JP2017213641A - Manufacturing method of phosphor resin sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a phosphor resin sheet by which a phosphor resin sheet can be manufactured efficiently.SOLUTION: A manufacturing method of a phosphor resin sheet 3 includes a process (1) of preparing a phosphor resin sheet 3 of a B stage, a process (2) of forming a through hole 5 and a through surface 6 facing to the through hole 5 on the phosphor resin sheet 3, and a process (3) of forming a plurality of phosphor resin sheets 3 including the through surface 6 by cutting the phosphor resin sheet 3. In the process (3), the phosphor resin sheet 3 is cut so that a first cutting line 31 passes the through hole 5, and thereby the through surface 6 is divided so that the through surface 6, which defines the one through hole 5, is divided to the plurality of phosphor resin sheets 3, and the plurality of phosphor resin sheets 3 having a cut part 23 cut from a peripheral end surface 4 to an inside are obtained.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a phosphor resin sheet.

  Conventionally, a phosphor-containing sheet containing a resin in a semi-cured state is cut in order to singulate into the size of the LED chip, and then corresponds to the electrode portion on the LED chip in the phosphor-containing sheet. It is known that a hole is formed in a part and then a phosphor resin sheet is attached to an LED chip (for example, refer to Patent Document 1).

  The electrode part on the LED is exposed from the hole of the phosphor-containing sheet, and then a wire is inserted into the hole of the phosphor-containing sheet, and the electrode part is wire-bonded.

JP2013-1792A

  However, according to the method described in Patent Document 1, since each of the singulated phosphor-containing sheets is perforated, there is a problem that the manufacturing efficiency is low.

  The objective of this invention is providing the manufacturing method of a phosphor resin sheet which can manufacture a phosphor resin sheet efficiently.

  The present invention (1) includes a step (1) of preparing a B-stage phosphor resin sheet, a step (2) of forming a through hole and a through surface facing the through hole in the phosphor resin sheet, A step (3) of cutting the phosphor resin sheet to form a plurality of phosphor resin sheets including the through surface, and in the step (3), the cutting line passes through the through hole. The phosphor resin sheet is cut, so that the through surface is divided so that the through surface defining one through hole is divided into each of the plurality of phosphor resin sheets. The manufacturing method of the fluorescent substance resin sheet which obtains the several fluorescent substance resin sheet which has a notch part notched inside from an end surface is included.

  According to this method, since the through surface is divided so that the through surface defining one through hole is divided into each of the plurality of phosphor resin sheets by cutting the phosphor resin sheet with a cutting line, A plurality of phosphor resin sheets having a portion can be efficiently produced.

  This invention (2) contains the manufacturing method of the phosphor resin sheet as described in (1) which cuts the said phosphor resin sheet with a cutting blade in the said process (3).

  According to this method, in the step (3), the phosphor resin sheet is cut by the cutting blade, so that the step (3) can be reliably performed.

  The present invention (3) includes the method for producing a phosphor resin sheet according to (1) or (2), wherein in the step (2), the phosphor resin sheet is punched.

  According to this method, since the phosphor resin sheet is punched in the step (2), the step (2) can be reliably performed.

  According to the present invention (4), in the step (1), the phosphor resin sheet is obtained by dynamic viscoelasticity measurement under conditions of a frequency of 1 Hz and a temperature rising rate of 20 ° C./min. And the temperature T has a minimum value, the temperature T at the minimum value is in the range of 40 ° C. or more and 200 ° C. or less, and the storage shear modulus G ′ at the minimum value is 1 The manufacturing method of the fluorescent substance resin sheet as described in any one of (1)-(3) which exists in the range of 1,000,000 Pa or more and 90,000 Pa or less is included.

  According to this method, the temperature T at the minimum value of the phosphor resin sheet is in the range of 40 ° C. or more and 200 ° C. or less, and the storage shear modulus G ′ at the minimum value is 1,000 Pa or more and 90,000 Pa or less. Therefore, when the phosphor resin sheet is used so as to adhere to the optical semiconductor element in the range of 40 ° C. or more and 200 ° C. or less, the phosphor resin sheet can be applied to the optical semiconductor element with excellent adhesion. Can be attached.

  Moreover, according to this method, since the phosphor resin sheet has the above-described storage shear modulus G ′, the through-hole can be formed with high accuracy in the step (2). Therefore, a phosphor resin sheet having excellent reliability can be obtained.

  According to the method for manufacturing a phosphor resin sheet of the present invention, a plurality of phosphor resin sheets having notches can be efficiently manufactured.

1A to 1C are partial process diagrams of a method for producing a second sheet member, which is an embodiment of the method for producing a phosphor resin sheet of the present invention, and FIG. 1A is a process for preparing the first sheet member. (1), FIG. 1B shows the process (2) which forms a through-hole, and FIG. 1C shows the process (3) which separates a phosphor resin sheet. 2D to 2F are partial process diagrams of the method for manufacturing the second sheet member shown in FIG. 1 following FIG. 1C. FIG. 2D is a process (4) of transferring the phosphor resin sheet to the stretched support sheet. 2E shows a step (5) of stretching the stretched support sheet, and FIG. 2F shows a step (6) of sticking the phosphor resin sheet to the optical semiconductor element. 3A to 3C are partial process diagrams of a modification of the method for manufacturing the second sheet member shown in FIGS. 1A to 2E, and FIG. 3A is a process of forming a through hole having a substantially rectangular shape in plan view (2 3B shows a step (3) in which the phosphor resin sheet is separated into pieces, and FIG. 3C shows a step (5) in which the stretched support sheet is stretched to obtain a phosphor resin sheet having a substantially pentagonal shape in plan view. . 4A to 4C are partial process diagrams of a modified example of the method for manufacturing the second sheet member shown in FIGS. 1A to 2E, and FIG. 4A is a process of forming a through hole having a substantially rectangular shape in plan view (2 ), FIG. 4B is a step (3) for separating the phosphor resin sheet, and FIG. 4C is a step (5) for obtaining a phosphor resin sheet having a substantially L shape in plan view by stretching the stretched support sheet. Show. 5A to 5C are partial process diagrams of a modified example of the method for manufacturing the second sheet member shown in FIGS. 1A to 2E, and FIG. 5A is a process of forming a through hole having a substantially rectangular shape in plan view (2 ), FIG. 5B shows a step (3) of separating the phosphor resin sheet, and FIG. 5C shows a step (5) of drawing the stretched support sheet to obtain a phosphor resin sheet having two notches. . FIG. 6 shows the relationship between the storage shear modulus G ′ and the temperature T of the phosphor resin sheet in Example A.

  Vertical direction (first direction, thickness direction, upper side is first direction one side, lower side is first direction other side), left and right direction (second direction orthogonal to first direction, left side is second) Direction one side, the right side is the second direction second side) and the front-rear direction (the third direction orthogonal to the first direction and the second direction, the front side is the third direction one side, the rear side is the third direction other side), It conforms to the direction indicated by the arrow in each figure.

<One Embodiment>
The manufacturing method of the 2nd sheet | seat member 7 which is one Embodiment of the manufacturing method of the fluorescent substance resin sheet of this invention is demonstrated with reference to FIG. 1A-FIG. 2E.

  In this method, a step (1) (see FIG. 1A) of preparing a first sheet member 1 including a release support sheet 10 and a phosphor resin sheet 3 and a step of forming a through hole 5 in the first sheet member 1 (2 ) (See FIG. 1B), step (3) of cutting the phosphor resin sheet 3 (see FIG. 1C), and transferring the phosphor resin sheet 3 from the release support sheet 10 to the stretched support sheet 11 to obtain a second sheet A step (4) (see FIG. 2D) for obtaining the member 7 and a step (5) (see FIG. 2E) for stretching the second sheet member 7 are sequentially provided.

1. Process (1)
As shown in FIG. 1A, in the step (1), a first sheet member 1 including a release support sheet 10 and a phosphor resin sheet 3 is prepared.

  In order to prepare the 1st sheet | seat member 1, the peeling support sheet 10 is prepared first.

1-1. Peeling Support Sheet The peeling support sheet 10 protects the lower surface of the phosphor resin sheet 3, and forms phosphors in the formation of the through holes 5 in the step (2) and the cutting of the phosphor resin sheet 3 in the step (3). The resin sheet 3 is supported. The peeling support sheet 10 is made of a flexible film. Examples of the release support sheet 10 include polymer films such as a polyethylene film and a polyester film (such as PET), for example, a ceramic sheet such as a metal foil. The peeling support sheet 10 has a substantially rectangular shape in plan view. The thickness of the peeling support sheet 10 is, for example, 1 μm or more, preferably 10 μm or more, and for example, 2,000 μm or less, preferably 1,000 μm or less.

1-2. Next, the B-stage phosphor resin sheet 3 is disposed on the upper surface of the release support sheet 10.

  The phosphor resin sheet 3 is formed as a B-stage sheet, for example, from a phosphor resin composition containing a phosphor and a resin.

1-2. (1) Phosphor The phosphor is a wavelength conversion material. Specifically, examples of the phosphor include a yellow phosphor capable of converting blue light into yellow light, and a red phosphor capable of converting blue light into red light.

Examples of the yellow phosphor include silicate phosphors such as (Ba, Sr, Ca) ₂ SiO ₄ ; Eu, (Sr, Ba) ₂ SiO ₄ : Eu (barium orthosilicate (BOS)), for example, Y ₃ Al Garnet-type phosphors having a garnet-type crystal structure such as ₅ O ₁₂ : Ce (YAG (yttrium, aluminum, garnet): Ce), Tb ₃ Al ₃ O ₁₂ : Ce (TAG (terbium, aluminum, garnet): Ce) Examples thereof include oxynitride phosphors such as Ca-α-SiAlON.

Examples of the red phosphor include nitride phosphors such as CaAlSiN ₃ : Eu and CaSiN ₂ : Eu.

  The phosphor is preferably a yellow phosphor, and more preferably a garnet phosphor.

  Examples of the shape of the phosphor include a spherical shape, a plate shape, and a needle shape.

  The average value of the maximum length of the phosphor (in the case of a sphere, the average particle diameter) is, for example, 0.1 μm or more, preferably 1 μm or more, and for example, 200 μm or less, preferably 100 μm or less. But there is.

  The phosphors can be used alone or in combination.

  The blending ratio of the phosphor is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, for example, 90% by mass or less, preferably 80% by mass with respect to the phosphor resin composition. It is as follows.

1-2. (2) Resin The resin is a matrix for uniformly dispersing the phosphor in the phosphor resin composition, and is preferably a transparent resin. Examples of the resin include a curable resin.

  Examples of the curable resin include silicone resin, epoxy resin, urethane resin, polyimide resin, phenol resin, urea resin, melamine resin, and unsaturated polyester resin.

  Examples of the curable resin include curable resins that can be in a B-stage state.

  Examples of the curable resin that can be in the B-stage state include thermosetting resins such as a two-stage reaction curable resin and a one-stage reaction curable resin.

  The two-stage reaction curable resin has two reaction mechanisms. In the first stage reaction, the A stage state is changed to the B stage (semi-cured), and then in the second stage reaction, the B stage state is obtained. To C-stage (complete curing). That is, the two-stage reaction curable resin is a thermosetting resin that can be in a B-stage state under appropriate heating conditions. The B stage state (semi-cured state) is a state between the A stage state (uncured state) in which the thermosetting resin is liquid and the fully cured C stage state (completely cured state). In addition, the gelation is slightly advanced and the shear elastic modulus is a semi-solid state or a solid state smaller than the shear elastic modulus in the C stage state.

  The one-stage reaction curable resin has one reaction mechanism, and can be changed from the A-stage state to the C-stage by the first-stage reaction. Such a one-stage reaction curable resin can stop the reaction in the middle of the first-stage reaction and change from the A-stage state to the B-stage state. The reaction is restarted and includes a thermosetting resin that can be changed from the B-stage state to the C-stage. That is, the first-stage reaction curable resin includes a thermosetting resin that can be in a B-stage state. On the other hand, the one-stage reaction curable resin cannot be controlled so as to stop in the middle of the one-stage reaction, that is, cannot enter the B stage state, and is thermosetting that changes from the A stage to the C stage at a time. Does not contain resin.

  The thermosetting resin that can be in the B-stage state preferably includes a silicone resin and an epoxy resin, and more preferably includes a silicone resin.

  The above-mentioned thermosetting resin may be the same type or a plurality of types.

  Examples of the silicone resin include silicone resin compositions such as an addition reaction curable silicone resin composition and a condensation / addition reaction curable silicone resin composition from the viewpoint of transparency, durability, heat resistance, and light resistance. Preferably, an addition reaction curable silicone resin composition is used. Silicone resins may be used alone or in combination.

  The addition reaction curable silicone resin composition is a one-stage reaction curable resin composition, and includes, for example, an alkenyl group-containing polysiloxane, a hydrosilyl group-containing polysiloxane, and a hydrosilylation catalyst.

  The alkenyl group-containing polysiloxane contains two or more alkenyl groups and / or cycloalkenyl groups in the molecule. The alkenyl group-containing polysiloxane is specifically represented by the following average composition formula (1).

Average composition formula (1):
R ¹ _a R ² _b SiO _{(4-ab) / 2}
(In the formula, R ¹ represents an alkenyl group having 2 to 10 carbon atoms and / or a cycloalkenyl group having 3 to 10 carbon atoms. R ² represents an unsubstituted or substituted monovalent carbon atom having 1 to 10 carbon atoms. A hydrogen group (excluding an alkenyl group and a cycloalkenyl group); a is from 0.05 to 0.50, and b is from 0.80 to 1.80.
In formula (1), examples of the alkenyl group represented by R ¹ include alkenyl having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, and octenyl group. Groups. Examples of the cycloalkenyl group represented by R ¹ include cycloalkenyl groups having 3 to 10 carbon atoms such as a cyclohexenyl group and a norbornenyl group.

R ¹ is preferably an alkenyl group, more preferably an alkenyl group having 2 to 4 carbon atoms, and still more preferably a vinyl group.

The alkenyl groups represented by R ¹ may be the same type or a plurality of types.

The monovalent hydrocarbon group represented by R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group and a cycloalkenyl group.

  Examples of the unsubstituted monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a pentyl group. , Heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group and other alkyl groups having 1 to 10 carbon atoms such as cyclopropyl, cyclobutyl group, cyclopentyl group and cyclohexyl group. Examples include alkyl groups such as aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl and naphthyl groups, and aralkyl groups having 7 to 8 carbon atoms such as benzyl and benzylethyl groups. Preferably, a C1-C3 alkyl group and a C6-C10 aryl group are mentioned, More preferably, a methyl group and / or a phenyl group are mentioned.

  On the other hand, examples of the substituted monovalent hydrocarbon group include those in which the hydrogen atom in the above-described unsubstituted monovalent hydrocarbon group is substituted with a substituent.

  Examples of the substituent include a halogen atom such as a chlorine atom, for example, a glycidyl ether group.

  Specific examples of the substituted monovalent hydrocarbon group include a 3-chloropropyl group and a glycidoxypropyl group.

  The monovalent hydrocarbon group may be unsubstituted or substituted, and is preferably unsubstituted.

The monovalent hydrocarbon groups represented by R ² may be of the same type or a plurality of types. Preferably, a methyl group and / or a phenyl group are mentioned, More preferably, combined use of a methyl group and a phenyl group is mentioned.

  a is preferably 0.10 or more and 0.40 or less.

  b is preferably 1.5 or more and 1.75 or less.

  The weight average molecular weight of the alkenyl group-containing polysiloxane is, for example, 100 or more, preferably 500 or more, and for example, 10,000 or less, preferably 5,000 or less. The weight average molecular weight of the alkenyl group-containing polysiloxane is a conversion value based on standard polystyrene measured by gel permeation chromatography.

  The alkenyl group-containing polysiloxane is prepared by an appropriate method, and a commercially available product can also be used.

  The alkenyl group-containing polysiloxanes may be of the same type or a plurality of types.

  The hydrosilyl group-containing polysiloxane contains, for example, two or more hydrosilyl groups (SiH groups) in the molecule. Specifically, the hydrosilyl group-containing polysiloxane is represented by the following average composition formula (2).

Average composition formula (2):
^{_{H c R 3 d SiO (4}} -c-d) / 2
(In the formula, R ³ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms (excluding an alkenyl group and a cycloalkenyl group). C is 0.30 or more, 1 0.0 or less, and d is 0.90 or more and 2.0 or less.)
In formula (2), the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ is an unsubstituted or substituted carbon group having 1 to 10 carbon atoms represented by R ² in formula (1). The same thing as the monovalent hydrocarbon group of is illustrated. Preferably, an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group. And / or a phenyl group.

  c is preferably 0.5 or less.

  d is preferably 1.3 or more and 1.7 or less.

  The weight average molecular weight of the hydrosilyl group-containing polysiloxane is, for example, 100 or more, preferably 500 or more, and for example, 10,000 or less, preferably 5,000 or less. The weight average molecular weight of the hydrosilyl group-containing polysiloxane is a conversion value based on standard polystyrene measured by gel permeation chromatography.

  The hydrosilyl group-containing polysiloxane is prepared by an appropriate method, and a commercially available product can also be used.

  Further, the hydrosilyl group-containing polysiloxane may be of the same type or a plurality of types.

Average composition formula described above (1) and the average compositional formula (2), at least one of the hydrocarbon groups R ² and R ³ preferably includes a phenyl group, more preferably, R ² and R ³ Both hydrocarbons contain a phenyl group. When at least one of the hydrocarbon groups of R ² and R ³ contains a phenyl group, the addition reaction curable silicone resin composition is a phenyl silicone resin composition.

  The blending ratio of the hydrosilyl group-containing polysiloxane is the ratio of the number of moles of alkenyl groups and cycloalkenyl groups of the alkenyl group-containing polysiloxane to the number of moles of hydrosilyl groups of the hydrosilyl group-containing polysiloxane (number of moles of alkenyl groups and cycloalkenyl groups). / Number of moles of hydrosilyl group) is adjusted to be, for example, 1/30 or more, preferably 1/3 or more, and for example, 30/1 or less, preferably 3/1 or less.

  The hydrosilylation catalyst is a substance (addition catalyst) that improves the reaction rate of the hydrosilylation reaction (hydrosilyl addition) between the alkenyl group and / or cycloalkenyl group of the alkenyl group-containing polysiloxane and the hydrosilyl group of the hydrosilyl group-containing polysiloxane. If it exists, it will not specifically limit, For example, a metal catalyst is mentioned. Examples of the metal catalyst include platinum catalysts such as platinum black, platinum chloride, chloroplatinic acid, platinum-olefin complexes, platinum-carbonyl complexes, and platinum-acetyl acetate, for example, palladium catalysts such as rhodium catalyst.

  The blending ratio of the hydrosilylation catalyst is, for example, 1.0 ppm or more on a mass basis with respect to the alkenyl group-containing polysiloxane and the hydrosilyl group-containing polysiloxane as the metal amount of the metal catalyst (specifically, metal atom). In addition, for example, it is 10,000 ppm or less, preferably 1,000 ppm or less, and more preferably 500 ppm or less.

  The addition reaction curable silicone resin composition is prepared by blending an alkenyl group-containing polysiloxane, a hydrosilyl group-containing polysiloxane, and a hydrosilylation catalyst in the above proportions.

  The above-described addition reaction curable silicone resin composition is prepared and used in an A stage (liquid) state by first blending an alkenyl group-containing polysiloxane, a hydrosilyl group-containing polysiloxane, and a hydrosilylation catalyst.

  As described above, the phenyl silicone resin composition undergoes a hydrosilylation addition reaction between the alkenyl group and / or cycloalkenyl group of the alkenyl group-containing polysiloxane and the hydrosilyl group of the hydrosilyl group-containing polysiloxane by heating under desired conditions. After that, the hydrosilylation addition reaction is once stopped. As a result, the A stage state can be changed to the B stage (semi-cured) state.

  After that, the phenyl-based silicone resin composition is completed by restarting the above-described hydrosilylation addition reaction by heating under further desired conditions. As a result, the B stage state can be changed to the C stage (fully cured) state.

  The condensation / addition reaction curable silicone resin composition is a two-stage reaction curable resin, and specifically described in, for example, JP 2010-265436 A, JP 2013-187227 A, and the like. 1 to 8 condensation / addition reaction curable silicone resin compositions, for example, JP2013-091705A, JP2013-001815A, JP2013-001814A, JP2013-001813A, Examples thereof include a cage-type octasilsesquioxane-containing silicone resin composition described in JP2012-102167A. The condensation / addition reaction curable silicone resin composition is solid and has both thermoplasticity and thermosetting properties.

  The resin is solid when it is at least in the B stage (semi-cured) state, that is, when the phosphor resin sheet 3 is formed. And such resin has both thermoplasticity and thermosetting property. That is, the resin is once cured by heating and then completely cured. More specifically, the viscosity of the resin gradually decreases as the temperature rises, and then the viscosity gradually increases as the temperature rise continues.

  The blending ratio of the resin is, for example, 20% by mass or more, preferably 25% by mass or more, and, for example, 97% by mass or less, preferably 95% by mass or less with respect to the phosphor resin composition. . The mixing ratio of the resin to 100 parts by mass of the phosphor is, for example, 25 parts by mass or more, preferably 30 parts by mass or more, and for example, 3000 parts by mass or less, preferably 2000 parts by mass or less.

1-2. (3). Filler The phosphor resin composition can contain a filler, for example.

  Examples of the filler include light diffusing particles. Examples of the light diffusing particles include inorganic particles and organic particles.

Examples of the inorganic particles include silica (SiO ₂ ), talc (Mg ₃ (Si ₄ O ₁₀ ) (HO) ₂ ), alumina (Al ₂ O ₃ ), boron oxide (B ₂ O ₃ ), calcium oxide (CaO). ), Zinc oxide (ZnO), strontium oxide (SrO), magnesium oxide (MgO), zirconium oxide (ZrO ₂ ), barium oxide (BaO), antimony oxide (Sb ₂ O ₃ ), and other oxides such as aluminum nitride Examples thereof include inorganic particles (inorganic materials) such as nitrides such as (AlN) and silicon nitride (Si ₃ N ₄ ). Examples of the inorganic particles include composite inorganic particles prepared from the inorganic materials exemplified above, and specifically, composite inorganic oxide particles (specifically, glass particles) prepared from an oxide. Can be mentioned.

  The inorganic particles are preferably silica particles and glass particles.

  Inorganic particles are usually insoluble in solvents such as toluene.

  Examples of organic materials for organic particles include acrylic resins, styrene resins, acrylic-styrene resins, silicone resins, polycarbonate resins, benzoguanamine resins, polyolefin resins, polyester resins, polyamide resins, and polyimide resins. Resin etc. are mentioned.

  The organic particles are preferably acrylic resin and silicone resin particles.

  The organic particles are insoluble in a solvent such as toluene. In addition, the organic particles can include, for example, those that dissolve in a solvent.

  The filler can be used alone or in combination.

  The average particle diameter of the filler is, for example, 1.0 μm or more, preferably 2.0 μm or more, more preferably 4.0 μm or more, and for example, 30 μm or less, preferably 25 μm or less, more preferably, 10 μm or less. The average particle size is measured by a particle size distribution measuring device.

  The content of the filler is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and, for example, 80% by mass or less with respect to the phosphor resin composition. Preferably, it is 50 mass% or less, More preferably, it is 30 mass% or less. The mixing ratio of the filler to 100 parts by weight of the resin is, for example, 2 parts by weight or more, preferably 5 parts by weight or more, and for example, 200 parts by weight or less, preferably 100 parts by weight or less.

1-3. Preparation of phosphor resin sheet In order to prepare the phosphor resin sheet 3, for example, the above-described components (phosphor, resin, and, if necessary, filler) are blended to prepare a varnish of the phosphor resin composition. To do. Subsequently, a varnish of the phosphor resin composition is applied to the upper surface of the release support sheet 10. Next, the phosphor resin composition is B-staged. Specifically, the phosphor resin composition is heated (baked).

  The heating (baking) conditions are appropriately set so that the storage shear modulus G ′ in the dynamic viscoelasticity measurement in the phosphor resin sheet 3 is in a desired range.

  That is, the heating temperature is appropriately set depending on the composition of the resin in the phosphor resin composition, and specifically, for example, 50 ° C. or higher, preferably 70 ° C. or higher, and for example, 120 ° C. or lower, preferably 100 ° C. or lower. When the heating temperature is not less than the above lower limit and / or the heating temperature is not more than the above upper limit, the minimum value of the above-described storage shear modulus G ′ can be set in a desired range.

  The heating time is, for example, 2.5 minutes or more, preferably 5.5 minutes or more, and for example, 4 hours or less, preferably 1 hour or less. If the heating time is not less than the above lower limit and / or not more than the above upper limit, the minimum value of the above-described storage shear modulus G ′ can be set in a desired range.

  Thereby, the phosphor resin sheet 3 is prepared.

  The thickness T1 of the phosphor resin sheet 3 is, for example, 25 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and, for example, 500 μm or less, preferably 250 μm or less, more preferably 200 μm or less. is there.

  If the thickness T1 of the phosphor resin sheet 3 is not less than the above lower limit or not more than the above upper limit, the step (2) described later can be reliably performed.

1-4. Dynamic viscoelasticity of phosphor resin sheet Storage shear elastic modulus G ′ and temperature obtained by measuring dynamic viscoelasticity of such phosphor resin sheet 3 under conditions of a frequency of 1 Hz and a heating rate of 20 ° C./min. The curve showing the relationship with T has a minimum value.

  And the temperature T in such a minimum value exists in the range of 40 degreeC or more and 200 degrees C or less, The storage shear elastic modulus G 'in the above-mentioned minimum value is the range of 1,000 Pa or more and 90,000 Pa or less, for example. It is in.

  If the temperature T at the minimum value is less than 40 ° C., the viscosity increases excessively in heating at 40 ° C. or higher in the step (3) described below, so that the optical semiconductor element 15 of the phosphor resin sheet 3 (FIG. 2F). There is a problem that the adhesion strength to the reference) is reduced.

  If the temperature T at the minimum value exceeds 200 ° C., the viscosity of the phosphor resin sheet 3 does not drop sufficiently in heating at 200 ° C. or lower in the step (3) described below. There is a problem that the adhesion to the element 15 (see FIG. 2E) is reduced.

  The temperature T at the minimum value is in the range of 40 ° C. or more and 200 ° C. or less, and the storage shear modulus G ′ at the above minimum value is preferably 10,000 Pa or more, more preferably 20,000 Pa or more. More preferably, it is 30,000 Pa or more, and preferably 70,000 Pa or less.

  If the storage shear modulus G ′ at the minimum value is equal to or greater than the above lower limit, the formation of the through-hole 5 in the step (2) described below can be reliably performed, and further, the phosphor resin sheet in the step (3) 3 can be cut reliably.

  If the storage shear modulus G ′ at the minimum value is less than or equal to the above upper limit, the viscosity of the phosphor resin sheet 3 is sufficiently lowered in the step (3) to be described next. Excellent adhesion to the element 15 (see FIG. 2F).

1-5. First Sheet Member The first sheet member 1 has a predetermined thickness, extends in the left-right direction and the front-rear direction, and has a flat upper surface (front surface) and a flat lower surface (back surface).

  The first sheet member 1 includes a release support sheet 10 and a phosphor resin sheet 3 located on the upper surface of the release support sheet 10. The first sheet member 1 is preferably composed only of the peeling support sheet 10 and the phosphor resin sheet 3.

  In the first sheet member 1, the upper surface of the peripheral end portion of the peeling support sheet 10 is exposed from the phosphor resin sheet 3.

2-2. Process (2)
As shown in FIG. 1B, in the step (2), the through hole 5 is formed in the first sheet member 1.

  In the first sheet member 1 including the phosphor resin sheet 3, a plurality of the through holes 5 are arranged and arranged at intervals in the front-rear direction and the left-right direction. Each of the plurality of through holes 5 is a round hole that penetrates the first sheet member 1 in the thickness direction (vertical direction). Since the through hole 5 is formed in both the peeling support sheet 10 and the phosphor resin sheet 3, the through surface 6 facing the through hole 5 is continuous over the peeling support sheet 10 and the phosphor resin sheet 3.

  As a method of performing the step (2), for example, a method of punching the first sheet member 1, for example, a method of blasting the first sheet member 1, for example, a method of drilling the first sheet member 1, for example, Examples of the drilling method include a laser processing method.

  In punching, the punching die 22 is moved so as to penetrate the first sheet member 1 from above or below the first sheet member 1. Preferably, the punching mold 22 is peeled down (specifically, peeled off) from above the first sheet member 1 (specifically, the phosphor resin sheet 3 side) so as to penetrate the first sheet member 1. Move toward the support sheet 10 side). If the punching die 22 is moved downward, the debris (dust) generated by punching can be easily removed as compared with the method of moving the punching die 22 upward.

  Examples of the blasting include direct pressure blasting and siphoning. In the blast processing, specifically, in the first sheet member 1, a resist is disposed at a place other than the portion where the through hole 5 is formed, the first sheet member 1 is covered with the resist, and then the spray material is applied to the first sheet member 1. To spray. The dimensions of the through-hole 5 are appropriately adjusted by appropriately adjusting the type, particle size, injection speed, method (direct pressure type, siphon type), etc. of the injection material used for blasting.

  In laser processing, a laser such as a YAG laser or a CO2 laser is used.

  Blasting can improve productivity more than laser processing.

  As a method for performing the step (2), from the viewpoint of shortening tact time and processing cost, a method of punching the first sheet member 1 and a method of drilling the first sheet member 1 are preferable.

  When drilling the first sheet member 1, since the drill is small in diameter, it is likely to be broken (broken), so that a long time is required for drilling to prevent it. Therefore, a method of punching the first sheet member 1 is more preferable from the viewpoint of shortening the tact time.

  In addition, as a method of performing the step (2), from the viewpoint of dimensional stability, a method of punching the first sheet member 1 is more preferable.

  Then, by forming the plurality of through holes 5 in the first sheet member 1, each of the plurality of through surfaces 6 facing each of the plurality of through holes 5 is formed in the first sheet member 1. That is, in this step (2), the through hole 5 and the through surface 6 are formed simultaneously.

  The through surface 6 is an inner peripheral surface of the through hole 5 extending in the thickness direction (vertical direction) in the first sheet member 1.

  In the next step (3), the through-hole 5 has a dimension such that the through-surface 6 is divided and provided to each of the plurality of phosphor resin sheets 3 (see FIG. 1C).

  Specifically, the diameter L1 of the through hole 5 is, for example, 30 μm or more, preferably 50 μm or more, and, for example, 500 μm or less, preferably 400 μm or less. The distance L2 between the through holes 5 adjacent in the front-rear direction and the left-right direction is preferably equal, for example, 50 μm or more, preferably 100 μm or more, and for example, 10 mm or less, preferably 5 mm or less. is there. Further, the pitch L3 of the adjacent through holes 5, that is, the sum of the diameter L1 and the interval L2 of the through holes 5 is, for example, 80 μm or more, preferably 150 μm or more, and for example, 10.5 mm or less, preferably Is 5.4 mm or less.

2-3. Process (3)
As shown in FIG. 1C, in the step (3), the phosphor resin sheet 3 is cut.

  Specifically, the through-surface 6 that divides one through-hole 5 is given to each of the plurality of phosphor resin sheets 3, and the phosphor resin sheet 3 is cut so that one through-surface 6 is divided. . Specifically, the phosphor resin sheet 3 is cut so that the through surface 6 that divides one through hole 5 is provided to each of the four phosphor resin sheets 3 and the one through surface 6 is divided into four.

  Examples of the method for performing the step (3) include processing with a cutting blade, blast processing, laser processing, and the like.

  Examples of the cutting blade include a dicing saw (dicing blade) having a disk shape and rotatable with respect to the axis thereof, for example, a Thomson blade (not shown) having a cutting edge extending substantially horizontally. The cutting blade is preferably a Thomson blade.

  As the blasting, the blasting described above is used.

  In the laser processing, the above-described laser is used.

  From the viewpoint of smooth cutting ability, preferably, processing with a cutting blade and blasting are mentioned, and from the viewpoint of dimensional stability, processing with a cutting blade is more preferable.

  First, in the step (3), the phosphor resin sheet 3 is cut so that the first cutting lines 31 are formed in the phosphor resin sheet 3.

  Specifically, the phosphor resin sheet 3 is cut so that the first cutting lines 31 pass through the centers of the plurality of through holes 5. Then, one through surface 6 is divided into a plurality (specifically, four).

  The first cutting line 31 extends in the front-rear direction and is disposed in the left-right direction with a distance from each other, and the first front-rear cutting line 32 extends in the left-right direction and is disposed in the front-rear direction at a distance from each other. And a cutting line 33.

  The first front-rear cutting line 32 and the first left-right cutting line 33 intersect each other at the centers of the plurality of through holes 5 so as to be orthogonal to each other.

  In addition, the phosphor resin sheet 3 along the second cutting line 34 is cut along with the cutting of the phosphor resin sheet 3 along the first cutting line 31.

  The second cutting line 34 does not pass through the through hole 5, and specifically passes between adjacent through holes 5. The second cutting line 34 extends in the front-rear direction, the second front-rear cutting line 35 that is adjacent to and parallel to the first front-rear cutting line 32, and the second cutting line 34 that extends in the left-right direction and is adjacent to the first left-right cutting line 33. 2 left and right cutting lines 36.

  The second front / rear cutting lines 35 and the first front / rear cutting lines 32 are alternately arranged at equal intervals in the left-right direction. The second left and right cutting lines 36 and the first left and right cutting lines 33 are alternately arranged at equal intervals in the front-rear direction.

  Then, by cutting the phosphor resin sheet 3 along the first cutting line 31 and the second cutting line 34 described above, the plurality of phosphor resin sheets 3 are obtained in a state of being supported by the release support sheet 10.

  In addition, with the cutting | disconnection of the above-mentioned fluorescent substance resin sheet 3, the 1st cutting line 31 and the 2nd cutting line 34 may be formed also in the upper surface of the peeling support sheet 10, for example.

2-4. Process (4)
As shown in FIG. 2D, in step (4), the phosphor resin sheet 3 is transferred from the release support sheet 10 to the stretched support sheet 11.

  In step (4), as shown in FIG. 1C, first, a stretched support sheet 11 is prepared.

  The stretched support sheet 11 is a sheet that can be stretched so as to be spaced apart from each other in the plane direction while supporting each of the plurality of separated phosphor resin sheets 3. There is a sheet. In addition, for example, the stretched support sheet 11 is a sheet that can be transferred to the optical semiconductor element 15 to be described later due to a decrease in pressure-sensitive bonding force due to processing (for example, irradiation with active energy rays).

  Examples of the stretched support sheet 11 include JP 2014-168036 A, JP 2014-168033 A, JP 2014-130918 A, JP 2014-090157 A, and JP 2014-0775450 A. Can be mentioned. A commercially available product is used as the stretched support sheet 11, for example, SPV series (SPV-224S, pressure-sensitive adhesive sheet, manufactured by Nitto Denko Corporation) or the like.

  The thickness of the extending | stretching support sheet 11 is 0.1 mm or more and 1 mm or less, for example.

  In step (4), as shown in FIG. 1C, the stretched support sheet 11 is disposed above the phosphor resin sheet 3. Next, the lower surface of the stretched support sheet 11 is brought into contact with the upper surface of the phosphor resin sheet 3, and they are pressure-bonded.

  Thereafter, as shown in FIG. 4D, the peeling support sheet 10 is peeled off from the phosphor resin sheet 3.

  Thereby, the 2nd sheet | seat member 7 provided with the extending | stretching support sheet 11 and the fluorescent substance resin sheet 3 is obtained. The stretched support sheet 11 preferably comprises only the stretched support sheet 11 and the phosphor resin sheet 3.

2-5. Process (5)
As shown in FIG. 2E, in the step (5), the second sheet member 7 is extended outward in the surface direction.

  Specifically, the peripheral edge part of the extending | stretching support sheet 11 is extended toward the front-back direction outer side and the left-right direction outer side (surface direction outer side).

  Thereby, the space | interval I between the some fluorescent substance resin sheet 3 separated into pieces arises, and they are separated in the surface direction.

  Further, the plurality of phosphor resin sheets 3 have notches 23 corresponding to the divided through surfaces 6. As shown in FIG. 2D, the notch 23 is provided in the phosphor resin sheet 3 in the cutting of the step (3). However, as shown in FIG. 2E, the plurality of phosphor resin sheets 3 in the step (4). Due to the occurrence of the interval I between the two, it appears in each of the plurality of phosphor resin sheets 3.

  The notch portion 23 is formed so as to cut out (chamfer) corner portions of the singulated phosphor resin sheet 3 along the thickness direction. Specifically, the cutout portion 23 has a substantially arc-shaped curved surface in a plan view by cutting out a corner portion of the phosphor resin sheet 3 into a substantially fan shape in a plan view.

  In this way, the plurality of phosphor resin sheets 3 having the notches 23 are obtained in a state where they are supported by the stretched support sheet 11.

2. Method for Producing Adhesive Optical Semiconductor Element and Method for Producing Optical Semiconductor Device Next, using the phosphor resin sheet 3 described above, a method for producing the adhesive optical semiconductor element 19 and an optical semiconductor device 30 are produced. How to do it.

2-1. Method for Producing Adhesive Optical Semiconductor Element To produce the adhesive optical semiconductor element 19, the phosphor resin sheet 3 supported by the stretched support sheet 11 is adhered to the optical semiconductor element 15 as shown in FIG. 2E. .

  The optical semiconductor element 15 is disposed on the upper surface of the substrate 16.

  The substrate 16 has a substantially plate shape and is made of an insulating material. The substrate 16 includes a terminal 17 in front of the optical semiconductor element 15. The terminal 17 is disposed on the upper surface of the substrate 16.

  The optical semiconductor element 15 is fixed to the upper surface of the substrate 16 and is arranged at a distance from the terminal 17. The optical semiconductor element 15 has a substantially rectangular plate shape and is made of an optical semiconductor material. In addition, a connection portion 18 is formed on the upper surface of the optical semiconductor element 15.

  In order to carry out the step (6), a pressing member (not shown) such as a needle is disposed above the second sheet member 7, and then the pressing member is stretched corresponding to one phosphor resin sheet 3. By pressing the support sheet 11, one phosphor resin sheet 3 is pushed down. The pressing of the phosphor resin sheet 3 is sequentially performed for each of the plurality of phosphor resin sheets 3.

  Separately, a heat source is disposed below the substrate 16, and the substrate 16 and the optical semiconductor element 15 are heated by the heat source. The heat source is arranged with respect to the substrate 16 so as not to directly heat the second sheet member 7.

  The heating temperature is, for example, 40 ° C. or higher, preferably 45 ° C. or higher, and 200 ° C. or lower, preferably 180 ° C. or lower, more preferably 150 ° C. or lower.

  Subsequently, the phosphor resin sheet 3 is brought into contact with the heated optical semiconductor element 15.

  Then, the phosphor resin sheet 3 in contact with the upper surface of the optical semiconductor element 15 is heated to the above temperature. Therefore, the phosphor resin sheet 3 is first attached to the upper surface of the optical semiconductor element 15 based on the plasticization of the phosphor resin composition (specifically, resin). Subsequently, the phosphor resin sheet 3 firmly adheres to the upper surface of the optical semiconductor element 15 based on the fact that the resin is slightly cured.

  The adhesion strength of the phosphor resin sheet 3 to the glass plate is, for example, 0.10 N / 8.5 mm or more, preferably 0.20 N / 8.5 mm or more, more preferably 0.30 N / 8.5 mm or more, It is preferably 0.40 N / 8.5 mm or more, particularly preferably 0.50 N / 8.5 mm or more, and for example, 10.00 N / 8.5 mm or less. If the adhesive force is greater than or equal to the above lower limit, good adhesive force between the phosphor resin sheet 3 and the optical semiconductor element 15 can be ensured. The method for measuring the adhesion will be described in detail in a later example.

  Thereafter, the stretched support sheet 11 is peeled from the phosphor resin sheet 3. Specifically, the pressing member is pulled upward, and the stretched support sheet 11 is pulled upward.

  Thereafter, the adhered optical semiconductor element 19 and the substrate 16 are heated by, for example, an oven. When the phosphor resin composition contains a thermosetting resin, the thermosetting resin is completely cured (C stage).

  The heating temperature is, for example, 100 ° C. or more, preferably 120 ° C. or more, and for example, 200 ° C. or less, preferably 160 ° C. or less. The heating time is, for example, 10 minutes or longer, preferably 30 minutes or longer, and for example, 480 minutes or shorter, preferably 300 minutes or shorter.

  Note that the heating can be performed a plurality of times at different temperatures.

  Thereby, when the resin is a thermosetting resin, the thermosetting resin is cured (C stage). Thereby, the thermosetting resin is completely reacted to produce a product.

(Product)
When the resin is a thermosetting silicone resin composition, the alkenyl group and / or cycloalkenyl group of the alkenyl group-containing polysiloxane and the hydrosilyl group-containing polysiloxane are used in the reaction of the silicone resin composition (C-staging reaction). The hydrosilyl addition reaction with the hydrosilyl group of siloxane is further accelerated. Thereafter, the alkenyl group and / or cycloalkenyl group or the hydrosilyl group of the hydrosilyl group-containing polysiloxane disappears, and the hydrosilyl addition reaction is completed, whereby the C-stage silicone resin composition, that is, the product (or cured product) Product) is obtained. That is, by completing the hydrosilylation reaction, curability (specifically, thermosetting) is exhibited in the silicone resin composition.

  In the above-mentioned C-stage product, the content of the phenyl group in the hydrocarbon group directly bonded to the silicon atom is, for example, 30 mol% or more, preferably 35 mol% or more, and for example, 55 mol%. Hereinafter, it is preferably 50 mol% or less.

The above-mentioned phenyl group content is calculated by ²⁹ Si-NMR. The details of the calculation method of the content ratio of the phenyl group are calculated by ²⁹ Si-NMR based on the description of WO2011 / 125463, for example.

  Thereby, the phosphor resin sheet 3 is bonded to the upper surface of the optical semiconductor element 15.

  As a result, on the substrate 16, the bonded optical semiconductor element 19 including the optical semiconductor element 15 and the phosphor resin sheet 3 in close contact with the upper surface of the optical semiconductor element 15 is obtained.

  The connection part 18 of the optical semiconductor element 15 is exposed from the notch part 23 of the phosphor resin sheet 3.

2-2. Manufacturing Method of Optical Semiconductor Device In order to manufacture the optical semiconductor device 30, as shown in FIG. 2F, the above-mentioned bonded optical semiconductor element 19 is prepared, and then the connecting portion 18 and the terminal 17 are electrically connected.

  Specifically, the connecting portion 18 and the terminal 17 are wire bonded.

  In wire bonding, first, a wire 29 is prepared, and then one end of the wire 29 is electrically connected to the connecting portion 18 and the other end of the wire 29 is electrically connected to the terminal 17. Moreover, the wire 29 bypasses the notch part 23 (penetrating surface 6). The wire 29 passes through the space that the through surface 6 faces.

  The wire 29 is disposed so as to bend upward. Specifically, the wire 29 is bent into a substantially U shape that opens downward.

  Thereby, the optical semiconductor device 30 including the bonded optical semiconductor element 19, the wire 29, the terminal 17, and the substrate 16 is obtained.

3. Action and Effect According to this method, the through surface 6 that divides one through hole 5 is provided to each of the plurality of phosphor resin sheets 3 by cutting the phosphor resin sheet 3 with the first cutting line 31. Since the through surface 5 is divided, the plurality of phosphor resin sheets 3 having the cutout portions 23 can be efficiently manufactured.

  Further, according to this method, in the step (3), the step (3) can be reliably performed by cutting the phosphor resin sheet with the cutting blade.

  Moreover, according to this method, in the step (2), if the phosphor resin sheet is punched, the step (2) can be reliably performed.

  According to this method, the temperature T at the minimum value of the phosphor resin sheet 3 is in the range of 40 ° C. or more and 200 ° C. or less, and the storage shear modulus G ′ at the minimum value is 1,000 Pa or more and 90,000 Pa. It is in the following range. Therefore, when using the phosphor resin sheet 3 so as to be adhered to the optical semiconductor element 15 in the range of 40 ° C. or more and 200 ° C. or less, the phosphor resin sheet 3 can be attached to the optical semiconductor element 15 with excellent adhesion. Can be attached.

  Moreover, according to this method, since the phosphor resin sheet 3 has the above-described storage shear modulus G ′, the through hole 5 can be formed with high accuracy in the step (2). Therefore, the phosphor resin sheet 3 having excellent reliability can be obtained.

4). In one embodiment, in step (2), as shown in FIG. 1B, the through hole 5 is a round hole, but the shape of the through hole 5 is not particularly limited. The through hole 5 can be formed in, for example, a polygonal shape, and specifically, can be formed in a rectangular shape (preferably a square shape) as shown in FIGS. 3A and 5A. That is, the through hole 5 can be a square hole.

  As shown in FIG. 3A, the through surface 6 facing the through hole 5 of the square hole is composed of four surfaces that are inclined with respect to the front-rear direction and the left-right direction in plan view. On the other hand, in plan view, each of the two diagonal lines of the through hole 5 is along the front-rear direction and the left-right direction.

  As shown in FIG. 3C, the notch 23 has a substantially rectangular shape in a side view.

  Each of the plurality of phosphor resin sheets 3 having the notches 23 has a substantially pentagonal shape in plan view. The through surface 6 is inclined with respect to the front-rear direction and the left-right direction.

  The notch 23 is formed by notching the corner of the phosphor resin sheet 3 into a substantially triangular shape in plan view (specifically, a right triangle or an isosceles triangle, preferably a right isosceles triangle). And a flat surface that is substantially linear in a plan view.

  Or as shown to FIG. 4A, the through-surface 6 which faces the through-hole 5 of a square hole follows the front-back direction and the left-right direction.

  As shown in FIG. 4C, each of the plurality of phosphor resin sheets 3 having the cutouts 23 has a substantially L shape in plan view.

  The notch 23 has a substantially L shape in plan view by cutting out a corner of the phosphor resin sheet 3 into a substantially rectangular shape (preferably square shape) in plan view.

  In one embodiment, one phosphor resin sheet 3 has one notch 23. However, the number of the notches 23 is not particularly limited. For example, as shown in FIG. 5C, one phosphor resin sheet 3 can also have a plurality of notches 23.

  In the step (2), as shown in FIG. 5A, in the phosphor resin sheet 3, the plurality of through holes 5 and the second cutouts 8 are arranged in the front / rear / left / right direction with an interval therebetween. In addition, the 2nd notch part 8 has the shape which notched each of the right side surface and the left side surface of the fluorescent substance resin sheet 3 in semicircle shape.

  Next, as shown in FIG. 5B, in the step (3), the phosphor resin sheet 3 is divided so that each of the two through surfaces 6 adjacent in the left-right direction is divided and given to one phosphor resin sheet 3. Disconnect.

  In this step (3), as shown in FIG. 5B, the second cutting line 34 does not have the second front-rear cutting line 35 (see FIG. 1C), but has only the second left-right cutting line 36.

  As shown in FIG. 5C, the phosphor resin sheet 3 has a plurality (two) of cutout portions 23.

  In one embodiment, as shown in FIGS. 1C and 2D, the method includes a step (4) of transferring the phosphor resin sheet 3 from the release support sheet 10 to the stretched support sheet 11.

  However, without the step (4), the phosphor resin sheet 3 is directly applied to the upper surface of the stretched support sheet 11, and the phosphor resin sheet 3 is directly provided on the upper surface of the stretched support sheet 11. And the second sheet member 7 made of the stretched support sheet 11, and then the through holes 5 are formed in the phosphor resin sheet 3, and then the stretched support sheet 11 is stretched to form a plurality of fluorescent light having the notch portions 23. The body resin sheet 3 can be separated into pieces.

  In the step (1) of one embodiment, the first sheet member 1 includes one release support sheet 10 with respect to the phosphor resin sheet 3. However, although not shown, the first sheet member 1 can also include two peeling support sheets 10 disposed on both sides in the thickness direction of the phosphor resin sheet 3.

  The peeling support sheet 10 disposed on the upper side of the phosphor resin sheet 3 protects the upper surface of the phosphor resin sheet 3 over the steps (2) and (3).

  Also according to each modification mentioned above, there can exist an effect similar to one embodiment mentioned above.

  Specific numerical values such as blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and the corresponding blending ratio (content ratio) ), Physical property values, parameters, etc. may be replaced with the upper limit values (numerical values defined as “less than” or “less than”) or lower limit values (numbers defined as “greater than” or “exceeded”). it can.

<Synthesis of alkenyl group-containing polysiloxane and hydrosilyl group-containing polysiloxane>
Synthesis example 1
In a four-necked flask equipped with a stirrer, reflux condenser, charging port and thermometer, 93.2 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 140 g of water, trifluoromethanesulfone 0.38 g of acid and 500 g of toluene were added and mixed. While stirring, a mixture of 729.2 g of methylphenyldimethoxysilane and 330.5 g of phenyltrimethoxysilane was added dropwise over 1 hour, and then heated under reflux for 1 hour. Then, it cooled, the lower layer (water layer) was isolate | separated and removed, and the upper layer (toluene solution) was washed with water 3 times. 0.40 g of potassium hydroxide was added to the toluene solution washed with water, and the mixture was refluxed while removing water from the water separation tube. After completion of water removal, the mixture was further refluxed for 5 hours and cooled. Thereafter, 0.6 g of acetic acid was added for neutralization, and then the toluene solution obtained by filtration was washed with water three times. Then, liquid alkenyl group containing polysiloxane A was obtained by concentrating under reduced pressure. The average unit formula and average composition formula of the alkenyl group-containing polysiloxane A are as follows.

Average unit formula:
((CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 ) _0.15 (CH ₃ C ₆ H ₅ SiO _2/2 ) _0.60 (C ₆ H ₅ SiO _3/2 ) _0.25
Average composition formula:
(CH ₂ = CH) _0.15 (CH ₃ ) _0.90 (C ₆ H ₅ ) _0.85 SiO _1.05
That is, the alkenyl group-containing polysiloxane A is represented by the above average composition formula (1) in which R ¹ is a vinyl group, R ² is a methyl group and a phenyl group, and a = 0.15 and b = 1.75. .

  Moreover, it was 2,300 when the weight average molecular weight of polystyrene conversion of alkenyl group containing polysiloxane A was measured by the gel permeation chromatography.

Synthesis example 2
In a four-necked flask equipped with a stirrer, reflux condenser, charging port and thermometer, 93.2 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 140 g of water, trifluoromethanesulfone 0.38 g of acid and 500 g of toluene were added and mixed. While stirring, a mixture of 173.4 g of diphenyldimethoxysilane and 300.6 g of phenyltrimethoxysilane was added dropwise over 1 hour. After completion of the addition, the mixture was heated to reflux for 1 hour. Then, it cooled, the lower layer (water layer) was isolate | separated and removed, and the upper layer (toluene solution) was washed with water 3 times. 0.40 g of potassium hydroxide was added to the toluene solution washed with water, and the mixture was refluxed while removing water from the water separation tube. After completion of water removal, the mixture was further refluxed for 5 hours and cooled. After neutralizing by adding 0.6 g of acetic acid, the toluene solution obtained by filtration was washed with water three times. Then, liquid alkenyl group containing polysiloxane B was obtained by concentrating under reduced pressure. The average unit formula and average composition formula of the alkenyl group-containing polysiloxane B are as follows.

Average unit formula:
(CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) _0.31 ((C ₆ H ₅ ) ₂ SiO _2/2 ) _0.22 (C ₆ H ₅ SiO _3/2 ) _0.47
Average composition formula:
(CH ₂ = CH) _0.31 (CH ₃ ) _0.62 (C ₆ H ₅ ) _0.91 SiO _1.08
That is, the alkenyl group-containing polysiloxane B is represented by the above average composition formula (1) in which R ¹ is a vinyl group, R ² is a methyl group and a phenyl group, and a = 0.31 and b = 1.53. .

  Moreover, it was 1,000 when the polystyrene conversion weight average molecular weight of the alkenyl group containing polysiloxane B was measured by gel permeation chromatography.

Synthesis example 3
Diphenyldimethoxysilane (325.9 g), phenyltrimethoxysilane (564.9 g), and trifluoromethanesulfonic acid (2.36 g) were added to a four-necked flask equipped with a stirrer, reflux condenser, inlet, and thermometer. Then, 134.3 g of 1,1,3,3-tetramethyldisiloxane was added, and 432 g of acetic acid was added dropwise over 30 minutes while stirring. After completion of dropping, the mixture was heated to 50 ° C. with stirring and reacted for 3 hours. After cooling to room temperature, toluene and water were added, mixed well and allowed to stand, and the lower layer (aqueous layer) was separated and removed. Thereafter, the upper layer (toluene solution) was washed with water three times and then concentrated under reduced pressure to obtain hydrosilyl group-containing polysiloxane C (crosslinking agent C).

  The average unit formula and average composition formula of the hydrosilyl group-containing polysiloxane C are as follows.

Average unit formula:
(H (CH ₃ ) ₂ SiO _1/2 ) _0.33 ((C ₆ H ₅ ) ₂ SiO _2/2 ) _0.22 (C ₆ H ₅ PhSiO _3/2 ) _0.45
Average composition formula:
H _0.33 (CH ₃ ) _0.66 (C ₆ H ₅ ) _0.89 SiO _1.06
That is, the hydrosilyl group-containing polysiloxane C is represented by the above average composition formula (2) in which R ³ is a methyl group and a phenyl group, and c = 0.33 and d = 1.55.

  Moreover, it was 1,000 when the weight average molecular weight of polystyrene conversion of hydrosilyl group containing polysiloxane C was measured by the gel permeation chromatography.

<Other raw materials>
Raw materials other than alkenyl group-containing polysiloxane and hydrosilyl group-containing polysiloxane will be described in detail below.
[Other materials used]
Platinum carbonyl complex:
Product name “SIP6829.2”, manufactured by Gelest, platinum concentration of 2.0% by mass
Phosphor:
Product name “Y468”, YAG: Ce, average particle size 17 μm, glass particles manufactured by Nemoto Lumi Materials, Inc .:
Composition and composition ratio (% by weight): SiO ₂ / Al ₂ O ₃ / CaO / MgO = 60/20/15/5 inorganic particles, average particle diameter: 20 μm
Aerosil particles:
Product name “R976S”, average particle size 7 nm, silicone resin particles manufactured by Evonik:
Product name “Tospearl 145”, average particle size 4.5 μm, manufactured by Momentive Performance Materials Japan

<Preparation of silicone resin composition>
Preparation Example 1
Alkenyl group-containing polysiloxane A 20 g, alkenyl group-containing polysiloxane B 25 g, hydrosilyl group-containing polysiloxane C 25 g, and platinum carbonyl complex 5 mg were mixed to prepare a silicone resin composition.

<Step (1)>
Example A
49.1 g of silicone resin composition, 34 g of phosphor, 5 g of silicone resin particles, 10 g of glass particles, and 1.9 g of aerosil particles were added and stirred for 3 minutes to prepare a phosphor resin composition.

  Next, the phosphor resin composition is applied to the surface of a release sheet (separator, product name “SE-1”, thickness 50 μm, manufactured by Fujiko Co., Ltd.) 10 with a comma coater so that the thickness after heating (baking) becomes 100 μm. Application was performed, followed by heating (baking) at 90 ° C. for 5.7 minutes. Thereby, the 1st sheet | seat member A provided with the peeling support sheet 10 and the fluorescent substance resin sheet 3 was obtained (refer FIG. 1A).

<Manufacture of second sheet member>
Example 1 (phosphor resin sheet having a notch)
<Step (2)>
As shown in FIG. 1B, the punching die 22 disposed above the first sheet member 1 is used to punch the first sheet member 1 from above, and the first sheet member 1 has a diameter L1 of 200 μm. A certain through hole (round hole) 5 was formed.

<Step (3)>
As shown in FIG. 1C, the phosphor resin sheet 3 was cut using a Thomson blade. Specifically, the phosphor resin sheet 3 is formed with a first cutting line 31 that passes through the through-hole 5 and a second cutting line 34 that does not pass through the through-hole 5. It was separated. A dicing saw was used as the cutting blade.

<Process (4)>
As shown in FIG. 2D, the phosphor resin sheet 3 was transferred from the release support sheet 10 to the stretched support sheet 11 to obtain a second sheet member 7.

<Step (5)>
As shown in FIG. 2E, the stretch support sheet 11 was stretched outward.

  Thereby, the 2nd sheet | seat member 7 which consists of the some fluorescent substance resin sheet 3 which has the notch part 23, and the extending | stretching support sheet 11 was obtained.

<Evaluation>
The following items were evaluated.

(Storage shear modulus G ′)
The dynamic viscoelasticity measurement of the phosphor resin sheet 3 in the first sheet member obtained in Example A was performed under the following conditions.

[conditions]
Viscoelastic device: Rotary rheometer (C-VOR device, manufactured by Malvern)
Sample shape: Disc shape Sample size: Thickness 225 μm, Diameter 8 mm
Distortion amount: 10%
Frequency: 1Hz
Plate diameter: 8mm
Gap between plates: 200 μm
Temperature rising rate 20 ° C / min Temperature range: 20-200 ° C
A curve showing the relationship between the storage shear modulus G ′ and the temperature T is shown in FIG.

  The minimum value of the storage shear modulus G ′ was 2,000 Pa.

(Adhesion of the phosphor resin sheet to the glass plate)
The 1st sheet | seat member 1 used in Example 1 was cut out by width 8.5mm, it vacuum-pressed on the glass plate of thickness 1mm on each hot press condition in Example 1, and after peeling a peeling sheet, it was 100 degreeC. For 10 minutes, and then heated at 150 ° C. for 8 hours to completely cure (full cure) (C stage) phosphor resin sheet 3, and adhesion of phosphor resin sheet 3 to the glass plate at 25 ° C. Was calculated. As a result, the adhesion of the phosphor resin sheet 3 to the glass plate was as high as 0.51 (N / 8.5 mm).

(Measurement of content ratio of hydrocarbon group directly bonded to silicon atom in product obtained by reaction of silicone resin composition)
In the product obtained by the reaction of the silicone resin composition (that is, the silicone resin composition containing no phosphor and filler), the content ratio (mol%) of the phenyl group in the hydrocarbon group directly bonded to the silicon atom , ²⁹ Si-NMR.

  Specifically, the A-stage silicone resin composition was reacted (completely cured, C-staged) at 100 ° C. for 1 hour without adding a phosphor and a filler to obtain a product.

Next, by measuring ¹ H-NMR and ²⁹ Si-NMR of the obtained product, the proportion (mol%) of the phenyl group in the hydrocarbon group (R ⁵ ) directly bonded to the silicon atom is calculated. did.

As a result, the phenyl group content in the hydrocarbon group (R ⁵ ) of the product obtained by the reaction of the silicone resin composition was 48%.

3 Phosphor Resin Sheet 5 Through Hole 6 Through Surface 31 First Cutting Line 23 Notch

Claims (4)

Preparing a B-stage phosphor resin sheet (1);
Forming a through hole and a through surface facing the through hole in the phosphor resin sheet (2);
Cutting the phosphor resin sheet to form a plurality of phosphor resin sheets including the penetrating surface (3) in order,
In the step (3), the phosphor resin sheet is cut so that a cutting line passes through the through hole, whereby the through surface defining one through hole has a plurality of the phosphor resin sheets. A method for producing a phosphor resin sheet, comprising: dividing the through surface to obtain a plurality of phosphor resin sheets having notches cut out inward from the peripheral end surface.   The method for producing a phosphor resin sheet according to claim 1, wherein in the step (3), the phosphor resin sheet is cut with a cutting blade.   3. The method for producing a phosphor resin sheet according to claim 1, wherein the phosphor resin sheet is punched in the step (2). In the step (1), the phosphor resin sheet is
The curve showing the relationship between the storage shear modulus G ′ and the temperature T obtained by dynamic viscoelasticity measurement at a frequency of 1 Hz and a temperature increase rate of 20 ° C./min has a minimum value,
The temperature T at the minimum value is in the range of 40 ° C. or higher and 200 ° C. or lower,
The production of the phosphor resin sheet according to any one of claims 1 to 3, wherein the storage shear elastic modulus G 'at the minimum value is in a range of 1,000 Pa or more and 90,000 Pa or less. Method.

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