TWI610985B - Liquid silicone resin composition and a cured product thereof, a sealing material for a semiconductor light-emitting device using the same, a light-emitting device using the same, and a method of manufacturing the light-emitting device - Google Patents

Abstract

A liquid composition of a polyoxyxylene resin, which is a liquid composition of a polyoxyxylene resin containing a polyoxyxylene resin, which is classified into an A3 atom in a ²⁹ Si-NMR measurement with respect to a total signal area from a germanium atom. The ratio of the signal area is 51% or more and 69% or less. (A3 矽 atom means that the oxygen atom bonded to other ruthenium atoms is three bonded ruthenium atoms.)

Description

Polyoxymethylene resin liquid composition, cured product thereof, sealing material for semiconductor light-emitting device using the same, light-emitting device using the same, and manufacturing method of light-emitting device

The present invention relates to a liquid composition of a polyoxyxylene resin.

In recent years, a cured product of a polyoxyxylene resin composition has been proposed as a sealing material for a semiconductor light-emitting device. However, the cured product of the polyoxymethylene resin composition has high gas permeability and low barrier property of hydrogen sulfide gas in the air. Therefore, when the cured product of the polyoxyxylene resin composition is sealed, the silver film of the back surface reflection plate of the sealed semiconductor light-emitting element is corroded by hydrogen sulfide in the air, so that the brightness of the semiconductor light-emitting element is lowered.

As a polyoxyxylene resin composition for solving the above problems, a curable polyoxyxene resin composition (refer to Patent Document 1) containing a refractive index of a cured polyoxyxene resin composition of 1.50 to 1.55 has been proposed. The polyoxynene resin is a cerium oxide filler having an average particle diameter of 1 to 10 μm uniformly dispersed in the polyfluorinated resin at a concentration of 1 to 30% by mass.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-41496

However, the polyoxymethylene resin composition described in Patent Document 1 is insufficient in heat resistance, chipping resistance, and barrier property against hydrogen sulfide gas. (Polyoxime, silicone, there is a case called helium oxygen, anthrone, referred to herein as polyoxane)

The present invention has been made in view of the above problems, and an object thereof is to provide a novel polyoxyxylene resin liquid composition as a sealing material for a semiconductor light-emitting device, which has heat resistance, barrier property against hydrogen sulfide gas, and suppression of semiconductor light emission. a high crack resistance of the substrate of the element or the interface with the package; a cured product of the liquid composition of the polyoxymethylene resin; a sealing material for a semiconductor light-emitting element comprising the cured product; and a semiconductor having the cured product A light emitting device and a method of manufacturing the same.

The inventors of the present invention have intensively studied in order to solve the above problems, and have achieved the present invention as described below.

That is, an aspect of the present invention provides a liquid composition of a polyoxyxylene resin which is a liquid composition of a polyoxyxylene resin containing a polyoxyxylene resin, which is derived from a germanium atom in a ²⁹ Si-NMR measurement. The area of the whole signal is the ratio of the signal area of the following A3 矽 atom, which is 51% or more and 69% or less.

Here, the "A3 矽 atom" means that the oxygen atom bonded to another ruthenium atom is three bonded ruthenium atoms.

The "full signal from a ruthenium atom" refers to a total signal derived from a ruthenium atom in a range of chemical shifts of -200 ppm or more and 100 ppm or less in a ²⁹ Si-NMR measurement.

The polyoxynoxy resin liquid composition is liquid, and it is preferably a liquid in a temperature range of from 20 ° C to 50 ° C. At the same time, the liquid composition of the polyoxymethylene resin is preferably a fluidity in a temperature range of from 20 ° C to 50 ° C.

The viscosity of the polyoxyxene resin composition at 25 ° C is 10,000 mPa. The following is better. Viscosity, generally 100mPa. s above. Viscosity can be measured using a cylindrical rotary viscometer.

In one aspect of the invention, the polyfluorene oxide resin may have a structure in which the following resin A and the following oligomer B are contained. Resin A: The total content of the A1 矽 atom, the following A2 矽 atom and the above A3 矽 atom, the ratio of the content of the A3 矽 atom is 20% or more and 90% or less, and the weight average molecular weight is 1,500 or more and 8,000. The following resin oligomer B is a total content of the following A1 矽 atom, the following A2 矽 atom and the above A3 矽 atom, and the ratio of the A3 矽 atom content is 0% or more and 30% or less, and the weight average Oligomers with molecular weights below 1,500

Here, the "A1 矽 atom" means that one oxygen atom bonded to another ruthenium atom is a bonded ruthenium atom. The "A2 矽 atom" means that the oxygen atom bonded to another ruthenium atom is two bonded ruthenium atoms.

In one aspect of the invention, the resin A may have a structure of a resin having an organopolyoxane structure represented by the formula (1).

(式(1)中，R¹分別獨立地表示烷基或芳基，R²分別獨立地表示烷氧基、烯基、氫原子或羥基，p¹、q¹、a¹及b¹表示形成[p¹+b¹×q¹]：[a¹×q¹]=1：0.25至9的任何正數。)

(In the formula (1), R ¹ each independently represents an alkyl group or an aryl group, and R ² each independently represents an alkoxy group, an alkenyl group, a hydrogen atom or a hydroxyl group, and p ¹ , q ¹ , a ¹ and b ¹ represent formation. [p ¹ +b ¹ ×q ¹ ]:[a ¹ ×q ¹ ]=1: Any positive number from 0.25 to 9.)

In one aspect of the invention, the oligomer B may be a structure having an oligomer having an organopolyoxyalkylene structure represented by the formula (2).

(式(2)中，R¹及R²表示與前述式(1)相同之意，p²、q²、r²、a²及b²表示形成[a²×q²]/[(p²+b²×q²)+a²×q²+(r²+q²)]=0至0.3的任何0以上之正數。)

(In the formula (2), R ¹ and R ² represent the same meanings as in the above formula (1), and p ² , q ² , r ² , a ² and b ² represent formation of [a ² × q ² ] / [(p ² + b ² × q ² ) + a ² × q ² + (r ² + q ² )] = 0 to 0.3 of any positive number of 0 or more.)

In one aspect of the present invention, the mixing ratio of the resin A to the oligomer B may also be a resin A: oligomer B = 100: 0.1 to 20 (quality The composition of the ratio.

In one aspect of the present invention, the composition may further contain inorganic particles.

In one aspect of the invention, the inorganic particles may be one or more selected from the group consisting of cerium oxide, titanium oxide, and aluminum oxide.

In one aspect of the invention, the composition of the phosphor may be additionally included.

In one aspect of the invention, the composition of the decane coupling agent may also be included.

In one aspect of the present invention, the specific gravity of the cured product obtained by heating the substrate at a temperature elevation rate of 5 ° C /min to 150 ° C and then heating at 150 ° C for 3 hours may be 1.20 g / cm. ^{A configuration of 3} or more in the range of 1.35 g/cm ³ or less.

According to an aspect of the invention, there is provided a cured product obtained by heating the liquid composition of the above polyoxyxylene resin to 40 ° C or more and 250 ° C or less.

In one aspect of the cured product, the specific gravity may be in a range of 1.20 g/cm ³ or more and 1.35 g/cm ³ or less.

According to an aspect of the invention, there is provided a sealing material for a semiconductor light-emitting element comprising the above-mentioned cured product.

One aspect of the present invention provides a semiconductor light-emitting device comprising the above-described cured product.

One aspect of the present invention provides a semiconductor light emitting A method for producing a device, comprising the step of heating the above-mentioned polyoxyxylene resin liquid composition to a temperature of 100 ° C or more and 250 ° C or less to be cured.

Fig. 1 is a ²⁹ Si-NMR chart of the polyoxyxylene resin liquid composition (α 1) of Example 2.

Fig. 2 is a ²⁹ Si-NMR chart of the polyoxyxylene resin liquid composition (?2) of Example 3.

Fig. 3 is a ²⁹ Si-NMR chart of the polyoxyxylene resin X1 of Comparative Example 2.

Fig. 4 is a ²⁹ Si-NMR chart of the polyoxyxylene resin X 2 of Comparative Example 2.

Fig. 5 is a ²⁹ Si-NMR chart of the liquid composition (β 3 ) of the polyanthracene resin of Comparative Example 3.

Hereinafter, although the present invention can be described in detail, the present invention The present invention is not limited to the embodiments described below, and may be modified into various forms and implemented within the scope of the gist of the invention.

[Polyoxygenated resin liquid composition]

The polyxanthene resin liquid composition of the present invention (hereinafter also referred to as the present composition) is a polyoxyxylene resin liquid composition containing a polyoxyxylene resin, which is contained in a ²⁹ Si-NMR measurement. The ratio of the area of the total signal of the cesium atom to the signal area of the following A3 矽 atom is 51% or more and 69% or less.

Here, the polyfluorene oxide resin or oligomer constituting the liquid composition of the polyoxyxylene resin of the present specification contains a repeating unit of the following formula.

(其中，R¹表示烷基或芳基，R²分別獨立地表示烷氧基、烯基、氫原子或羥基。)

(wherein R ¹ represents an alkyl group or an aryl group, and R ² each independently represents an alkoxy group, an alkenyl group, a hydrogen atom or a hydroxyl group.)

In the present specification, a repeating unit containing three oxygen atoms bonded to another germanium atom and a germanium atom bonded to R ^{1 is} referred to as a repeating unit A3 (the above formula (A3)).

Similarly, a repeating unit containing two oxygen atoms bonded to another germanium atom and a germanium atom bonded to R ¹ and R ^{2 is} referred to as repeating unit A2 (the above formula (A2)).

A repeating unit containing one oxygen atom bonded to another germanium atom and a germanium atom bonded to R ¹ and two R ^{2 is} referred to as a repeating unit A1 (the above formula (A1)).

A repeating unit containing a deuterium atom bonded to R ¹ and two R ² and which is bonded to an oxygen atom in another repeating unit is referred to as a repeating unit A1′ (the above formula (A1′)).

In the following description, the "oxide atom to which three atomic atoms are bonded to another germanium atom in the present invention" is referred to as "A3 germanium atom". "A3 矽 atom" is equivalent to 矽 contained in repeating unit A3 atom.

The "oxygen source combined with other germanium atoms" in the present invention The child is a combination of two helium atoms, which is called "A2矽 atom." The "A2 germanium atom" is equivalent to the germanium atom contained in the repeating unit A2.

The "oxygen source combined with other germanium atoms" in the present invention The child is a combined atom of cesium, which is called "A1 矽 atom." The "A1 矽 atom" is equivalent to the ruthenium atom contained in the repeating units A1, A1'.

Repeating units A1 and A1' constitute an organopolyoxane The end of the chain. The repeating unit A3 is a branched chain structure composed of 1 or 2 organopolyoxyalkylene chains. That is, the repeating unit A3 is a part of a network structure or a ring structure forming a resin.

In this composition, such as the signal from the aforementioned A3 矽 atom When the area is within the above range, the cured product of the polyoxyxylene resin liquid composition (hereinafter also referred to as the cured product) is improved in heat resistance, chipping resistance, and barrier property against hydrogen sulfide gas. If the signal area from the aforementioned A3 germanium atom exceeds 69%, the cured product is liable to be cracked. When the signal area from the A3 germanium atom is less than 51%, the barrier property and heat resistance of the cured product to hydrogen sulfide gas are lowered. The area of the signal from the A3 germanium atom is preferably 55% or more and 68% or less.

In the present specification, the NMR signal area of the ruthenium atom is calculated from the NMR chart measured by ²⁹ Si-NMR.

Specifically, an analysis device on an NMR measuring device generally attached to a ruthenium atom is used to obtain an integral value of a signal to be measured. The area of the signal.

Such as the signal from each atom and other species When the signals of the helium atoms do not overlap and are independently observed, the start point and the end point of the integral can be set on the baselines on both sides of the signal of the helium atom corresponding to the measurement object, and the signal area can be obtained.

Such as the signal from each atom and other species When the signals of the helium atoms are overlapped and observed, the waveform separation processing software generally attached to the analysis device can be used to separate the overlapping signals to obtain the area of each signal. For example, using a Gauss function as a fitting function, after separating the overlapping signal waveforms, the starting point and the end point of the integration are set as in the case of observing the above-mentioned signals independently. Signal area.

In the NMR measurement, the atom, the official attached to the helium atom The structure of the energy group and the substituent can be determined by referring to a known data database or literature.

The composition is heated to 150 ° C at a temperature increase rate of 5 ° C / min from room temperature, and then cured by heating at 150 ° C for 3 hours to obtain a specific gravity of the cured product of 1.20 g / cm ³ or more and 1.35 g / cm ^{3 .} The following range is preferred. The specific gravity is more preferably 1.23 g/cm ³ or more and 1.30 g/cm ³ or less.

When the specific gravity is within the above range, the barrier property against hydrogen sulfide gas can be further improved. When the specific gravity exceeds 1.35 g/cm ³ , the cured product is likely to be broken. The above specific gravity can be adjusted by changing the content of the polyoxyxylene resin contained in the present composition and the existence ratio of the A3 germanium atom.

The aforementioned specific gravity can generally be obtained from volume and quality. Such as When the shape of the cured product is indeterminate, it can be measured by a specific gravity measuring device of the commercially available Archimedes method.

The polyxanthene resin may correspond to a polyoxygen tree Each of the above repeating units of the lipid is synthesized by using an organic ruthenium compound having a functional group capable of generating a decane bond as a starting material. The "functional group capable of generating a decane bond" includes a halogen atom, a hydroxyl group, and an alkoxy group. For example, an organic trihalodecane or an organotrialkoxydecane or the like can be used as a starting material corresponding to the organic hydrazine compound of the repeating unit A3. The polyoxyxylene resin can be synthesized by reacting such a starting material in a ratio corresponding to the existence ratio of each repeating unit by a hydrolysis condensation method. The ratio of the presence of the A3 germanium atom to the specific gravity of the hardened material can be adjusted by selecting this starting material. The polyoxyxylene resin thus synthesized has been industrially sold as a polyoxyxylene resin or an alkoxy oligomer.

The polysiloxane resin contained in the composition is as follows Resin A and oligomer B are preferred.

Resin A is a resin having a total content of A1矽 atoms, A2矽 atoms and A3矽 atoms, a content of A3矽 atoms of 20% or more and 90% or less, and a weight average molecular weight of 1,500 or more and 8,000 or less. The ratio of the content of the A3 矽 atom to the A3 矽 atom is preferably 50% or more and 90% or less, and more preferably 60% or more and 90% or less, and 70% or less. More than 85% of the above is even better. The content ratio of silicon atoms in A3, the signal area may be used in the home A3 silicon atoms ²⁹ Si-NMR measurement ascertained, attribution signal A1 is divided by silicon atoms ²⁹ Si-NMR measurement area is obtained, the home The area of the signal of the A2 矽 atom is determined by the total area of the area of the signal belonging to the A3 矽 atom.

The oligomer B is an oligomer having a total content of A1矽 atoms, A2矽 atoms and A3矽 atoms, a content of A3矽 atoms of 0% or more and 30% or less, and a weight average molecular weight of less than 1,500. The ratio of the content of the A3矽 atom to the total content of the A2矽 atom, the A1矽 atom and the A3矽 atom is preferably 0% or more and 25% or less. The content ratio of the silicon atoms of A3, using ²⁹ Si-NMR measurement signals obtained silicon atoms A3 home area, divided by the signal area of ²⁹ Si-NMR measurement ascertained the home silicon atoms A1, A2 silicon attribution The area of the signal of the atom is determined by the total area of the signal area belonging to the atom of A3.

A3 矽 atom, consisting of 3 organopolyoxyalkylene chains The branched chain structure allows the resin A and the oligomer B having an A3 fluorene atom to form a network structure or a ring structure.

The type and existence ratio of the functional group bonded to the ruthenium atom in the resin such as the resin A and the oligomer B can be measured by, for example, nuclear magnetic resonance spectroscopy (NMR). A detailed description of the measurement method has been made in various documents and the like, and a dedicated measurement device has been widely sold. Specifically, the resin to be measured is dissolved in a specific solvent, and a strong magnetic field of a hydrogen nucleus or a ruthenium nucleus in the resin and a high-frequency radio wave are given to resonate the nuclear magnetic moment in the nucleus. The type and existence ratio of each functional group in the resin were measured. The method of measuring the hydrogen nucleus is called ¹ H-NMR, and the method of measuring the ruthenium nucleus is called ²⁹ Si-NMR. The solvent may be selected from the group of various functional groups, such as deuterated chloroform, deuterated dimethyl hydrazine, deuterated methanol, deuterated acetone, heavy water, and the like.

[Resin A]

When R ¹ is an alkyl group, the alkyl group may be linear, may be branched, or may have a cyclic structure, but is preferably a linear or branched alkyl group, and is linear. The alkyl group is better. Although the carbon number of the alkyl group is not particularly limited, it is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. good.

The alkyl group may be substituted with other groups to form the alkyl group. One or more hydrogen atoms. The substituent of the alkyl group may, for example, be an aryl group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group, and a phenyl group is preferred.

The alkyl group represented by R ¹ may, for example, be specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group or an octyl group. An unsubstituted alkyl group such as a fluorenyl group or a fluorenyl group; an aralkyl group such as a phenylmethyl group, a phenylethyl group or a phenylpropyl group. Among these alkyl groups, a methyl group, an ethyl group, a propyl group and a butyl group are preferred, and a methyl group, an ethyl group and an isopropyl group are more preferred.

When R ¹ is an aryl group, the aryl group is preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be substituted with another group to form one or more hydrogen atoms of the aryl group. The substituent of the aryl group may, for example, be an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group.

The aryl group represented by R ¹ may, for example, be an unsubstituted aryl group such as a phenyl group or a naphthyl group, or an alkyl aryl group such as an alkylphenyl group such as a methylphenyl group, an ethylphenyl group or a propylphenyl group. Etc., and phenyl is preferred.

R ² each independently represents an alkoxy group, an alkenyl group, a hydrogen atom or a hydroxyl group. Preferred are alkoxy or hydroxy groups.

When R ² is an alkoxy group, the alkoxy group may be linear, may be branched, or may have a cyclic structure, but a linear or branched alkoxy group is preferred. A linear alkoxy group is more preferred. Although the carbon number of the alkoxy group is not particularly limited, it is preferably an alkoxy group having 1 to 4 carbon atoms. The alkoxy group represented by R ² is specifically a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group or a third butoxy group, and is preferably a methoxy group. More preferably, ethoxy, isopropoxy.

When R ² is an alkenyl group, the alkenyl group may be linear, may be branched, or may have a cyclic structure, but a linear or branched chain alkenyl group is preferred, and a linear chain is preferred. The alkenyl group is more preferred. Although the carbon number of the alkenyl group is not particularly limited, it is preferably an alkenyl group having 2 to 4 carbon atoms. The alkenyl group represented by R ¹ is specifically an ethenyl group, an allyl group (2-propenyl group), a 1-propenyl group, an isopropenyl group or a butenyl group, and more preferably a vinyl group.

Resin A is preferably one having no alkenyl group or hydroquinone group. That is, a preferred resin A is a resin in which R ² does not have an alkenyl group or a hydrogen atom. When the resin A has an alkenyl group or a hydroquinone group, the barrier property and heat resistance of the cured product to hydrogen sulfide gas tend to be lowered.

The resin A preferably has an organopolyoxyalkylene structure represented by the following formula (1).

(其中，R¹及R²表示與前述相同之意，p¹、q¹、a¹及b¹表示形成[p¹+b¹×q¹]：[a¹×q¹]=1：0.25至9的任何正數。)

(wherein R ¹ and R ² represent the same meaning as described above, and p ¹ , q ¹ , a ¹ and b ¹ represent formation of [p ¹ + b ¹ × q ¹ ]: [a ¹ × q ¹ ] = 1:0.25 Any positive number up to 9.)

A plurality of R ¹ and R ² may be the same kind of groups, or may be different groups.

Resin A is a resin having an organopolyoxane structure represented by the above formula (1), and R ¹ has any one of the groups exemplified by the above preferred group as an alkyl group and an aryl group, R ^It is preferred that the base having a preferred alkoxy group as the alkoxy group and any one of the hydroxyl groups is preferred. The resin A, in particular, a resin having an organic polyoxane structure represented by the formula (1), has one or more selected from the group consisting of a methyl group, an ethyl group and a phenyl group as R ¹ . One or more of the group consisting of a methoxy group, an ethoxy group, an isopropoxy group, and a hydroxyl group is preferably R ² and is one having a group selected from the group consisting of a methyl group and an ethyl group. The above R ^{1 is} preferably ^one or more selected from the group consisting of a methoxy group, an ethoxy group, an isopropoxy group and a hydroxyl group as R ² , and has a group selected from a methyl group and an ethyl group. One or more of the groups formed are preferably R ¹ and have one or more selected from the group consisting of a methoxy group, an ethoxy group and an isopropoxy group, and a hydroxyl group as R ² .

The existence ratio of each repeating unit in the resin represented by the formula (1) can be expressed by the existence ratio of the A 2 矽 atom and the A 3 矽 atom. That is, in theory, it is an A2 矽 atom: A3 矽 atom = [p ¹ + b ¹ × q ¹ ]: [a ¹ × q ¹ ]. That is, the ratio of the existence of the A2矽 atom and the A3矽 atom in the resin A can be adjusted by appropriately adjusting the values of p ¹ , q ¹ , a ¹ and b ¹ .

In the formula (1), p ¹ , q ¹ , a ¹ and b ¹ represent any positive number forming [p ¹ + b ¹ × q ¹ ]: [a ¹ × q ¹ ] = 1: 0.25 to 9. That is, p ¹ , q ¹ , a ¹ and b ^{1 can be} suitably adjusted such that the ratio of the number of A 2 矽 atoms (x ¹ ) to the number of A 3 矽 atoms ( y ¹ ) is in x ¹ : y ¹ =1: 0.25 to 9 range.

Resin A is preferably a polyfluorene-oxygen resin having an organopolyoxane structure represented by the above formula (1), wherein the content of A3 矽 atoms is relative to the total content of A2 矽 atoms and A3 矽 atoms [y ¹ / (x ¹ + y ¹ )] is in the range of 0.2 to 0.9. Resin A is relatively high in the presence of A3 ruthenium atoms, and can be obtained by curing resin A to obtain a cured product having a network of organic polyoxyalkylene chains. When the ratio of the presence of the A3 ruthenium atom is higher than the above range, the chipping resistance of the cured product may be lowered. If the ratio is lower than the above range, the barrier property against hydrogen sulfide gas may be lowered.

Resin A is a polyfluorene resin having an organopolyoxane structure having a ratio of A3 fluorene atoms in the above formula (1), and the cured product of resin A is blocked from a gas such as hydrogen sulfide. High sex. Resin A, preferably in the range of 0.5 to 0.9 (x ¹ : y ¹ = 1:1 to 9) with [y ¹ /(x ¹ +y ¹ )], and in the range of 0.6 to 0.9 ( x ¹ : y ¹ =1: 1.5 to 9) is better, and in the range of 0.7 to 0.85 (x ¹ : y ¹ = 1: 2.33 to 5.67) is even better.

A2 矽 atom per molecule of resin A is appropriately adjusted Further, the number of the A3 ruthenium atoms can be such that the resin having the organopolyoxane structure represented by the above formula (1) has a desired molecular weight. In the present invention, the sum of the number of A2矽 atoms and A3矽 atoms per molecule of the resin A is preferably 5 or more.

Resin A has a weight average molecular weight (Mw) of 1,500 or more 8,000 or less. When the weight average molecular weight of the resin A is too small, the barrier property of the cured product to hydrogen sulfide gas tends to be low. Since the weight average molecular weight of the resin A is within this range, a cured product having more excellent barrier properties against hydrogen sulfide gas can be obtained. The weight average molecular weight of the resin A is preferably 1,500 or more and 7,000 or less, and more preferably 2,000 or more and 5,000 or less.

Resin A may correspond to the above-mentioned respective weights constituting the resin A The complex unit is synthesized by using an organic ruthenium compound having a functional group capable of forming a decane bond as a starting material. The "functional group capable of generating a decane bond" means that it is synonymous with the above. For example, an organic trihalomene or an organic trialkoxysilane or the like can be used as a starting material corresponding to the organic hydrazine compound of the repeating unit A3. The polyoxyxylene resin can be synthesized by a hydrolysis condensation reaction by reacting such a starting material in a ratio corresponding to the existence ratio of each repeating unit. The polyoxyxylene resin thus synthesized is industrially sold as a polyoxyxylene resin or an alkoxy oligomer.

[Oligomer B]

R ¹ and R ² represent the same as above.

The oligomer B preferably has substantially no alkenyl group and hydroquinone group. That is, the preferred one of the oligomers B, R ^{2 ,} does not have an alkenyl group and a hydrogen atom bonded to a ruthenium atom. When the oligomer B has an alkenyl group or a hydroxyl group, the barrier property and heat resistance of the cured product to hydrogen sulfide gas tend to be lowered.

Preferred of the oligomer B is an oligomer having an organic polyoxoxane structure represented by the formula (2).

(其中，R¹及R²表示與前述相同之意，p²、q²、r²、a²及b²表示可形成[a²×q²]/[p²+b²×q²]+a²×q²+(r²+q²)]=0至0.3的任何0以上之數。)

(wherein R ¹ and R ² represent the same meaning as described above, and p ² , q ² , r ² , a ² and b ² represent that [a ² × q ² ] / [p ² + b ² × q ² ] can be formed] +a ² ×q ² +(r ² +q ² )] = 0 to 0.3 of any number above 0.)

A plurality of R ¹ and R ² may be the same type of groups, or may be different from each other.

B oligomers, alkoxy-based resin having a structure of silicon oxide organopolysiloxane represented by the formula (2), and R ¹ has the order as mentioned in the foregoing as the preferred group of any base as of alkyl and aryl, R ² Any group having a preferred group as mentioned above is preferably an alkoxy group, an alkenyl group, a hydrogen atom or a hydroxyl group. The oligomer B, in particular, a resin having an organic polyoxosiloxane structure represented by the formula (2), and having R ¹ having at least ^one selected from the group consisting of a methyl group, an ethyl group and a phenyl group, R ² is preferably one or more selected from the group consisting of a methoxy group, an ethoxy group, an isopropoxy group, and a hydroxyl group, and R ¹ has a group selected from the group consisting of a methyl group and an ethyl group. One or more kinds of R ² may be one or more selected from the group consisting of a methoxy group, an ethoxy group, and an isopropoxy group.

The existence ratio of each repeating unit of the oligomer represented by the formula (2) can be represented by the existence ratio of the A1矽 atom, the A2矽 atom, and the A3矽 atom. That is, theoretically, A1 矽 atom: A2 矽 atom: A3 矽 atom = [r ² + q ² ]: [p ² + b ² × q ² ]: [a ² × q ² ]. That is, the existence ratio of each of the ruthenium atoms in the oligomer B can be adjusted by appropriately adjusting the values of p ² , q ² , r ² , a ² and b ² . For example, when at least one of a ² and q ² is 0, the oligomer B does not have an A 3 fluorene atom but only a linear or cyclic molecule. On the other hand, when both of r ² and q ² are 0, the oligomer B contains only an A 2 矽 atom and contains only a cyclic molecule.

In the formula (2), when the number of A2 矽 atoms is x ² and the number of A3 矽 atoms is y ² and the number of A1 矽 atoms is z ² , the repeating unit in the formula (2) The existence ratio of the A3 ruthenium atom is represented by [y ² /(x ² +y ² +z ² )].

In the formula (2), p ² , q ² , r ² , a ² and b ² represent formation of [a ² × q ² ] / [(p ² + b ² × q ² ) + a ² × q ² + (r ² +q ² )] = 0 to 0.3 of any number above 0.

Here, [a ² ×q ² ]/[(p ² +b ² ×q ² )+a ² ×q ² +(r ² +q ² )] is equal to the repeating unit A3 in the formula (2) The ratio of existence is [y ² /(x ² +y ² +z ² )]. That is, by appropriately adjusting p ² , q ² , r ² , a ² and b ² in the formula (2), the existence ratio of the A 3 矽 atom is in the range of 0 to 0.3.

In other words, the oligomer B contained in the polyoxyxylene resin composition of the present invention is preferably a polyfluorene-oxygen resin having an organic polyoxyalkylene structure represented by the above formula (2), and is preferably a relative to the A1 germanium atom. The total content of the A2 ruthenium atom and the A3 ruthenium atom, the content of the A3 ruthenium atom [y ² /(x ² +y ² +z ² )] is 0 to 0.3, and the weight average molecular weight (Mw) is less than 1,500. As long as the existence of the A3 germanium atom is within the above range, the existence ratio of the A2 germanium atom is greater than that of [x ² /(x ² +y ² +z ² )] and the A1 germanium atom [z ² /(x ² +y ^{2 )} +z ² )] is not particularly limited. The oligomer B is preferably in the range of 0 to 0.25 for [y ² /(x ² +y ² +z ² )], and more preferably in the range of 0.05 to 0.2.

Oligomer B, because of the relatively low presence of A3 ruthenium atoms, contains less branched chain structures and contains more linear or cyclic molecules. The oligomer B may contain only a cyclic molecule, but it is preferably a linear one. For example, oligomer B, is present in the A1-based silicon atomic ratio ^{[z 2 / (x 2 +} y 2 + z 2)] is preferred in the range of 0 to 0.80, and is 0.30 to 0.80 in The inner one is more preferable, and it is preferably in the range of 0.35 to 0.75, and more preferably in the range of 0.35 to 0.55.

The weight average molecular weight of the oligomer B was less than 1,500. Such as

When the weight average molecular weight of the oligomer B is too large, the chipping resistance of the obtained cured product is insufficient. The weight average molecular weight of the oligomer B is preferably 200 or more and less than 1,500, and more preferably 250 to 1,000.

A1矽 per molecule of oligomer B is appropriately adjusted

The number of atoms, A21 ruthenium atoms and A3 ruthenium atoms can be such that the resin having the organopolyoxane structure represented by the formula (2) has a desired molecular weight. In the present invention, the sum of the number of A1矽 atoms, the number of A21矽 atoms, and the number of A3矽 atoms per molecule of the oligomer B is preferably 2 or more.

By hardening the resin A in which the oligomer B is formulated, It is possible to obtain a cured product which does not impair the high gas barrier properties of the resin A and is excellent in chipping resistance and adhesion. The addition of the oligomer B does not clarify the chipping resistance of the resin composition containing the resin A and the adhesion to other materials, but the resin A is made of a low molecular oligomer. As a result of the intermolecular cross-linking, it is presumed that the flexibility is increased, and the polarity of the entire resin is increased by the functional groups in the oligomer to improve the adhesion with other materials.

The oligomer B may correspond to the above-mentioned one constituting the oligomer B Each repeating unit is synthesized by using an organic ruthenium compound having a functional group capable of forming a decane bond as a starting material. The "functional group capable of generating a decane bond" is synonymous with the above. For example, an organic trihalodecane or an organotrialkoxydecane or the like can be used as a starting material corresponding to the organic hydrazine compound of the repeating unit A3. The polyoxyxylene resin can be synthesized by a hydrolysis condensation reaction by reacting such a starting material in a ratio corresponding to the existence ratio of each repeating unit.

In the synthesis of the oligomer B, an organic ruthenium compound corresponding to the above-mentioned repeating units A1, A1' is mixed in the starting material. The organic ruthenium compound corresponding to the repeating units A1 and A1' is bonded to the end of the polymerization reaction to terminate the polymerization reaction when the starting material is subjected to a hydrolysis condensation reaction. Therefore, it is easy to make the polymerization average molecular weight smaller than the resin A in the starting material which does not contain the organic sulfonium compound corresponding to the repeating units A1, A1'.

Different from the weight average molecular weight of the resin A, for example, by controlling the reaction temperature at the time of hydrolysis and condensation reaction of the starting material, or The rate of addition of the starting materials in the reaction system is controlled.

The polyoxyxylene resin thus synthesized is industrially sold as a polyoxyxylene resin or an alkoxy oligomer.

Weight average molecular weight (Mw), generally used as a gel The value measured by a permeation chromatography (GPC) method. Specifically, after dissolving the resin (or oligomer) in a soluble solvent, it is passed through a column of a mobile phase solution using a filler having a plurality of pores, and is allowed to pass through the column. It is separated by the molecular weight, and is detected using a detector of a differential refractometer or a UV meter, a viscometer, a light scattering detector, or the like. Actually, GPC-dedicated equipment has been widely sold, and it is generally measured by conversion into standard polystyrene, and the weight average molecular weight (Mw) in the present invention is measured by conversion into the standard polystyrene.

The solvent to be used for dissolving the resin (or oligomer) is preferably the same solvent as the mobile phase solvent used in the GPC measurement, and specifically, tetrahydrofuran, chloroform, toluene, xylene, dichloromethane, or the like can be used. Ethyl chloride, methanol, ethanol, isopropanol, and the like.

Most of the columns used are commercially available as long as a specific column is used according to the assumed molecular weight.

In the present invention and the specification of the present application, the presence or absence of an alkenyl group or a hydroquinone group in the polyfluorene oxide resin can be determined by the above-described ¹ H-NMR or ²⁹ Si-NMR or infrared spectrophotometer.

The polyoxyxylene resin liquid composition of the present invention is preferred It is obtained by mixing of resin A and oligomer B. For the resin A, it is preferred to mix a small amount of the oligomer B with respect to the resin A. Especially by using the hair The mixing ratio of the resin A to the oligomer B of the liquid composition of the polyoxyl resin is set to be a resin A: oligomer B = 100: 0.1 to 20 (mass ratio), and a barrier to hydrogen sulfide gas can be obtained. A hardened material with better fracture resistance. The mixing ratio of the resin A to the oligomer B is preferably resin A: oligomer B = 100: 0.2 to 15 (mass ratio), and resin A: oligomer B = 100: 0.5 to 10 (mass Better than.)

There is no special mixing method between resin A and oligomer B. For the limitation, any known method generally carried out when two or more kinds of polymers are mixed can be used. For example, the resin A and the oligomer B (other resin as needed) may be dissolved in an organic solvent and mixed.

Preferably, in order to achieve more uniform mixing and to improve the stability of the subsequent resin solution, it is preferred to dissolve the resin A or the like in an organic solvent having high volatility and high solubility, and then replace it with another solvent. . Specifically, the resin A is introduced into a highly volatile organic solvent (hereinafter referred to as an organic solvent P), and the resin A or the like is dissolved by heating to a temperature near the boiling point of the organic solvent P. Next, the oligomer B was introduced, and the mixture was dissolved and dissolved in the same manner. Then, a solvent having a lower volatility than the organic solvent P (hereinafter referred to as solvent Q) is introduced into the solution in which the resin A or the like and the oligomer B are dissolved, and the concentration of the organic solvent P can be made 1% or less by heating distillation. Substitution of the solvent from the organic solvent P to the solvent Q is carried out. At this time, it is also possible to use a state in which the inside of the vessel is decompressed, and it is also possible to replace the solvent more effectively.

By carrying out such a treatment, it is possible to remove the residual solvent used in the synthesis of the resin A or the oligomer B or the water remaining without being reacted, as the solvent is substituted. Therefore, such treatment is effective for the resin solution Stability.

The organic solvent P is an organic solvent having a boiling point of less than 100 ° C. The agent is better. Specifically, a ketone solvent such as acetone or methyl ethyl ketone; an alcohol solvent such as methanol, ethanol, isopropanol or n-propanol; a hydrocarbon solvent such as hexane, cyclohexane, heptane or benzene; An ester solvent such as methyl ester or ethyl acetate; an ether solvent such as dimethyl ether or tetrahydrofuran is preferred, and an alcohol solvent such as methanol, ethanol, isopropanol or n-propanol is more preferred.

Solvent Q is an organic solvent with a boiling point above 100 ° C It is better. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol single ethyl Hexyl hexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, two Ethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monoethylhexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether , propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol monoethylhexyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol monoethylhexyl ether, dipropylene glycol monophenyl ether, dipropylene glycol monophenyl Glycol ether solvent such as ether; ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether vinegar Ester, ethylene glycol monohexyl ether acetate, ethylene glycol monoethylhexyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol monobenzyl ether acetate, etc. in the aforementioned glycol ether Attached to the solvent An acetic acid-based glycol ester-based solvent or the like is preferable, and ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and ethylene glycol monobutyl ether acetate are more preferable.

[Other Additives]

The composition further preferably contains inorganic particles, a phosphor, a decane coupling agent, and a curing catalyst.

(inorganic particles, phosphors)

When the cured product is used as a sealing material for a semiconductor light-emitting device, the composition can be used as it is when the light from the light-emitting element is used as it is. When it is desired to increase the light from the light-emitting element, the present composition may contain a phosphor and inorganic particles which emit fluorescence by light. The inorganic particles can scatter light in the cured product to effectively excite the phosphor and prevent sedimentation of the phosphor in the resin.

To mix a phosphor or inorganic particle in the composition At the time of mixing the inorganic particles, the inorganic particles are mixed, and after the phosphor is mixed, the sealing of the semiconductor light-emitting element is quickly applied, and the sedimentation of the phosphor can be more effectively prevented.

The inorganic particles are preferably an oxide of cerium, titanium, zirconium, aluminum, iron or zinc, carbon black, barium titanate, calcium citrate or calcium carbonate. Among them, oxides of cerium, oxides of titanium and oxides of aluminum are more preferable.

The shape of the inorganic particles may be a substantially spherical shape, a plate shape, a column shape, a needle shape, a whisker shape, or a fiber shape, or any shape thereof. In the case where a more uniform composition can be obtained, the shape of the inorganic particles is preferably a spherical shape.

Inorganic particles which may be contained in the composition, may be only 1 The species may be two or more. When the inorganic particles are contained in the present composition, it is preferred to contain two or more kinds of inorganic particles having different particle sizes. For example, the inorganic particles A having an average particle diameter of primary particles of 100 nm or more and 500 nm or less are more preferable than the inorganic particles B having an average primary particle diameter of less than 100 nm. When the composition contains two or more kinds of inorganic particles having different average particle diameters of primary particles, the excitation efficiency of the phosphor by light scattering is further improved, and the effect of preventing sedimentation of the phosphor can be exhibited.

The average particle size of the primary particles here can be obtained by electricity A sub-microscope or the like directly observes the image imaging method of the particles and the like. Specifically, the inorganic particles to be measured are irradiated with ultrasonic waves or the like in any solvent, and the droplets are sufficiently dispersed on a slide glass or the like to be dried, or directly by the inorganic particles on the adhesive tape. Then, the surface is vibrated and attached, and the particles are directly observed by a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and the shape is obtained by estimating the shape.

The content of inorganic particles in this composition is not special However, when the content of the polyoxyxylene resin is 100 parts by mass, the total content of the inorganic particles is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass.

a composition or species of a phosphor that may be contained in the composition The type is not particularly limited, and may include a red phosphor that emits fluorescence in a wavelength range of 570 nm to 700 nm, a green phosphor that emits fluorescence in a wavelength range of 490 nm to 570 nm, and emits at a wavelength of 420 nm to 480 nm. Fluorescent blue phosphor, etc. Can also be made of several kinds depending on brightness or chromaticity Fluorescent body mixing.

The content of the phosphor contained in the composition is not particularly limited, and the ratio can be adjusted in time according to the amount of light of the light-emitting element or the necessary chromaticity or brightness of the semiconductor light-emitting device.

(decane coupling agent)

The decane coupling agent has an effect of improving the adhesion between the cured product and the semiconductor light-emitting device or the package. a decane coupling agent having a group selected from the group consisting of a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryl group, an amine group, a urea group, a thiol group, a fluorenylene group, and an isocyanate group. Preferably, at least one of the decane coupling agents is preferred, and a decane coupling agent containing an epoxy group or a thiol group is preferred. Specifically, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-dehydroglyceryloxypropylmethyldimethoxydecane, 3-dehydroglyceryloxypropane Trimethoxy decane, 3-dehydroglyceryloxypropyl methyl diethoxy decane, 3-dehydroglyceryloxypropyl triethoxy decane, 3-thiol propyl methyl dimethoxy Preferably, decane or 3-thiol propyl trimethoxy decane is preferred.

When the decane coupling agent is contained in the composition, although the ruthenium atom contained in the decane coupling agent can be detected by the ²⁹ Si-NMR signal, in the present invention, the decane coupling is also included in the calculation of the signal area of the composition. The signal of the agent.

The content of the decane coupling agent in the composition is relative When the content of the polyoxyxene resin is 100 parts by mass, it is preferably 0.0001 to 1.0 part by mass, and more preferably 0.001 to 0.1 part by mass. If the content of the decane coupling agent is more than the above range, the decane coupling agent absorbs light by itself. It is possible to lower the transparency of the cured product.

The decane coupling agent can be mixed in the composition to make Alternatively, a method in which the decane coupling agent is adhered to the surface of the semiconductor light-emitting device or the package by coating or immersion treatment, and then the composition is cured by potting or the like may be used.

(hardening catalyst)

The catalyst for hardening is not particularly limited as long as it is a crosslinking reaction which promotes the component of the polyoxymethylene resin. When the functional group (the above R ² ) in the resin A and the oligomer B is an alkoxy group or a hydroxyl group, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid may be used to promote the hydrolysis condensation reaction; formic acid, acetic acid, oxalic acid, An organic acid such as citric acid, propionic acid, butyric acid, lactic acid or succinic acid is used as a catalyst for curing. The catalyst for curing is not only an acidic compound but also a basic compound. Specifically, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide or the like can be used as the basic compound.

When the functional group (the above R ² ) in the resin A and the oligomer B is an alkenyl group or a hydrogen atom, a platinum-based, palladium-based or lanthanide-based metal catalyst can be used to promote the hydroquinone reaction. For the platinum system, platinum, platinum black, chloroplatinic acid or the like may be used, for example, H ₂ PtCl ₆ . mH ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ . mH ₂ O, K ₂ PtCl ₄ , KHPtCl ₄ . mH ₂ O, PtO ₂ . mH ₂ O (m is a positive integer) or the like, or a mixture with such a hydrocarbon such as an olefin, an alcohol or a vinyl group-containing organic polyoxyalkylene.

The catalyst for hardening can be added at a set concentration. It is added in a state of being diluted with a polyfluorene-based monomer or an alkoxydecane oligomer which is easily adjusted in a liquid composition of water, an organic solvent or a polyoxymethylene resin. In the liquid composition of the polyoxyl resin.

The amount of the hardening catalyst added to the composition can be The heating temperature, the reaction time, the type of the catalyst, and the like at the time of the hardening reaction are appropriately adjusted. The content of the hardening catalyst is preferably 0.01 to 20 parts by mass, and more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the composition. The curing catalyst may be added to the composition before the hardening reaction, or may be originally contained in the composition. Preferably, it is added to the present composition before the hardening reaction.

(other additives)

The composition may further contain a polyfluorene oxide compound different from the resin A and the oligomer B, and an additive.

The polyoxonium compound different from the resin A and the oligomer B is exemplified by a total content of the A1矽 atom, the A2矽 atom and the A3矽 atom, and the content ratio of the A3矽 atom is more than 30% and 90% or less. And an oligomer having a weight average molecular weight of less than 1,500, an aggregate content of A1矽 atom, A2矽 atom and A3矽 atom, an A3矽 atom content ratio exceeding 90%, and a weight average molecular weight of less than 1,500 With respect to the total content of the A1矽 atom, the A2矽 atom and the A3矽 atom, the ratio of the content of the A3矽 atom is 0% or more and less than 20%, and the weight average molecular weight is 1,500 or more and 8,000 or less, relative to A1矽The total content of atoms, A2 矽 atoms and A3 矽 atoms, the content ratio of A3 矽 atoms exceeds 90%, and the weight average molecular weight The content of the resin of 1,500 or more and 8,000 or less, the total content of the A1矽 atom, the A2矽 atom and the A3矽 atom, the content ratio of the A3矽 atom is 0% or more and less than 30%, and the weight average molecular weight is more than 8,000 and 15,000 or less. The resin, the total content of the A1 矽 atom, the A2 矽 atom and the A3 矽 atom, the content ratio of the A3 矽 atom is 30% or more and 90% or less, and the weight average molecular weight is more than 8,000, 15,000 or less of the resin, relative to the A1 The total content of ruthenium atom, A2 矽 atom and A3 矽 atom, the content ratio of A3 矽 atom is 0% or more and less than 30%, and the weight average molecular weight exceeds 15,000 resin, relative to A1 矽 atom, A2 矽 atom and A3 矽The total content of atoms, the content ratio of A3 矽 atoms is 30% or more and 90% or less, and the weight average molecular weight exceeds 15,000, the total content of A1 矽 atoms, A2 矽 atoms and A3 矽 atoms, A3 矽 atoms A resin having a ratio of more than 90% and a weight average molecular weight of more than 8,000.

As the polyoxyxene compound, a general polyoxynitride compound which is commercially available for sale can be mentioned. By adding the polyoxyl oxide for the modification, flexibility can be imparted to the cured product.

When the polyoxyxasiloxane is contained in the composition, the ruthenium atom contained in the polyfluorene oxide can be detected by the ²⁹ Si-NMR signal, but in the present invention, the signal area of the composition is also included. The signal of polyoxyl compounds.

The group is 100 parts by mass relative to the content of the polyoxyl resin. The content of the polyphosphonium for reforming in the product is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass. If the content of the polyfluorene oxide for reforming is more than the above range, the transparency of the cured product may be impaired.

The above-mentioned additives include antifoaming agents for suppressing bubbles generated when the present composition is mixed.

[hardened material]

The composition can be hardened.

In order to harden the composition, the composition is generally heated.

The heating temperature is preferably 40 to 250 °C. The heating time is generally 5 minutes to 6 hours. In order to harden it, it is preferable to add a catalyst for hardening.

The condition for hardening the composition is preferably a method of heating at 40 to 250 ° C for 5 minutes to 6 hours. After the curing catalyst is added to the composition, it is preferably cured by placing it in an ambient gas at a temperature of 250 ° C or lower, and hardening it in an ambient gas placed at a temperature of 40 to 200 ° C. Better. In the case of hardening, in order to remove the solvent or water present in the present composition and control the condensation reaction rate of the polyoxynoxy resin, the temperature and time may be adjusted stepwise to harden it, for example, at 40 to 60 ° C. To 30 minutes, followed by 60 to 100 ° C for 10 to 60 minutes, and then 140 to 200 ° C for 30 minutes to 5 hours.

In order to carry out the hardening reaction efficiently, it is preferred to include a step of heating in a temperature range of from 100 to 250 °C. The heating time in the temperature range of 100 to 250 ° C is usually from 1 to 5 hours.

In this hardened material, it can be used in cesium atoms and other samarium One or more atoms are interposed between the sub-forms to form a bond, so that the whole forms a network structure and exhibits barrier properties. For example, an oxygen atom bonded to a ruthenium atom is combined with another ruthenium atom to form a ruthenium oxide bond, or a carbon atom is used to crosslink two ruthenium atoms to form a network structure.

Here, if the oxygen atom bound to the germanium atom is no longer When other ruthenium atoms are bonded, and a hydrogen atom is bonded to form a sterol group, a network structure is not formed at the point of forming the sterol group. Therefore, the amount of residual sterol groups can be evaluated under the understanding of the physical properties of the cured product.

Relative to the total mass of the hardened material, such a sterol group The amount can be evaluated as a ratio of the mass of the sterol group. Hereinafter, such a ratio is referred to as "sterol content rate". The unit of the sterol content is % by mass.

The sterol content can be obtained as follows.

First, the solid ²⁹ Si-NMR spectrum of the cured product was measured, and the ratio of the signal area from the sterol to the total signal area in the obtained spectrum was calculated. Thereby, the ratio of the ruthenium atom contained in the decyl group to the total ruthenium atom contained in the sinter can be determined. When the obtained NMR spectrum is a spectrum containing a large amount of noise, for example, the obtained spectrum may be subjected to Fourier conversion to remove high-frequency components of 100 Hz or more, and then subjected to reverse-transformation conversion or the like. The method performs smoothing.

On the other hand, it can be derived from the hardened material. In combination with high-frequency plasma spectroscopic analysis, the cerium content (% by mass) contained in the present hardened material was determined.

The product of such measurement results can be obtained as "relative to this The mass ratio of the ruthenium-based ruthenium atom of the total mass of the cured product (% by mass).

Multiply the resulting mass ratio by 45/28 ((=Si, O, H The sum of the atomic weights) / (the atomic weight of Si)), the mass ratio of the sterol groups to the total mass of the cured product, that is, the "sterol content" can be obtained. The obtained sterol content can be used in the evaluation of the cured product.

The hardened material obtained by hardening the composition due to sulfur Since the hydrogen gas has high barrier properties, heat resistance, and chipping resistance, it can be used as a sealing material for a semiconductor light-emitting device, a light-emitting diode, a CCD, or a CMOS, and is particularly useful as a sealing material for a semiconductor light-emitting device. .

The semiconductor light-emitting element on the substrate is dense with the composition After the sealing, the semiconductor light-emitting device having the semiconductor light-emitting device sealed by the cured product can be produced by curing the composition. The cured product has high adhesion to the substrate or the package, and has high barrier property against hydrogen sulfide gas. Therefore, in the semiconductor light-emitting device in which the semiconductor light-emitting device is sealed with the cured material, it is difficult to cause discoloration or peeling of the silver film on the back surface reflector of the semiconductor light-emitting device, and it is difficult to cause cracking or peeling at the interface between the substrate and the package. The advantage of decreasing brightness over time. The semiconductor light-emitting device has good light-emitting luminance and can also be used for general illumination.

Specifically, the semiconductor on the substrate is emitted by the composition After the optical element is sealed, the semiconductor light-emitting device can be manufactured by performing a heat hardening reaction. The sealing method of the semiconductor light-emitting device is not particularly limited. For example, the composition can be dropped on the surface of the semiconductor light-emitting device, or the surface of the semiconductor light-emitting device can be coated with the composition. The semiconductor light emitting element is covered and sealed. The composition may be hardened into a sheet shape in advance, and the cured sheet may be attached to the surface of the semiconductor light emitting element to be sealed.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the examples described below.

The type and the ratio of the presence of the resin A and the oligomer B using the organopolysiloxane as the main chain used in the following examples were measured by a ¹ H-NMR method or a ²⁹ Si-NMR method. The molecular weight of the resin A and the oligomer B was measured by the GPC method. The measurement conditions in each measurement method are as follows.

< ¹ H-NMR measurement conditions>

Device name: ECA-500 made by JEOL RESONANCE

Observation core: ¹ H

Observation frequency: 500.16MHz

Measuring temperature: room temperature

Determination of solvent: DMSO-d6

Pulse amplitude: 6.60μsec (45°)

Pulse round trip time: 7.0 seconds

Cumulative number: 16 times

Sample concentration (sample / determination solvent): 300mg / 0.6mL

< ²⁹ Si-NMR measurement conditions>

Device name: 400-MR manufactured by Agilent

Observation core: ²⁹ Si

Observation frequency: 79.42MHz

Measuring temperature: room temperature

Determination of solvent: CDCl ₃

Pulse amplitude: 8.40μsec (45°)

Pulse round trip time: 15.0 seconds

Cumulative number: 4,000 times

Sample concentration (sample / determination solvent): 300mg / 0.6mL

<GPC measurement conditions of Resin A>

Device: HTC-8220 made by Tosoh Corporation

Column: TSKgel Multipore HXL-M×3+Guard column-MP(XL)

Flow rate: 1.0mL/min

Detection condition: RI (polarity +)

Concentration: 100mg + 5mL (THF)

Injection volume: 100μL

Column temperature: 40 ° C

Dissolution: THF

<GPC measurement conditions of oligomer B>

Device: HTC-8220 made by Tosoh Corporation

Column: TSKgel G2000HHR×2+G1000HHR×2

Flow rate: 1.0mL/min

Detection conditions: RI (polarity -)

Concentration: 100mg + 5mL (THF)

Injection volume: 200μL

Column temperature: 40 ° C

Dissolution: THF

<Measurement method of specific gravity of hardened polyoxyl resin>

Device name: Alf Mirage company electronic hydrometer MDS-300

Use liquid: water

Measuring temperature: 24 ° C

Calculation formula: use ρ=A/(A-B)×ρ 0

ρ: specific gravity of hardened resin (unit: g/cm ³ )

A: Weight of hardened resin in air (unit: g)

B: Weight of hardened resin in liquid (unit: g)

ρ 0: specific gravity of liquid (unit: g/cm ³ )

(Level 1)

<Reagent preparation example> [Example 1]

Resin 1 having a structure of an organopolyoxane represented by the above formula (1) (Mw=3,500, in the above formula (1), R ¹ =methyl group, R ² =methoxy group or hydroxyl group) is used as the resin A and has The resin 2 of the organopolyoxane structure represented by the above formula (2) (Mw=450, R ¹ =methyl group, R ² =methoxy group in the above formula (2)) is used as the oligomer B to obtain a resin. Composition. The ratios of the respective repeating units of the resin 1 and the resin 2 which were obtained by measuring ²⁹ Si-NMR were shown in Tables 1 and 2, respectively.

Specifically, 354 g of the above-mentioned resin 1 and 190 g of isopropyl alcohol were placed in a flask which was placed in an oil bath, and the temperature was raised until the liquid temperature became 85 ° C, and the resin 1 was sufficiently dissolved in isopropyl alcohol. Next, 35 g of the above resin 2 was charged, and the mixture was stirred for 1 hour or more to be dissolved.

Then, after adding 123 g of 2-butoxyethyl acetate and 0.1 g of 3-dehydroglyceryloxypropyltrimethoxydecane (decane coupling agent) to the obtained resin composition, the resulting mixture was charged. Into the evaporator, the mixture was placed under the conditions of a temperature of 70 ° C and a pressure of 4 kPa A, and isopropyl alcohol was distilled off until the concentration of isopropyl alcohol in the resin composition was 1% by mass or less. Thereby, a polyoxyxylene resin liquid composition in which the mixing ratio of the resin A and the oligomer B was a resin A: oligomer B = 100:10 was obtained.

[Comparative Example 1]

The same operation as in Example 1 was carried out except that the input of the oligomer B was omitted, and a liquid composition of a polyoxyxylene resin containing only the polymer component of the resin A was obtained.

<Preparation of a liquid composition of a polyoxyl resin containing a catalyst for curing>

In each of the liquid compositions of the polyanthracene resin obtained in Example 1 and Comparative Example 1, 15% of phosphoric acid and an alkane represented by the following formula (3) were added to 100 parts by mass of the liquid composition of the polyanthracene resin. 1 part by mass of a mixture of oxydecane (n=3 to a positive number of 7) is used as a catalyst for curing, and is sufficiently stirred and mixed to obtain a liquid composition of a polyoxymethylene resin containing a catalyst for curing.

<Fracture resistance evaluation>

The chipping resistance of the obtained catalyst-containing polyoxyl resin liquid composition was evaluated. Specifically, a liquid composition of a polyoxyl resin containing a catalyst was spin-coated to form a film on an alkali-free glass substrate so as to have a film thickness of 50 μm. The film-formed glass substrate was placed in an oven at a temperature of 40 ° C for 10 minutes, and then placed in an oven at 160 ° C for 3 hours to cure the resin.

Then, observing the result of the glass substrate taken out from the oven, the embodiment will be The film thermally cured by the liquid composition of the polyoxyxylene resin obtained in the first embodiment (resin cured film) was not broken and was good. On the other hand, when the film (resin cured film) which hardened the liquid composition of the polyxanthoxy resin obtained in the comparative example 1 was fractured, it fractured.

<Sulphide tolerance evaluation>

Sulfate resistance (barrier to hydrogen sulfide gas) was evaluated for the obtained catalyst-containing polyoxyl resin liquid composition. Specifically, first, a chromium film having a film thickness of 10 nm and an alkali-free glass substrate (silver film glass substrate) having a silver film having a thickness of 100 nm thereon are prepared, so that the polysiloxane containing each catalyst can be made thereon. The resin liquid composition was spin-coated under the conditions of a film thickness of 20 μm, and heat-treated at 40 ° C for 10 minutes, followed by 160. The heat treatment was performed at ° C for 3 hours to form a resin cured film on the silver film.

The silver film glass substrate on which the resin cured film has been formed and the silver film glass substrate on which no film is formed are placed in a sealed environment having a hydrogen sulfide concentration of 2 to 6 ppm, a temperature of 85 to 90 ° C, and a relative humidity of 90% or more. minute.

As a result, the silver film glass substrate in which no film is formed becomes black due to corrosion by hydrogen sulfide. On the other hand, the silver film glass substrates which were formed by adding the catalyst for curing to each of the polyoxynoxy resin liquid compositions obtained in Example 1 and Comparative Example 1 were completely discolored.

(Level 2)

[Embodiment 2]

A resin (A-1) having an organopolyoxyalkylene structure represented by the above formula (1) (Mw=3,500, in the above formula (1), R ¹ =methyl group, R ² =methoxy group or hydroxyl group) ( Hereinafter, it is referred to as a resin (A-1) and an oligomer (B-1) having an organopolyoxyalkylene structure represented by the above formula (2) (Mw=450, in the above formula (2), R ¹ = After mixing methyl group and R ² = methoxy group (hereinafter referred to as resin (B-1)), a liquid composition (α 1 ) of a polyoxyxylene resin is obtained.

The existence ratio of the repeating unit of the aforementioned resin (A-1) is shown in Table 3. The existence ratio of the repeating unit of the aforementioned oligomer (B-1) is shown in Table 4.

The ratio of the existence of the repeating unit of the resin (A-1) and the oligomer (B-1) was determined by measuring the ²⁹ Si-NMR of the resin (A-1) and the oligomer (B-1) under the above-described measurement conditions. And ask for it.

Resin (A-1), as defined in the specification The total content of the A1 ruthenium atom, the A2 ruthenium atom and the A3 ruthenium atom is 77% in the content of the A3 ruthenium atom.

The ratio of the content of A2 germanium atom to the content of the aforementioned A3 germanium atom is [A2 The content of ruthenium atoms]: [A3 矽 atomic content] = 1: 3.35.

Oligomer (B-1), as defined in the specification The total content of the A1矽 atom, the A2矽 atom and the A3矽 atom, and the ratio of the A3矽 atom content is 12%.

Specifically, in a flask that has been placed in an oil bath, 311 g of the above-mentioned resin (A-1) and 190 g of isopropyl alcohol were added, and the mixture was heated and stirred until the internal temperature became 85 ° C to dissolve the resin (A-1). Next, 78 g of the above oligomer (B-1) was added to the dissolved mixture, and the mixture was stirred for 1 hour or more to dissolve the oligomer (B-1) to obtain a mixture.

To the obtained mixture, after adding 123 g of 2-butoxyethyl acetate and 0.1 g of 3-dehydroglyceryloxypropyltrimethoxydecane (decane coupling agent), the temperature was 70 ° C and the pressure was 4 kPa A using an evaporator. The isopropyl alcohol is distilled off until the isopropyl alcohol concentration is 1% by mass or less, and a liquid composition of the polyoxyxylene resin having a mixing ratio of the resin (A-1) and the oligo (B1) of 80:20 is obtained. (α 1).

As a result of ²⁹ Si-NMR measurement of the obtained polyoxyxylene resin liquid composition (α 1), the ratio of the signal area from the A3 germanium atom was 60% with respect to the total signal from the germanium atom. In the first drawing, a ²⁹ Si-NMR chart of the polyoxyxylene resin liquid composition (α 1) is shown. The polyoxynene resin liquid composition (α 1) does not contain an alkenyl group or a hydroquinone group.

Compared with polyoxyl resin liquid composition (α 1) 100 quality In an amount of 1 part by mass of a hardening catalyst containing 15% phosphoric acid, the liquid composition (α 1-1) of the polyxanthoxy resin was obtained by thorough stirring and mixing, and then the obtained liquid composition of the polyoxyl resin was obtained ( α 1-1) about 5g into an aluminum cup, baked The temperature was raised from room temperature to 150 ° C at a rate of 5 ° C /min, and left at 150 ° C for 3 hours to obtain a cured product of the polyoxyxylene resin liquid composition (α 1-1). The specific gravity of the obtained hardened material was 1.27.

[Example 3]

354 g of the resin (A-1) used in Example 2 was added to 190 g of isopropyl alcohol, and the mixture was stirred under heating until the internal temperature became 85 ° C, and the resin (A-1) was dissolved in isopropyl alcohol. Next, 35 g of the oligomer (B-1) used in Example 2 was similarly added to the dissolved mixture, and then, commercially available polyoxyl oxide different from the resin A and the oligomer B in the present specification was added. 3.8 g of the compound was dissolved by stirring for 1 hour or more.

The polyoxyxene compound used is a total content of the A1矽 atom, the A2矽 atom and the A3矽 atom, and the ratio of the A3矽 atom content is 0% or more and less than 30%, and the weight average molecular weight exceeds 8,000, 15,000. The following resins.

Then, the same treatment as in Example 2 was carried out to obtain a polyoxyxylene resin liquid composition (α 2) having a mixing ratio of the resin (A-1) and the oligomer (B-1) of 100:10.

As a result of ²⁹ Si-NMR measurement of the obtained polyoxyxylene resin liquid composition (α 2 ), the ratio of the signal area from the A3 germanium atom was 65% with respect to the total signal from the germanium atom. In Fig. 2, a ²⁹ Si-NMR chart of the polyoxyxylene resin liquid composition (?2) is shown. The polyoxynene resin liquid composition (α 2) does not contain an alkenyl group or a hydroquinone group.

2 parts by mass of a curing catalyst containing 15% phosphoric acid is added to 100 parts by mass of the polyoxyl resin liquid composition (α 2 ). The cured product of the polyoxyxylene resin liquid composition was obtained under the same conditions as in Example 2. The specific gravity of the obtained hardened material was 1.26.

[Comparative Example 2]

Polyoxyxylene resin X1 (Mw=5,100) represented by the following formula (A) and polyoxyxylene resin X2 (Mw=2,100) represented by the following formula (B), X1:X2=1:4 (mass ratio) Mixing, adding a platinum-containing catalyst to obtain a liquid composition of polyoxyxylene resin (β 1)

As a result of ²⁹ Si-NMR measurement of the polyoxyxylene resin X1, the ratio of the signal area from the A3 germanium atom was 8% with respect to the total signal from the germanium atom. In Fig. 3, a ²⁹ Si-NMR chart of polyoxyxylene resin X1 is shown.

As a result of ²⁹ Si-NMR measurement of the polyoxyxylene resin X2, the ratio of the signal area from the A3 germanium atom was 60% with respect to the total signal from the germanium atom. In Fig. 4, a ²⁹ Si-NMR chart of polyoxyxylene resin X2 is shown.

Among the total signals derived from the ruthenium atom of the obtained liquid composition of the polyoxyxylene resin (β 1 ), the signal area from the atom of A3 is represented by the polyoxyl resin X1 represented by the formula (A) and the formula (B) The mixing ratio of the polyoxyl resin X2 was calculated to be 50%.

(其中，c、d、e及f表示呈示各重複單元之單元數的整數)

(where c, d, e, and f represent integers that represent the number of units of each repeating unit)

(其中，k、l、m及n表示呈示各重複單元之單元數的整數)

(where k, l, m, and n represent integers that represent the number of units of each repeating unit)

A liquid composition (β 1 ) of polyoxyl resin was placed in an aluminum cup to about 5 g, and the temperature was raised from room temperature to 150 ° C at a rate of 5 ° C/min in an oven, and held at 150 ° C for 4 hours to obtain a poly A cured product of a liquid composition of a silicone resin (β 1 ). The specific gravity of the obtained hardened material was 1.18.

<Sulphide tolerance evaluation 1>

For the polyoxynene resin liquid composition (α 1-1), the polyoxymethylene resin liquid composition (α 2), and the polyoxyxylene resin liquid composition (β 1), the barrier property against hydrogen sulfide gas is performed. evaluation of.

Specifically, first, a chromium film having a film thickness of 10 nm and an alkali-free glass substrate (silver film glass substrate) on which a silver film having a thickness of 100 nm is formed are prepared thereon, so that each polyoxyn resin composition is formed thereon. The material was spin-coated under the conditions of a film thickness of 20 μm, and heat treatment was carried out under the same conditions as those of the cured product of the liquid composition of the polyoxynoxy resin in Example 2, whereby the cured product of the liquid composition of the polyoxyxylene resin was Film formation on the silver film.

One piece of a silver film glass substrate formed by forming a cured product of a liquid composition of a polyoxyn resin, and a glass substrate with a silver film not formed by a cured product of a liquid composition of a polyoxymethylene resin, with hydrogen sulfide gas Concentration 2 to Placed in an environment of 6 ppm, a temperature of 85 to 90°, and a relative humidity of 90% or more, for 90 minutes.

As a result, the polyoxyl resin liquid composition (α 1-1) Or the silver film formed by the hardening of the liquid composition of the polyoxyxylene resin (α 2 ) is almost unchanged before being placed, but the cured film of the liquid composition of the polyoxyxylene resin (β 1) is formed. The silver film and the silver film which does not form a cured film become black due to corrosion by hydrogen sulfide.

<Sulphide tolerance evaluation 2>

For the polyoxyxylene resin liquid composition (α 2 ), the barrier property against hydrogen sulfide gas was evaluated.

Specifically, the silver reflective film has been plated into a film. A resin package SMD-3602B (manufactured by Matsushita Semiconductor Components Co., Ltd.), which is a commercially available semiconductor light-emitting device at the bottom of the package, is dropped into a liquid crystal of a polyoxyl resin by completely reflecting a silver-reflecting film. The material (α 2) is then subjected to heat treatment under the same conditions as those of the cured product of the liquid composition of the polyoxyxylene resin of Example 2, and the liquid composition of the polyoxyxylene resin is formed in the package. Hardened material.

At a hydrogen sulfide concentration of 2 to 6 ppm, a temperature of 85 to 90 °, The package was placed in a closed environment having a relative humidity of 90% or more for 5 hours.

As a result, the polyxanthene resin liquid composition (α) 2) In the hardened package, the silver reflective film at the bottom of the package has almost no change.

<heat resistance evaluation>

Evaluation of heat resistance for liquid composition of polyoxyxylene resin (α 1), liquid composition of polyoxyxylene resin (α 2), and liquid composition of polyoxyxylene resin (β 1) estimate.

Specifically, in addition to adjusting the liquid amount to a thickness of 1 mm The heat treatment was carried out under the same conditions as those of the cured product of the liquid composition of the polyoxyxylene resin of Example 2 to obtain a cured product of each liquid composition of the polyoxynoxy resin, which was taken out from the aluminum cup. The transmittances at wavelengths of 400 nm and 350 nm were measured. Then, the hardened materials were placed in an oven at 200 ° C for 60 minutes, and then the transmittance at the same wavelength was measured. The results are shown in Table 5.

Polyoxyl resin liquid composition (α 1) and polyoxyl resin The transmittance of the cured product of the liquid composition (α 2 ) for each wavelength hardly changes before and after the placement at 200 ° C, and the cured product of the liquid composition of the polyoxyxylene resin (β 1 ) can be clearly seen. The change in transmittance, and the appearance of the cured product at the same time, is that the cured product of the liquid composition of the polyoxyxylene resin (α 2) is transparent before and after standing at 200 ° C, and the liquid composition of the polyphthalocyanine resin (β 1) The cured product was transparent before being placed at 200 ° C, but became yellowish after standing, and the environment at 200 ° C deteriorated heat resistance.

[Comparative Example 3]

A liquid composition of a polyoxyxylene resin containing only the resin (A-1) as a polyoxyxylene resin component was obtained by the same operation as in Example 2 except that the oligomer (B-1) was not added. β 3).

As a result of ²⁹ Si-NMR measurement of the polyoxyxylene resin liquid composition (β 3 ), the signal area from the A 3 矽 atom was 70% in the total signal from the ruthenium atom.

In Fig. 5, a ²⁹ Si-NMR chart of the polyoxyxylene resin liquid composition (?3) is shown. The polyoxynene resin liquid composition (β 3 ) does not contain an alkenyl group or a hydroquinone group.

Compared with polyoxyl resin liquid composition (β 3) 100 quality In a part by weight, 2 parts by mass of a curing catalyst containing 15% phosphoric acid was added, and a cured product of the resin composition was obtained under the same conditions as in Example 2. The specific gravity of the obtained hardened material was 1.28.

<Fracture resistance evaluation>

The chipping resistance was evaluated for the polyoxynoxy resin liquid composition (α 1-1), the polyoxymethylene resin liquid composition (α 2 ), and the polyoxyxylene resin liquid composition (β 3 ).

Specifically, the liquid composition of each of the polyoxyl resins is The product was placed in a commercially available resin package SMD-3602B for a semiconductor light-emitting device, and the container was placed in an oven at a temperature of 40 ° C for 10 minutes, and then placed in an oven at 150 ° C for 3 hours. A cured product of each of the above polyoxyalkylene resin liquid compositions.

Then, observe the results of the package taken out of the oven, The cured product of the liquid composition of the polyoxyxylene resin (α 1-1) and the liquid composition of the polyoxynoxy resin (α 2) is not cracked and is good, and the liquid composition of the polyoxyxylene resin (β 3) The hardened material is cracked.

The polyxanthene resin liquid composition of the present invention is very effective because it has high barrier properties against hydrogen sulfide gas and high heat resistance at a high temperature such as 200 ° C, and excellent chipping resistance at the time of hardening. A sealing material for a semiconductor light emitting element.

[Possibility of application in industry]

The polyxanthene resin liquid composition of the present invention can impart a cured product of a polyoxyxylene resin liquid composition excellent in heat resistance, chipping resistance, and barrier property against hydrogen sulfide gas. Therefore, the cured product of the polyoxyxylene resin liquid composition of the present invention can be used as a sealing material for a semiconductor light-emitting element.

Since the figure in the present case is the ²⁹ Si-NMR chart of the embodiment, it is not a representative figure of the present case. Therefore, there is no designated representative map in this case.

Claims (13)

A liquid composition of a polyoxyxylene resin, which is a liquid composition of a polyoxyxylene resin containing a polyoxyxylene resin, wherein the area of the total signal from the germanium atom in the ²⁹ Si-NMR measurement is attributed to the following A3矽The ratio of the signal area of the atom is 51% or more and 69% or less. The polyfluorene oxide resin contains the following resin A and the following oligomer B, and the resin A is based on the following A1 矽 atom, the following A2 矽 atom The resin oligomer B of the total content of the A3 ruthenium atom, the content of the A3 ruthenium atom is 20% or more and 90% or less, and the weight average molecular weight is 1,500 or more and 8,000 or less is based on the following A1 矽 atom, The oligomer content of the total A2 矽 atom and the A3 矽 atom, the ratio of the A3 矽 atom content is 0% or more and 30% or less, and the weight average molecular weight is less than 1,500, wherein the A1 矽 atom represents The atomic atom bound to the helium atom is a bonded helium atom, the A2 helium atom indicates that the oxygen atom bonded to the other helium atom is two bonded helium atoms, and the A3 helium atom indicates that the oxygen atom combined with the other helium atom is 3 combined helium atoms The resin A is a resin having an organopolysiloxane structure represented by the following formula (1), and the mixing ratio of the resin A to the oligomer B is resin A: oligomer B = 100: 0.1 to 20 (mass ratio) In the formula (1), R ¹ each independently represents an alkyl group or an aryl group; R ² each independently represents an alkoxy group or a hydroxyl group; and p ¹ , q ¹ , a ¹ and b ¹ represent formation of [p ¹ + b ¹ × q ¹ ]: [a ¹ ×q ¹ ]=1: Any positive number from 0.25 to 9. The polyoxymethylene resin liquid composition according to the first aspect of the invention, wherein the oligomer B is an oligomer having an organopolysiloxane structure represented by the following formula (2). (In the formula (2), R ¹ and R ² represent the same meanings as in the above formula (1), and p ² , q ² , r ² , a ² and b ² represent formation of [a ² × q ² ] / [(p ² + b ² × q ² ) + a ² × q ² + (r ² + q ² )] = 0 to a positive number of any of 0 to 0.3). The polyoxyl resin liquid group as described in claim 1 or 2 The product in which the mixing ratio of the resin A and the oligomer B is Resin A: oligo B = 100: 0.2 to 15 (mass ratio). The polyoxymethylene resin liquid composition according to claim 1 or 2, which further contains inorganic particles. The polyxanthoxy resin liquid composition according to claim 4, wherein the inorganic particles are one selected from the group consisting of cerium oxide, titanium oxide, and aluminum oxide. the above. The polyxanthoxy resin liquid composition according to claim 1 or 2, further comprising a phosphor. The polyxanthene resin liquid composition according to claim 1 or 2, further comprising a decane coupling agent. The liquid composition of the polyoxyxylene resin according to claim 1 or 2, wherein the temperature is raised from room temperature to 150 ° C at a temperature increase rate of 5 ° C /min, and then heated at 150 ° C for 3 hours to be hardened. The specific gravity of the obtained cured product is in the range of 1.20 g/cm ³ or more and 1.35 g/cm ³ or less. A cured product obtained by heating the polyoxyxylene resin liquid composition according to any one of claims 1 to 8 to 40 ° C or more and 250 ° C or less. The cured product according to claim 9, wherein the specific gravity is in the range of 1.20 g/cm ³ or more and 1.35 g/cm ³ or less. A sealing material for a semiconductor light-emitting element, comprising the cured product according to claim 9 or 10. A semiconductor light-emitting device comprising the cured product according to claim 9 or 10. A method of producing a semiconductor light-emitting device, comprising the step of heating a liquid composition of the polyoxynoxy resin according to any one of claims 1 to 8 to 40° C. or higher and 250° C. or lower.