface area of the silica particles (b) is 1,000 m ² / B in terms of the BET specific surface area from the viewpoint of the viscosity of the condensation reaction product of the polysiloxane compound (a) and the silica particles (b) and the hardness of the cured product. g or less is preferable, and 800 m ² / g or less is more preferable. The BET specific surface area is a value measured by a method calculated from the pressure of N ₂ molecules and the gas adsorption amount.

  As the silica particles (b), those that meet the above requirements can be preferably used, but there is no limitation, and commercially available products can also be used.

  As a commercially available product, as colloidal silica, for example, LEVASIL series (manufactured by HC Starck Co., Ltd.), methanol silica sol IPA-ST, same MEK-ST, same NBA-ST, same XBA-ST, same DMAC-ST, Same ST-UP, Same ST-OUP, Same ST-20, Same ST-40, Same ST-C, Same ST-N, Same ST-O, Same ST-50, Same ST-OL (Nissan Chemical Industries) (Manufactured by Co., Ltd.), Quatlon PL series (manufactured by Fuso Chemical Co., Ltd.), OSCAL series (manufactured by Catalytic Chemical Industry Co., Ltd.), etc .; TT600, OX50 (above, Nippon Aerosil Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122 (above, Asahi Glass Co., Ltd.) ), E220A, E220 (Nippon Silica Industry Co., Ltd.), SYLYSIA470 (Fuji Silysia Co., Ltd.), SG Flakes (Nihon Sheet Glass Co., Ltd.), etc .; 300, 380, TT600, OX50 (manufactured by Nippon Aerosil Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122 (manufactured by Asahi Glass Co., Ltd.) , E220A, E220 (manufactured by Nippon Silica Industry Co., Ltd.), SYLYSIA470 (manufactured by Fuji Silysia Co., Ltd.), SG flake (manufactured by Nippon Sheet Glass Co., Ltd.) and the like.

<Characteristics of silica particle-containing condensation reaction product>

  In the silica particle-containing condensation reaction product, the silicon in the condensation reaction product is based on the total number of bonds forming a siloxane bond, a direct bond with a hydroxyl group, and a direct bond with the hydrolyzable group. The condensation rate of the condensation reaction product, which is defined as the ratio of the number of bonds forming the siloxane bond, is preferably 50 mol% or more and 100 mol% or less. The condensation rate of the condensation reaction product is preferably 50 mol% or more from the viewpoint of obtaining good effects of increasing hardness and reducing tackiness by forming a condensed structure. Silica particle-containing condensation reaction product in which no silane coupling agent is used (or the condensation product in the case of further reacting the silane coupling agent with the condensation product of the polysiloxane compound (a) and the silica particles (b)) ), The condensation rate of the condensation reaction product is more preferably 60 mol% to 100 mol%, and still more preferably 70 mol% to 100 mol%. In the condensation reaction product containing silica particles in which a silane coupling agent is used, the condensation rate of the condensation reaction product is more preferably 75 mol% or more and 100 mol% or less, and still more preferably 85 mol% or more and 100 mol% or less.

<Production of silica particle-containing condensation reaction product>
The silica particle-containing condensation reaction product of the present invention is obtained by subjecting the polysiloxane compound (a) and the silica particles (b) to a condensation reaction. In the condensation reaction, the silica particles (b) dispersed in the solvent can be reacted with the polysiloxane compound (a). As the solvent, water, an organic solvent, or a mixed solvent thereof can be used. The kind of organic solvent used varies depending on the dispersion medium of the silica particles (b) used. When the dispersion medium of the silica particles (b) used is aqueous, water and / or alcohol solvent is added to the aqueous dispersion medium of the silica particles (b), and then the silica particles (b) are added to the polysiloxane compound (a). Alternatively, the solvent in the aqueous solution of the silica particles (b) may be once substituted with an alcohol solvent, and then the silica particles (b) may be reacted with the polysiloxane compound (a). Examples of alcohol solvents that can be used include methanol, ethanol, n-propanol, 2-propanol, n-butanol, methoxyethanol, ethoxyethanol, and the like, and these are preferable because they are easily mixed with water.

  When the dispersion medium of the silica particles (b) used is a solvent such as alcohol, ketone, ester or hydrocarbon, water or a solvent such as alcohol, ether, ketone or ester can be used. Examples of alcohols include methanol, ethanol, n-propanol, 2-propanol, and n-butanol. Examples of the ether solvent include dimethoxyethane. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, ethyl formate, propyl formate, and γ-butyrolactone.

  The condensation reaction between the silica particles (b) and the polysiloxane compound (a) is preferably performed in an acidic atmosphere. Examples of the acid catalyst include the same acid catalyst as that used in the production of the polysiloxane compound (a). When the acid catalyst is removed after the production of the polysiloxane compound (a), it is necessary to add the acid catalyst again when the silica particles (b) are reacted with the polysiloxane compound (a). ) When the silica particles (b) are reacted as they are without removing the acid catalyst after the production, the polysiloxane compound (a) is used with the acid catalyst used for reacting the polysiloxane compound (a) without adding the acid catalyst again. ) And silica particles (b). However, in this case, an acid catalyst may be added again during the reaction between the polysiloxane compound (a) and the silica particles (b).

  Further, after the silica particles (b) and the polysiloxane compound (a) are subjected to a condensation reaction with an acid catalyst, a base catalyst may be added for further condensation. Examples of the base catalyst include inorganic bases and organic bases. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, lithium carbonate, potassium carbonate, and carbonate. Examples thereof include alkali or alkaline earth metal carbonates such as sodium, metal hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate. Examples of the organic base include trialkylamines such as triethylamine and ethyldiisopropylamine; N, N-dialkylaniline derivatives having 1 to 4 carbon atoms such as N, N-dimethylaniline and N, N-diethylaniline; pyridine, 2,6 -The pyridine derivative etc. which may have a C1-C4 alkyl substituent, such as lutidine, are mentioned.

  The reaction temperature for producing the condensation reaction product of the polysiloxane compound (a) and the silica particles (b) is not particularly limited, but is preferably −50 ° C. or higher and 200 ° C. or lower, more preferably 0 ° C. or higher and 150 ° C. or lower. Perform in the range. By performing the reaction in the above range, the condensation rate (polysiloxane-silica condensation rate) between the polysiloxane compound (a) and the silica particles (b) can be controlled.

  The water used in the condensation reaction of the polysiloxane compound (a) and the silica particles (b) is removed by a method such as distillation after adding a solvent selected from the above, and water and / or Or it is preferable to make alcohol into 1 mass% or less. When the moisture and / or alcohol content is within the above range, the silica particle-containing condensation reaction product of the present invention is preferably cured because shrinkage is reduced and cracks are less likely to occur.

  In the present invention, after the condensation reaction during synthesis of the polysiloxane compound (a) and / or after the condensation reaction of the polysiloxane compound (a) and the silica particles (b), washing by distillation, extraction, ion exchange, etc. It is preferable to adjust the pH of the silica particle-containing condensation reaction product of the present invention to 6 or more and 8 or less by removing the catalyst by the above method. It is preferable for the pH to be within the above range since the pot life of the condensation reaction product of the present invention is prolonged.

<Silane coupling agent>
The silica particle-containing condensation reaction product of the present invention is preferably obtained by further reacting with a silane coupling agent. A silane coupling agent can be contained in the reaction component. In this case, the condensation reaction is performed by adding a silane coupling agent to a condensation product obtained by condensing the polysiloxane compound (a) and the silica particles (b) (hereinafter, this may be simply referred to as a condensation product). You may carry out by making it react, and it may carry out by making a silane coupling agent coexist at the time of condensation reaction of a polysiloxane compound (a) and a silica particle (b), and condensing these simultaneously. In particular, in the former case, the condensation product of the polysiloxane compound (a) and the silica particles (b) can be sealed with a silane coupling agent monomer. In this case, specifically, after finishing the condensation reaction of the polysiloxane compound (a) and the silica particles (b), a silane coupling agent can be added to the reaction system to cause the reaction.

  Although a silane coupling agent will not be specifically limited if it can react with a silanol group and can form a Si-O-Si bond, As a preferable example, the compound shown to the following general formula (1) and (5) is mentioned, for example. Can be mentioned.

R ¹ _n1 SiX ¹ _4-n1 (1)
{Wherein n1 is an integer of 1 to 3, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ¹ is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. A group selected from a group and an acetoxy group, and when there are plural groups, R ¹ and X ¹ may be the same or different}
_{^{R 6 n7 R 7 n8 Si-}} NX 5 -SiR 6 n7 R 7 n8 (5)
{In the formula, n7 is an integer of 0 to 3, n8 is an integer satisfying n7 + n8 = 3, R ⁶ is a hydrogen atom or a monovalent organic group containing an unsaturated hydrocarbon; R ⁷ is a monovalent organic group having a saturated hydrocarbon group having 1 to 10 carbon atoms or containing an aromatic group, and X ⁵ is an atom selected from a hydrogen atom, Li, Na and K. . }

  The said silane coupling agent can be used by 1 type or in combination of 2 or more types. Moreover, the said silane coupling agent may be added neat and may be diluted and added in the solvent which does not have the active hydrogen mentioned later.

R ¹ in the general formula (1) is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, for example, specifically, exemplified for the unsaturated hydrocarbon group and R ³ exemplified for R ² Examples thereof include an organic group containing one or more selected from a saturated hydrocarbon group and an aromatic group. Especially, a C1-C10 organic group is preferable from a heat resistant viewpoint, More preferably, they are a hydrogen atom, a vinyl group, a methyl group, an ethyl group, and a phenyl group.

X ¹ in the general formula (1) is a hydroxyl group or a hydrolyzable substituent, and the substituents exemplified above for X ² , X ³ and X ⁴ can be used. Of these, halogen atoms such as chlorine, bromine and iodine, alkoxy groups such as methoxy group and ethoxy group, and acetoxy group are preferable from the viewpoint of easy formation of Si—O—Si bond.

In the compound of the general formula (1) that can be used as a silane coupling agent, X ¹ is preferably a halogen atom, particularly a Cl atom, from the viewpoint of reactivity with silanol.

Specific examples of the silane coupling agent in which X ¹ is a Cl (chlorine) atom include alkylchlorosilanes such as trimethylchlorosilane, dimethylchlorosilane, methyltrichlorosilane, dimethylchlorosilane, dichloromethylsilane, and trichlorosilane, dimethylvinylchlorosilane, Unsaturated hydrocarbon group-containing chlorosilanes such as methylvinyldichlorosilane and vinyltrichlorosilane, triphenylchlorosilane, diphenylmethylchlorosilane, dimethylphenylchlorosilane, diphenyldichlorosilane, phenylmethyldichlorosilane, phenyltrichlorosilane and other aromatic group-containing chlorosilanes, Dimethylcyclohexylchlorosilane, dicyclohexylmethylchlorosilane, dicyclohexyldichlorosilane, methylcyclohexyldimethyl Roshiran, cyclohexyl trichlorosilane, dimethyl cyclopentyl chlorosilane, dicyclopentyl methylchlorosilanes, dicyclopentyldichlorosilane, methylcyclopentyl dichlorosilane, aliphatic group containing chlorosilane such as cyclopentyl trichlorosilane and the like.

R ⁶ in the general formula (5) is a hydrogen atom or a monovalent organic group containing an unsaturated hydrocarbon. Specific examples of the monovalent organic group containing an unsaturated hydrocarbon include a hydrogen atom and an organic group containing one or more types selected from the unsaturated hydrocarbon-containing groups exemplified for R ² . Especially, a C1-C10 organic group is preferable from a heat resistant viewpoint, More preferably, they are a hydrogen atom and a vinyl group.

R ⁷ in the general formula (5) is a monovalent organic group having a saturated hydrocarbon group having 1 to 10 carbon atoms or containing an aromatic group. Specifically, the saturated carbonization exemplified for R ³ Examples thereof include an organic group containing one or more selected from a hydrogen group and an aromatic group. Especially, a C1-C10 organic group is preferable from a heat resistant viewpoint, More preferably, they are a methyl group, an ethyl group, and a phenyl group.

X ⁵ in the general formula (5) is an atom selected from a hydrogen atom, Li, Na and K, and is preferably a hydrogen atom from the viewpoint of polymer purification.

  Specific examples of the silane coupling agent represented by the general formula (5) include hexamethyldisilazane, tetramethyldisilazane, divinyltetramethyldisilazane, hexamethyldisilazane lithium, tetramethyldisilazane lithium, Examples include divinyltetramethyldisilazane lithium, hexamethyldisilazane sodium, tetramethyldisilazane sodium, divinyltetramethyldisilazane sodium, hexamethyldisilazane potassium, tetramethyldisilazane potassium, and divinyltetramethyldisilazane potassium.

The amount of the silane coupling agent used is the polysiloxane compound (a) (when the silane coupling agent is also reacted during the condensation of the polysiloxane compound (a) and the silica particles (b)) or the polysiloxane compound (a). With respect to the silanol content of the condensation product of the silica particles (b) (when the silane coupling agent is further reacted with the condensation product) (in molar equivalents), preferably 0.1 times to 10 times, more preferably 0.5 times to 5 times, further preferably 0.7 times to 2 times, and most preferably 0.7 times to 1.5 times. The amount used is preferably 0.1 times or more from the viewpoint of heat resistance, and preferably 10 times or less from the viewpoint of yield. The silanol content can be measured by the following method. That is, the hydrolysis rate is calculated by gas chromatogram analysis, the condensation rate is calculated by ²⁹ Si NMR analysis, and in the polysiloxane compound (a) or the condensation product of the polysiloxane compound (a) and silica particles (b). The amount of silanol contained (M ³ ) mol is calculated.

  When the silane coupling agent is alkoxysilane, the silane coupling agent can be subjected to a condensation reaction using the same method as the reaction between the polysiloxane compound (a) and the silica particles (b).

  When the silane coupling agent is highly reactive with active hydrogen such as halogenated silane or disilazane derivative, the reaction of the silane coupling agent is carried out in a solvent that does not have active hydrogen such as water or alcohol. It is preferable to carry out with. Examples of preferable solvents include esters, ketones, ethers, aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, amide compounds, and the like.

  Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, and γ-butyrolactone. Examples of ketones include acetone, methyl ethyl ketone, methyl isoamyl ketone, and the like.

  Examples of the ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl. Polyhydric alcohol ethers obtained by alkyl etherifying all hydroxyl groups of a polyhydric alcohol such as ether, polyhydric alcohol esters obtained by alkyl etherifying and / or esterifying all hydroxyl groups of a polyhydric alcohol, and tetrahydrofuran, 1 , 4-dioxane, anisole and the like.

  Examples of the aliphatic hydrocarbon compound include hexane, heptane, octane, nonane, decane, and the like.

  Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene and the like.

  Examples of the amide compound include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  These solvents may be used alone or in combination with a plurality of solvents. Moreover, you may react in a bulk, without using the said solvent.

  The reaction of the silane coupling agent is preferably performed in a reaction system in which the content of a solvent having active hydrogen such as water or alcohol is 1% by mass or less. 1 mass% or less is preferable at the point from which the polymer production | generation of a low molecular-weight component is few and heat resistance is favorable.

  In the reaction of the silane coupling agent, an organic base is preferably used as a catalyst from the viewpoint of the condensation rate.

  Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclononane, diaza. Bicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, N, N-dimethylamine, N, N- Diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine , Tripropylamine, tributylamine, and the like. These organic bases can be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of making a silane coupling agent react, Preferably it is -78 degreeC or more and 200 degrees C or less, More preferably, it performs in -20 degreeC or more and 150 degrees C or less.

  After the reaction of the silane coupling agent, it is preferable to remove and purify the generated hydrochloride and the organic base in the reaction system by methods such as washing with water, extraction, precipitation, and ion exchange. By these methods, it is preferable to adjust the pH of the silica particle-containing condensation reaction product of the present invention to 6 or more and 8 or less. It is preferable for the pH to be within the above range since the pot life of the condensation reaction product of the present invention is prolonged.

  When purifying the silica particle-containing condensation reaction product, it is preferable to remove water in the system by a method such as distillation after adding a solvent selected from the above.

  The water content in the silica particle-containing condensation reaction product of the present invention is preferably 1% by mass or less. In this case, when the condensation reaction product of the present invention is cured, shrinkage is reduced and cracks are less likely to occur. The water content can be measured, for example, by the Karl Fischer method.

  Moreover, it is preferable that the solvent contained in the silica particle containing condensation reaction material of this invention is 1 mass% or less. In this case, when the condensation reaction product of the present invention is cured, shrinkage is reduced and cracks are less likely to occur. The content of the solvent can be measured using, for example, a gas chromatogram.

  In the present invention, the polysiloxane compound (a) and / or silane coupling agent preferably contains an unsaturated hydrocarbon group and / or a SiH group. In particular, the silane coupling agent is a silane compound represented by the general formula (1), and the polysiloxane compound (a) and / or the silane coupling agent contains an unsaturated hydrocarbon group and / or a SiH group. It is preferable. In these cases, a hardened resin cured product can be obtained. As unsaturated hydrocarbon groups in these cases, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, cyclohexenylethyl group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group And acyclic and alkenyl groups such as decenyl group and styryl group, and araalkenyl groups such as PhCH═CH— group.

  In particular, at least one of the silane compounds represented by the general formulas (2) to (4) and the condensates thereof, and the silane coupling agents represented by the general formulas (1) and (5) is not suitable. The proportion of silicon atoms containing a saturated hydrocarbon group and / or SiH group to which the unsaturated hydrocarbon group and / or SiH group is bonded is 5 mol% or more and 80 mol of all silicon atoms contained in these components. % Or less, more preferably 10 mol% or more and 70 mol% or less, and further preferably 15 mol% or more and 50 mol% or less. The ratio is preferably 5 mol% or more from the viewpoint of the hardness of the cured product using the resin of the present invention, and preferably 80 mol% or less from the viewpoint of the heat resistance and light resistance of the cured product.

The ratio can also be calculated by subjecting the silica particle-containing condensation reaction product to ¹ HNMR analysis and ²⁹ SiNMR analysis in solution or solid.

The Q component contained in the silica particle-containing condensation reaction product of the present invention preferably has a high condensation rate from the viewpoint of pot life and viscosity. The Q component of the silica particle-containing condensation reaction product refers to silica particles (b) in the silica particle-containing condensation reaction product, n6 = 0 among the silane compounds represented by the above general formula (4), and general It is a part derived from the silane compound represented by the formula (1) where n1 = 0. The condensation rate of the Q component can be evaluated by determining the amount of a component corresponding to 0 to 4 siloxane bonds from ²⁹ Si NMR analysis of a solution or solid. In the silica particle-containing condensation reaction product, the component corresponding to zero siloxane bond (Q0 component), the component corresponding to one siloxane bond (Q1 component), and the component corresponding to two siloxane bonds (Q2 component) The ratio of the peak intensity of the Q4 component to the total peak intensity of the component corresponding to 3 siloxane bonds (Q3 component) and the component corresponding to 4 siloxane bonds (Q4 component) is 50% or more. Preferably, it is 60% or more, more preferably 70% or more. When the ratio is within the above range, since there are few terminal groups such as hydrosilyl groups and alkoxy groups, the curing shrinkage of the resin can be reduced, and the pot life of the silica particle-containing condensation reaction product is preferably increased. The peak intensity of each Q component is calculated from the peak area.

  The weight average molecular weight of the silica particle-containing condensation reaction product of the present invention in terms of standard polymethyl methacrylate by gel permeation chromatography (GPC) is preferably in the range of 1,000 to 200,000, more preferably 1,000. More than 100,000. When the weight average molecular weight of the condensation reaction product is 1,000 or more, the heat resistance and the pot life of the silica particle-containing condensation reaction product are long, and when the weight average molecular weight is 200,000 or less, the silica particle-containing condensation reaction. Since the viscosity of a thing becomes low, it is preferable.

  Another aspect of the present invention includes the silica particle-containing condensation reaction product (A) of the present invention described above and a hydrosilylation catalyst (B), and the silica particle-containing condensation reaction product (A) is an unsaturated hydrocarbon group. And / or a resin composition containing an SiH group, wherein the content of the silica particle-containing condensation reaction product (A) is 20% by mass or more, and contains an unsaturated hydrocarbon group and an SiH group.

  Still another embodiment of the present invention is the above-described silica particle-containing condensation reaction product (A) of the present invention, hydrosilylation catalyst (B), component (C) containing an unsaturated hydrocarbon group and / or SiH group. And a content ratio of the silica particle-containing condensation reaction product (A) is 20% by mass or more, and an unsaturated hydrocarbon group and a SiH group are provided.

  In any of the above embodiments, the resin composition of the present invention contains an unsaturated hydrocarbon group and a SiH group, so that they can undergo an addition reaction by heating to cure the resin composition. That is, in an embodiment in which the silica particle-containing condensation reaction product (A) has an unsaturated hydrocarbon group and an SiH group, these unsaturated hydrocarbon group and SiH group can undergo an addition reaction. On the other hand, when the resin composition contains a component (C) containing an unsaturated hydrocarbon group and a SiH group, the unsaturated hydrocarbon group and SiH group in the component (C) can undergo an addition reaction. In the embodiment of the resin composition containing the component (C), the silica particle-containing condensation reaction product (A) may further contain an unsaturated hydrocarbon group and / or a SiH group.

  Examples of the compound having an unsaturated hydrocarbon group and / or the compound having an SiH group (that is, containing a hydrogen atom directly bonded to a silicon atom) constituting the component (C) include those represented by the general formulas (2) to (2) to The polyorganosiloxane formed by hydrolyzing and condensing 1 or more types chosen from the silane compound each represented by (4) can be mentioned. This may be an uncondensed polysiloxane compound (a) in the condensation reaction between the polysiloxane compound (a) and the silica particles (b). Preferred examples of the resin composition include silica particle-containing condensation reaction product (A), hydrosilylation catalyst (B), and as component (C), a compound containing an unsaturated hydrocarbon and / or a direct bond to a silicon atom. And a resin composition comprising a compound containing a hydrogen atom.

  In the resin composition, the content of the silica particle-containing condensation reaction product (A) is preferably 20% by mass or more and 100% by mass or less, more preferably 30% by mass or more and 100% by mass or less, and still more preferably. Is 40 mass% or more and 100 mass% or less. It is preferable that the said content rate is 20 to 100 mass% from a viewpoint of the hardness of the cured film obtained.

It is preferable that the total number of unsaturated hydrocarbon groups Z ¹ and the total number of SiH groups Z ² in the resin composition satisfy 0.25 ≦ Z ¹ / Z ² ≦ 2, more preferably 0.5 ≦ Z ¹ / Z. ² ≦ 1.5 is satisfied, more preferably 0.7 ≦ Z ¹ / Z ² ≦ 1.5. Z ¹ / Z ² is preferably 0.25 or more, particularly 0.7 or more from the viewpoint of transparency of the cured product, and preferably 2 or less, particularly 1.5 or less from the viewpoint of shrinkage.

The hydrosilylation catalyst (B) is a catalyst for promoting the addition reaction between the unsaturated hydrocarbon in the unsaturated hydrocarbon group and the hydrogen atom directly bonded to the silicon atom in the SiH group. Can be used. Specifically, platinum group metals such as platinum (including platinum black), rhodium, palladium, etc .; H ₂ PtCl ₄ · nH ₂ O, H ₂ PtCl ₆ · nH ₂ O, NaHPtCl ₆ · nH ₂ O, KHPtCl ₆ NH ₂ O, Na ₂ PtCl ₆ · nH ₂ O, K ₂ PtCl ₄ · nH ₂ O, PtCl ₄ · nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · nH ₂ O (where n is 0 to 0) An integer of 6, preferably 0 or 6), such as platinum chloride, chloroplatinic acid and chloroplatinate; alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972); Platinum acid and olefin complex (see US Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum black, palladium, etc. Platinum group metals such as alumina, silica, Supported on a carrier such as carbon; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane such as divinyltetramethyl Examples thereof include a disiloxane platinum complex and a complex with a vinyl group-containing cyclic siloxane. These hydrosilylation catalysts may be used alone or in combination of two or more hydrosilylation catalysts. The hydrosilylation catalyst (B) may be used in an effective amount, and is usually 0.01 to 1000 ppm, preferably 0.2 to 100 ppm in terms of the mass of the platinum group metal with respect to the total amount of the resin composition. From the viewpoint of curing speed, 0.01 ppm or more is preferable, and from the viewpoint of transparency of the cured product, 1000 ppm or less is preferable.

  An adhesive aid may be added to the resin composition of the present invention for the purpose of improving the adhesion to various supporting substrates. As an adhesion assistant, a silane coupling agent, more specifically, for example, an alkoxysilane containing a hydrogen atom directly bonded to a silicon atom, an alkoxysilane containing an epoxy group, an unsaturated bond such as a vinyl group, etc. Examples thereof include organic alkoxysilane compounds such as alkoxysilane, compounds obtained by hydrolyzing some or all of these organic alkoxysilane compounds, and condensates thereof.

  The addition amount of the silane coupling agent is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin composition of the present invention. The addition amount of the silane coupling agent is preferably 0.01 parts by mass or more from the viewpoint of improving adhesiveness, and preferably 10 parts by mass or less from the viewpoint of storage stability.

  An inorganic filler may be added to the resin composition of the present invention. In order to avoid an adverse effect on light transmittance, the inorganic filler preferably has an average particle diameter equal to or smaller than the wavelength used in the intended application, and the average particle diameter is more preferably 100 nm or less. In the inorganic filler, in the resin, for example, mechanical properties may be improved and thermal conductivity may be improved. The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.1 nm or more because the resin composition has a low viscosity and good moldability. The average particle diameter is a value obtained by calculation from the specific surface area of BET. Although the addition amount of an inorganic filler can be selected according to the objective, it is 1-60 mass parts with respect to 100 mass parts of resin compositions, More preferably, it is 5-60 mass parts, More preferably, it is 5-40 mass parts. Can be.

  In the resin composition of the present invention, a phosphor or a phosphor can be added for the purpose of converting the color of the emission wavelength. These materials are preferably mixed with the resin composition and any other components using a known method such as centrifugation, and the resulting mixture is preferably defoamed by a known method such as vacuum defoaming.

  The resin composition of the present invention can be cured using a known method. Specifically, a method of curing by heating and a method of curing by irradiating ultraviolet rays (UV) can be mentioned. The temperature for curing by heating is preferably in the range of 20 to 200 ° C.

  The curing reaction can be carried out under an atmosphere of inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, lower saturated hydrocarbon gas or air, under reduced pressure or under pressure. . These gases can be used as 1 type, or 2 or more types of mixed gas.

  Another aspect of the present invention provides a sealing resin containing the above-described resin composition of the present invention. The sealing resin is typically obtained by arbitrarily adding a phosphor, an adhesion aid, or the like to the above-described resin composition of the present invention. The sealing resin is particularly useful for sealing a light emitting element to form a light emitting diode.

  As a specific example of the light emitting element to be used, for example, a light emitting element formed by stacking semiconductor materials on a substrate can be exemplified. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

  As a method of sealing a light emitting element with the sealing resin of the present invention containing the resin composition of the present invention, for example, a lead frame in which a sealing resin is previously injected into a mold mold and the light emitting element is fixed thereto For example, a method of curing the sealing resin after dipping the sealing resin, a method of curing the sealing resin after injecting the sealing resin into a mold with the light emitting element inserted, and the like. In this case, examples of the method for injecting the sealing resin include injection by a dispenser, transfer molding, injection molding, and the like. Further, as other sealing methods, a sealing resin is dropped onto a light emitting element, stencil printing, screen printing, or a method of applying and curing through a mask, a cup having a light emitting element arranged in a lower part, etc. Examples include a method of injecting a sealing resin with a dispenser or the like and curing.

  Examples of the shape of the sealing portion include a concave lens shape, a convex lens shape, a shell shape, a plate shape, and a thin film shape.

  Another aspect of the present invention provides a lens formed using a curable composition containing the above-described resin composition of the present invention. Such a curable composition can be cured by a conventionally known method to form a lens.

  The curable composition containing the resin composition of the present invention can also be used as a material such as a die bond material for fixing a light emitting element to a lead terminal or a package, a passivation film on the light emitting element, and a package substrate.

  Another aspect of the present invention provides an underfill material comprising the above-described resin composition of the present invention. Such an underfill material can be inserted between a chip and a substrate for the purpose of stress relaxation and joint reinforcement, for example, and can be cured by a conventionally known method.

  The performance of the light-emitting diode obtained using the resin composition of the present invention can be improved by a conventionally known method. As a method for improving the performance, for example, a method of providing a light reflecting layer or a condensing layer on the back surface of the light emitting device, a method of forming a complementary colored portion on the bottom, and a layer that absorbs light having a wavelength shorter than the main light emitting peak Method of providing on top, Method of molding light emitting element after sealing with hard material, Method of inserting light emitting diode into through hole and fixing, Light emitting element connected to lead member etc. by flip chip connection etc. And a method of extracting light from the light source.

  The light-emitting diode obtained by using the resin composition of the present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, an instrument light source for vehicles, a signal lamp, a display lamp, and a display device It is useful as a light source for a planar light emitter, a display, a decoration, various lights, and the like.

  Hereinafter, embodiments of the present invention will be described in detail with reference to Examples and Comparative Examples. The present invention is not limited to these.

  About the sample by Example 1- Example 10, Manufacturing Example 1- Manufacturing Example 4, and Comparative Example 1- Comparative Example 2, the measurement about (1)-(5) was performed.

(1) NMR measurement (condensation rate evaluation)
Sample preparation: A sample was prepared by adding 0.5% by mass of tris (2,4-pentanedionato) chromium (III) to a heavy acetone solution having a condensation reaction product concentration of 30% by mass.
Measurement condition:
²⁹ SiNMR
Using an NMR (Nuclear Magnetic Resonance) apparatus GSX400 manufactured by JEOL, the number of integrations was set to 2048.
From the obtained data, the condensation rate of the polysiloxane compound (a) was calculated by the following procedure.
The condensation rate of the polysiloxane compound (a) is determined based on the area ratio of each silicon peak of ²⁹ SiNMR (M0, M1, D0, D1, D2, T0, T1, T2, T3, Q0, Q1, Q2, Q3). Q4) was calculated by measuring the silicon abundance.
Specifically, the calculation was performed as follows.
The peak area of the aforementioned D1 component is represented as (D1).
Condensed silicon area:
{(M1) + (D1) + (D2) × 2 + (T1) + (T2) × 2 + (T3) × 3 + (Q1) + (Q2) × 2 + (Q3) × 3 + (Q4) × 4}
Total silicon area:
{(M0) + (M1)} + {(D0) + (D1) + (D2)} × 2 + {(T0) + (T1) + (T2) + (T3)} × 3 + {(Q0) + ( Q1) + (Q2) + (Q3) + (Q4)} × 4
Polysiloxane compound (a) condensation rate = (condensed silicon area) / (total silicon area) × 100

(2) Gas chromatogram measurement (hydrolysis rate evaluation and silanol group content rate evaluation)
A solution obtained by diluting a reaction solution of the condensation reaction product with isopropyl alcohol and adding a standard substance so as to be 1 wt% is a gas chromatography analyzer (HP 6890 manufactured by Agilent Technologies, column: DB-WAX 30 m × 0). 250 mm, 0.25 μm thickness). From the obtained results, the contents of methanol and ethanol were quantified using a separately prepared internal standard calibration curve, and the hydrolysis rate was calculated.
The silanol group content in the polysiloxane compound (a) was calculated from the condensation rate and hydrolysis rate calculated by the method described above.

(3) Molecular weight measurement Using Tosoh gel permeation chromatography (GPC), HLC-8220, and TSKgelGMH _HR- M column, the condensation reaction product was measured as a 1% by mass solution in acetone solvent, and differential refraction was performed. A weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was determined by a rate meter (RI).

(4) Viscosity measurement Using a RE80 viscometer manufactured by Toki Sangyo Co., Ltd., the viscosity of each produced polymer was measured. Table 2 summarizes the polymers of 100 poise or less as ◯ and the polymers having a viscosity higher than 100 poise as x.

(5) Pot life 5 g of the obtained polymer was taken in a glass sample bottle and left to stand at room temperature for 1 month. Summarized in

[Preparation of polymer]
[Example 1]
In a 200 mL eggplant-shaped flask, 3.76 g (25 mmol) of ethyltrimethoxysilane, 4.00 g (33 mmol) of dimethyldimethoxysilane, 4.92 g (42 mmol) of methoxydimethylvinylsilane, and 12.5 g of isopropyl alcohol were added and stirred. Separately, 9.88 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then dropped into a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 1 containing the polysiloxane compound (a). A part of the reaction solution 1 was recovered, xylene was added, the solvent was removed using an evaporator, and ²⁹ Si NMR and gas chromatogram were measured. As a result, the condensation rate was 63.1 mol%, and the silanol group content was 33. It was 7 mol%.

  Into a 300 mL eggplant-shaped flask, 10.0 g (silica particles (b)) of PL-2L (average primary particle diameter 20 nm, 20% by mass concentration manufactured by Fuso Chemical Industries) and 12.5 g of isopropyl alcohol are added. And stirred. Then, the reaction liquid 1 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 10 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream.

  After refluxing, 40 g of propylene glycol methyl ethyl acetate (hereinafter referred to as PGMEA) was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump, and the oil bath temperature was finally raised to 120 ° C. to obtain Polymer 1 which is a silica particle-containing condensation reaction product.

  The content of silica particles in the reaction component of polymer 1 was 19% by mass. When the molecular weight of polymer 1 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 2200.

[Example 2]
In a 200 mL eggplant-shaped flask, 8.23 g (55 mmol) of ethyltrimethoxysilane, 8.78 g (73 mmol) of dimethyldimethoxysilane, 7.24 g (55 mmol) of dimethoxymethylvinylsilane, and 25 g of isopropyl alcohol were added and stirred. Separately, 22.7 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then dropped into a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 2 containing the polysiloxane compound (a). A part of the reaction solution 2 was recovered, xylene was added, the solvent was removed using an evaporator, and ²⁹ SiNMR and gas chromatogram were measured. As a result, the condensation rate was 64.6 mol% and the silanol group content was 32. It was 3 mol%.

  Into a 300 mL eggplant-shaped flask, PL-2L (30.0 g (silica particles (b))) having an average primary particle diameter of 20 nm and a concentration of 20% by mass manufactured by Fuso Chemical Co., Ltd.) and 25 g of isopropyl alcohol are added. And stirred. Then, the reaction liquid 2 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 10 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream.

  After the reflux, 80 g of PGMEA was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump, and the oil bath temperature was finally raised to 120 ° C. to obtain Polymer 2 which is a silica particle-containing condensation reaction product.

  The content of silica particles in the reaction component of polymer 2 was 29% by mass. . When the molecular weight of polymer 2 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 2300.

[Example 3]
Into a 200 mL eggplant-shaped flask, 11.27 g (75 mmol) of ethyltrimethoxysilane, 6.37 g (53 mmol) of dimethyldimethoxysilane, 7.24 g (55 mmol) of dimethoxymethylvinylsilane, and 25 g of isopropyl alcohol were added and stirred. Separately, 23.8 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then dropped into a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 3 containing the polysiloxane compound (a). A part of the reaction solution 3 was recovered, xylene was added, the solvent was removed using an evaporator, and ²⁹ SiNMR and gas chromatogram were measured. As a result, the condensation rate was 64.2 mol% and the silanol group content was 32. It was 5 mol%.

  30 g (silica particles (b)) of PL-2L (manufactured by Fuso Chemical Industries, water-dispersed silica particles having an average primary particle diameter of 20 nm and a concentration of 20% by mass) and 25 g of isopropyl alcohol were added to a 300 mL eggplant-shaped flask and stirred. . Then, the reaction liquid 3 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 10 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream.

  After the reflux, 80 g of PGMEA was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump, and the oil bath temperature was finally raised to 120 ° C. to obtain Polymer 3 which is a silica particle-containing condensation reaction product.

  The content of silica particles in the reaction component of polymer 3 was 29% by mass. When the molecular weight of polymer 3 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 2100.

[Example 4]
In a 200 mL eggplant-shaped flask, 8.23 g (55 mmol) of ethyltrimethoxysilane, 6.37 g (53 mmol) of dimethyldimethoxysilane, 9.91 g (75 mmol) of dimethoxymethylvinylsilane, and 25 g of isopropyl alcohol were added and stirred. Separately, 22.7 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then dropped into a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 2 hours in a nitrogen stream using an oil bath to obtain a reaction solution 4 containing the polysiloxane compound (a). A part of the reaction solution 4 was recovered, xylene was added, the solvent was removed using an evaporator, and ²⁹ SiNMR and gas chromatogram were measured. As a result, the condensation rate was 62.1 mol%, and the silanol group content was 34. It was 5 mol%.

  30 g (silica particles (b)) of PL-2L (manufactured by Fuso Chemical Industries, water-dispersed silica particles having an average primary particle diameter of 20 nm and a concentration of 20% by mass) and 25 g of isopropyl alcohol were added to a 300 mL eggplant-shaped flask and stirred. . Then, the reaction liquid 4 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 10 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream.

  After the reflux, 80 g of PGMEA was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump, and the oil bath temperature was finally raised to 120 ° C. to obtain Polymer 4 which is a silica particle-containing condensation reaction product.

  The content of silica particles in the reaction component of polymer 4 was 29% by mass. When the molecular weight of the polymer 4 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 2200.

[Example 5]
In a 200 mL eggplant-shaped flask, 8.23 g (55 mmol) of ethyltrimethoxysilane, 8.78 g (73 mmol) of dimethyldimethoxysilane, 7.24 g (55 mmol) of dimethoxymethylvinylsilane, and 25 g of isopropyl alcohol were added and stirred. Separately, 22.7 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then dropped into a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 5 containing the polysiloxane compound (a). A part of the reaction solution 5 was recovered, xylene was added, the solvent was removed using an evaporator, and ²⁹ SiNMR and gas chromatogram were measured. As a result, the condensation rate was 67.2 mol% and the silanol group content was 29. It was 8 mol%.

  Into a 300 mL eggplant-shaped flask, PL-1 (water dispersion silica particles having an average primary particle size of 12 nm and a concentration of 12% by mass manufactured by Fuso Chemical Industries) 50.0 g (silica particles (b)) and 25 g of isopropyl alcohol were added. Stir. Then, the reaction liquid 5 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 10 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream.

  After the reflux, 80 g of PGMEA was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, using a vacuum pump, PEGMEA was removed under reduced pressure, and the oil bath temperature was finally raised to 120 ° C. to obtain Polymer 5 which is a silica particle-containing condensation reaction product.

  The content of silica particles in the reaction component of polymer 5 was 29% by mass. When the molecular weight of the polymer 5 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 2200.

[Example 6]
In a 200 mL eggplant-shaped flask, 8.23 g (55 mmol) of ethyltrimethoxysilane, 8.78 g (73 mmol) of dimethyldimethoxysilane, 7.24 g (55 mmol) of dimethoxymethylvinylsilane, and 25 g of isopropyl alcohol were added and stirred. Separately, 22.7 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then dropped into a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 6 containing the polysiloxane compound (a). A part of the reaction solution 6 was recovered, xylene was added, the solvent was removed using an evaporator, and ²⁹ SiNMR and gas chromatogram were measured. As a result, the condensation rate was 63.6 mol% and the silanol group content was 33. It was 1 mol%.

  Into a 300 mL eggplant-shaped flask, 30.0 g (silica particles (b)) of water-dispersed silica particles having an average primary particle diameter of 20 nm and a concentration of 20% by mass manufactured by Fuso Chemical Industry, 25 g of isopropyl alcohol were added. Stir. Then, the reaction liquid 6 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 10 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream.

  After the reflux, 80 g of PGMEA was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump.

  To this polymer, 80 g of PEGMEA and 25 g (315 mmol) of pyridine were added and mixed, and 22.8 g (210 mmol) of trimethylchlorosilane (silane coupling agent) was added dropwise over 5 minutes while stirring. Then, after heating at 50 degreeC for 3 hours, it cooled to room temperature. To the obtained reaction solution, 50 g of water and 20 g of toluene were added, and the extraction operation was repeated three times, washed, the solvent was removed under reduced pressure using a vacuum pump, and polymer 6 which is a silica particle-containing condensation reaction product. Got.

The content of silica particles in the reaction component of polymer 6 was 28% by mass. When the molecular weight of polymer 6 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 2400.

[Example 7]
Into a 200 mL eggplant-shaped flask, 8.15 g (54 mmol) of ethyltrimethoxysilane, 8.70 g (65 mmol) of diethoxymethylsilane, and 25 g of isopropyl alcohol were added and stirred. Separately, 15.7 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then dropped into a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 7 containing a polysiloxane compound (a). A part of the reaction solution 7 was recovered, xylene was added, the solvent was removed using an evaporator, and ²⁹ SiNMR and gas chromatogram were measured. As a result, the condensation rate was 62.4 mol% and the silanol group content was 35. It was 2 mol%.

  Into a 300 mL eggplant-shaped flask, 20 g (silica particles (b)) of PL-2L (average primary particle diameter 20 nm, 20% by mass concentration, manufactured by Fuso Chemical Co., Ltd.) and 25 g of isopropyl alcohol were added and stirred. . Subsequently, using a dropping funnel, the reaction solution 7 cooled to room temperature and 20.51 g (175 mmol) of trimethylethoxysilane (silane coupling agent) were added dropwise to the eggplant flask over 10 minutes, and 30 minutes at room temperature. Stir. After stirring, a condenser tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream.

  After the reflux, 80 g of PGMEA was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump, and the oil bath temperature was finally raised to 120 ° C. to obtain Polymer 7 which is a silica particle-containing condensation reaction product.

The content of silica particles in the reaction component of polymer 7 was 26% by mass. When the molecular weight of the polymer 7 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 5300.

[Example 8]
In a 200 mL eggplant-shaped flask, 6.01 g (40 mmol) of ethyltrimethoxysilane, 10.74 g (80 mmol) of diethoxymethylsilane, and 25 g of isopropyl alcohol were added and stirred. Separately, 15.1 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then added dropwise to a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 8 containing the polysiloxane compound (a). A part of the reaction solution 8 was recovered, xylene was added, the solvent was removed using an evaporator, and ²⁹ SiNMR and gas chromatogram were measured. As a result, the condensation rate was 66.2 mol% and the silanol group content was 30. It was 8 mol%.

  Into a 300 mL eggplant-shaped flask, 20 g (silica particles (b)) of PL-2L (average primary particle diameter 20 nm, 20% by mass concentration, manufactured by Fuso Chemical Co., Ltd.) and 25 g of isopropyl alcohol were added and stirred. . Subsequently, using a dropping funnel, the reaction solution 8 cooled to room temperature and 20.51 g (175 mmol) of trimethylethoxysilane (silane coupling agent) were added dropwise to the eggplant flask over 10 minutes, and 30 minutes at room temperature. Stir. After stirring, a condenser tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream.

  After the reflux, 80 g of PGMEA was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump, and the oil bath temperature was finally raised to 120 ° C. to obtain polymer 8 which is a silica particle-containing condensation reaction product.

  The content of silica particles in the reaction component of polymer 8 was 27% by mass. When the molecular weight of the polymer 8 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 5500.

[Example 9]
Into a 200 mL eggplant-shaped flask, 8.15 g (54 mmol) of ethyltrimethoxysilane, 8.70 g (65 mmol) of diethoxymethylsilane, and 25 g of isopropyl alcohol were added and stirred. Separately, 15.7 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then dropped into a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 9 containing the polysiloxane compound (a). A part of the reaction solution 2 was recovered, xylene was added, the solvent was removed using an evaporator, and ²⁹ SiNMR and gas chromatogram were measured. As a result, the condensation rate was 64.3 mol% and the silanol group content was 32. It was 6 mol%.

  In a 300 mL eggplant-shaped flask, PL-1 (water dispersion silica particles having an average primary particle diameter of 12 nm and a concentration of 12% by mass manufactured by Fuso Chemical Industries) 33 g (silica particles (b)) (content in the reaction component of 26% by mass) ), 25 g of isopropyl alcohol was added and stirred. Subsequently, using a dropping funnel, the reaction liquid 9 cooled to room temperature and 20.51 g (175 mmol) of trimethylethoxysilane (silane coupling agent) were dropped into the eggplant flask over 10 minutes, and the mixture was stirred at room temperature for 30 minutes. Stir. After stirring, a condenser tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream.

  After the reflux, 80 g of PGMEA was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump, and the oil bath temperature was finally raised to 120 ° C. to obtain polymer 9 as a silica particle-containing condensation reaction product.

  The content of silica particles in the reaction component of polymer 9 was 26% by mass. When the molecular weight of the polymer 9 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 5300.

[Example 10]
In a 200 mL eggplant type flask, 8.23 g (55 mmol) of ethyltrimethoxysilane, 7.81 g (65 mmol) of dimethyldimethoxysilane, and 25 g of isopropyl alcohol were added and stirred. Separately, 22.7 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then dropped into a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 2 hours under a nitrogen stream using an oil bath to obtain a reaction solution 10 containing the polysiloxane compound (a). A part of the reaction solution 10 was recovered, xylene was added, the solvent was removed using an evaporator, and ²⁹ SiNMR and gas chromatogram were measured. As a result, the condensation rate was 65.6 mol% and the silanol group content was 31. It was 6 mol%.

  Into a 300 mL eggplant-shaped flask, PL-2L (water dispersion silica particles having an average primary particle size of 20 nm and a concentration of 20% by mass manufactured by Fuso Chemical Industries) 20.0 g (silica particles (b)) and 25 g of isopropyl alcohol were added. Stir. Then, the reaction liquid 10 cooled to room temperature using the dropping funnel was dripped at the said eggplant flask over 10 minutes, and it stirred at room temperature for 30 minutes. After stirring, a condenser tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream.

  After the reflux, 80 g of PGMEA was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump.

  To this polymer, 80 g of PEGMEA and 25 g (315 mmol) of pyridine were added and mixed, and 19.8 g (210 mmol) of dimethylchlorosilane (silane coupling agent) was added dropwise over 5 minutes while stirring. Subsequently, the mixture was stirred at room temperature for 3 hours.

  To the obtained reaction solution, 50 g of water and 20 g of toluene were added, and the extraction operation was repeated three times, washed, the solvent was removed under reduced pressure using a vacuum pump, and the polymer 10 which is a silica particle-containing condensation reaction product. Got.

  The content of silica particles in the reaction component of polymer 10 was 23% by mass. When the molecular weight of the polymer 10 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 5500.

[Production Example 1]
In a 300 mL Nasuf-type flask, 25.41 g (211 mmol) of dimethyldimethoxysilane, 7.93 g (53 mmol) of ethyltrimethoxysilane, 2.01 g (17 mmol) of ethoxytrimethylsilane, and 25 g of isopropyl alcohol were stirred. To this container, 17.4 g of 37% hydrochloric acid was dropped using a dropping funnel while adjusting the temperature so as not to exceed 10 ° C. in an ice bath. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 6 hours under a nitrogen stream. After cooling to room temperature, 20 g of water and 5 g of acetonitrile were added and extraction was repeated 3 times. After confirming that the aqueous layer was neutral with pH test paper, the silicone layer and 54 g of PEGMEA were placed in a 300 mL eggplant-shaped flask, and a distillation tower and a vacuum pump were set. Finally, the temperature of the oil bath was raised to 140 ° C., and PEGMEA was removed under reduced pressure to obtain polymer 11. The condensation rate was 96.2 mol%, and the silanol group content was 0.7 mol%.
When the molecular weight of the obtained polymer 11 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 8900.

[Production Example 2]
In a 300 mL Nasf flask, 19.03 g (158 mmol) of dimethyldimethoxysilane, 6.98 g (53 mmol) of dimethoxymethylvinylsilane, 7.93 g (53 mmol) of ethyltrimethoxysilane, 1.97 g (17 mmol) of dimethylmethoxyvinylsilane, 25 g of isopropyl alcohol And stirred. To this container, 17.4 g of 37% hydrochloric acid was dropped using a dropping funnel while adjusting the temperature so as not to exceed 10 ° C. in an ice bath. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 6 hours under a nitrogen stream. After cooling to room temperature, 20 g of water and 5 g of acetonitrile were added and extraction was repeated 3 times. After confirming that the aqueous layer was neutral with pH test paper, the silicone layer and 54 g of PEGMEA were placed in a 300 mL eggplant-shaped flask, and a distillation tower and a vacuum pump were set. Finally, the temperature of the oil bath was raised to 140 ° C., and PEGMEA was removed under reduced pressure to obtain polymer 12. The condensation rate was 97.5 mol%, and the silanol group content was 0.5 mol%.

  When the molecular weight of the obtained polymer 12 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 9300.

[Production Example 3]
In a 300 mL Nasuf-type flask, 19.03 g (158 mmol) of dimethyldimethoxysilane, 6.98 g (53 mmol) of dimethoxymethylvinylsilane, 7.93 g (53 mmol) of ethyltrimethoxysilane, and 25 g of isopropyl alcohol were stirred. To this container, 16.6 g of 37% hydrochloric acid was dropped using a dropping funnel while adjusting the temperature so as not to exceed 10 ° C. in an ice bath. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 6 hours under a nitrogen stream. After cooling to room temperature, 20 g of water and 5 g of acetonitrile were added and extraction was repeated 3 times. After confirming that the aqueous layer was neutral with pH test paper, the silicone layer and 50 g of PEGMEA were placed in a 300 mL eggplant-shaped flask, and a distillation tower and a vacuum pump were set. Finally, the temperature of the oil bath was raised to 140 ° C., and PEGMEA was removed under reduced pressure to obtain polymer 13. The condensation rate was 97.8 mol%, and the silanol group content was 0.3 mol%.

  When the molecular weight of the obtained polymer 13 was measured by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 12,000.

[Production Example 4]
In a 300 mL Nasuf flask, 29.81 g (248 mmol) of dimethyldimethoxysilane, 11.10 g (104 mmol) of dimethoxymethylsilane, 12.42 g (83 mmol) of ethyltrimethoxysilane, 10.75 g (91 mmol) of trimethylethoxysilane, isopropyl alcohol 37 .5 g was added and stirred. To this container, 28.5 g of 37% hydrochloric acid was dropped using an addition funnel while adjusting the temperature so as not to exceed 10 ° C. in an ice bath. After completion of dropping, a cooling tube was set and heated at 50 ° C. for 6 hours under a nitrogen stream. After cooling to room temperature, 20 g of water and 5 g of acetonitrile were added and extraction was repeated 3 times. After confirming that the aqueous layer was neutral with pH test paper, the silicone layer and 50 g of PEGMEA were placed in a 300 mL eggplant-shaped flask, and a distillation tower and a vacuum pump were set. Finally, the temperature of the oil bath was raised to 140 ° C., and PEGMEA was removed under reduced pressure to obtain polymer 14. The condensation rate was 97.6 mol%, and the silanol group content was 0.5 mol%.

  When the obtained polymer 14 was measured for molecular weight by GPC, the weight average molecular weight (Mw) in terms of standard polymethyl methacrylate was 9,000.

[Comparative Example 1]
In a 200 mL eggplant-shaped flask, 8.23 g (55 mmol) of ethyltrimethoxysilane, 8.78 g (73 mmol) of dimethyldimethoxysilane, 7.24 g (55 mmol) of dimethoxymethylvinylsilane, ethyl silicate 40 (solid content concentration 40 manufactured by Colcoat Co., Ltd.) %) 15 g and isopropyl alcohol 25 g were added and stirred. Separately, 22.7 g of distilled water and 1 μL of 37% hydrochloric acid were placed in a container, mixed, and then dropped into a 200 mL eggplant flask over 10 minutes using a dropping funnel. After completion of the dropping, a cooling tube was set and refluxed at 100 ° C. for 4 hours under a nitrogen stream using an oil bath. After the reflux, 80 g of PGMEA was added, a distillation column was set, and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump, and when the oil bath temperature was finally raised to 120 ° C., gelation occurred. The resulting gel had a condensation rate of 83.1 mol% and a silanol group content of 15.4 mol%.

[Comparative Example 2]
In a 100 ml eggplant-shaped flask, 3 g of the polymer 12 produced in Production Example-2, 25 g of isopropyl alcohol, and 25 g of PEGMEA were taken and mixed, and then PL-2L (average primary particle size 20 nm, 20% by mass, manufactured by Fuso Chemical Industries). 3 g of water-dispersed silica particles) was added and mixed. A distillation tower was set and isopropyl alcohol and water were removed. Subsequently, PEGMEA was removed under reduced pressure using a vacuum pump, and when the oil bath temperature was finally raised to 120 ° C., gelation occurred. In addition, since the polymer 12 used 17.4g of 37% hydrochloric acid at the time of synthesis | combination, the silanol group hardly remains.

[Preparation of resin composition]
[Example 11]
100 parts by mass of polymer 2, 168 parts by mass of polymer 8 and a platinum complex of divinyltetramethyldisiloxane were uniformly mixed so that the total mass of the platinum was 3 ppm. After mixing, vacuum degassing was performed to prepare a thermosetting resin composition.

This resin composition was cured by the method shown in the following (6), and the obtained cured products were evaluated in the following (7) to (11). Note Z ¹ / Z ² in the resin composition (of the total unsaturated hydrocarbon groups Z ^1, the ratio to the total SiH groups Z ²⁾ was calculated by the following method (11). The results are summarized in Table 3.

[Examples 12 to 24, Comparative Examples 3 to 5]
A thermosetting resin composition was prepared in the same manner as in Example 11 except that the polymers 1 to 14 and the divinyltetramethyldisiloxane platinum complex were blended in the ratios shown in Table 3.

  These resin compositions were cured by the method shown in the following (6), and the obtained cured products were evaluated in the following (7) to (11). The results are summarized in Table 3.

  About Comparative example 4 and Comparative example 5, since both samples did not harden | cure, it was impossible to measure.

(6) Curing Size 30mm x 30mm x 1mm or 10mm x 10mm x 5mm mold is filled with thermosetting resin composition and heated in an oven at 100 ° C for 30 minutes, then heated to 140 ° C and heated for 30 minutes. Further, the temperature was raised to 150 ° C. and heated for 1 hour, and then cooled to room temperature to prepare a cured product sample.

(7) Heat resistant yellowing measurement A cured product sample is formed on a glass plate of 50 mm × 50 mm using the above mold of 30 mm × 30 mm × 1 mm, and an ultraviolet-visible light spectrophotometer UV-1600PC manufactured by Shimadzu Corporation is used. Then, the transmittance at a wavelength of 800 nm to 300 nm was measured. Subsequently, the cured product sample was heated in the air at 260 ° C. for 30 minutes using a hot plate. The transmittance after heating was measured in the same manner. The transmittance of each wavelength of 800 nm to 300 nm of the sample immediately after curing was set to 100%, and when the transmittance change rate after heating at 260 ° C. was 90% or more, ○, and less than 90% were evaluated as ×.

(8) Light yellowing resistance measurement A cured product sample was formed on a 50 mm × 50 mm glass plate using the above 30 mm × 30 mm × 1 mm mold, and UV-visible light spectrophotometer UV-1600PC manufactured by Shimadzu Corporation was used. The transmittance of 800 nm to 300 nm was measured. Subsequently, the cured product sample was irradiated with UV for 190 hours using HC-98 (high pressure mercury lamp: HL400DL-1) manufactured by Sen Engineering Co., Ltd. At this time, the PET film was used to irradiate light with a wavelength of 300 nm or less cut. The transmittance after UV irradiation was measured in the same manner. The transmittance at each wavelength of 800 nm to 300 nm of the sample immediately after curing was taken as 100%, and the change rate of the transmittance after UV irradiation was evaluated as ◯, and the transmittance less than 90% was evaluated as ×.

(9) Hardness measurement The 10 mm × 10 mm × 5 mm mold is filled with the prepared thermosetting resin composition and heated in an oven at 100 ° C. × 30 minutes, 140 ° C. × 30 minutes, 150 ° C. × 1 hour. Cured. The cured product was cooled to room temperature and taken out of the mold, and then the hardness was measured using GS-702N TYPE D (Tecrock Durometer) manufactured by Teclock Corporation. Samples with a measured value of ShoreD 30 or higher were evaluated as ◯, and those with a measured value of less than 30 were evaluated as ×.

(10) Tackiness measurement A cured product sample was formed on a 50 mm × 50 mm glass plate using the above 30 mm × 30 mm × 1 mm mold. After the sample was cooled to room temperature, it was placed on the alumina powder with the cured sample surface facing downward. The cured product sample was taken out, air was blown onto the surface using an air gun, the sample with no powder remaining on the surface was evaluated as ◯, and the sample that remained attached to the surface was evaluated as ×.

(11) Z ¹ / Z ²
For the polymers 1 to 14, ¹ HNMR was measured by the following method, and the vinyl group amount (mmol) and SiH group amount (mmol) relative to 1 g of the polymer were calculated. Table 3 summarizes Z ¹ / Z ² obtained by calculation.
Sample preparation: Each polymer was weighed so that xylene was 10 wt%. Furthermore, it diluted with the 1% tetramethylsilane containing heavy solvent so that a polymer concentration might be 5 mass%.
The prepared sample solution was subjected to ¹ HNMR measurement, and the peak area of hydrogen atom of vinyl group (3H), the peak area of hydrogen atom of SiH group (1H), the peak area of hydrogen atom directly connected to the aromatic ring of xylene (4H )), The concentration of crosslinking groups (ie, vinyl groups and SiH groups) per gram of polymer was calculated.
¹ HNMR Measurement An NMR (Nuclear Magnetic Resonance) apparatus GSX400 manufactured by JEOL Ltd. was used, and the integration was performed with a pulse width of 0.5 seconds, a waiting time of 2 seconds, and an integration count of 2048.
Incidentally, also measured in the same manner ¹ HNMR for the components excluding the hydrosilylation catalyst from the formulation of Table 3, the calculated value and it was confirmed that not shifted significantly.

  The present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copy machine, an instrument light source for a vehicle, a signal light, an indicator light, a display device, a light source for a planar light emitter, a display, a decoration, Light emitting diodes that can be used for various lights and the like can be suitably applied to die bond materials, underfill materials, passivation films on light emitting elements, package substrates, and the like that fix the light emitting elements to lead terminals or packages.

Claims (14)

A resin composition comprising a silica particle-containing condensation reaction product (A) and a hydrosilylation catalyst (B),
The content of the silica particle-containing condensation reaction product (A) in the resin composition is 20% by mass or more, and the resin composition contains unsaturated hydrocarbon groups and SiH groups,
The silica particle-containing condensation reaction product (A) contains an unsaturated hydrocarbon group and / or SiH group, and a polysiloxane compound (a) containing a silanol group and silica particles (b) are condensed. Obtained by a condensation reaction of a reaction component comprising at least the polysiloxane compound (a) and the silica particles (b),
The polysiloxane compound (a) is a polymerization product of a silane compound having one or more groups selected from a hydroxyl group and a hydrolyzable group or a condensate thereof,
The hydrolyzable group is at least one of a halogen atom, an alkoxy group having 1 to 6 carbon atoms and an acetoxy group;
In the polysiloxane compound (a), the hydroxyl group with respect to the total number of bonds forming any of a siloxane bond, a direct bond with the hydroxyl group, and a direct bond with the hydrolyzable group The resin composition whose silanol group content rate defined as a ratio of the number of the bonds which form the direct bond of 1-90 mol% is 1-90 mol%. Shi silica particle-containing condensation product with (A), a hydrosilylation catalyst (B), the component containing an unsaturated hydrocarbon group and / or SiH groups and (C) an including resin composition,
The content of the silica particle-containing condensation reaction product (A) in the resin composition is 20% by mass or more, and the resin composition contains unsaturated hydrocarbon groups and SiH groups ,
The silica particle-containing condensation reaction product (A) has at least a structure obtained by condensing a silanol group-containing polysiloxane compound (a) and silica particles (b), and the polysiloxane compound (a) And a condensation reaction of a reaction component containing at least the silica particles (b),
The polysiloxane compound (a) is a polymerization product of a silane compound having one or more groups selected from a hydroxyl group and a hydrolyzable group or a condensate thereof,
The hydrolyzable group is at least one of a halogen atom, an alkoxy group having 1 to 6 carbon atoms and an acetoxy group;
In the polysiloxane compound (a), the hydroxyl group with respect to the total number of bonds forming any of a siloxane bond, a direct bond with the hydroxyl group, and a direct bond with the hydrolyzable group The resin composition whose silanol group content rate defined as a ratio of the number of the bonds which form the direct bond of 1-90 mol% is 1-90 mol% . The resin composition according to claim 1 or 2 , wherein the polysiloxane compound (a) has an unsaturated hydrocarbon group and / or a SiH group. The reaction component further comprises a silane coupling agent;
In the condensation reaction, a condensation product obtained by condensing the polysiloxane compound (a) and the silica particles (b) is further reacted with a silane coupling agent, or the polysiloxane compound (a) and the silica particles ( The resin composition according to any one of claims 1 to 3 , which is carried out by condensing b) and a silane coupling agent at the same time. The resin composition according to claim 4 , wherein the polysiloxane compound (a) and / or the silane coupling agent has an unsaturated hydrocarbon group and / or a SiH group. The silane coupling agent has the following general formula (1):
R ¹ _n1 SiX ¹ _4-n1 (1)
{Wherein n1 is an integer of 1 to 3, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ¹ is a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. A group selected from a group and an acetoxy group, and when there are plural groups, R ¹ and X ¹ may be the same or different}
The resin composition of Claim 4 or 5 which is a silane compound represented by these . The resin composition according to any one of claims 1 to 6 , wherein the content of the silica particles (b) in the reaction component is 1% by mass or more and 70% by mass or less. The resin composition according to any one of claims 1 to 7 , wherein an average primary particle diameter of the silica particles (b) is 1 nm or more and 120 nm or less. In the polysiloxane compound (a), the siloxane bond is formed with respect to the total number of bonds that form a siloxane bond, a direct bond with a hydroxyl group, and a direct bond with a hydrolyzable group, respectively. The resin composition according to any one of claims 1 to 8 , wherein a condensation rate defined as a ratio of the number of bonding hands is 5 mol% or more and 95 mol% or less. The resin composition according to any one of claims 1 to 9 , wherein the silanol group content is 5 mol% or more and 90 mol% or less. In the resin composition, all unsaturated hydrocarbon groups Z ¹ and total SiH number Z ² satisfies the 0.25 ≦ Z ¹ / Z ² ≦ 2, resin according to any one of claims 1 to 10 Composition. Sealing resin containing the resin composition of any one of Claims 1-11 . The lens formed using the curable composition containing the resin composition of any one of Claims 1-11 . The underfill material containing the resin composition of any one of Claims 1-11 .