JP2011107717A - Method for producing phosphor-containing silicone resin lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a lens comprising a silicone cured product having excellent crack and impact resistances and low surface tackiness. <P>SOLUTION: The lens is obtained by hot forming and curing a silicone resin composition containing: (A) an organopolysiloxane which includes an R<SP>1</SP>SiO<SB>1.5</SB>unit (T unit), an R<SP>2</SP><SB>2</SB>SiO unit (D unit) and an R<SP>3</SP><SB>a</SB>R<SP>4</SP><SB>b</SB>SiO<SB>(4-a-b)/2</SB>unit (R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are methyl or the like; R<SP>4</SP>is vinyl or allyl; a is an integer of 0-2 and b is 1 or 2, provided that a+b is 2 or 3), the number of repetitions of the D unit being 5-300; (B) an Si-H containing polysiloxane which includes the T unit, the D unit and an R<SP>3</SP><SB>c</SB>H<SB>d</SB>SiO<SB>(4-c-d)/2</SB>unit (c is an integer of 0-2 and d is 1 or 2, provided that c+d is 2 or 3), the number of repetitions of the D unit being 5-300, by an amount that a molar ratio of an Si-bonded hydrogen atom in (B) to vinyl or allyl groups in (A) is 0.1-4.0; (C) a catalyst; and (D) a phosphor. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a lens suitably used particularly for LED applications. Specifically, silicone used in LED devices and the like that converts the emission color of the LED chip by mixing the fluorescent material into the mold member by utilizing the property of the fluorescent material that shifts the wavelength of light to the longer wavelength side. The present invention relates to a lens and an addition-curable silicone resin composition suitable for lens molding. The present invention particularly relates to a phosphor-containing silicone lens having excellent transparency and molding processability, almost no surface tackiness, and excellent impact resistance, and a silicone resin composition for molding the lens.

  A large number of lenses for LED light emitting devices are manufactured by mechanical molding such as injection molding. Conventionally, it has been molded using thermoplastic resins such as acrylic and polycarbonate, but with the increase in output of LED light emitting devices, there has been a problem that thermoplastic resins have insufficient heat resistance and discoloration resistance. .

  Recently, a lot of lead-free solder has been used. Since lead-free solder has a higher melting temperature than conventional solder, the optical element is usually soldered to the substrate at a temperature of 260 ° C. or higher. When soldering is performed at such a temperature, a conventional lens made of a thermoplastic material may be deformed or may be unusable due to problems such as yellowing due to high temperatures.

  Under such circumstances, many studies have been made to use a silicone resin for a lens such as an LED, and further, a lens containing a phosphor is demanded. Phosphor-containing lenses molded with materials conventionally used for silicone lenses are prone to separation of the phosphor and the resin during molding and curing. Uniform hard materials have poor impact resistance and soft rubber materials do not deform. As a result, there is a problem in that the light characteristics as a lens are easily lowered, and stress is generated on the LED chip, the wire, and the like inside the apparatus. When phosphor is added to the lens, separation of the phosphor occurs during molding and storage in conventional liquid silicone, and color spots occur due to insufficient dispersion of the phosphor in the molded lens after curing. There was a problem to do.

  Therefore, the present invention eliminates the above-mentioned drawbacks of the prior art, has excellent impact resistance that does not break even in a drop test of general devices, and at the same time has good transparency and molding processability and almost no surface tackiness. An object of the present invention is to provide a silicone lens in which a phosphor is well dispersed and a silicone resin composition for molding the lens.

  As a result of intensive studies to solve the above problems, the present inventor has found that an addition-curable silicone using an alkenyl group-containing organopolysiloxane having a specific resin structure and an organohydrogenpolysiloxane having a specific resin structure It has been found that this problem can be solved by molding a lens with a resin composition, and the present invention has been made.

  That is, the present invention provides the following silicone lens and the lens molding silicone resin composition.

That is, first,
(A) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit (provided that R ¹ , R ² and R ³ are each independently a methyl group, An ethyl group, a propyl group, a cyclohexyl group or a phenyl group, R ⁴ represents a vinyl group or an allyl group, a is 0, 1 or 2, b is 1 or 2, and a + b is 2 or 3. An organopolysiloxane having a resin structure in which the number of repeating R ² ₂ SiO units is 5 to 300;
(B) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _c H _d SiO _{(4-cd) / 2} unit (provided that R ¹ , R ² and R ³ are as described above, (c is 0, 1 or 2, d is 1 or 2, and c + d is 2 or 3), and the resin structure organohydrogenpolysiloxane has a repeating number of 5 to 300 R ² ₂ SiO units: (A) The quantity by which the hydrogen atom bonded to the silicon atom in the component (B) relative to the vinyl group or allyl group in the component is 0.1 to 4.0 in molar ratio,
(C) A platinum group metal catalyst: an effective amount and (D) a silicone lens formed by heat curing a silicone resin composition containing a phosphor.

  This lens is preferably formed by heat-curing the silicone resin composition in a mold under pressure.

  The silicone resin composition is preferably solid at room temperature. For this reason, the phosphor of component (D) dispersed in the composition does not settle even during long-term storage or in the process of molding and curing, and a uniformly dispersed lens can be obtained.

  In the silicone resin composition, the component (A) and / or the component (B) preferably contain a silanol group. Therefore, since the silanol group is not blocked by silylation treatment or the like, white turbidity at the time of water absorption can be reduced.

  The silicone resin composition is preferably such that the cured product of the composition excluding the component (D) has a light transmittance of 90% or more in the visible light region from 400 nm. Thereby, a lens having excellent optical characteristics can be obtained.

  In the silicone resin composition, preferably, the phosphor of component (D) is an inorganic phosphor having a particle size of 10 nm or more. This is because it is advantageous in terms of light conversion efficiency.

  Since the silicone lens of the present invention is excellent in light characteristics as described above, it is particularly suitable for an LED element.

Thus, the present invention secondly,
(A) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit (provided that R ¹ , R ² and R ³ are each independently a methyl group, An ethyl group, a propyl group, a cyclohexyl group or a phenyl group, R ⁴ represents a vinyl group or an allyl group, a is 0, 1 or 2, b is 1 or 2, and a + b is 2 or 3. An organopolysiloxane having a resin structure in which the number of repeating R ² ₂ SiO units is 5 to 300;
(B) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _c H _d SiO _{(4-cd) / 2} unit (provided that R ¹ , R ² and R ³ are as described above, (c is 0, 1 or 2, d is 1 or 2, and c + d is 2 or 3), and the resin structure organohydrogenpolysiloxane has a repeating number of 5 to 300 R ² ₂ SiO units: (A) The quantity by which the hydrogen atom bonded to the silicon atom in the component (B) relative to the vinyl group or allyl group in the component is 0.1 to 4.0 in molar ratio,
(C) A platinum group metal-based catalyst: an effective amount, and (D) a silicone resin composition for lens molding comprising a phosphor.

  According to the present invention, a phosphor that is a hard resin but has excellent flexibility, transparency and molding processability, a cured product with less surface tack, and can be easily molded by a conventional molding apparatus. And a silicone resin composition for molding the lens are obtained.

The front view which shows the sample molded lens in order to measure the mechanical characteristic of a silicone lens in an Example. The front view which shows the sample molded lens which used for the drop test in order to measure impact resistance in an Example. The front view of the sample shaping | molding lens for measuring the dispersibility of the fluorescent substance in a lens hardened | cured material in an Example.

Hereinafter, the present invention will be described in more detail.
[Curable silicone resin composition]
Hereinafter, the present invention will be described in more detail.
-(A) Resin-structured organopolysiloxane-
An organopolysiloxane having a resin structure (that is, a three-dimensional network structure), which is an important component of the composition of the present invention, includes (A) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _a R ⁴ _b SiO. _{(4-ab) / 2} units (wherein R ¹ , R ² and R ³ independently represent a methyl group, an ethyl group, a propyl group, a cyclohexyl group or a phenyl group, and R ⁴ represents a vinyl group or an allyl group) A is 0, 1 or 2, b is 1 or 2, and a + b is 2 or 3, and the number of repeating R ² ₂ SiO units is 5 to 300. The number of repeating R ² ₂ SiO units is 5 to 300, preferably 10 to 300, more preferably 15 to 200, and still more preferably 20 to 100.
In the above, the number of repetitions of R ² ₂ SiO units is 5 to 300 amino means that the structure R ² ₂ SiO units are repeated 5 to 300 pieces in succession is present. That is, in the molecule of the component (A), the formula (1):

（１）
（但し、ｍは５〜３００の整数）
で表される直鎖状ジオルガノポリシロキサン連鎖構造が存在していることを意味する。

(1)
(Where m is an integer from 5 to 300)
It means that a linear diorganopolysiloxane chain structure represented by

The R ² ₂ SiO unit may be present in the component (A) without constituting the structure represented by the formula (1) (for example, alone or in a chain structure of 4 or less). However, 50 mol% or more (50 to 100 mol%), preferably 80 mol% or more (80 to 100 mol%) of the entire R ² ₂ SiO unit present in the component (A) is represented by the formula (1). It is desirable to exist in the structure.

Here, the R ² ₂ SiO unit forms a chain polymer, and by introducing the R ¹ SiO _1.5 unit into this, the chain polymer can be branched or three-dimensional networked. R ⁴ (vinyl group or allyl group) in R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit is R ³ _c H _d SiO _{(4-cd) / 2} unit of component (B) described later A cured product is formed by a hydrosilylation addition reaction with a hydrogen atom (ie, SiH group) bonded to a silicon atom.

The proportion of each unit constituting the component (A) is preferably from the viewpoint of the properties (particularly physical strength) of the obtained cured product,
R ¹ SiO _1.5 units, from 90 to 24 mol%, more preferably, from 70 to 28 mol%,
R ² ₂ SiO unit is 75-9 mol%, more preferably 70-20 mol%
R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit is 50 to 1 mol%, more preferably 10 to 2 mol%.
(However, the total of these three units is 100 mol%)
It is.

In this specification, the organopolysiloxane has “resin structure” or “resin-like” means that the ratio of trifunctional siloxane units R ¹ SiO _1.5 units to all siloxane units constituting the organopolysiloxane is It means 20 mol% or more and a three-dimensional network siloxane structure is formed.

  Moreover, the polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC) of this (A) component is usually in the range of 3,000 to 1,000,000, particularly 10,000 to 100,000. Since the component (A) is solid or semi-solid at normal temperature, it is preferable from the viewpoint of workability and curability.

  The organopolysiloxane having a resin structure as the component (A) is prepared by converting a compound as a raw material of each unit into the above-mentioned ratio in the product from which each unit is obtained by a method well known to those skilled in the art. It can synthesize | combine by combining so that it may become, for example, performing cohydrolysis condensation in presence of an acid.

Here, as raw materials for the R ¹ SiO _1.5 unit, MeSiCl ₃ , EtSiCl ₃ , PhSiCl ₃ (Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, the same shall apply hereinafter), propyltrichlorosilane, cyclohexyltri Examples include chlorosilane and alkoxysilane such as methoxysilane corresponding to each chlorosilane.

As a raw material of the R ² ₂ SiO unit,
ClMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ Cl,
HOMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ OH,
HOMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ OH,
HOMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ OH,
MeOMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ OMe,
MeOMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ OMe,
MeOMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ OMe
(However, m = integer of 5-150, n = integer of 5-300)
Etc. can be illustrated.

R ³ _a R ⁴ _b SiO _{(4-ab) / 2} units are composed of R ³ R ⁴ SiO units, R ³ ₂ R ⁴ SiO _0.5 units, R ⁴ ₂ SiO units, and R ³ R ⁴ ₂ SiO _0.5 units. It shows that it is an arbitrary combination of one or two or more kinds of siloxane units selected, and the raw materials thereof are Me ₂ ViSiCl, MeViSiCl ₂ , Ph ₂ ViSiCl (Vi represents a vinyl group, the same applies hereinafter), PhViSiCl. ₂ and alkoxysilanes such as methoxysilane corresponding to the respective chlorosilanes.

In the component (A), R ¹ SiO _1.5 units, R ² ₂ SiO units and / or R ³ _a R ⁴ _b SiO _{(4-ab) / 2} units are by-produced during the cohydrolysis and condensation reaction. The silanol group-containing siloxane unit is usually contained in an amount of about 10 mol% or less (0 to 10 mol%), preferably about 5 mol% or less (0 to 5 mol%) based on all siloxane units in the component (A). It may be a thing. Silanol group-containing siloxane units corresponding to the above siloxane units include R ¹ (HO) SiO units, R ¹ (HO) ₂ SiO _0.5 units, R ² ₂ (HO) SiO _0.5 units, R ³ _a R ⁴ _b ( HO) SiO _{(3-ab) / 2} units, R ³ _a R ⁴ _b (HO) ₂ SiO _{(2-ab) / 2} units (where a is 0 or 1, b is 1 or 2, a + b is 1 or 2).
-(B) Resin-structured organohydrogenpolysiloxane-
An organohydrogenpolysiloxane having a resin structure (that is, a three-dimensional network structure), which is an important component of the composition of the present invention, includes R ¹ SiO _1.5 units, R ² ₂ SiO units, and R ³ _c H _d SiO _{(4 -cd) / 2} units (where R ¹ , R ² and R ³ are as described above, c is 0, 1 or 2, d is 1 or 2, and c + d is 2 or 3) The number of repeating R ² ₂ SiO units is 5 to 300. The number of repeating R ² ₂ SiO units is preferably 10 to 300, more preferably 15 to 200, still more preferably 20 to 100. It is a piece.
In the above, the number of repetitions of R ² ₂ SiO units is 5 to 300 amino means that the structure R ² ₂ SiO units are repeated 5 to 300 pieces in succession is present. That is, as in the case of the component (A), the formula (1):

（１）
で表される直鎖状ジオルガノポリシロキサン連鎖構造が存在していることを意味する。

(1)
It means that a linear diorganopolysiloxane chain structure represented by

The R ² ₂ SiO unit may exist in the component (B) without constituting the structure represented by the formula (1) (for example, each alone or in a chain structure of 4 or less). However, 50 mol% or more (50 to 100 mol%), preferably 80 mol% or more (80 to 100 mol%) of the entire R ² ₂ SiO unit present in the component (B) is represented by the formula (1). It is desirable to exist in the structure.

In this case, the functions of the R ¹ SiO _1.5 unit, the R ² ₂ SiO unit, and the R ³ _c H _d SiO _{(4-cd) / 2} unit are as described for the component (A).

The proportion of each unit constituting the component (B) is preferably from the viewpoint of the properties (particularly physical strength) of the obtained cured product,
R ¹ SiO _1.5 units, from 90 to 24 mol%, more preferably, from 70 to 28 mol%,
R ² ₂ SiO unit is 75-9 mol%, more preferably 70-20 mol%
R ³ _c H _d SiO _{(4-cd) / 2} unit is 50 to 1 mol%, more preferably 10 to 2 mol%.
(However, the total of these three units is 100 mol%)
It is.

  Moreover, the polystyrene conversion weight average molecular weight by GPC of this (B) component is usually in the range of 3,000 to 1,000,000, particularly 10,000 to 100,000. From the point of view, it is preferable.

  Such a resin-structured organohydrogenpolysiloxane is prepared by a method well known to those skilled in the art so that the compound as a raw material of each unit is in the above-mentioned ratio in the product from which each unit is obtained. They can be synthesized by combination and cohydrolysis.

Here, examples of the raw material of the R ¹ SiO _1.5 unit include MeSiCl ₃ , EtSiCl ₃ , PhSiCl ₃ , propyltrichlorosilane, cyclohexyltrichlorosilane, and alkoxysilanes such as methoxysilane corresponding to each chlorosilane.

As a raw material of the R ² ₂ SiO unit,
ClMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ Cl,
HOMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ OH,
HOMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ OH,
HOMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ OH,
MeOMe ₂ SiO (Me ₂ SiO) _n SiMe ₂ OMe,
MeOMe ₂ SiO (Me ₂ SiO) _m (PhMeSiO) _n SiMe ₂ OMe,
MeOMe ₂ SiO (Me ₂ SiO) _m (Ph ₂ SiO) _n SiMe ₂ OMe
(However, m = integer of 5-150, n = integer of 5-300)
Etc. can be illustrated.

The R ³ _c H _d SiO _{(4-cd) / 2} unit is selected from R ³ R ⁵ SiO unit, R ³ ₂ R ⁵ SiO _0.5 unit, R ⁵ ₂ SiO unit, and R ³ R ⁵ ₂ SiO _0.5 unit. The raw material is Me ₂ HSiCl, MeHSiCl ₂ , Ph ₂ HSiCl, PhHSiCl ₂ , methoxysilane corresponding to each chlorosilane, etc. An alkoxysilane etc. can be illustrated. Silanol group-containing siloxane units corresponding to the above siloxane units include R ¹ (HO) SiO units, R ¹ (HO) ₂ SiO _0.5 units, R ² ₂ (HO) SiO _0.5 units, R ³ _c H _d (HO ) SiO _{(3-cd) / 2} units, R ³ _c H _d (HO) ₂ SiO _{(2-cd) / 2} units (where c is 0 or 1, d is 1 or 2, c + d is 1 or 2) .).

  The blending amount of the organohydrogenpolysiloxane of component (B) is such that the number of hydrogen atoms (SiH groups) bonded to silicon atoms in component (B) relative to the total amount of vinyl groups and allyl groups in component (A) is mol. The amount is preferably 0.1 to 4.0, more preferably 0.5 to 3.0, and still more preferably 0.8 to 2.0. If it is less than 0.1, the curing reaction does not proceed and it is difficult to obtain a silicone cured product. If it exceeds 4.0, a large amount of unreacted SiH groups remain in the cured product. Causes changes over time.

In the component (B), by-products in the R ¹ SiO _1.5 unit, R ² ₂ SiO unit and / or R ³ _c H _d SiO _{(4-cd) / 2} unit are produced during the co-hydrolysis and condensation reaction. The silanol group-containing siloxane unit is usually present in an amount of 10 mol% or less (0 to 10 mol%), preferably 5 mol% or less (0 to 5 mol%) based on the total siloxane units in component (B). May be.
-(C) Platinum group metal catalyst-
This catalyst component is blended in order to cause an addition curing reaction of the composition of the present invention, and there are platinum-based, palladium-based, and rhodium-based ones. From the viewpoint of cost, platinum-based materials such as platinum, platinum black, chloroplatinic acid, for example, H ₂ PtCl ₆ · mH ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ · mH ₂ O, K ₂ PtCl ₄ , K ₂ Platinum compounds such as PtCl ₄ · mH ₂ O, PtO ₂ · mH ₂ O (m is a positive integer); and complexes of these with hydrocarbons such as olefins, alcohols or vinyl group-containing organopolysiloxanes Can do. These can be used singly or in combination of two or more. The compounding amount of these catalyst components may be an effective amount, that is, a so-called catalyst amount, and specifically, usually in terms of the mass of the platinum group metal with respect to the total amount of the component (A) and the component (B). It is used in the range of 0.1 to 500 ppm, particularly preferably 0.5 to 100 ppm.

-(D) phosphor-
The phosphor of component (D) may be any phosphor as long as it is a known phosphor, and the blending amount is usually 0.1 to 100 with respect to 100 parts by mass of all components (A) to (C). The range is in mass parts. The phosphor of component (D), for example, as a particle size range in particle size distribution measurement by a laser beam diffraction method such as a Cirrus laser measuring device, usually has a particle size of 10 nm or more, preferably 10 nm to 10 μm. More preferably, a film of about 10 nm to 1 μm is used.
The fluorescent substance may be any substance that absorbs light from a semiconductor light emitting diode having a nitride semiconductor as a light emitting layer and converts the light to light of a different wavelength. For example, nitride phosphors / oxynitride phosphors mainly activated by lanthanoid elements such as Eu and Ce, lanthanoid phosphors such as Eu, and alkalis mainly activated by transition metal elements such as Mn Earth halogen apatite phosphor, alkaline earth metal borate halogen phosphor, alkaline earth metal aluminate phosphor, alkaline earth silicate phosphor, alkaline earth sulfide phosphor, alkaline earth thiogallate phosphor , Alkaline earth silicon nitride phosphors, germanate phosphors, or lanthanoid elements such as rare earth aluminate phosphors, rare earth silicate phosphors or Eu that are mainly activated by lanthanoid elements such as Ce This is at least one selected from organic and organic complex phosphors activated mainly, Ca—Al—Si—O—N-based oxynitride glass phosphors, etc. It is preferred. As specific examples, the following phosphors can be used, but are not limited thereto.

A nitride-based phosphor mainly activated by a lanthanoid element such as Eu or Ce is M ₂ Si ₅ N ₈ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn) .)and so on. In addition to M ₂ Si ₅ N ₈ : Eu, MSi ₇ N ₁₀ : Eu, M _1.8 Si ₅ O _0.2 N ₈ : Eu, M _0.9 Si ₇ O _0.1 N ₁₀ : Eu (M Is at least one selected from Sr, Ca, Ba, Mg, and Zn.

An oxynitride phosphor mainly activated by a lanthanoid element such as Eu or Ce is MSi ₂ O ₂ N ₂ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, and Zn). There is.)

Alkaline earth halogen apatite phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include M ₅ (PO ₄ ) ₃ X: R (M is Sr, Ca, Ba, X is at least one selected from F, Cl, Br, and I. R is at least one of Eu, Mn, Eu and Mn. .)and so on.

In the alkaline earth metal borate phosphor, M ₂ B ₅ O ₉ X: R (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is F, Cl, And at least one selected from Br and I. R is Eu, Mn, or any one of Eu and Mn.).

Alkaline earth metal aluminate phosphors include SrAl ₂ O ₄ : R, Sr ₄ Al ₁₄ O ₂₅ : R, CaAl ₂ O ₄ : R, BaMg ₂ Al ₁₆ O ₂₇ : R, BaMg ₂ Al ₁₆ O ₁₂ : R, BaMgAl ₁₀ O ₁₇ : R (R is one or more of Eu, Mn, Eu and Mn).

Examples of the alkaline earth sulfide phosphor include La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, and Gd ₂ O ₂ S: Eu.

Examples of rare earth aluminate phosphors mainly activated with lanthanoid elements such as Ce include Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y _{3 (Al 0.8 Ga 0.2) 5 O} 12: Ce, and the like (Y, Gd) 3 (Al , Ga) YAG -based phosphor represented by the composition formula of _{5 O 12.} Further, there are Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which a part or all of Y is substituted with Tb, Lu or the like.

Other phosphors include ZnS: Eu, Zn ₂ GeO ₄ : Mn, MGa ₂ S ₄ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is F) , Cl, Br, or I.).

  The phosphor described above contains at least one selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti instead of Eu or in addition to Eu as desired. You can also.

The Ca—Al—Si—O—N-based oxynitride glass phosphor is expressed in terms of mol%, CaCO ₃ is converted to CaO, 20 to 50 mol%, Al ₂ O ₃ is 0 to 30 mol%, SiO 25 to 60 mol%, AlN 5 to 50 mol%, rare earth oxide or transition metal oxide 0.1 to 20 mol%, and oxynitride glass having a total of 5 components of 100 mol% as a base material This is a phosphor. In addition, in the phosphor using oxynitride glass as a base material, the nitrogen content is preferably 15 wt% or less, and other rare earth element ions serving as a sensitizer in addition to rare earth oxide ions are used as rare earth oxides. It is preferable to contain as a co-activator in content in the range of 0.1-10 mol% in fluorescent glass.

  Moreover, it is fluorescent substance other than the said fluorescent substance, Comprising: The fluorescent substance which has the same performance and effect can also be used.

-Other ingredients-
Other optional components as described below can be added to the curable silicone resin composition of the present invention as needed as long as the object and effect of the present invention are not impaired.

・ Release agent This release agent component is optionally blended as needed to remove the molded product from the mold without damage after pressure-molding and curing the silicone resin composition of the present invention in the mold. Is a possible component.
The properties required for the release agent must be completely compatible with the silicone resin composition and give a colorless and transparent cured product. In addition, when used as a lens for LEDs of blue or white, there should be no deterioration due to light having a short wavelength, discoloration under high temperature, etc. as well as transparency.
Any release agent can be used as long as it satisfies these requirements. Among them, fatty acid series (manufactured by Riken Vitamin, trade names: Riquemar AZ-01, Riquemar B-100, Riquemar HC-100, Riquemar HC-200, Riquemar S-95, Riquemar S-200, Riquemar TG-12, Rikestar EW-100, Rikestar EW-200, Rikestar EW-250, Rikestar EW-400, Rikestar EW-440A, Rikestar HT-10) , Polyethylene (Clariant, trade name: LICOWAX PED 136, LICOWAX PED 153, LICOWAX PED 371FP; Hoechst, trade name: HOE WAX PE 130 PDR, HOE WAX PED 191 PDR, HOE WAX PE 191 PDR, HOE WAX PE 191 Flakes, HOE WAX PE 520 Powder), carnauba system (product name: YTS-040625-03, carnauba candelilla, refined granucarnaba) or montanic acid ester system (made by Clariant, product name: LICOLUBU WE40, etc.) It is exemplified. Among these, the fatty acid-based release agent is excellent in compatibility with the silicone resin, transparency after curing, and discoloration resistance after leaving at high temperature.

  A mold release agent is normally 5 mass% or less (0-5 mass%) with respect to the total amount of the said (A) and (B) component, Preferably it is mix | blending in the quantity of 0.05-5 mass%. A lens molded by injection molding or the like can be easily taken out from the mold. If the blending amount is too small, it is difficult to improve the releasability from the mold, and when it is continuously molded, the releasability may deteriorate if it exceeds 50 shots. descend. On the other hand, if the amount exceeds 5% by mass, the amount of the release agent oozes out on the surface of the lens to be obtained, and the characteristics as a lens may be impaired. You may add a mold release agent to what mixed the main ingredient ((A) component) and hardening | curing agent ((B) component), or each, or only to one of them.

  The silicone resin composition of the present invention is prepared by uniformly mixing the above-described components, but is usually stored separately in two liquids so that curing does not proceed. Curing is performed. Of course, a small amount of a curing inhibitor such as acetylene alcohol can be added and used as one liquid.

  In addition, the composition of the present invention includes inorganic fillers that match conventionally known antioxidants, ultrafine silica such as Aerosil, and silicone resin with a refractive index cured, as long as the transparency is not impaired. It can mix | blend suitably in order to adjust the improvement of an intensity | strength and an expansion coefficient.

[Silicone lens]
When molding a lens by compression molding, transfer molding, injection molding or the like using the composition of the present invention, it is possible to increase productivity in handling by storing and using the powder in a two-component type. Mixing is performed by using a mixing device such as a mixer or a screw mixer before use, and the mixture is directly injected into a molding device and molded. Although the molding conditions are not particularly limited, the molding conditions are usually 50 to 200 ° C., particularly 30 to 30 seconds at a temperature of 70 to 180 ° C., although depending on the curability of the silicone resin composition. Can be cured in minutes, especially in 1-10 minutes. Further, post-cure (secondary curing) can be performed at 50 to 200 ° C., particularly 70 to 180 ° C. for 0.1 to 10 hours, particularly about 1 to 4 hours.

  This composition is solid or semi-solid at room temperature and can be easily handled, and can be applied to the conventional molding method described above.

  The lens molding silicone resin composition of the present invention has a colorless cured product obtained by heat-curing a composition containing the components (A) to (C) before blending the phosphor of component (D). It is transparent, and the light transmittance in the visible light region from 400 nm is preferably 90% or more (90-100%), more preferably 92% or more.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the viscosity is a value of 25 ° C. The weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC). Ph represents a phenyl group, Me represents a methyl group, and Vi represents a vinyl group.

[Synthesis Example 1]
-Vinyl group-containing organopolysiloxane resin (A1)-
Organosilane represented by PhSiCl ₃ : 27 mol, ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 1 mol, MeViSiCl ₂ : 3 mol was dissolved in toluene solvent, dropped into water, co-hydrolyzed, further washed with water, alkali After neutralization and dehydration by washing, the solvent was stripped to synthesize a vinyl group-containing resin (A1). This resin had a weight average molecular weight of 62,000 and a melting point of 60 ° C.

[Synthesis Example 2]
-Hydrosilyl group-containing organopolysiloxane resin (B1)-
Organosilane represented by PhSiCl ₃ : 27 mol, ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 1 mol, MeHSiCl ₂ : 3 mol were dissolved in toluene solvent, dropped into water, co-hydrolyzed, further washed with water, alkali After neutralization and dehydration by washing, the solvent was stripped to synthesize a hydrosilyl group-containing resin (B1). This resin had a weight average molecular weight of 58,000 and a melting point of 58 ° C.

[Synthesis Example 3]
-Vinyl group-containing organopolysiloxane resin (A2)-
Organosilane represented by PhSiCl ₃ : 27 mol, ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 1 mol, Me ₂ ViSiCl: 3 mol dissolved in toluene solvent, dropped into water, cohydrolyzed, further washed with water, After neutralization and dehydration by alkali washing, the solvent was stripped to synthesize a vinyl group-containing resin (A2). The resin had a weight average molecular weight of 63,000 and a melting point of 63 ° C.

[Synthesis Example 4]
-Hydrosilyl group-containing organopolysiloxane resin (B2)-
Organosilane represented by PhSiCl ₃ : 27 mol, ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 1 mol, Me ₂ HSiCl: 3 mol dissolved in toluene solvent, dropped into water, cohydrolyzed, further washed with water, After neutralization and dehydration by alkali washing, the solvent was stripped to synthesize a hydrosilyl group-containing resin (B2). This resin had a weight average molecular weight of 57,000 and a melting point of 56 ° C.

[Example 1]
Vinyl group-containing resin (A1) of Synthesis Example 1: 189 g, Hydrosilyl group-containing resin (B1) of Synthesis Example 2: 189 g, acetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor: 0.2 g, octyl alcohol of chloroplatinic acid Denaturing solution: 90 parts by mass of the composition to which 0.1 g was added, and 10 parts by mass of a phosphor (YAG) having a particle size of 5 μm (average particle size) was added and stirred well with a planetary mixer heated to 60 ° C. Then, a silicone resin composition was prepared. This composition was a plastic solid at 25 ° C.

This composition was subjected to the following evaluation test.
1) Mechanical properties Heated to 60 ° C. with an injection molding machine, injection molded, and heat molded at 150 ° C. for 5 minutes to obtain a cured hollow lens 1 shown in FIG. 1 (front view). When viewed from above (that is, in a plan view (not shown)), this lens has a circular shape with a diameter of 3.0 mm, a height of 1.6 mm, and has a hollow shape with the inner side opened to one side as indicated by a broken line 2. . The inner hollow portion has a height of 1.5 mm, and the wall has a thickness of 0.1 mm. Further, a material obtained by secondarily curing at 150 ° C. for 4 hours, in accordance with JIS K 6251 and JIS K 6253, tensile strength (0.2 mm thickness), hardness (measured using a type D spring tester) And the elongation (0.2 mm thickness) was measured.
2) Impact resistance When viewed from above the shape shown in FIG. 2 (front view), a dome-shaped hollow lens 3 that is circular is molded, and a 3 g weight 4 is attached to this by a double-sided adhesive tape 5 to a height of 1 m. Dropped into PVC tiles. The presence or absence of cracks was examined.
2) Surface tackiness The tackiness of the surface of the cured product secondarily cured as described above was confirmed by touch. Further, the cured product was placed in a commercially available silver powder (average particle size: 5 μm), and after taking out, it was tested whether or not silver powder adhering to the surface like dust could be removed by blowing air.
3) Dispersion stability of phosphor The resin composition just prepared above is placed in a recess formed on an alumina substrate with a diameter of 6 mm, a center depth of 2 mm, and a bottom having a concave curved surface, and heated under the same conditions as above. When cured, a lens molding 6 that is circular when viewed from above the shape shown in FIG. 3 (front view) was molded. A part is cut out from each of the upper part 7 and the lower part 8 of this lens molding 6, each is heated and ashed at 800 degreeC, The content (mass%) of the fluorescent substance in the obtained ash is measured, and upper part is measured. 7 and the content in the lower part 8 were compared. Further, after the composition was stored in a freezer at −20 ° C. for 3 months, the composition was molded into a lens molding in the same manner as described above, and the phosphor contents in the upper part and the lower part were compared in the same manner. Thus, the dispersion stability of the phosphor was measured.
4) Thermal shock resistance The cured sample was subjected to 100 cycles of -50 ° C to 150 ° C cooling cycle (one cycle 30 minutes) to examine whether cracks occurred.
These measurement results are shown in Table 1.

[Example 2]
Vinyl group-containing resin (A2) of synthesis example 3: 189 g, hydrosilyl group-containing resin (B2) of synthesis example 4: 189 g, acetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor: 0.2 g, octyl alcohol of chloroplatinic acid Denaturing solution: After adding 30 parts by weight of a phosphor (YAG) having a particle size of 5 μm (average particle size) to 70 parts by weight of the composition to which 0.1 g was added, the planetary was heated to 60 ° C. The mixture was thoroughly stirred with a Lee mixer to prepare a silicone resin composition. This composition was a plastic solid at 25 ° C. The composition was evaluated as in Example 1. The results are shown in Table 1.

[Example 3]
Example 2 was the same as Example 2 except that the amount of the phosphor added was changed to 10% by mass (that is, 10 parts by mass of the phosphor with respect to 90 parts by mass of the composition before the phosphor was blended). Thus, a silicone resin composition was prepared. Furthermore, to 100 parts by mass of this composition, 1.0 part by mass of a fatty acid release agent (RIKEN VITARIC LIQUESTER EW-440A, pentaerythritol tetrastearate) is added, and the mixture is thoroughly stirred and mixed, and a silicone resin composition containing a release agent is added. Was prepared. This composition was a plastic solid at 25 ° C. The composition was evaluated as in Example 1. The results are shown in Table 1.

[Synthesis Example 5]
A mixture of 698 parts by mass of phenyltrichlorosilane, 169 parts by mass of methylvinyldichlorosilane, 194 parts by mass of dimethyldichlorosilane, and 530 parts by mass of toluene was dropped into 2500 parts by mass of water over 60 minutes with vigorous stirring. The mixture was further stirred for 60 minutes, and then washed with water until neutrality. After washing with water, a toluene solution having a siloxane concentration of 25% by mass was added, 0.42 parts by mass of potassium hydroxide was added, and polymerization was carried out under heating and reflux for 5 hours. Next, 13.8 parts by mass of trimethylchlorosilane was added and the mixture was stirred at room temperature for 60 minutes to neutralize the alkali. Thereafter, filtration was performed, and toluene was distilled off under reduced pressure by heating to obtain a transparent vinyl group-containing organopolysiloxane.

[Comparative Example 1]
Formula (i) below

で示されるポリシロキサン（ＶＦ）５０質量部に、ＳｉＯ₂単位５０モル％、（ＣＨ₃）₃ＳｉＯ_0.5単位４２．５モル％及びＶｉ₃ＳｉＯ_0.5単位７．５モル％からなるレジン構造のビニルメチルシロキサン（ＶＭＱ）５０質量部、ＳｉＨ基量が前記ＶＦ及びＶＭＱ成分中のビニル基の合計量当り１．５倍モルとなる量の下記式（ｉｉ）

Resin-structure vinyl comprising 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi ₃ SiO _0.5 units in 50 parts by mass of polysiloxane (VF) 50 parts by mass of methylsiloxane (VMQ), and the amount of SiH group is 1.5 times mol per the total amount of vinyl groups in the VF and VMQ components.

A phosphor (YAG) having a particle diameter of 5 μm (average particle diameter) is further added to 90 parts by mass of a composition obtained by adding 0.05 part by mass of an organohydrogenpolysiloxane and an octyl alcohol modified solution of chloroplatinic acid represented by 10 parts by mass was added and stirred well with a planetary mixer heated to 60 ° C. to prepare a silicone resin composition. This composition was a plastic solid at 25 ° C. The composition was evaluated as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
With respect to 70 parts by mass of a composition in which 30 parts by mass of an organohydrogensiloxane represented by the following formula and 0.05 part by mass of an octyl alcohol solution of chloroplatinic acid represented by the following formula are mixed with 100 parts by mass of the vinyl group-containing silicone of Synthesis Example 5. Further, 30 parts by mass of a phosphor (YAG) having a particle size of 5 μm (average particle size) was added and stirred well with a planetary mixer heated to 60 ° C. to prepare a silicone resin composition. This composition was a plastic solid at 25 ° C. The composition was evaluated as in Example 1. The results are shown in Table 1.

1. 1. Hollow lens cured product 2. Broken line indicating hollow 3. Dome-shaped hollow lens Weight 5 Double-sided adhesive tape

Claims (9)

(A) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit (provided that R ¹ , R ² and R ³ are each independently a methyl group, An ethyl group, a propyl group, a cyclohexyl group or a phenyl group, R ⁴ represents a vinyl group or an allyl group, a is 0, 1 or 2, b is 1 or 2, and a + b is 2 or 3. An organopolysiloxane having a resin structure in which the number of repeating R ² ₂ SiO units is 5 to 300;
(B) R ¹ SiO _1.5 unit, R ² ₂ SiO unit, and R ³ _c H _d SiO _{(4-cd) / 2} unit (provided that R ¹ , R ² and R ³ are as described above, (c is 0, 1 or 2, d is 1 or 2, and c + d is 2 or 3), and the resin structure organohydrogenpolysiloxane has a repeating number of 5 to 300 R ² ₂ SiO units: (A) The quantity by which the hydrogen atom bonded to the silicon atom in the component (B) relative to the vinyl group or allyl group in the component is 0.1 to 4.0 in molar ratio,
(C) A platinum group metal catalyst: an effective amount, and (D) a silicone lens comprising a silicone resin composition, which is a solid that is plastic at room temperature, and is molded and cured under heating. Production method.   The said (A) component is a manufacturing method of Claim 1 which has the polystyrene conversion weight average molecular weight by the gel permeation chromatography in the range of 3,000-1,000,000.   The said (B) component is a manufacturing method of Claim 1 or 2 which has the polystyrene conversion weight average molecular weight by gel permeation chromatography in the range of 3,000-1,000,000.   The manufacturing method according to any one of claims 1 to 3, wherein the silicone resin composition is heat-cured under pressure in a mold.   The manufacturing method as described in any one of Claims 1-4 in which the (A) component and / or (B) component of the said silicone resin composition contain a silanol group.   The silicone resin composition according to any one of claims 1 to 5, wherein a cured product of the composition excluding the component (D) has a light transmittance of 90% or more in a visible light region from 400 nm. The manufacturing method as described.   The production method according to any one of claims 1 to 6, wherein the phosphor of component (D) is an inorganic phosphor having a particle size of 10 nm or more.   The manufacturing method according to any one of claims 1 to 7, wherein the silicone resin composition is molded and cured at 50 to 200 ° C.   The silicone resin composition is molded and cured at 50 to 200 ° C for 30 seconds to 30 minutes, and then post-cured at 50 to 200 ° C for 0.1 to 10 hours. Production method.

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