JP6553139B2 - Method for producing wavelength conversion material-containing condensed silicone composition and method for producing wavelength conversion sheet - Google Patents

Description

  The present invention relates to a method for producing a wavelength conversion material-containing condensed silicone composition and a method for producing a wavelength conversion sheet.

In recent years, development of illumination using a semiconductor laser light source has been advanced. In particular, an illumination device has been developed that emits white light by irradiating a phosphor sheet having a wavelength conversion function with a semiconductor laser light source and converting the wavelength of excitation light. By adopting such a method, the light emitting unit can be miniaturized by separating the light emitting unit and the excitation unit.
For this reason, it attracts attention as next-generation lighting. Since a high energy laser beam is emitted to a phosphor sheet for semiconductor laser illumination, high light resistance and high heat resistance are required.

Currently used LEDs are encapsulated by applying a phosphor-containing composition containing a phosphor and a specific matrix resin on a light-emitting element and curing it. It has been pointed out that when a sealing agent is produced using a wavelength conversion material-containing composition, the light output becomes nonuniform due to sedimentation of the wavelength conversion material such as a phosphor and the efficiency is lowered. .
In Patent Document 1, as a method of uniformly dispersing a phosphor, a method of adding a phosphor after mixing a matrix resin and a curing catalyst and a method of simultaneously adding a phosphor and a curing catalyst to the matrix resin and mixing them Is described.

JP 2009-96947 A

In the method described in Patent Document 1, an anti-settling agent such as silica particles is contained in order to prevent settling of a wavelength conversion material such as a phosphor. When silica particles are contained as an anti-settling agent, although the anti-settling effect of the phosphor can be obtained, there is a problem that the light transmittance of the matrix resin is reduced and the light output is reduced.
The present invention has been made in view of the above circumstances, and a method for producing a wavelength conversion material-containing condensation silicone composition capable of preventing precipitation of a wavelength conversion material while improving light output, and the wavelength conversion material-containing condensation It is an object of the present invention to provide a method for producing a wavelength conversion sheet using a wavelength conversion material-containing condensed silicone composition produced by a method for producing a type silicone composition.

[1] The present invention is a method for producing a wavelength conversion material-containing condensation-type silicone composition containing a condensation-type silicone resin and a wavelength conversion material, wherein the condensation-type silicone resin containing substantially no silica particles and curing acceleration A method for producing a wavelength conversion material-containing condensed silicone composition, comprising: a first step of mixing an agent; and a second step of adding and mixing the wavelength conversion material after the first step. It is.
[2] The present invention includes the first step A after the first step according to [1], wherein the first step A is allowed to stand for 30 minutes to 95 hours before the second step. It is a manufacturing method of a wavelength conversion material containing condensation type silicone composition.
[3] The present invention includes a step of curing a wavelength conversion material-containing condensed silicone composition produced by the method for producing a wavelength conversion material-containing condensed silicone composition according to [1] or [2] on a substrate. It is a manufacturing method of the wavelength conversion sheet | seat which has these.

  According to the present invention, it is produced by a method for producing a wavelength conversion material-containing condensed silicone composition capable of preventing sedimentation of the wavelength conversion material while improving light output, and a method for producing the wavelength conversion material-containing condensed silicone composition. Further, a method for producing a wavelength conversion sheet using the wavelength conversion material-containing condensed silicone composition can be provided.

The schematic diagram which shows the light-emitting device of this embodiment. The schematic diagram which shows the light-emitting device of this embodiment.

<Method for Producing Wavelength Conversion Material-Containing Condensed Silicone Composition>
First Embodiment
The first embodiment of the method for producing a wavelength conversion material-containing condensation-type silicone composition of the present invention comprises a first step of mixing a condensation-type silicone resin substantially free of silica particles and a curing accelerator; And a second step of adding and mixing a wavelength conversion material after the step.

When silica particles are added as an anti-settling agent as in the method described in Patent Document 1 when producing a wavelength-converting material-containing condensation-type silicone composition, the light transmittance of the silicone resin is reduced and the light output is reduced. It contributes. However, when the anti-settling agent is not added, there is a possibility that the wavelength conversion material may cause sedimentation or dispersion unevenness.
In the present invention, the condensation type silicone resin substantially free of silica particles and the curing accelerator are mixed in the first step, and the wavelength conversion material is added in the subsequent second step. The production method of the present invention uses a condensation type silicone resin that does not substantially contain silica particles, so it can impart high light transmittance to the silicone resin and can improve light output. In addition, since the condensation-type silicone resin and the curing accelerator are first mixed in the first step, and the wavelength conversion material is added in the second step after the increase in viscosity is started, the wavelength conversion material is difficult to precipitate and has good dispersibility Can be held.
Each step will be described below.

[First step]
It does not specifically limit as a method of mixing the condensation type silicone resin and curing accelerator which do not contain a silica particle substantially. For example, the condensation type silicone resin and the curing accelerator can be mixed by dissolving or dispersing in an organic solvent.
For example, conventional methods such as homomixer, high-speed disper, homogenizer, 3-roll, 2-roll, kneader, ball mill, self-revolution type stirrer, etc. can be used. In the present invention, it is preferable to use one having little heat generation and one having little mixing of metal abrasion particles derived from a mixer at the time of dispersion.
In the present step, only one type of the above method may be performed, or two or more types may be performed in combination.
In the first step, it is preferable to mix and disperse the condensation type silicone resin substantially free of silica particles and the curing accelerator by the above method.

After completion of the first step, the viscosity of the condensation-type silicone composition is preferably, for example, 500 mPa · s or more and 100000 mPa · s or less measured at a temperature of 25 ° C. More preferably, the viscosity is 1000 mPa · s or more and 50000 mPa · s or less.
When the viscosity of the condensation-type silicone composition is in the above range, the sedimentation of the wavelength conversion material added in the second step can be suppressed while ensuring the uniformity of the reaction of the condensation-type silicone composition.

[Second step]
After the first step, a wavelength conversion material is added and mixed. The method for mixing the wavelength conversion material is not particularly limited, and is not particularly limited as long as the wavelength conversion material can be dispersed uniformly without damaging the crystal structure of the wavelength conversion material such as a phosphor. Absent.
In the second step, it is preferable to add, mix and disperse a wavelength conversion material.

Second Embodiment
The second embodiment of the method for producing a wavelength conversion material-containing condensation-type silicone composition of the present invention comprises a first step of mixing a condensation-type silicone resin and a curing accelerator, and a first step of standing for 30 minutes to 95 hours. It is characterized by having a process and a second process of adding and mixing a wavelength conversion material in this order.
In the present embodiment, after the first step but before the second step, the interaction between the condensation type silicone resin and the phosphor to be added later acts by passing through the first step A of standing. It is possible to make it easy to do. It is also possible to increase the uniformity of the curing accelerator. Thereby, sedimentation of the wavelength conversion material added at a 2nd process can be suppressed.

  In the present embodiment, the description regarding the first step and the second step is the same as the description in the first embodiment.

[Step 1A]
This step is a step of allowing the dispersion of the condensation type silicone resin and the curing accelerator obtained in the first step to stand for 30 minutes to 95 hours. The standing time is preferably 1 hour to 90 hours, more preferably 2 hours to 50 hours, and further preferably 5 hours to 20 hours. It is preferable that it is 5 to 50 degreeC, and, as for the temperature at the time of leaving still, it is more preferable that it is 15 to 35 degreeC.
In the present embodiment, the structure in which the polymer chains are entangled can be formed by allowing to stand for a predetermined time in the 1A step, and the sedimentation of the wavelength conversion material added in the subsequent 2nd step can be prevented. . By being in the above temperature range, the anti-settling effect of entanglement is exhibited in an appropriate range. When it is longer than 95 hours, the wavelength conversion material-containing condensation type silicone composition may be gelled, or a lump may be generated in the wavelength conversion sheet due to the effect of the entanglement of molecular chains of the condensation type silicone resin.
Here, “dama” refers to particles having a size of 100 μm or more that are segregated from a wavelength conversion material that can be visually observed.

  One example of the wavelength conversion material-containing condensation-type silicone composition produced according to the present invention may be a liquid having a viscosity at 25 ° C. of 1000 mPa · s to 500,000 mPa · s.

  Hereinafter, each material used in the present invention will be described.

(Condensed silicone resin)
The condensation type silicone resin used in this embodiment will be described.
In this specification, the condensation type silicone resin is a resin that polycondenses a hydroxyl group bonded to a silicon atom and an alkoxy group or hydroxyl group bonded to another silicon atom with dealcoholization or dehydration. The addition type silicone resin is a resin which is polymerized by the addition reaction between a hydrosilyl group and a carbon-carbon double bond. There are also resins that polymerize by the simultaneous occurrence of addition reaction and polycondensation reaction, but here, they are treated as a type of addition type.

  It is preferable that the condensation type silicone resin used in the present embodiment includes at least a structural unit represented by the following formula (A3). Moreover, it is preferable to have 1 or more types of the structural units represented by Formula (A1), Formula (A1 ′), or Formula (A2). The condensation type silicone resin used in the present embodiment preferably has all of the structural units represented by the formula (A1), the formula (A1 ′), and the formula (A2).

［式（Ａ１）、式（Ａ１’）、式（Ａ２）または式（Ａ３）中、Ｒ^１は、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表す。Ｒ^２は、炭素数１〜４のアルコキシ基または水酸基を表す。複数あるＲ^１およびＲ^２は、それぞれ同一であっても異なっていてもよい。］

[In Formula (A1), Formula (A1 '), Formula (A2), or Formula (A3), R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. R ² represents an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. Plural R ¹ and R ² may be the same or different. ]

In the present specification, a structural unit containing a silicon atom bonded to three oxygen atoms is referred to as "T-body".
A structural unit containing a silicon atom in which all of the three oxygen atoms are bonded to another silicon atom is referred to as a “T3 body”.
A structural unit containing a silicon atom in which two of the three oxygen atoms are bonded to another silicon atom is referred to as a “T2 body”.
In addition, a structural unit including a silicon atom in which one of the three oxygen atoms is bonded to another silicon atom is referred to as a “T1 body”.
That is, "T body" means "T1 body", "T2 body" and "T3 body".

  In this specification, a structural unit including a silicon atom bonded to two oxygen atoms is referred to as a “D body”. A structural unit containing a silicon atom bonded to one oxygen atom is referred to as an “M body”.

The structural unit represented by the formula (A3) includes three oxygen atoms bonded to other silicon atoms and a silicon atom bonded to R ¹ . Since R ¹ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, the structural unit represented by the formula (A3) is a T3 body.

The structural unit represented by the formula (A2) includes two oxygen atoms bonded to other silicon atoms, a silicon atom bonded to R ¹ and R ² . Since R ² is an alkoxy or hydroxyl group having 1 to 4 carbon atoms, the structural unit represented by formula (A2) is a T2-body.

The structural unit represented by the formula (A1) contains a silicon atom bonded to one oxygen atom bonded to another silicon atom, R ¹ and two R ² . R ¹ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, and thus the structural unit represented by formula (A1) Is a T1 body.

The structural unit represented by the formula (A1 ′) includes a silicon atom bonded to R ¹ and two R ^2, and the silicon atom is an oxygen bonded to a silicon atom in another structural unit. Bonded to an atom. Since R ¹ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² is an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms, the structure represented by formula (A1 ′) The unit is T1.

  The structural unit represented by the formula (A1) and the structural unit represented by the formula (A1 ′) constitute the end of the organopolysiloxane chain contained in the condensed silicone resin. Moreover, the structural unit represented by Formula (A3) comprises the branched chain structure of the organopolysiloxane chain | strand contained in condensation type silicone resin. That is, the structural unit represented by the formula (A3) forms a part of a network structure or a ring structure in the condensed silicone resin.

  In this specification, the silicon atom contained in the T3 body is referred to as “T3 silicon atom”. A silicon atom contained in the T2 body is referred to as “T2 silicon atom”. The silicon atom contained in the T1 body is referred to as “T1 silicon atom”.

  The total content of “T1 body”, “T2 body” and “T3 body” is preferably 50 mol% or more based on the total content of all structural units of the condensation type silicone resin. In other words, the total content of T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms is preferably 50 mol% or more based on the total content of all the silicon atoms. Furthermore, the total content of T1 silicon atom, T2 silicon atom, and T3 silicon atom is more preferably 60 mol% or more, and 70 mol% or more with respect to the total content of all silicon atoms. Is more preferably 80 mol% or more, and still more preferably 90 mol% or more.

  The content of “D-form” is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total content of all structural units of the condensation type silicone resin. Further, the content of “D form” is more preferably 10 mol% or less, still more preferably 5 mol% or less, based on the total content of all structural units of the condensation type silicone resin. It is particularly preferable that the amount is 4 mol% or less.

  The content of the “T3 body” is preferably 50 mol% or more with respect to the total content of the “T1 body”, the “T2 body”, and the “T3 body”. In other words, the content of T3 silicon atoms is preferably 50 mol% or more based on the total content of all structural units of the condensation-type silicone resin. Further, the content of the T3 silicon atom is more preferably 60 mol% or more, and more preferably 70 mol% or more with respect to the total content of the T1 silicon atom, the T2 silicon atom, and the T3 silicon atom. Further preferred.

In the present specification, the content of T3 silicon atom can be determined by dividing the area of the signal assigned as T3 silicon atom by the area of the sum of signals of all the silicon atoms determined in ²⁹ Si-NMR measurement. . The content of silicon atoms other than T3 silicon atoms can also be determined in the same manner.

When R ¹ is an alkyl group having 1 to 10 carbon atoms, the alkyl group may be linear, branched, or have a cyclic structure. Of these, the alkyl group represented by R ¹ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

In the alkyl group having 1 to 10 carbon atoms represented by R ¹ , one or more hydrogen atoms constituting the alkyl group may be substituted with another functional group. As a substituent of an alkyl group, C6-C10 aryl groups, such as a phenyl group and a naphthyl group, are mentioned, for example, and a phenyl group is preferable.

As a C1-C10 alkyl group represented by R ¹ , for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group And unsubstituted alkyl groups such as neopentyl group, hexyl group, octyl group, nonyl group and decyl group, and aralkyl groups such as phenylmethyl group, phenylethyl group and phenylpropyl group. Among these, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group is preferable, a methyl group, an ethyl group or an isopropyl group is more preferable, and a methyl group is more preferable.

In the aryl group having 6 to 10 carbon atoms represented by R ¹ , one or more hydrogen atoms constituting the aryl group may be substituted with another functional group. As a substituent of an aryl group, C1-C10 alkyl groups, such as a methyl group, an ethyl group, n-propyl group, n-butyl group, are mentioned, for example.

Examples of the aryl group having 6 to 10 carbon atoms represented by R ¹ include unsubstituted aryl groups such as phenyl and naphthyl; and alkylaryl groups such as methylphenyl, ethylphenyl and propylphenyl. It is done. Among these, a phenyl group is preferable.

In the structural unit represented by the above formula (A1), the structural unit represented by the above formula (A1 ′) and the structural unit represented by the above formula (A2), R ² is a methoxy group, an ethoxy group, isopropoxy A group or a hydroxyl group is preferred.

The C 1-4 alkoxy group represented by R ² may be a linear alkoxy group, a branched alkoxy group, or an alkoxy group having a cyclic structure. Good. Among these, a linear or branched alkoxy group is preferable, and a linear alkoxy group is more preferable.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ² include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group and a tert-butoxy group. A methoxy group, an ethoxy group or an isopropoxy group is preferred.

The condensation type silicone resin used in the present embodiment is a structural unit represented by the above formula (A1), a structural unit represented by the above formula (A1 ′), a structural unit represented by the above formula (A2) or the above formula In the structural unit represented by (A3), R ¹ is preferably a methyl group, and R ² is preferably an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group.

  The condensation type silicone resin used in the present embodiment is represented by the following formula (C1), formula (C1 ′), formula (C2), formula (C3), or formula (C4) as long as the effects of the invention are not impaired. May have a structural unit.

［式（Ｃ１）、式（Ｃ１’）、式（Ｃ２）、式（Ｃ３）または式（Ｃ４）中、Ｒ^７は、炭素数１〜４のアルコキシ基または水酸基を表す。複数あるＲ^７は、同一であっても異なっていてもよい。］

[In Formula (C1), Formula (C1 '), Formula (C2), Formula (C3), or Formula (C4), R ⁷ represents an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. Plural R ⁷ may be the same or different. ]

In the present specification, a structural unit containing a silicon atom bonded to four oxygen atoms is referred to as "Q body".
A structural unit containing a silicon atom in which one of the four oxygen atoms is bonded to another silicon atom is referred to as “Q1 body”. The structural unit represented by the formula (C1) and the structural unit represented by the formula (C1 ′) are Q1 form.
Further, a structural unit containing a silicon atom in which two of the four oxygen atoms are bonded to another silicon atom is referred to as “Q2 body”. The structural unit represented by the formula (C2) is Q2 isomer.
In addition, a structural unit including a silicon atom in which three oxygen atoms among the four oxygen atoms are bonded to other silicon atoms is referred to as “Q3 body”. The structural unit represented by the formula (C3) is Q3 body.
A structural unit containing a silicon atom in which all of the four oxygen atoms are bonded to another silicon atom is referred to as “Q4 body”. The structural unit represented by formula (C4) is "Q4 body".

  That is, Q body means Q1, Q2, Q3 and Q4 bodies.

<< Silicone resin A >>
The condensation type silicone resin contained in the condensation type silicone resin composition of the present embodiment is a mixture of a silicone resin as a main component (hereinafter referred to as “silicone resin A”) and an oligomer component described later. It is preferable.

  Silicone resin A includes a structural unit represented by the above formula (A3). In addition, silicone resin A is selected from the group consisting of a structural unit represented by the above formula (A1), a structural unit represented by the above formula (A1 ′) and a structural unit represented by the above formula (A2) It is preferable that a structural unit of more than seeds is further included.

In the silicone resin A, the total content of the T1 body, the T2 body, and the T3 body is usually 70 mol% or more with respect to the total content of all the structural units of the silicone resin A.
In the silicone resin A, the content of the T3 body is usually 60 mol% or more and 90 mol% or less with respect to the total content of all the structural units of the silicone resin A.
The polystyrene equivalent weight average molecular weight of the silicone resin A is usually 1,500 or more and 8,000 or less.

  In silicone resin A, the total content of T1 body, T2 body and T3 body is preferably 80 mol% or more, more preferably 90 mol% or more, based on the total content of all structural units of silicone resin A. Is more preferable, and 95 mol% or more is more preferable.

  In the silicone resin A, the content of the T3 body is preferably 65% to 90%, and more preferably 70% to 85%, based on the total content of all the structural units of the silicone resin A. preferable.

  The weight average molecular weight of the silicone resin A in terms of polystyrene is preferably 1500 or more and 7000 or less, and more preferably 2000 or more and 5000 or less. When the weight average molecular weight in terms of polystyrene of the silicone resin A is within this range, the mixing property with the phosphor described later is good.

  As silicone resin A, a commercially available silicone resin can be used.

  The silicone resin A preferably has a silanol group (Si—OH). In the silicone resin A, the silicon atom having a silanol group is preferably 1 to 30 mol%, more preferably 5 to 27 mol%, based on all silicon atoms contained in the silicone resin A. More preferably, it is ˜25 mol%. In the silicone resin A, if the content of the silicon atom having a silanol group is within the above range, a hydrogen bond is formed between the silicone resin A and the surface of the wavelength conversion material when mixed with the wavelength conversion material described later. Therefore, the mixing property with the wavelength conversion material is improved. Moreover, since the curing reaction of the wavelength conversion material-containing condensation type silicone resin composition of the present embodiment is likely to proceed, a wavelength conversion sheet with high heat resistance can be obtained.

  Further, in the silicone resin A, the silicon atom having an alkoxy group is preferably more than 0 mol% and not more than 20 mol%, more than 0 mol% and not more than 10 mol% with respect to all silicon atoms contained in the silicone resin A. More preferably, it is 1 mol% or more and 10 mol% or less. In the silicone resin A, if the content of silicon atoms having an alkoxy group is within the above range, the storage stability of the condensation type silicone resin composition is good, and the fluidity is within an appropriate range. The handling property of the condensation type silicone resin composition is improved.

  The silicone resin A can be synthesized using an organosilicon compound having a functional group capable of generating a siloxane bond as a starting material. Here, examples of the “functional group capable of generating a siloxane bond” include a halogen atom, a hydroxyl group, and an alkoxy group. Examples of the organosilicon compound corresponding to the structural unit represented by the above formula (A3) include organotrihalosilane and organotrialkoxysilane. Silicone resin A is obtained by reacting an organic silicon compound, which is a starting material, with a hydrolysis condensation method in the presence of an acid such as hydrochloric acid or a base such as sodium hydroxide at a ratio corresponding to the existing ratio of each structural unit. Can be synthesized by By appropriately selecting the organosilicon compound as the starting material, the abundance ratio of T3 silicon atoms contained in the silicone resin A can be adjusted.

  Content of the silicone resin A contained in the condensation type silicone resin composition used for this embodiment is 60 mass%-100 mass% with respect to the total content of all the silicone resins contained in the condensation type silicone resin composition. Is preferable, and 70 to 95% by mass is more preferable.

[Modifying silicone]
The condensation type silicone resin may contain the following modifying silicone in addition to the silicone resin A described above. By adding the modifying silicone, for example, flexibility and crack resistance can be imparted to the cured product of the silicone resin composition.
Examples of the modifying silicone include the following oligomer components (oligomer B, oligomer C).

<< Oligomer B (first oligomer) >>
Examples of the oligomer component include an oligomer containing a structural unit represented by the following formula (B1), formula (B1 ′), formula (B2), or formula (B3).

［式（Ｂ１）、式（Ｂ１’）、式（Ｂ２）または式（Ｂ３）中、Ｒ^３は、炭素数１〜１０のアルキル基または炭素数６〜１０のアリール基を表す。Ｒ^４は、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、炭素数１〜４のアルコキシ基または水酸基を表す。
複数あるＲ^３およびＲ^４は、それぞれ同一であっても異なっていてもよい。］

[In Formula (B1), Formula (B1 '), Formula (B2), or Formula (B3), R ³ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group.
Plural R ³ and R ⁴ may be the same or different. ]

  The weight average molecular weight in terms of polystyrene of the oligomer containing the structural unit represented by formula (B1), formula (B1 ′), formula (B2), or formula (B3) is preferably 1000 to 10000, and 2000 to 8000. It is more preferable that it is 3000-6000. If the weight average molecular weight of polystyrene conversion of an oligomer is in this range, the mixing property with the silicone resin A and the oligomer C mentioned later will become favorable.

  In the following description, an oligomer component containing a structural unit represented by formula (B1), formula (B1 ′), formula (B2) or formula (B3) and having a polystyrene-equivalent weight average molecular weight of 1,000 to 10,000 is used. , Referred to as “oligomer B”.

  Oligomer B is preferably (a) an oligomer containing T2 form or (b) an oligomer containing D form, more preferably an oligomer satisfying (a) and (b), that is, (c) an oligomer containing T2 form and D form. . When the condensation type silicone resin composition used in the present embodiment contains an oligomer satisfying (c), it is easy to produce a phosphor sheet free from wrinkles and cracks.

(A) Oligomer Containing T2 Form (a) The oligomer containing T2 form is a structural unit represented by the formula (B2) and is a structural unit in which R ⁴ is an alkoxy group having 1 to ⁴ carbon atoms or a hydroxyl group That is, the content of T2 isomer is preferably 30 to 60 mol%, more preferably 40 to 55 mol%.

  When the oligomer B is an oligomer containing (a) T2 form, if the content of T2 form is in the above-mentioned range, the condensation type silicone resin composition used in this embodiment will dissolve the silicone resin A and the oligomer B. Good curing reactivity is exhibited at the time of heat curing while securing the properties.

(B) Oligomer containing D isomer (b) The oligomer containing D isomer is a silicone resin containing a structural unit represented by formula (B1), formula (B1 ′), formula (B2) or formula (B3). Preferred is a silicone resin having an average composition formula represented by the following formula (I).
(R ⁵ ) _n Si (OR ⁶ ) _m O _{(4-nm) / 2} (I)
[In formula (I), ^{R 5} represents an alkyl group or an aryl group having 6 to 10 carbon atoms having 1 to 10 carbon atoms. R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydrogen atom. n represents a real number satisfying 1 <n <2. m represents a real number satisfying 0 <m <1. ]

  The oligomer B whose average composition formula is represented by the above formula (I) includes the above-mentioned “T-form” and “D-form”.

In formula (I), R ⁵ is preferably a methyl group, and R ⁶ is preferably a methyl group or a hydrogen atom. n is preferably a real number satisfying 1 <n ≦ 1.5, and m is preferably a real number satisfying 0.5 ≦ m <1, and n is a real number satisfying 1.1 ≦ n ≦ 1.4. And m is more preferably a real number satisfying 0.55 ≦ m ≦ 0.75. When n and m in the formula (I) are within these ranges, the compatibility between the oligomer B and the silicone resin A is improved.

Among all structural units contained in the oligomer B, it is a structural unit represented by the formula (B1) and a structural unit represented by the formula (B1 ′), one of two R ⁴ having 1 to 10 carbon atoms The structural unit in which the alkyl group or aryl group having 6 to 10 carbon atoms and the other is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group is “D1 body”.

Among all structural units contained in the oligomer B, a structural unit represented by the formula (B2) in which R ⁴ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms is , "D2 body".

  When oligomer B is an oligomer containing (b) D isomer, the total content of D1 isomer and D2 isomer among all structural units contained in oligomer B is preferably 5 to 80 mol%, More preferably, it is 70 mol%, and it is still more preferable that it is 15-50 mol%.

(C) Oligomer containing T2-form and D-form Oligomer containing (c) T2-form and D-form satisfies both requirements of (a) T2-form-containing oligomer and (b) D-form-containing oligomer is there.

Among all structural units contained in the oligomer B, a structural unit represented by the formula (B1) and a structural unit represented by the formula (B1 ′), wherein two R ⁴ are an alkoxy group having 1 to ⁴ carbon atoms Or the structural unit which is a hydroxyl group is T1 body.

Among all structural units contained in the oligomer B, a structural unit represented by the formula (B2), in which R ⁴ is an alkoxy group having 1 to ⁴ carbon atoms or a hydroxyl group, is a T2 form.

  Of all the structural units contained in the oligomer B, the structural unit represented by the formula (B3) is a T3 isomer.

  When the oligomer B is an oligomer containing (c) the T2 form and the D form, among the total structural units contained in the oligomer B, the total content of the T1 form, the T2 form and the T3 form, and the content of the D form The molar ratio (T-form: D-form) is preferably 60:40 to 90:10, and more preferably 75:25 to 85:15. If the molar ratio of T-form: D-form is in the above range, the compatibility between silicone resin A and oligomer B will be good.

  The oligomer B can be synthesized using, as a starting material, an organosilicon compound having a functional group that can form a siloxane bond, corresponding to each structural unit described above that constitutes the condensation type silicone resin. Here, examples of the “functional group capable of generating a siloxane bond” include a halogen atom, a hydroxyl group, and an alkoxy group.

  Examples of the organosilicon compound corresponding to the structural unit represented by the above formula (B3) include organotrihalosilane and organotrialkoxysilane. Examples of the organosilicon compound corresponding to the structural unit represented by the above formula (B2) include organodihalosilane and organodialkoxysilane.

  Oligomer B is obtained by reacting an organosilicon compound as a starting material at a ratio corresponding to the abundance ratio of each structural unit in the presence of an acid such as hydrochloric acid or a base such as sodium hydroxide by a hydrolytic condensation method. Can be synthesized. By appropriately selecting the organosilicon compound as the starting material, the ratio of silicon atoms in T-form and silicon atoms in D-form contained in the oligomer B can be adjusted.

  The content of the oligomer B contained in the condensation-type silicone resin composition used in the present embodiment is 0.1 to 20% by mass with respect to the total content of all silicone resins contained in the condensation-type silicone resin composition It is preferable that it is 0.2-15 mass%, It is more preferable that it is 0.5-10 mass%.

  Further, the content of the oligomer B contained in the condensation type silicone resin composition used in the present embodiment is 0.1 to 20% by mass with respect to the content of the silicone resin A contained in the condensation type silicone resin composition It is preferably 1 to 15% by mass, more preferably 5 to 12% by mass.

  In the molecular weight distribution of the oligomer B measured by GPC method, the peak may be single or plural. In the molecular weight distribution of the oligomer B, the total area of peaks existing in a region having a polystyrene-equivalent weight average molecular weight of 7500 or more is 20% or more of the total area of all peaks, and the polystyrene-equivalent weight. The sum total of the peak areas existing in the region having an average molecular weight of 1000 or less may be 30% or more with respect to the total sum of the areas of all the peaks.

<< Oligomer C (second oligomer) >>
Another example of the oligomer component is, for example, a silicone resin containing a structural unit represented by the above formula (A1), formula (A1 ′), formula (A2) or formula (A3), which is a compound represented by the above formula (A3) ), The structural unit represented by the above formula (A1), the structural unit represented by the above formula (A1 ′), the structural unit represented by the above formula (A2), and the above The silicone resin which is 0-30 mol% with respect to the total content of the structural unit represented by Formula (A3), and whose weight average molecular weight of polystyrene conversion is less than 1500 is mentioned.
In the following description, such silicone resin is referred to as "oligomer C".

  The oligomer C is represented by the structural unit represented by the above formula (A1), the structural unit represented by the above formula (A1 ′), the structural unit represented by the above formula (A2), and the above formula (A3) Among the structural units, it may be a silicone resin containing one or more types of structural units, and may be a silicone resin containing all four types of structural units.

  Oligomer C is a silicone in which the ratio of the content of T3 silicon atoms to the total content of T1 silicon atoms, T2 silicon atoms and T3 silicon atoms is 0 to 30 mol%, and the weight average molecular weight in terms of polystyrene is less than 1,500. Resin. The ratio of the content of T3 silicon atoms to the total content of T1 silicon atoms, T2 silicon atoms and T3 silicon atoms is preferably 0 to 25 mol%.

The oligomer C preferably has substantially no alkenyl group and no hydrosilyl group. That is, the oligomer C is represented by the structural unit represented by the above formula (A1), the structural unit represented by the above formula (A1 ′), the structural unit represented by the above formula (A2) and the above formula (A3) It is preferable that R ² in the structural unit to have no alkenyl group and no hydrogen atom. When the oligomer C has an alkenyl group or a hydrosilyl group, the heat resistance of the cured product of the condensation type silicone resin composition becomes low.

  The oligomer C is preferably an oligomer having an organopolysiloxane structure represented by the following formula (2).

［式（２）中、Ｒ^１およびＲ^２は、前記と同じ意味を表す。複数あるＲ^１およびＲ^２は、それぞれ同一であっても異なっていてもよい。ｐ^２、ｑ^２、ｒ^２、ａ^２およびｂ^２は、［ａ^２×ｑ^２］／［（ｐ^２＋ｂ^２×ｑ^２）＋ａ^２×ｑ^２＋（ｒ^２＋ｑ^２）］＝０〜０．３となる任意の０以上の数を表す。］

[In Formula (2), R ¹ and R ² represent the same meaning as described above. Plural R ¹ and R ² may be the same or different. p ² , q ² , r ² , a ² and b ² are [a ² × q ² ] / [(p ² + b ² × q ² ) + a ² × q ² + (r ² + q ² )] = 0 to 0 It represents an arbitrary number of 0 or more that becomes 0.3. ]

In the organopolysiloxane structure represented by the formula (2), R ¹ is one or more groups selected from the group consisting of methyl group, ethyl group and phenyl group, and R ² is methoxy group, ethoxy group, iso R ¹ is preferably one or more groups selected from the group consisting of propoxy group and hydroxyl group, and R ¹ is one or more group selected from the group consisting of methyl group and ethyl group, and R ² is a methoxy group It is more preferable that it is at least one group selected from the group consisting of an ethoxy group and an isopropoxy group. In particular, from the viewpoint of the heat resistance of the cured product of the condensation type silicone resin composition, R ¹ is preferably a methyl group.

The abundance ratio of each structural unit of the oligomer C having the organopolysiloxane structure represented by the formula (2) can be represented by the abundance ratio of T1 silicon atom, T2 silicon atom and T3 silicon atom. That is, T1 silicon atom: T2 silicon atom: T3 silicon atom = [r ² + q ² ]: [p ² + b ² × q ² ]: [a ² × q ² ]. The abundance ratio of each silicon atom in the oligomer C can be adjusted by appropriately adjusting the numerical 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, there is no T3 silicon atom in the oligomer C, and only a linear or cyclic molecule is included. On the other hand, when both r ² and q ² are 0, only the T2 silicon atom is present in the oligomer C, and only cyclic molecules are included.

If the organopolysiloxane structure represented by formula (2), the number of T2 silicon atoms and x _2, the number of T3 silicon atoms and y _2, and the number of T1 silicon atoms and z _2, formula (2) The abundance ratio of the T3 silicon atom in the organopolysiloxane structure represented by is represented by [y ₂ / (x ₂ + y ₂ + z ₂ )].

[A ² × q ² ] / [(p ² + b ² × q ² ) + a ² × q ² + (r ² + q ² )] is a T3 silicon atom in the organopolysiloxane structure represented by formula (2) Present ratio: [y ₂ / (x ₂ + y ₂ + z ₂ )]. That, ^{p 2,} q ^2, r 2, ^{a 2} and ^{b 2} in the formula (2), the existence ratio of T3 silicon atom is suitably adjusted to be within the range of 0 to 0.3.

The oligomer C that may be contained in the condensation-type silicone resin composition used in the present embodiment is a silicone resin having an organopolysiloxane structure represented by the formula (2), and includes a T1 silicon atom, a T2 silicon atom, and a T3. The ratio of the content of T3 silicon atoms to the total content of silicon atoms: [y ₂ / (x ₂ + y ₂ + z ₂ )] is 0 to 0.3, and the weight average molecular weight in terms of polystyrene is less than 1500. Oligomers that are If the abundance ratio of T3 silicon atoms falls within this range, the abundance ratio of T2 silicon atoms: [x ₂ / (x ₂ + y ₂ + z ₂ )] and the abundance ratio of T1 silicon atoms: [z ₂ / (x ₂ + y) ₂ + z ₂ )] is not particularly limited. The oligomer _{C, [y 2 / (x} 2 + y 2 + z 2)] is preferably has in the range of 0 to 0.25, it is more preferable in the range of 0.05 to 0.2.

Oligomer C has a relatively low abundance ratio of T3 silicon atoms, and therefore has a small branched chain structure and contains many linear and cyclic molecules. The oligomer C may contain only a cyclic molecule, but preferably contains a large number of linear molecules. As the oligomer C, for example, one having an abundance ratio of T1 silicon atom: [z ₂ / (x ₂ + y ₂ + z ₂ )] in the range of 0 to 0.80 is preferable, and 0.30 to 0.80 Those within the range are more preferable, those within the range of 0.35 to 0.75 are still more preferable, and those within the range of 0.35 to 0.55 are particularly preferable.

  The content of the oligomer C contained in the condensation type silicone resin composition used in the present embodiment is 0.1 to 20% by mass with respect to the total content of all silicone resins contained in the silicone resin composition Preferably, the content is 0.2 to 15% by mass, and more preferably 0.5 to 10% by mass.

  The content of the oligomer C contained in the condensation type silicone resin composition used in the present embodiment is 0.1 to 20% by mass with respect to the content of the silicone resin A contained in the condensation type silicone resin composition. It is preferable that it is 0.3 to 10% by mass, and particularly preferably 0.5 to 5% by mass.

  The weight average molecular weight in terms of polystyrene of the oligomer C measured by GPC method is less than 1500. When the weight average molecular weight in terms of polystyrene of the oligomer C is too large, the crack resistance of the cured product of the condensation type silicone resin composition may be insufficient. The polystyrene-converted weight average molecular weight of the oligomer C may be less than 1000.

  The number of T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms in one molecule of oligomer C is appropriately adjusted so that the resin having an organopolysiloxane structure represented by formula (2) has a desired molecular weight. . In one embodiment, the sum of the number of T1 silicon atoms, the number of T2 silicon atoms and the number of T3 silicon atoms in the oligomer C1 molecule is preferably 2 or more.

  The oligomer C can be synthesized by using an organosilicon compound having a functional group capable of generating a siloxane bond as a starting material, corresponding to each of the above-described structural units constituting the oligomer C. Here, the “functional group capable of generating a siloxane bond” has the same meaning as described above. Examples of the organosilicon compound corresponding to the structural unit represented by the above formula (A3) include organotrihalosilane and organotrialkoxysilane. The oligomer C can be synthesized by reacting such a starting material, an organosilicon compound, by a hydrolysis condensation method at a ratio corresponding to the abundance ratio of each structural unit.

  At the time of synthesis of the oligomer C, as a starting material, an organosilicon compound corresponding to the structural unit represented by the above formula (A1) and an organosilicon compound corresponding to the structural unit represented by the above formula (A1 ′) are mixed. Will be. When these organosilicon compounds are polymerized by hydrolytic condensation reaction, these organosilicon compounds are bonded to the terminals of the polymerization reaction to stop the polymerization reaction.

  The condensation-type silicone resin composition used in the present embodiment preferably includes silicone resin A and oligomer B or oligomer C, and more preferably includes silicone resin A, oligomer B, and oligomer C.

[solvent]
Since the condensation type silicone resin used in the present embodiment has a high T3 content, it is preferable to use a condensation type silicone resin composition containing a solvent in order to exhibit good coating properties. The solvent is not particularly limited as long as the silicone resin can be dissolved. As the solvent, for example, two or more kinds of solvents having different boiling points (for example, the solvent P and the solvent Q) can be used.
In the present specification, the “condensation type silicone resin composition” means a composition containing a condensation type silicone resin composition and a solvent.
In the present specification, the “wavelength conversion material-containing condensed silicone composition” means a composition comprising a condensed silicone resin or a condensed silicone resin composition and a wavelength converting material.

  As the solvent P, an organic solvent having a boiling point of less than 100 ° C. is preferable. Specifically, ketone solvents such as acetone and methyl ethyl ketone; alcohol solvents such as methanol, ethanol, isopropyl alcohol and normal propyl alcohol; hydrocarbon solvents such as hexane, cyclohexane, heptane and benzene; methyl acetate, ethyl acetate and the like An acetate solvent such as diethyl ether or tetrahydrofuran is preferred.

  Among these, as the solvent P, alcohol solvents such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol are more preferable.

  As the solvent Q, an organic solvent having a boiling point of 100 ° C. or higher is preferable. Specifically, glycol ether solvents or glycol ester solvents are preferable.

  Specific examples of the glycol ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethyl hexyl ether, ethylene glycol monophenyl ether, ethylene Glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monoethyl hexyl ether, diethylene glycol monophenyl ether, die 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 monoethyl hexyl ether, propylene glycol monophenyl ether, propylene glycol monophenyl ether, propylene glycol monobenzyl ether 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 monobenzyl ether.

  Specific examples of the glycol ester solvent include ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monohexyl ether acetate, ethylene glycol monoethyl hexyl ether acetate, ethylene glycol monophenyl ether acetate, Ethylene glycol monobenzyl ether acetate and the like can be mentioned.

  Among them, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and ethylene glycol monobutyl ether acetate are more preferable as the solvent Q.

"mixing ratio"
The silicone resin composition used in the present embodiment includes a silicone resin as an essential component, and may contain an oligomer, a solvent, a curing catalyst, a filler, and other components described later.

  The ratio (mass ratio) of the silicone resin to the oligomer component is preferably 0.1 to 80 parts by mass, and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the silicone resin. It is more preferably 1 to 30 parts by mass, still more preferably 1 to 20 parts by mass, and still more preferably 5 to 15 parts by mass.

  Moreover, when using the above-mentioned silicone resin A, oligomer B, and C, the mixing ratio of silicone resin is silicone resin A: oligomer B: oligomer C = 100: 0.2-15: 0.2-15 (mass) Ratio) is preferable, and silicone resin A: oligomer B: oligomer C = 100: 1 to 10: 1 to 10 (mass ratio) is more preferable.

  The mixing method of the silicone resin A, the oligomer B and the oligomer C is not particularly limited, and any of known methods generally used when mixing two or more kinds of polymers may be used. For example, the silicone resin A and, if necessary, the oligomer B, the oligomer C and other components can be mixed by dissolving them in an organic solvent.

  Preferably, since the silicone resin can be mixed more uniformly and the stability of the subsequent resin solution can be improved, the silicone resin is once dissolved in an organic solvent having high volatility and solubility and then dissolved in another solvent. Substitution is preferred. Specifically, first, the silicone resin A is put into a highly volatile organic solvent (hereinafter sometimes referred to as “solvent P”), heated to a temperature in the vicinity of the boiling point of the solvent P, and stirred. Dissolve resin A.

  Subsequently, if necessary, oligomer B, oligomer C and other components are added and mixed and dissolved in the same manner. Thereafter, a solvent having a lower volatility than solvent P (hereinafter referred to as solvent Q) is added to the solution in which each component is dissolved, and the solvent P is removed from solvent P by heating and distillation until the concentration of solvent P becomes 1% or less. Solvent replacement to Q can be performed. At that time, as a means for performing solvent replacement more efficiently, it is also possible to heat the container in a state of reduced pressure.

  By performing such treatment, the residual solvent used when the silicone resin A, oligomer B, oligomer C, and other components are synthesized, water remaining unreacted, and the like can be removed together. For this reason, such a treatment is effective in improving the stability of the silicone resin composition.

[Wavelength conversion material]
The wavelength conversion material is not particularly limited, and examples thereof include a phosphor, a quantum dot and the like.
The fluorescent substance is a red fluorescent substance that emits fluorescence in the range of 570 nm to 700 nm, a yellow fluorescent substance that emits fluorescence in the range of 530 nm to 620 nm, a green fluorescent substance that emits fluorescence in the range of 490 nm to 570 nm, a range of 420 nm to 480 nm And blue phosphors that emit fluorescence. These phosphors may be used alone or in combination of two or more.

《Red phosphor》
As the red phosphor, for example, a europium-activated alkaline earth represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu that is composed of fractured particles having a red fracture surface and emits light in the red region. A silicon nitride-based phosphor, composed of growing particles having a substantially spherical shape as a regular crystal growth shape, emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Europium represented by Eu Examples include activated rare earth oxychalcogenide phosphors and the like.

  Furthermore, a phosphor containing an oxynitride or an oxysulfide or both containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo, A phosphor containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used in this embodiment. These are phosphors containing oxynitrides and / or oxysulfides.

In addition, examples of red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, and Y ₂ O ₃ : Eu. Eu-activated oxide _{phosphor, (Ba, Sr, Ca,} Mg) 2 SiO 4: Eu, Mn, (Ba, Mg) 2 SiO 4: Eu, Eu such as Mn, Mn-activated silicate phosphor, Eu-activated sulfide phosphors such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphors such as YAlO ₃ : Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca ₂ Y ₈ ( Eu-activated silicate phosphor such as SiO ₄ ) ₆ O ₂ : Eu, (Sr, Ba, Ca) ₃ SiO ₅ : Eu, Sr ₂ BaSiO ₅ : Eu, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce , Ce-activated aluminate phosphors, such as (Tb, Gd) ₃ Al ₅ O ₁₂ : Ce _{Ca, Sr, Ba) 2 Si} 5 N 8: Eu, (Mg, Ca, Sr, Ba) SiN 2: Eu, (Mg, Ca, Sr, Ba) AlSiN 3: Eu -activated nitride phosphor such as Eu Ce activated nitride phosphors such as (Mg, Ca, Sr, Ba) AlSiN ₃ : Ce, Eu, Mn such as (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn Activated halophosphate phosphor, (Ba ₃ Mg) Si ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn, etc. (Gd, activated silicate phosphor, Mn activated germanate phosphor such as 3.5MgO · 0.5MgF ₂ · GeO ₂ : Mn, etc., Eu activated oxynitride phosphor such as Eu activated α sialon, (Gd, _{Y, Lu, La) 2 O} 3: Eu, Bi, etc. Eu, Bi-activated oxide _{Phosphor, (Gd, Y, Lu,} La) 2 O 2 S: Eu, Eu Bi, etc., Bi Tsukekatsusan sulfide phosphor, (Gd, Y, Lu, La) VO 4: Eu, Bi, etc. Eu, Bi activated vanadate phosphor, Eu, Ce activated sulfide phosphor such as SrY ₂ S ₄ : Eu, Ce etc., Ce activated sulfide phosphor such as CaLa ₂ S ₄ : Ce etc, (Ba, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn-activated phosphate phosphor such as Eu, Mn, (Y, Lu) ) ₂ WO ₆ : Eu, Mo activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) _x Si _y N _z : Eu, Ce (where x, y, z is 1 or more) integer), such as Eu, Ce-activated nitride _{phosphor, (Ca, Sr, Ba,} Mg) 10 (PO 4) 6 (F, l, Br, OH): Eu , Eu such as Mn, Mn-activated halophosphate _{phosphor, ((Y, Lu, Gd} , Tb) 1-x Sc x Ce y) 2 (Ca, Mg) 1-r It is also possible to use Ce-activated silicate phosphors such as (Mg, Zn) _{2 + r} Si _z-q Ge _q O _{12 + δ} .

  Examples of red phosphors include red organic phosphors, perylene pigments (eg, β-diketonates, β-diketones, aromatic carboxylic acids, or rare earth element ion complexes having a ligand such as Bronsted acid). Dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone pigment, Lake based pigments, azo based pigments, quinacridone based pigments, anthracene based pigments, isoindoline based pigments, isoindolinone based pigments, phthalocyanine based pigments, triphenylmethane based basic dyes, indanthrone based pigments, indophenol based pigments, It is also possible to use a cyanine pigment or a dioxazine pigment.

Among the red phosphors, those having a peak wavelength of 580 nm or more, preferably 590 nm or more, and 620 nm or less, preferably 610 nm or less can be suitably used as an orange phosphor. Examples of such orange phosphors include (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Mg) ₃ PO ₄ ) ₂ : Sn ²⁺ , SrCaAlSiN ₃ : Eu, and the like.

《Yellow phosphor》
Examples of yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors. In particular, RE ₃ M ₅ O ₁₂ : Ce (wherein RE represents at least one element of Y, Tb, Gd, Lu, and Sm, and M represents at least one element of Al, Ga, and Sc). . representing) and ^{_{M 2 3 M 3 2 M 4}} 3 O 12: Ce ( here, ^{M 2} is a divalent metal element, ^{M 3} is a trivalent metal element, ^{M 4} is a tetravalent metal element), etc. Garnet-based phosphor having a garnet structure, AE ₂ M ⁵ O ₄ : Eu (where AE represents at least one element of Ba, Sr, Ca, Mg, Zn, and M ⁵ represents Si) , Or Ge represents at least one element) or the like, an orthosilicate fluorescent substance, an oxynitride fluorescent substance in which a part of oxygen of the constituent element of the fluorescent substance of these systems is replaced by nitrogen, AEAlSiN _3: Ce (here, AE is, Ba, Sr, Ca, Mg Represents at least one element of Zn.) Activated with phosphor, etc. with Ce of the nitride-based fluorescent material or the like having a CaAlSiN ₃ structure, or the like.

In addition, as yellow phosphors, sulfide-based phosphors such as CaGa ₂ S ₄ : Eu (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu, etc. It is also possible to use a Eu-activated phosphor such as an oxynitride-based phosphor having a SiAlON structure such as Ca _x (Si, Al) ₁₂ (O, N) ₁₆ : Eu.

<Green phosphor>
The green phosphor is composed of, for example, fractured particles having a fractured surface, and emits light in the green region (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Europium activated alkaline earth represented by Eu. A silicon oxynitride phosphor, composed of fractured particles having a fracture surface, emits light in the green region (Ba, Ca, Sr, Mg) ₂ SiO ₄ : europium activated alkaline earth silicate fluorescence represented by Eu Body etc. can be mentioned.

In addition, as the green phosphor, Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, (Sr, Ba) Al ₂ Si ₂ O ₈ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca) ₂ (Mg, Zn) Si ₂ O ₇ : Eu activated silicate phosphor such as Eu; Ce, Tb activated silicate phosphor such as Y ₂ SiO ₅ : Ce, Tb etc; Eu such as Sr ₂ P ₂ O ₇ -Sr ₂ B ₂ O ₅ : Eu etc. Activated oxalate phosphate phosphor, Eu activated halosilicate phosphor such as Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu, Mn activated silicate phosphor such as Zn ₂ SiO ₄ : Mn, CeMgAl ₁₁ O _{19: Tb, Y 3 Al 5} O 12: Tb and Tb such Activated aluminate _{phosphors, Ca 2 Y 8 (SiO 4} ) 6 O 2: Tb, La 3 Ga 5 SiO 14: Tb -activated silicate phosphors such as Tb, (Sr, Ba, Ca ) Ga 2 S 4 : Eu, Tb, Sm activated thiogallate phosphor such as Eu, Tb, Sm, etc. Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al , Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce, etc. Ce-activated silicate phosphor, Ce-activated oxide phosphor such as CaSc ₂ O ₄ : Ce, SrSi ₂ O ₂ N ₂ : Eu, (Sr, Ba, Ca) Si ₂ O ₂ N ₂ : Eu, Eu Eu activated oxynitriding such as activated β sialon, Eu activated α sialon Object _{phosphor, BaMgAl 10 O 17: Eu,} Eu such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O _4: Eu-activated aluminate phosphor such as Eu, (La, Gd, Y ) 2 T ₂ O ₂ S: Tb etc. Tb-activated oxysulfide phosphors, LaPO ₄ : Ce, Tb etc. Ce, Tb-activated phosphate phosphors, ZnS: Cu, Al, ZnS: Cu, Au, Al etc. sulfide _{phosphor, (Y, Ga, Lu,} Sc, La) BO 3: Ce, Tb, Na 2 Gd 2 B 2 O 7: Ce, Tb, (Ba, Sr) 2 (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb activated borate phosphors such as K, Ce, Tb etc., Eu, Mn activated halosilicate phosphors such as Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn etc., (Sr , Ca, Ba) (Al, Ga, in) 2 S 4: Eu activated thiophosphorous such as Eu Laminate-phosphor or thiogallate _{phosphor, (Ca, Sr) 8 (} Mg, Zn) (SiO 4) 4 Cl 2: are possible Eu, Eu such as Mn, the use of the Mn-activated halo-silicate phosphors such .

  Examples of green phosphors include pyridine-phthalimide condensed derivatives, benzoxazinone-based, quinazolinone-based, coumarin-based, quinophthalone-based, naltalimide-based fluorescent dyes, terbium complexes having hexyl salicylate as a ligand, etc. It is also possible to use organic phosphors.

"Blue phosphor"
As the blue phosphor, a europium-activated barium magnesium aluminate-based phosphor represented by BaMgAl ₁₀ O ₁₇ : Eu, which is composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape, and which emits light in a blue region, Europium-activated calcium halophosphate fluorescence represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, which is composed of growing particles having a substantially spherical shape as a regular crystal growth shape and emits light in the blue region. Body, growth particles having an almost cubic shape as a regular crystal growth shape, and emits light in the blue region. Europium-activated alkaline earths represented by (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu Chloroborate phosphor, composed of fractured particles having fractured surface, emits light in blue-green region ( Europium-activated alkaline earth aluminate-based phosphors represented by Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu can be mentioned.

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, Sr ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O ₁₃ : Eu-activated aluminate phosphors such as Eu, Ce-activated thiogallate phosphors such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ Eu activated aluminate phosphor such as O ₁₇ : Eu, Tb, Sm, etc., Eu, Mn activated aluminate phosphor such as (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn, etc., (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu such as Eu, Mn, Sb, etc. activated Halophosphate _{Phosphor, BaAl 2 Si 2 O 8:} Eu, (Sr, Ba) 3 MgSi 2 O 8: Eu -activated silicate phosphors such as _{Eu, Sr 2 P 2 O 7} : Eu -activated phosphate such as Eu Phosphors, sulfide phosphors such as ZnS: Ag, ZnS: Ag, Al, Ce activated silicate phosphors such as Y ₂ SiO ₅ : Ce, tungstate phosphors such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB ₂ O ₃ : Eu, ₂ SrO · 0.84 P ₂ O ₅ · 0.16 B ₂ O ₃ : Eu, etc. Eu, Mn It is also possible to use an activated borate phosphate phosphor, an Eu activated halosilicate phosphor such as Sr ₂ Si ₃ O ₈ .2SrCl ₂ : Eu, or the like.

  In addition, as the blue phosphor, for example, it is possible to use a fluorescent dye of naphthalimide, benzoxazole, styryl, coumarin, pyrarizone, triazole compound, organic phosphor such as thulium complex, etc. .

《Quantum dots》
As mentioned above, it is also possible to use quantum dots as wavelength conversion material. Examples of the types of quantum dots that can be used include InAs and CdE (E = S, Se, Te) (CdS _x Se _1-x / ZnS, etc.).

  The content of the condensation type silicone resin composition with respect to the total amount of the condensation type silicone resin composition and the wavelength conversion material is preferably 10% by mass or more and 95% by mass or less, and more preferably 30% by mass or more and 90% by mass or less. More preferably, it is more preferably 40% by mass or more and 85% by mass or less, and particularly preferably 50% by mass or more and 80% by mass or less. When the wavelength conversion material is within the above range, the handling property during screen printing tends to be good.

[Curing accelerator]
The curing accelerator (hereinafter sometimes referred to as "curing catalyst") used in the present embodiment is not particularly limited as long as it can accelerate the crosslinking reaction of the silicone resin and the oligomer. When the functional group (the above R ² ) in the silicone resin and the oligomer is an alkoxy group or a hydroxyl group, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid is used as a curing catalyst to accelerate the hydrolysis condensation reaction. Organic acids such as formic acid, acetic acid, succinic acid, citric acid, propionic acid, butyric acid, lactic acid, and succinic acid can be used.
In the present embodiment, a phosphoric acid catalyst is preferable. Specifically, phosphoric acid, phosphorous acid, phosphoric acid ester, phosphorous acid ester and the like can be mentioned. Among these, phosphoric acid is preferable from the viewpoint of high transparency and easy to obtain a cured product having a terminal silicon content of less than 0.1% by mass.

  Further, not only an acidic compound but also an alkaline compound can be used as a curing catalyst. Specifically, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or the like can be used.

  In addition, an organometallic compound catalyst can also be used as a curing catalyst. Examples of the organometallic compound catalyst include those containing aluminum, zirconium, tin, titanium, and zinc.

  Specifically, examples of the organometallic compound catalyst containing aluminum include aluminum triacetyl acetate and aluminum triisopropoxide.

  Examples of organometallic compound catalysts containing zirconium include zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconium tetranormal propoxide, zirconium tetraisopropoxide, zirconium tetranormal butoxide, Examples include zirconium acylate and zirconium tributoxy systemate.

  Examples of organometallic compound catalysts containing tin include tetrabutyltin, monobutyltin trichloride, dibutyltin dichloride, dibutyltin oxide, tetraoctyltin, dioctyltin dichloride, dioctyltin oxide, tetramethyltin, dibutyltin laurate, dioctyltin laurate , Bis (2-ethylhexanoate) tin, bis (neodecanoate) tin, di-n-butyl bis (ethyl hexyl malate) tin, di-normal butyl bis (2,4-pentanedionate) tin, di-normal Examples thereof include butyl butoxychlorotin, di-normal butyl diacetoxy tin, di-normal butyl dilaurate tin, dimethyl dineodecanoate tin and the like.

  Examples of titanium-containing organometallic compound catalysts include titanium tetraisopropoxide, titanium tetranormal butoxide, butyl titanate dimer, tetraoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium ethyl acetoacetate, etc. It is done.

  Examples of the organometallic compound catalyst containing zinc include zinc triacetylacetonate.

  Among these, from the viewpoint of transparency up to the ultraviolet region, phosphoric acid esters and phosphoric acid are preferred as the curing catalyst, and phosphoric acid is particularly preferred.

  In order to add the curing catalyst at a predetermined concentration, it can be added to the present composition in a state diluted with water, an organic solvent, or a silicone-based monomer or alkoxysilane oligomer that is easily compatible with the present composition.

  The content of the curing catalyst can be appropriately adjusted in consideration of the heating temperature during the curing reaction, the reaction time, the type of catalyst, and the like. The content of the curing catalyst relative to 100 parts by mass of the present composition is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.01 parts by mass or more and 10 parts by mass or less.

[Silane coupling agent]
In the present embodiment, a silane coupling agent may be contained as an optional component.
The silane coupling agent used in the present embodiment is at least one selected from the group consisting of a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryl group, an amino group, a ureido group, a mercapto group, a sulfide group and an isocyanate group. A silane coupling agent having at least one is preferred. Among them, as a silane coupling agent, a coupling agent containing an epoxy group or a mercapto group is preferable.

  Specifically, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane 3-glycidoxypropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane are preferred.

When the composition contains a silane coupling agent, the silicon atom contained in the silane coupling agent is also detected as a ²⁹ Si-NMR signal, but in the present embodiment, the signal area of the present composition is calculated. The signal of the silane coupling agent shall be included.

  The content of the silane coupling agent in the composition is preferably 0.0001 parts by mass or more and 1.0 parts by mass or less, with respect to 100 parts by mass of the total content of the silicone resin and the oligomer, and 0.001 mass It is more preferable that the content is not less than 0.1 parts by mass and not less than 0.1 parts by mass. When content of a silane coupling agent is higher than the said range, the transparency of the wavelength conversion sheet obtained may be reduced when silane coupling agent itself absorbs light.

  The condensation type silicone resin composition can contain additives such as inorganic particles and a silane coupling agent as needed as long as the effects of the present invention are not impaired.

[Other additives]
As long as the effects of the present invention are not impaired, additives other than the above-described materials may be contained as needed. As a specific example of an additive, a dispersing agent, a leveling agent, an antifoamer etc. are mentioned.

<Method of manufacturing wavelength conversion sheet>
The present invention provides a step of applying and curing a wavelength conversion material-containing condensation silicone composition produced by the method of producing a wavelength conversion material-containing condensation silicone composition of the first aspect of the present invention on a substrate A method for producing a wavelength conversion sheet is provided.

  Hereinafter, although an example of the manufacturing method of the wavelength conversion sheet which concerns on this embodiment is demonstrated, this embodiment is not limited to the following aspects.

  First, the wavelength conversion material-containing condensation silicone composition produced by the method for producing a wavelength conversion material-containing condensation silicone composition of the first aspect of the present invention is coated on a supporting substrate. Application | coating of the wavelength conversion material containing condensation type silicone composition can be performed using a well-known coating device. Known coating devices include, for example, reverse roll coaters, blade coaters, slit die coaters, direct gravure coaters, offset gravure coaters, reverse roll coaters, blade coaters, kiss coaters, natural roll coaters, air knife coaters, roll blade coaters, varivers. A roll blade coater, toe stream coater, rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater and the like can be mentioned. Among them, the wavelength conversion material-containing condensation-type silicone composition is preferably applied by a slit die coater or an applicator because the film thickness of the wavelength conversion sheet to be obtained tends to be uniform.

  Another application method includes printing methods such as screen printing, gravure printing, and lithographic printing. Especially, it is preferable to apply | coat the wavelength conversion material containing condensed silicone composition by screen printing from a viewpoint of simplicity.

  A method for applying the wavelength conversion material-containing condensed silicone composition to the surface of the substrate by a screen printing method will be described below. First, the surface of the substrate is covered with a mask having an opening of a required pattern, and the wavelength conversion material-containing condensation-type silicone composition is introduced into the squeegee portion. Next, the wavelength conversion material-containing condensed silicone composition is filled in the opening of the mask by moving the squeegee and moving the mask on the wavelength-converting material-containing condensed silicone composition while applying pressure (filling step). . After the filling process, the mask is removed. In this way, a pattern of the wavelength conversion material-containing condensed silicone composition can be formed on the surface of the substrate.

  Next, the coating film formed on the support substrate is cured by heating to obtain a wavelength conversion sheet. The coating film is heated using an apparatus such as a natural convection oven, a blower oven, a vacuum oven, an inert oven, a hot plate, a heat press, an infrared heater, and the like. Among these, it is preferable to use a blower oven from the viewpoint of high productivity.

  As a heating condition of the coating film, for example, a method of heating at 40 ° C. to 250 ° C. for 5 minutes to 100 hours can be mentioned. The heating time is preferably 1 to 30 hours, more preferably 2 to 10 hours, and even more preferably 3 to 8 hours. By being in this range, the solvent can be sufficiently removed and coloring during heating can be prevented.

  For example, after applying the coating solution on the support substrate, it may be cured by leaving it in an atmosphere at a temperature of 250 ° C. or lower, for example, by allowing it to stand in an atmosphere at a temperature of 40 ° C. to 200 ° C. May be. Moreover, in the case of hardening, in order to reduce the solvent and water which exist in a coating liquid, and to control the condensation reaction rate of a silicone resin and a silicone oligomer, for example, it is 40 minutes-60 degreeC for 5 minutes-30 minutes. Then, it may be cured stepwise, such as at 60 ° C. to 100 ° C. for 10 minutes to 60 minutes, and then at 140 ° C. to 200 ° C. for 30 minutes to 5 hours.

  The wavelength conversion sheet formed using the wavelength conversion material-containing condensation-type silicone composition obtained according to the first aspect of the present invention has good screen printability and can obtain a wavelength conversion sheet free from blurring.

<Wavelength conversion sheet>
The wavelength conversion sheet obtained by the above <Method for producing a wavelength conversion sheet> has a polymer of a condensation type silicone resin, and a filler which is dispersed in a polymer of a condensation type silicone resin to make a wavelength conversion material a forming material A cured product is used as a forming material. Such a wavelength conversion sheet is formed into a thin plate shape by using such a cured product as a forming material.
The wavelength conversion sheet of the present embodiment can be used for wavelength conversion in LEDs, solar cells, semiconductor lasers, photodiodes, CCDs, CMOSs, and the like. In particular, since the wavelength conversion sheet of this embodiment is excellent in heat resistance, it can be suitably used for a light emitting part of a semiconductor laser that is expected to be used at high temperatures.

  The thickness (film thickness) of the wavelength conversion sheet is preferably 10 μm or more because the wavelength conversion sheet can be stably produced. Further, from the viewpoint of enhancing the optical characteristics and heat resistance of the wavelength conversion sheet, it is preferably 1 mm or less, more preferably 500 μm or less, and still more preferably 200 μm or less. When the thickness of the wavelength conversion sheet is 1 mm or less, light absorption and light scattering by the silicone resin can be reduced.

(Film thickness)
The film thickness of the wavelength conversion sheet can be obtained, for example, by measuring the film thickness at a plurality of locations of the wavelength conversion sheet using a micrometer and calculating the average value. For example, when the shape of the wavelength conversion sheet is a quadrangle, the plurality of locations may include a total of five locations including one central portion of the wavelength conversion sheet and four corner portions of the wavelength conversion sheet.

  The wavelength conversion sheet may be formed on the support base material, and there may be no support base material. There is no restriction | limiting in particular as a support base material, The base material which uses a well-known metal, a film, glass, a ceramic, paper etc. as a forming material can be used.

  Specifically, transparent inorganic oxide glass such as quartz glass, borosilicate glass, sapphire etc. as a forming material of the supporting base; metal plate such as aluminum (including aluminum alloy), zinc, copper, iron etc. and foil; Cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, aramid and other plastic films; paper laminated with the plastic; or coated with the plastic Examples thereof include: a paper on which the above metal is laminated or vapor-deposited; a plastic film on which the above metal is laminated or vapor-deposited. Among these, inorganic oxide glass or metal plate is preferable.

  The thickness of the support substrate is not particularly limited, but is preferably 30 μm or more, and more preferably 50 μm or more. When the thickness of the support substrate is 30 μm or more, the support substrate has sufficient strength to protect the shape of the wavelength conversion sheet. Further, the thickness of the supporting base material is preferably 5000 μm or less, and more preferably 3000 μm or less from the viewpoint of economy.

<Light emitting device>
FIG. 1 is a cross-sectional view showing the structure of a light emitting device provided with the wavelength conversion sheet of this embodiment.
As shown in FIG. 1, the light emitting device 1000 includes a substrate 110, a semiconductor laser element (light source) 120, a light guide unit 130, a wavelength conversion sheet 140, and a reflecting mirror 150. The wavelength conversion sheet 140 can use the above-described configuration.

  The semiconductor laser element 120 is set on the substrate 110.

The light guide unit 130 receives the laser beam La emitted from the semiconductor laser element 120 and guides the laser beam La therein. The semiconductor laser element 120 is optically connected to one end of the light guide unit 130, and the wavelength conversion sheet 140 is optically connected to the other end.
The light guiding portion 130 has a spindle shape whose width gradually decreases from one end to the other end, and the laser light La emitted from the semiconductor laser element 120 is focused on the wavelength conversion sheet 140. .

  The reflecting mirror 150 is a bowl-shaped member disposed around the wavelength conversion sheet 140, and a curved surface facing the wavelength conversion sheet 140 is a light reflecting surface. The reflecting mirror 150 deflects the light emitted from the wavelength conversion sheet 140 toward the front of the apparatus (irradiation direction of the laser light La).

  The laser light La irradiated to the wavelength conversion sheet 140 is converted into white light Lb by the wavelength conversion material contained in the wavelength conversion sheet 140, and is output from the light emitting device 1000.

  The light emitting device 1000 illustrated in FIG. 1 includes only one semiconductor laser element 120, but is not limited thereto. FIG. 2 is a cross-sectional view illustrating a modification of the light emitting device. 2 and the following description, the same components as those described in FIG. 1 are denoted by the same reference numerals as those in FIG.

  The light emitting device 1100 shown in FIG. 2 includes a plurality of substrates 110, a plurality of semiconductor laser elements (light sources) 120, a plurality of optical fibers 180, a light guide 130, a wavelength conversion sheet 140, a reflecting mirror 150, and a transparent support 190. There is.

The optical fiber 180 receives the laser beam La emitted from the semiconductor laser element 120 and guides the laser beam La therein. The semiconductor laser element 120 is optically connected to one end of each of the plurality of optical fibers 180. Further, the plurality of optical fibers 180 are bundled at the other end side, and are optically connected to the light guide 130 at the other end in a state of being bundled into one bundle.
The light guide portion 130 receives the laser light La emitted from the semiconductor laser element 120 inside, guides the laser light La inside, and emits the light toward the front of the device. The light guiding unit 130 may have a function of condensing the laser light La emitted to the front of the apparatus.

  The wavelength conversion sheet 140 is disposed so as to be separated from the light guide unit 130 and opposed to the light guide unit 130 while being supported by the transparent support 190. The transparent support 190 is provided in front of the apparatus so as to cover the opening of the reflecting mirror 150. The transparent support 190 is a member made of a transparent material that does not deteriorate due to heat generated during use of the apparatus, and for example, a glass plate can be used.

  The laser light La irradiated to the wavelength conversion sheet 140 is converted to white light Lb by the wavelength conversion material contained in the wavelength conversion sheet 140, and is output from the light emitting device 1100.

  In the light emitting devices 1000 and 1100, as described above, the light source (semiconductor laser element 120) and the light emitting unit (wavelength conversion sheet 140) are separated. Thereby, it becomes easy to reduce the size and improve the design of the light emitting device.

  The light emitting device configured as described above has high reliability because it includes the wavelength conversion sheet of the present embodiment having high hardness, high crack resistance, and heat resistance.

  The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but it goes without saying that the present invention is not limited to such examples. The shapes, combinations, and the like of the constituent members shown in the above-described example are merely examples, and various changes can be made based on design requirements and the like without departing from the spirit of the present invention.

  EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to the following examples.

<Preparation of condensation type silicone resin component>
«Production example 1»
Resin 1 (weight average molecular weight 3500) was used as a silicone resin. The abundance ratio of each structural unit of the resin 1 is shown in Table 1 below. The abundance ratio of each structural unit was calculated based on the measurement result of solution NMR under the following measurement conditions.

[Solution NMR]
In addition, ¹ H-NMR method and ²⁹ Si-NMR method were used as a means for measuring the kind and presence ratio of resin A and the oligomer B which have organopolysiloxane used in the following Example as a principal chain.

^<1 H-NMR measurement conditions>
Device name: ECA-500 manufactured by JEOL RESONANCE
Observation nucleus: ¹ H
Observation frequency: 500.16 MHz
Measurement temperature: room temperature measurement solvent: DMSO-d ₆
Pulse width: 6.60 μsec (45 °)
Pulse repetition time: 7.0 sec
Integration count: 16 times Sample concentration (sample / measurement solvent): 300 mg / 0.6 ml

^<29 Si-NMR measurement conditions>
Device name: 400-MR manufactured by Agilent
Observation nucleus: ²⁹ Si
Observation frequency: 79.42 MHz
Measurement temperature: room temperature measurement solvent: CDCl ₃
Pulse width: 8.40 μsec (45 °)
Pulse repetition time: 15.0 sec
Number of integrations: 4000 times Sample concentration (sample / measurement solvent): 300 mg / 0.6 ml

In addition, Resin 2 (weight average molecular weight <1000) and Resin 3 (weight average molecular weight 3400) were used as the modifying silicone. The abundance ratio of each structural unit of the resin 2 is shown in Table 2 below.
The abundance ratio of each structural unit was calculated based on the measurement result of solution NMR under the above measurement conditions.

Further, the abundance ratio of each structural unit of the resin 3 is shown in Table 3 below. In the resin 3, 95% or more of the entire resin was the following structural unit. In the resin 3, the sum of the areas of the peaks present in the region of a weight average molecular weight of 7500 or more measured by GPC is 20% or more of the whole, and the peak of the peak present in a region of a weight average molecular weight of 1000 or less The total area was 30% or more. The abundance ratio of each structural unit was calculated based on the measurement result of solution ²⁹ Si-NMR under the above measurement conditions.

[Gel permeation chromatography (GPC) measurement]
The sample was dissolved in an eluent and filtered through a membrane filter with a pore size of 0.45 μm to obtain a measurement solution. Subsequently, the weight average molecular weight was measured by standard polystyrene conversion under the following measurement conditions.
Device name: Tosoh HLC-8220 GPC
Column: TSKgel SuperHM-H × 2 + SuperH2500 × 1 (inner diameter 6.0 mm × 150 mm × 3)
Eluent: Toluene flow rate: 0.6 mL / min Detector: RI detector (polarity:-)
Column temperature: 40 ° C
Injection volume: 40 μL
Molecular weight standard: Standard polystyrene

  First, 789.60 g of resin 1, 96.00 g of propyl acetate and 314.40 g of isopropyl alcohol were charged into a flask placed in an oil bath, and the temperature was raised and stirred until the liquid temperature reached 80 ° C. Dissolved well. Next, 8.47 g of resin 2 and 75.08 g of resin 3 were added and stirred for 1 hour to dissolve.

  Subsequently, 274.49 g of 2-butoxyethyl acetate and 0.22 g of 3-glycidoxypropyltrimethoxysilane were added to the obtained mixture. Thereafter, the mixture is set in an evaporator, and the mixture is left at 85 ° C. under a pressure of 2.0 kPa until the total concentration of propyl acetate and isopropyl alcohol in the mixture is 1% by mass or less, acetic acid Propyl and isopropyl alcohol were distilled off to obtain a silicone resin composition of Production Example 1.

<Production of wavelength conversion material-containing condensed silicone composition>
Example 1
[First step]
To the condensation-type silicone resin component prepared in Production Example 1, 2% by weight of a curing accelerator relative to the amount of the silicone resin component was added and sufficiently stirred and mixed.
[Step 1A]
After the first step, it was stored at 25 ° C. for 15 hours.
[Second step]
After the first step A, a wavelength conversion material equivalent to the amount of the condensation type silicone resin component was added and mixed to produce a wavelength conversion material-containing condensation type silicone composition.

The following materials were used as the wavelength conversion material and the curing accelerator.
Wavelength conversion material: YAG: Ce Average particle size 5.8 μm (manufactured by Tokyo Chemical Laboratory Co., Ltd.),
Curing accelerator: Curing catalyst solution containing 15% by mass of phosphoric acid

[Evaluation]
-Precipitation evaluation After the wavelength conversion material containing condensation type silicone composition of Example 1 was stirred uniformly, the viscosity after standing at 25 degreeC conditions for 7 hours was measured. With the solution in the screw bottle, the solution in the region of 20% in height from the top was collected with a dropper and the viscosity was measured to obtain the upper viscosity A. Moreover, the solution in the area | region of 20% in height from the bottom was sampled with the dropper with the solution in a screw bottle, the viscosity measurement was implemented, and the viscosity B of the lower part was obtained. Settability was evaluated by calculating the value of Settability Index B / A. When B / A is 1, the solution viscosity has no difference between the upper and lower parts and is in a uniform state. On the other hand, it can be said that as the B / A value is larger than 1, the solution viscosity has a larger difference between the upper part and the lower part, is in a non-uniform state, and has more sedimentation.
As a result, the sedimentation index B / A of Example 1 was 1.0.

Example 2
[First step]
To the condensation-type silicone resin component prepared in Production Example 1, 2% by weight of a curing accelerator relative to the amount of the silicone resin component was added and sufficiently stirred and mixed.
[Step 1A]
After the first step, it was stored at 25 ° C. for 1 hour.
[Second step]
After the first step A, a wavelength conversion material equivalent to the amount of the condensation type silicone resin component was added and mixed to produce a wavelength conversion material-containing condensation type silicone composition.

The following materials were used as the wavelength conversion material and the curing accelerator.
Wavelength conversion material: YAG: Ce Average particle diameter 4.2 μm (manufactured by Tokyo Chemical Laboratory Co., Ltd.),
Curing accelerator: Curing catalyst solution containing 15% by mass of phosphoric acid

[Evaluation]
Sedimentation evaluation When the viscosity was measured in the same manner as in Example 1, the sedimentation index B / A was 1.1.

Example 3
[First step]
To the condensation-type silicone resin component prepared in Production Example 1, 2% by weight of a curing accelerator relative to the amount of the silicone resin component was added and sufficiently stirred and mixed.
[Step 1A]
After the first step, it was stored at 25 ° C. for 48 hours.
[Second step]
After the first step A, a wavelength conversion material equivalent to the amount of the condensation type silicone resin component was added and mixed to produce a wavelength conversion material-containing condensation type silicone composition.

The following materials were used as the wavelength conversion material and the curing accelerator.
Wavelength conversion material: YAG: Ce Average particle diameter 4.2 μm (manufactured by Tokyo Chemical Laboratory Co., Ltd.),
Curing accelerator: Curing catalyst solution containing 15% by mass of phosphoric acid

[Evaluation]
Sedimentation evaluation When the viscosity was measured in the same manner as in Example 1, the sedimentation index B / A was 0.9.

«Comparative Example 1»
[First step]
Equal amounts of the condensation-type silicone resin component prepared in Production Example 1 and the wavelength conversion material were mixed and sufficiently stirred and mixed.
[Step 1A]
After the first step, it was stored for 15 hours.
[Second step]
After the first step A, a curing accelerator was added in an amount of 2% by weight based on the amount of the condensation type silicone resin component and mixed to prepare a wavelength conversion material-containing condensation type silicone composition.

[Evaluation]
Sedimentation evaluation When the viscosity was measured in the same manner as in Example 1, the sedimentation index B / A was 1.3.

  As shown in the above results, in Example 1 to which the present invention was applied, sedimentation of the wavelength conversion material was suppressed. On the other hand, the wavelength conversion material of Comparative Example 1 to which the present invention is not applied has settled.

Example 4
[First step]
To the condensation-type silicone resin component prepared in Production Example 1, 2% by weight of a curing accelerator relative to the amount of the silicone resin component was added and sufficiently stirred and mixed.
[Step 1A]
After the first step, it was stored at 25 ° C. for 96 hours. As a result of gelation, the viscosity could not be measured, but no appearance was observed.

DESCRIPTION OF SYMBOLS 1000, 1100 ... Light emitting device, 110 ... Substrate, 120 ... Semiconductor laser element (light source) 130 ... Light guide part, 140 ... Wavelength conversion sheet, 150 ... Reflector, La ... Laser light, Lb ... White light, 180 ... Optical fiber

Claims (3)

A method for producing a wavelength conversion material-containing condensation type silicone composition comprising a condensation type silicone resin and a wavelength conversion material,
A first step of mixing a condensation-type silicone resin substantially free of silica particles and a curing accelerator;
After the first step, a second step of adding and mixing a wavelength conversion material;
The condensing type silicone resin, saw including a structural unit represented by at least the following formula (A3), and the following formula formula (A1), the formula (A1 '), or the structural unit represented by the formula (A2) Among them, a method for producing a wavelength conversion material-containing condensation-type silicone composition comprising one or more kinds .

[In Formula (A3), R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. ]

[In Formula (A1), Formula (A1 ′) and Formula (A2), R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. R ² represents an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. Plural R ¹ and R ² may be the same or different. ]   The method for producing a wavelength conversion material-containing condensation-type silicone composition according to claim 1, further comprising a step 1A of standing for 30 minutes or more and 95 hours or less after the first step and before the second step. .   A wavelength conversion sheet comprising a step of curing a wavelength conversion material-containing condensation silicone composition produced by the method for producing a wavelength conversion material-containing condensation silicone composition according to claim 1 or 2 on a substrate. Method.

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