JP2016011329A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition that exhibits high total luminous flux, when used for an LED as an encapsulation agent, without large changes in color coordinate from the LED which uses the conventional curable resin composition containing inorganic phosphor as the encapsulation agent.SOLUTION: There is provided a curable resin composition containing organopolysiloxane having at lest two silicon atom-binding hydrogen atoms in a molecule (A), organopolysiloxane having at least two alkenyl groups in a molecule (B), a catalyst for hydrosilylation reaction (C), an organic phosphor having a maximum absorption wavelength of 450 to 550 nm and a maximum emission wavelength of 460 to 600 nm, (D) and an inorganic phosphor (E), with the content of the inorganic phosphor (E) of 0.1 to 50 pts.mass based on total 100 pts.mass of the organosiloxane (A), the organosiloxane (B) and the catalyst for hydrosilylation reaction (C).

Description

  The present invention relates to a curable resin composition.

An optical semiconductor device (hereinafter also referred to as an LED) has features such as long life, low power consumption, shock resistance, high-speed response, lightness, thinness, and the like. Development in various fields such as lights, in-vehicle lighting, indoor / outdoor advertising, indoor / outdoor lighting, etc. is making dramatic progress.
An LED is usually manufactured by applying a curable composition containing a phosphor on an optical semiconductor element and curing the composition to seal the optical semiconductor element.

  As a curable composition used for such an LED sealing material, for example, Patent Document 1 discloses an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule and a specific average composition formula. The curable silicone composition containing the organopolysiloxane represented by these, the catalyst for hydrosilylation reaction, and an inorganic type fluorescent material (phosphor) is disclosed.

JP 2014-62198 A

In recent years, as LED applications have been expanded, further improvements in LED brightness (total luminous flux) have been demanded.
With reference to Patent Document 1, the present inventors prepared a composition containing an organopolysiloxane, a hydrosilylation catalyst and an inorganic phosphor, and used it as an LED sealing material. It became clear that the total luminous flux of the LED does not necessarily satisfy the level required recently.
In addition, for the purpose of improving the total luminous flux of the LED, the combined use of organic phosphors was examined, and the color coordinates greatly changed from the LED using a curable resin composition containing a conventional inorganic phosphor as a sealing material. It became clear that there was a case to be done.

  Therefore, when the present invention is used for an LED encapsulant, the color coordinates are not greatly changed from the LED using a curable resin composition containing a conventional inorganic phosphor as an encapsulant. It aims at providing the curable resin composition which shows a light beam.

As a result of earnest research to achieve the above problems, the present inventors have found that the above problems can be solved by using an inorganic phosphor together with a specific organic phosphor having a maximum absorption wavelength and a maximum emission wavelength. Invented.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) Organopolysiloxane (A) having at least two silicon-bonded hydrogen atoms in one molecule;
An organopolysiloxane (B) having at least two alkenyl groups in one molecule;
A hydrosilylation catalyst (C);
An organic phosphor (D) having a maximum absorption wavelength of 450 to 550 nm and a maximum emission wavelength of 460 to 600 nm;
Containing an inorganic phosphor (E),
Content of the said inorganic fluorescent substance (E) is 0.1 with respect to a total of 100 mass parts of the said organopolysiloxane (A), the said organopolysiloxane (B), and the said catalyst for hydrosilylation reaction (C). Curable resin composition which is -50 mass parts.
(2) The above-mentioned organopolysiloxane (A) has at least two silicon-bonded hydrogen atoms and at least one aryl group in one molecule, and has a degree of polymerization exceeding 10 Polysiloxane,
The curable resin composition according to (1), wherein the organopolysiloxane (B) is a branched organopolysiloxane having at least three alkenyl groups and at least one aryl group in one molecule. .
(3) The content of the organic phosphor (D) is 100 parts by mass in total of the organopolysiloxane (A), the organopolysiloxane (B), and the hydrosilylation catalyst (C). Curable resin composition as described in said (1) or (2) which is 0.000001-0.1 mass part.
(4) The curable resin composition according to any one of (1) to (3), wherein the organic phosphor (D) is a perylene derivative.
(5) Curable resin composition in any one of said (1)-(4) whose solubility with respect to toluene of the said organic fluorescent substance (D) is 0.01 mass% or more.
(6) The curable resin composition according to any one of (1) to (5), which is cured into a sheet.
(7) Curable resin composition in any one of said (1)-(6) which is a composition for optical semiconductor element sealing.

  As shown below, according to the present invention, when used as an LED encapsulant, the color coordinate changes greatly from an LED using a curable resin composition containing a conventional inorganic phosphor as an encapsulant. Therefore, it is possible to provide a curable resin composition that exhibits a high total luminous flux.

Below, the curable resin composition of this invention is demonstrated.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  The curable resin composition of the present invention (hereinafter also referred to as the composition of the present invention) includes an organopolysiloxane (A) having at least two silicon atom-bonded hydrogen atoms in one molecule, and one molecule. An organopolysiloxane (B) having at least two alkenyl groups, a hydrosilylation catalyst (C), an organic phosphor having a maximum absorption wavelength of 450 to 550 nm and a maximum emission wavelength of 460 to 600 nm (D ) And an inorganic phosphor (E). Here, the content of the inorganic phosphor (E) is 0 with respect to 100 parts by mass in total of the organopolysiloxane (A), the organopolysiloxane (B), and the hydrosilylation catalyst (C). .1 to 50 parts by mass.

Since the composition of this invention takes such a structure, when it uses for the sealing material of LED, color coordinates are from LED which used the curable resin composition containing the conventional inorganic fluorescent substance for sealing material. It is considered that a high total luminous flux is exhibited without greatly changing. The reason is not clear, but it is thought to be as follows.
That is, in the composition of the present invention, in addition to the inorganic phosphor, an organic phosphor having a specific maximum absorption wavelength and maximum emission wavelength is used in combination. Converts light into wavelength convertible light. Therefore, it can be considered that the wavelength conversion region of the inorganic phosphor is apparently expanded and the total luminous flux is improved. Here, as described above, since the maximum absorption wavelength and the maximum emission wavelength of the organic phosphor of the present invention are specific, there is little conversion of the inorganic phosphor outside the wavelength conversion region. As a result, when the composition of the present invention is used for an LED encapsulant, it is considered that the color coordinate does not change significantly from an LED using a curable resin composition containing an inorganic phosphor as an encapsulant.

  Hereinafter, each component contained in the composition of this invention is explained in full detail. In addition, it is preferable that the composition of this invention is uniform.

[Organopolysiloxane (A)]
The organopolysiloxane (A) contained in the composition of the present invention is not particularly limited as long as it is an organopolysiloxane having at least two silicon-bonded hydrogen atoms (Si—H) in one molecule.
The organopolysiloxane (A) undergoes an addition reaction (hydrosilylation reaction) with respect to an alkenyl group of the organopolysiloxane (B) described later. At this time, since the organopolysiloxane (A) has at least two silicon-bonded hydrogen atoms, it can function as a crosslinking agent for crosslinking the organopolysiloxane (B).
The composition of the present invention may contain two or more different organopolysiloxanes (A).

The weight average molecular weight (Mw) of the organopolysiloxane (A) is preferably 500 to 1,000,000, more preferably 1,000 to 150,000, because toughness is likely to occur in the cured product.
In addition, in this invention, a weight average molecular weight shall be the weight average molecular weight of polystyrene conversion by the gel permeation chromatography (GPC) which uses chloroform as a solvent.
The viscosity of the organopolysiloxane (A) at 25 ° C. is preferably 20 to 1,000,000 mPa · s, and more preferably 200 to 100,000 mPa · s.
In the present invention, the viscosity is measured at 25 ° C. in accordance with 4.1 (Brookfield rotary viscometer) of JIS K7117-1.

[Linear organopolysiloxane (a)]
The organopolysiloxane (A) is a linear organopolysiloxane (a) having at least two silicon-bonded hydrogen atoms and at least one aryl group in one molecule and having a polymerization degree of more than 10. ) Is preferred.

The degree of polymerization of the linear organopolysiloxane (a) is preferably 15 or more, more preferably more than 30 because the change in color coordinates is smaller and the total luminous flux is further improved. More preferably, it is more than 30 and 1,000 or less, and particularly preferably more than 30 and 500 or less.
In the present specification, the degree of polymerization of the linear organopolysiloxane (a) is a number obtained by subtracting the number of silicon atoms at both ends from the number of silicon atoms in the linear organopolysiloxane (a). be equivalent to.
For example, when the linear organopolysiloxane (a) is an organopolysiloxane represented by the formula (1) described later, the polymerization degree is a value indicated by n in the formula (1).

In addition, the linear organopolysiloxane (a) has at least one aryl group because it has a small attenuation due to light refraction, reflection, scattering, and the like of the resulting cured product. It is preferred that at least 30 mole percent of the groups are aryl groups, and more preferred that at least 40 mole percent is an aryl group.
Examples of the aryl group include aryl groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group, and a phenyl group is preferable.

  Examples of the group bonded to the silicon atom in the linear organopolysiloxane (a) include a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated group, specifically, For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, C1-C18 alkyl groups such as cyclopentyl and cyclohexyl groups; C6-C18 aryl groups such as phenyl, tolyl and xylyl groups; C7-C18 aralkyl groups such as benzyl and phenethyl groups A halogenated alkyl group having 1 to 18 carbon atoms such as a 3-chloropropyl group and a 3,3,3-trifluoropropyl group; and the like.

  In the present invention, it is preferable that the linear organopolysiloxane (a) has only two silicon-bonded hydrogen atoms because the cured product has toughness, and silicon-bonded hydrogen atoms are present only at both ends. The aspect which has is more preferable.

Such a linear organopolysiloxane (a) is preferably a linear organopolysiloxane having both ends of the molecular chain blocked with diorganohydrogensiloxy groups. For example, in the following formula (1): The organopolysiloxane represented is mentioned.
HR ¹ ₂ SiO (R ¹ ₂ SiO) _n SiR ¹ ₂ H (1)

In the formula (1), each R ¹ is independently a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond. Examples of the monovalent hydrocarbon group for R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, and various types. C1-C18 alkyl groups such as hexyl group, various octyl groups, various decyl groups, cyclopentyl group, cyclohexyl group; aryl groups having 6-18 carbon atoms such as phenyl group, tolyl group, xylyl group; benzyl group, phenethyl Aralkyl groups having 7 to 18 carbon atoms such as groups; halogenated alkyl groups having 1 to 18 carbon atoms such as 3-chloropropyl groups and 3,3,3-trifluoropropyl groups; It is preferably an alkyl group of 1 to 18 and more preferably a methyl group (hereinafter sometimes referred to as “Me”).
Note that at least one of R ¹ is an aryl group, preferably at least 30 mol% is an aryl group, and more preferably at least 40 mol% is an aryl group. The aryl group is an aryl group having 6 to 18 carbon atoms, and is preferably a phenyl group (hereinafter sometimes referred to as “Ph”).

  In the formula (1), n is a positive number having an average value of more than 10, preferably a positive number of 15 or more, more preferably a positive number of more than 30, and a positive number of more than 30 and not more than 1,000. A positive number of more than 30 and 500 or less is particularly preferable.

<Method for producing linear organopolysiloxane (a) (1)>
The production method of the linear organopolysiloxane (a) is not particularly limited. For example, an organopolysiloxane (a1) having two or more silanol groups in one molecule and a hydrogen atom bonded to a silicon atom. The above-mentioned linear organopolysiloxane (a2) is reacted with water (H ₂ O) as a by-product, and optionally dehydrating and condensing silanol groups remaining by the reaction. The method of obtaining a) as a main product is mentioned.

At this time, for example, the reaction is traced by ¹ H-NMR, and the disappearance of the peak derived from the silanol group of the organopolysiloxane (a1) or the appearance of the peak derived from a component other than the component used in the reaction is confirmed. By doing this, the reaction can be completed as a reaction product containing the linear organopolysiloxane (a), which is the main product, and by-products.

Examples of the organopolysiloxane (a1) used in the above reaction include organopolysiloxanes represented by the following formula (2). Examples of the disiloxane (a2) include those represented by the following formula (3). The disiloxane represented is mentioned.
HO (R ¹ ₂ SiO) _m H (2)
HR ¹ ₂ SiOSiR ¹ ₂ H (3)
In formula (2) and formula (3), R ¹ has the same meaning as R ¹ described above. Moreover, in Formula (2), m is an average value and is the positive number below n mentioned above.

The above manufacturing method, for example, a part of the silanol groups organopolysiloxane (a1) has the formula (2), and sealed with -SiR ¹ ₂ H derived from the disiloxane (a2) of the formula (3), the remaining It is polymerized by condensing the silanol group. For this reason, the degree of polymerization of the linear organopolysiloxane (a) depends on the charged amount of disiloxane (a2).

The blending ratio of each component in the above reaction is preferably such that the disiloxane (a2) is 0.001 to 0.2 mol with respect to 10 mol of silanol groups in the organopolysiloxane (a1).
The above reaction is preferably carried out by stirring. In stirring, it is preferable to heat in a temperature range of 50 to 65 ° C., for example, and the stirring time (reaction time) is preferably 1 to 5 hours, for example.

<Method for producing linear organopolysiloxane (a) (2)>
As another production method of the linear organopolysiloxane (a), for example, a cyclic methylphenylsiloxane oligomer is used as a molecular chain terminal blocker (for example, 1,1,3,3-tetramethyldisiloxane) and a polymerization catalyst ( (E.g., potassium hydroxide, potassium dimethylsiloxanolate, tetramethylammonium hydroxide or tetramethylammonium dimethylsiloxalate) in the presence of equilibration polymerization to neutralize or thermally decompose the polymerization catalyst, The cyclic organosiloxanes described below that can occur as products (for example, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane and 1,3,5,7-tetramethyl-1,3,5, 7-cyclotetraphenylcyclotetrasiloxane) is removed by heating under reduced pressure. Can.

In the composition of the present invention, the total content of the cyclic organosiloxane having a molecular weight of 150 to 1200 is 7.5% by mass or less because the change in color coordinates is smaller and the total luminous flux is further improved. It is more preferable that it is not substantially contained. Therefore, as the method for producing the linear organopolysiloxane (a), it is preferable to employ the above-described method for producing the linear organopolysiloxane (a) (Part 1).
Here, as cyclic organosiloxane, the compound represented by a following formula (I) is mentioned, for example.
(R ¹ ₂ SiO _2/2 ) _p (I)

In formula (I), each R ¹ is independently a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and has the same meaning as R ¹ in formula (1), ^At least one of 1 is an aryl group.
Moreover, in formula (I), p is an integer of 3-6.

  Examples of the compound represented by the formula (I) include 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5. , 7-tetraphenylcyclotrisiloxane and the like.

[Organopolysiloxane (B)]
The organopolysiloxane (B) contained in the composition of the present invention is not particularly limited as long as it is an organopolysiloxane having at least two alkenyl groups in one molecule.

  The weight average molecular weight (Mw) of the organopolysiloxane (B) is preferably 1,000 to 300,000, and more preferably 1,000 to 100,000.

[Branched organopolysiloxane (b)]
The organopolysiloxane (B) is preferably a branched organopolysiloxane (b) having at least three alkenyl groups and at least one aryl group in one molecule.
Examples of the alkenyl group include alkenyl groups having 2 to 18 carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, etc., and vinyl group (hereinafter referred to as “Vi”). Is preferred).
2-12 mass% is preferable and, as for the alkenyl group in 1 molecule, 3-10 mass% is more preferable.

The branched organopolysiloxane (b) has at least one aryl group, and preferably at least 30 mol% of the silicon-bonded total organic groups are aryl groups, and at least 40 mol% More preferably, it is an aryl group.
As said aryl group, C6-C18 aryl groups, such as a phenyl group, a tolyl group, a xylyl group, are mentioned, for example, It is preferable that it is a phenyl group.
As a result, attenuation of the resulting cured product due to light refraction, reflection, scattering, etc. is reduced, and when the organopolysiloxane (A) is a linear organopolysiloxane (a) having an aryl group, Excellent compatibility with the chain organopolysiloxane (a), turbidity and the like are suppressed, and the cured product is excellent in transparency.

  Examples of the group bonded to the other silicon atom in the branched organopolysiloxane (b) include substituted or unsubstituted monovalent hydrocarbon groups excluding alkenyl groups and aryl groups. Specifically, For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, An alkyl group having 1 to 18 carbon atoms such as cyclopentyl group and cyclohexyl group; an aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group; a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, etc. C1-C18 halogenated alkyl group; etc., and other small groups include silicon atom-bonded hydroxyl groups and silicon atom-bonded groups. It may have a Kokishi group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

Such a branched organopolysiloxane (b) is preferably an organopolysiloxane represented by the following average unit formula (4). Here, the average unit formula represents the number of moles of each siloxane unit when the total number of siloxane units constituting the organopolysiloxane is 1 mole.
(R ³ SiO _3/2 ) _a (R ³ ₂ SiO _2/2 ) _b (R ³ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (X ¹ O _1/2 ) _e (4) )

In formula (4), each R ³ is independently a substituted or unsubstituted monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, and various hexyl groups. Alkyl groups having 1 to 18 carbon atoms such as various octyl groups, various decyl groups, cyclopentyl groups, and cyclohexyl groups; those having 2 to 18 carbon atoms such as vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, and octenyl groups. Alkenyl group; aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group and xylyl group; aralkyl group having 7 to 18 carbon atoms such as benzyl group and phenethyl group; 3-chloropropyl group, 3,3,3- C1-C18 halogenated alkyl groups, such as a trifluoropropyl group;
However, in one molecule, at least three of R ³ are alkenyl groups, and the amount of R ³ that is an alkenyl group is preferably 2 to 12% by mass, and more preferably 3 to 10% by mass.
In addition, in one molecule, at least one of R ³ is an aryl group, and at least 30 mol% of all R ³ is preferably an aryl group, and at least 40 mol% is more preferably an aryl group.

In formula (4), X ¹ is a hydrogen atom or an alkyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, and various octyl groups. Groups, various decyl groups, cyclopentyl groups, cyclohexyl groups and the like, and alkyl groups having 1 to 18 carbon atoms are preferable, and a methyl group is preferable.

  In formula (4), a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, e is 0 or a positive number, and , B / a is a number in the range 0-10, c / a is a number in the range 0-5, d / (a + b + c + d) is a number in the range 0-0.3, e / (a + b + c + d) is a number in the range of 0 to 0.4.

  The molar ratio of the silicon atom-bonded hydrogen atom of the organopolysiloxane (A) and the alkenyl group of the organopolysiloxane (B) (hereinafter also referred to as “Si—H / Si—Vi molar ratio”) is particularly limited. However, it is preferably 0.05 to 5.0, more preferably 0.1 to 2.0, because the change in color coordinates is smaller and the total luminous flux is further improved. More preferably, it is 5-1.5.

  The mass ratio (A / B) between the content of the organopolysiloxane (A) and the content of the organopolysiloxane (B) is not particularly limited, but the change in color coordinates is smaller and the total luminous flux is further improved. For the reason, it is preferably 0.05 to 5.0, more preferably 0.1 to 2.0, and further preferably 0.5 to 1.5.

[Catalyst for hydrosilylation reaction (C)]
The hydrosilylation reaction catalyst (C) contained in the composition of the present invention is used in combination with the organopolysiloxane (A) to accelerate the addition reaction (hydrosilylation reaction) to the alkenyl group of the organopolysiloxane (B). Functions as a catalyst.
As the hydrosilylation catalyst (C), a conventionally known catalyst can be used, and examples thereof include a platinum-based catalyst, a rhodium-based catalyst, a palladium-based catalyst, and the like, and a platinum-based catalyst is preferable. Specific examples of the platinum catalyst include chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-alcohol coordination compound, platinum diketone complex, platinum divinyltetramethyldi A siloxane complex etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.

  The content of the hydrosilylation reaction catalyst (C) is a catalytic amount, but the total of the above-mentioned organopolysiloxane (A) and organopolysiloxane (B) because the curability of the composition of the present invention is excellent. The amount is preferably 0.0000001 to 0.1 parts by mass, more preferably 0.000001 to 0.01 parts by mass with respect to 100 parts by mass.

[Organic phosphor (D)]
The organic phosphor (D) is not particularly limited as long as it is an organic phosphor (an organic substance that emits fluorescence) having a maximum absorption wavelength of 450 to 550 nm and a maximum emission wavelength (maximum emission wavelength) of 460 to 600 nm. Two or more organic phosphors (D) may be used in combination.
The maximum absorption wavelength is preferably 460 to 530 nm.
The maximum emission wavelength is preferably 480 to 540 nm.
In the present specification, the maximum absorption wavelength means an absorption wavelength at which the light absorption rate is maximum. The maximum emission wavelength means an emission wavelength at which the emission intensity is maximum.

  Preferred examples of the organic phosphor (D) include arylamine derivatives, anthracene derivatives (phenylanthracene derivatives), pentacene derivatives, azole derivatives (oxadiazole derivatives, oxazole derivatives, triazole derivatives, benzoxazole derivatives, benzoaza Triazole derivatives), thiophene derivatives (oligothiophene derivatives), carbazole derivatives, dienes (cyclopentadiene derivatives, tetraphenylbutadiene derivatives), styryl derivatives, (distyrylbenzene derivatives, distyrylpyrazine derivatives, distyrylarylene derivatives, stilbene derivatives) , Silole derivatives, spiro compounds, triphenylamine derivatives, trifumanylamine derivatives, pyrazoloquinoline derivatives, hydrazone derivatives, pyrazole derivatives Pyrazoline derivatives), pyridine ring compounds, pyrrole derivatives (porphyrin derivatives, phthalocyanine derivatives), fluorene derivatives, phenanthroline derivatives, pyrene derivatives (phenanthrene derivatives), perinone derivatives, perylene derivatives, phenylene compounds, rhodamines, coumarin derivatives, naphthalimide derivatives, Examples include benzoxazinone derivatives, quinazolinone derivatives, quinophthalone derivatives, rubrene derivatives, and quinacridone derivatives. Among these, a perylene derivative is preferable because the change in color coordinates is smaller and the total luminous flux is further improved.

  The thermal decomposition temperature of the organic phosphor (D) is not particularly limited, but is preferably 250 ° C. or higher. In this specification, the thermal decomposition temperature represents a temperature at which the mass is reduced by 5 mass% when thermogravimetric analysis (TGA measurement) is performed in a nitrogen atmosphere.

  The solubility of the organic phosphor (D) in toluene is not particularly limited, but is preferably 0.01% by mass or more. When the solubility of the organic phosphor (D) in toluene is 0.01% by mass or more, the organic phosphor (D) can be mixed as a toluene solution in the production of the composition of the present invention. The uniformity of the composition is improved. In addition, in this specification, the solubility with respect to toluene of organic fluorescent substance (D) is the organic fluorescent substance with respect to toluene (D) when organic fluorescent substance (D) is dissolved in 25 degreeC toluene until it becomes saturated. ) Ratio (mass%).

  In the composition of the present invention, the content of the organic phosphor (D) is not particularly limited, but the total of the organopolysiloxane (A), the organopolysiloxane (B), and the hydrosilylation reaction catalyst (C). It is preferable that it is 0.000001-0.1 mass part with respect to 100 mass parts, and it is more preferable that it is more than 0.001 mass part.

[Inorganic phosphor (E)]
The inorganic phosphor (E) contained in the composition of the present invention is not particularly limited as long as it is an inorganic substance that emits fluorescence. Specific examples thereof include oxide phosphors and acids widely used in LEDs. Examples thereof include yellow, red, green, and blue light emitting phosphors composed of nitride phosphors, nitride phosphors, sulfide phosphors, oxysulfide phosphors, and the like. Two or more inorganic phosphors (E) may be used in combination. The inorganic phosphor is preferably a powdery inorganic phosphor powder.
Examples of oxide phosphors include yttrium, aluminum, and garnet-based YAG green to yellow light-emitting phosphors containing cerium ions, terbium, aluminum, garnet-based TAG yellow light-emitting phosphors including cerium ions, and Examples include silicate green to yellow light emitting phosphors containing cerium and europium ions.
Examples of the oxynitride phosphor include silicon, aluminum, oxygen, and nitrogen-based sialon-based red to green light-emitting phosphors containing europium ions.
Examples of nitride-based phosphors include calcium, strontium, aluminum, silicon, and nitrogen-based casoon-based red light-emitting phosphors containing europium ions.
Examples of the sulfide type include ZnS type green coloring phosphors including copper ions and aluminum ions.
Examples of oxysulfide phosphors include Y2O2S red light-emitting phosphors containing europium ions.

The maximum absorption wavelength of the inorganic phosphor (E) is not particularly limited, but is preferably 400 to 1000 nm, and more preferably 420 to 800 nm.
The maximum emission wavelength (maximum emission wavelength) of the inorganic phosphor (E) is not particularly limited, but is preferably 450 to 1000 nm, and more preferably 470 to 800 nm.

  In the composition of the present invention, the content of the inorganic phosphor (E) is 100 parts by mass in total of the organopolysiloxane (A), the organopolysiloxane (B), and the hydrosilylation catalyst (C). On the other hand, it is 0.1-50 mass parts. Especially, it is preferable that it is 1-10 mass parts. The content of the inorganic phosphor (E) is 0.1 to 100 parts by mass in total of 100 parts by mass of the organopolysiloxane (A), the organopolysiloxane (B), and the hydrosilylation catalyst (C). If it is out of the range of 50 parts by mass, the change in color coordinates becomes large, and the total luminous flux becomes insufficient.

[Optional ingredients]

(Curing retarder)
The composition of the present invention may further contain a curing retarder. The curing retarder is a component for adjusting the curing rate and working life of the composition of the present invention, such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyne. Alcohol derivatives having a carbon-carbon triple bond such as 3-ol, phenylbutynol, 1-ethynyl-1-cyclohexanol; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexene Ene-in compounds such as -1-yne; alkenyl group-containing low molecular weight siloxanes such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; methyl-tris (3-methyl-1-butyne-3-oxy) silane Alkyne-containing silanes such as vinyl-tris (3-methyl-1-butyne-3-oxy) silane; , May be used those either alone, or in combination of two or more.
In the composition of the present invention, the content of the curing retarder is not particularly limited, but is 0.00001 to 0.001 with respect to 100 parts by mass in total of the organopolysiloxane (A) and the organopolysiloxane (B). The amount is preferably 1 part by mass, and more preferably 0.0001 to 0.01 part by mass.

〔Additive〕
The composition of the present invention is within a range not impairing the object of the present invention, for example, an ultraviolet absorber, a filler (particularly silica), an anti-aging agent, an antistatic agent, a flame retardant, an adhesion promoter, a dispersant, an oxidation agent. Additives such as inhibitors, antifoaming agents, matting agents, light stabilizers, dyes, pigments can be further contained.
Of these additives, silica is preferably used as a filler.
The type of silica is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate.

[Method for producing curable resin composition]
The manufacturing method of the composition of this invention is not specifically limited, For example, the method of manufacturing by mixing the essential component mentioned above and an arbitrary component is mentioned. Especially, from the reason for improving the uniformity of the composition of the present invention, it is preferable to previously dissolve the organic phosphor (D) in toluene and mix the organic phosphor (D) as a toluene solution.
Moreover, the method of hardening the composition of this invention and obtaining hardened | cured material is not specifically limited, For example, the method of heating the composition of this invention for 80-200 degreeC and 10 minutes-720 minutes is mentioned.

[Usage]
The composition of the present invention is, for example, in the field of display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, semiconductor integrated circuit peripheral materials, etc. It can be used as a primer, a sealing material and the like.

In particular, when the composition of the present invention is used as an LED encapsulant, the color coordinates of the LED using the curable resin composition containing a conventional inorganic phosphor as the encapsulant do not change significantly. Since it exhibits a high total luminous flux, it can be suitably used as a composition for encapsulating an optical semiconductor.
The optical semiconductor to which the composition of the present invention can be applied is not particularly limited, and examples thereof include a light emitting diode (LED), an organic electroluminescent element (organic EL), a laser diode, and an LED array.
As a method for using the composition of the present invention as an optical semiconductor sealing composition, for example, the composition of the present invention is applied to an optical semiconductor, and the optical semiconductor to which the composition of the present invention is applied is heated. The method of hardening the composition of invention is mentioned. At this time, it may be cured into a sheet.
The method for applying and curing the composition of the present invention is not particularly limited, and examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

<Manufacture of organopolysiloxane (A)>
(Linear organopolysiloxane A1)
A flask with a stirrer and a reflux condenser was charged with 100 g of a linear organopolysiloxane having a silanol group represented by the following formula (8) and 0.1 g of trifluoromethanesulfonic acid, stirred and heated at 70 ° C. . When the polymer reaches the target viscosity, 100 g of toluene is added, and the acid is removed by washing with water to obtain a both-end silanol polymer represented by the following formula (9). To this polymer, 10 g of 1,1,3,3-tetramethyldisiloxane and 0.1 g of trifluoromethanesulfonic acid were added, stirred and heated at 60 ° C. for 2 hours. Thereafter, 150 g of toluene was added, and the generated water was discharged out of the system. The toluene layer was washed three times with water and then concentrated under reduced pressure to obtain a linear organopolysiloxane A1 represented by the following formula (10). The linear organopolysiloxane A1 is “a linear organopolysiloxane having at least two silicon-bonded hydrogen atoms and at least one aryl group in one molecule and having a polymerization degree of more than 10. Polysiloxane ".
HO (MePhSiO) ₆ H (8)
HO (MePhSiO) ₅₀ H (9)
HMe ₂ SiO (MePhSiO) ₅₀ SiMe ₂ H (10)

(Linear organopolysiloxane A2)
The linear chain represented by the following formula (11) is the same as the above except that the target viscosity at the time of dehydration condensation of the linear organopolysiloxane having a silanol group represented by the above formula (8) is changed. Organopolysiloxane A2 was obtained. The linear organopolysiloxane A2 is “a linear organopolysiloxane having at least two silicon-bonded hydrogen atoms and at least one aryl group in one molecule and having a degree of polymerization of more than 10. Polysiloxane ".
HMe ₂ SiO (MePhSiO) ₁₈₀ SiMe ₂ H (11)

<Production of organopolysiloxane (B)>
(Branched organopolysiloxane B1)
In a four-necked flask equipped with a stirrer, reflux condenser, inlet and thermometer, 21.4 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 60 g of water, 0.14 g of trifluoromethanesulfonic acid Then, 200 g of toluene was added and mixed, and 151.5 g of phenyltrimethoxysilane was added dropwise over 1 hour while stirring. After completion of the addition, the mixture was heated to reflux for 1 hour. After cooling, the lower layer was separated, and the toluene solution layer was washed with water three times. 100 g of 5% aqueous sodium hydrogen carbonate solution was added to the toluene solution layer that had been washed with water, and the mixture was heated to 75 ° C. with stirring and refluxed for 1 hour. After cooling, the lower layer was separated, and the upper toluene solution layer was washed with water three times. The remaining toluene solution layer was concentrated under reduced pressure to obtain a branched organopolysiloxane B1 that is a methylphenylvinylpolysiloxane resin represented by the following average unit formula (17) that is semisolid at 25 ° C. The branched organopolysiloxane B1 is “a branched organopolysiloxane having at least three alkenyl groups and at least one aryl group in one molecule”.
(ViMe ₂ SiO _1/2 ) _0.22 (PhSiO _3/2 ) _0.78 (17)

<Preparation of curable resin composition>
The aforementioned linear organopolysiloxane A1 (50 parts by mass), the aforementioned linear organopolysiloxane A2 (50 parts by mass), the aforementioned branched organopolysiloxane B1 (160 parts by mass), and hydrosilylation Platinum divinyltetramethyldisiloxane complex (trade name: 3% Pt-VTS-VTS, manufactured by N.E. Chemcat) (0.00001 parts by mass) as a reaction catalyst, and 3-methyl-1-butyne as a curing retarder -3-ol (Tokyo Chemical Industry Co., Ltd.) (0.001 part by mass) was mixed. With this mixture as 100 parts by mass, a toluene solution (concentration: 0.1% by mass) of the organic phosphor shown in Table 1 below (the amount (part by mass) shown in Table 1 below as the organic phosphor) and , YAG0902 (YAG phosphor, manufactured by Nemoto Lumi Material Co., Ltd.) (amount (parts by mass) shown in Table 1 below) is blended as an inorganic phosphor, and mixed uniformly with a vacuum stirrer to produce a curable resin composition (A curable resin composition of Reference Examples, Examples and Comparative Examples) was prepared. In Reference Example 1, no organic phosphor was blended. In Comparative Examples 1 and 2, no inorganic phosphor was blended.

<Preparation of sample for evaluation>
The obtained curable resin composition was injected into an LED package (reflector: PPA (polyphthalamide)) using a dispenser. Then, it heated, the curable resin composition was hardened, and the sample for evaluation was produced.

<Evaluation of total luminous flux>
With respect to the obtained sample for evaluation, the total luminous flux [lm] at a current of 20 mA was measured. The results are shown in Table 1 (total luminous flux). The result was expressed as a relative value with the total luminous flux of Reference Example 1 as 1.000. Practically, the total luminous flux is preferably higher than 1.000.

<Evaluation of color coordinates>
About the obtained sample for evaluation, the color coordinate (x, y) in current 20mA was measured. Then, the deviation from the color coordinates (x, y) of Reference Example 1 is calculated. When both the x and y deviations are within ± 5%, “A”, and at least one deviation between x and y is ± 5%. The case of exceeding was evaluated as “B”. The results are shown in Table 1 (color coordinates). "A" is preferable from the viewpoint that the color coordinate does not change significantly from an LED using a curable resin composition containing a conventional inorganic phosphor as a sealing material.

Details of each component shown in Table 1 are as follows. In addition, all the solubility with respect to toluene of organic fluorescent substance D1 was 0.01 mass% or more. The organic phosphor D1 corresponds to the above-described organic phosphor (D), and the organic phosphor X1 does not correspond to the above-described organic phosphor (D).
Organic phosphor D1: Lumogen F Yellow 170 (perylene derivative, maximum absorption wavelength: 505 nm, maximum emission wavelength: 528 nm, manufactured by BASF)
Organic phosphor X1: Lumogen F Red 305 (perylene derivative, maximum absorption wavelength: 578 nm, maximum emission wavelength: 613 nm, manufactured by BASF)
Inorganic phosphor E1: YAG0902 (YAG phosphor, manufactured by Nemoto Lumi Material)

As can be seen from Table 1, the LED using the curable resin composition of Example of the present application in which the organic phosphor (D) and the inorganic phosphor (E) are used in combination as an encapsulant is an inorganic phosphor (E). The LED using the curable resin composition of Reference Example 1 containing only as a sealing material showed a high total luminous flux without greatly changing color coordinates. In addition, the curable resin composition of Examples of the present application has an inorganic phosphor although the content of the inorganic phosphor is smaller than that of the curable resin composition of Reference Example 1 containing only the inorganic phosphor (E). Compared to Reference Example 1 containing only (E), it showed a higher total luminous flux when used as an LED encapsulant.
From the comparison between Examples 1 and 2, the total content of the organic phosphor (D) is 100 masses of the organopolysiloxane (A), the organopolysiloxane (B), and the hydrosilylation reaction catalyst (C). Example 1, which is more than 0.001 parts by mass with respect to parts, showed a higher total luminous flux.

  On the other hand, the LED using the curable resin composition of Comparative Example 3 in which the phosphor other than the organic phosphor (D) and the inorganic phosphor (E) are used in combination as an encapsulant is only an inorganic phosphor (E). The color coordinate greatly changed from LED which used the curable resin composition of the reference example 1 contained for a sealing material, and the total luminous flux was also insufficient.

Claims (7)

An organopolysiloxane (A) having at least two silicon-bonded hydrogen atoms in one molecule;
An organopolysiloxane (B) having at least two alkenyl groups in one molecule;
A hydrosilylation catalyst (C);
An organic phosphor (D) having a maximum absorption wavelength of 450 to 550 nm and a maximum emission wavelength of 460 to 600 nm;
Containing an inorganic phosphor (E),
The content of the inorganic phosphor (E) is 0.1 with respect to a total of 100 parts by mass of the organopolysiloxane (A), the organopolysiloxane (B), and the hydrosilylation catalyst (C). Curable resin composition which is -50 mass parts. The organopolysiloxane (A) is a linear organopolysiloxane having at least two silicon-bonded hydrogen atoms and at least one aryl group in one molecule and having a degree of polymerization of more than 10. Yes,
The curable resin composition according to claim 1, wherein the organopolysiloxane (B) is a branched organopolysiloxane having at least three alkenyl groups and at least one aryl group in one molecule.   Content of the said organic fluorescent substance (D) is 0.000001 with respect to a total of 100 mass parts of the said organopolysiloxane (A), the said organopolysiloxane (B), and the said catalyst for hydrosilylation reaction (C). The curable resin composition of Claim 1 or 2 which is -0.1 mass part.   The curable resin composition according to any one of claims 1 to 3, wherein the organic phosphor (D) is a perylene derivative.   The curable resin composition of any one of Claims 1-4 whose solubility with respect to toluene of the said organic fluorescent substance (D) is 0.01 mass% or more.   The curable resin composition of any one of Claims 1-5 hardened to the sheet form.   The curable resin composition of any one of Claims 1-6 which is a composition for optical semiconductor element sealing.