JP7032052B2 - Silicone resin film and its manufacturing method, and semiconductor device manufacturing method - Google Patents

Description

The present invention relates to a silicone resin film and a method for producing the same. More specifically, the present invention relates to a method for producing a silicone resin film by curing a curable organopolysiloxane composition containing no catalyst. The present invention also relates to a silicone resin film that does not substantially contain a metal catalyst.
Further, the present invention relates to a method for manufacturing a semiconductor device including a film-like cured product of a curable organopolysiloxane that does not contain the catalyst.

LEDs are used in various fields of modern society, and the demand is expanding more and more. In particular, white LEDs have come to be used very widely not only in mobile phones and small lighting, but also in general lighting and large displays. As a method for manufacturing this white LED, a method using a phosphor called YAG (yttrium aluminum garnet) that excites light of 450 nm into a blue LED and a red / green / blue LED called 3in1 are simultaneously emitted. The method of making it is known. Compared to the 3in1 method, the above method using a blue LED and a phosphor can be manufactured at low cost because the number of LEDs and the number of wires is small, so this method is used for various LEDs.

However, when the LED device is sealed with a liquid silicone encapsulant mixed with a phosphor such as YAG and heat-cured, the liquid encapsulant becomes less viscous due to heating, so that the phosphor in the encapsulant Has settled down, and there has been a problem that the color variation of the LED becomes large. As a countermeasure, it has been proposed to improve color variation by adhering a semi-solid or solid film provided with a phosphor layer and a transparent layer to a chip (Patent Document 1).

Electronic material-related materials are required to minimize the base material used, have fine patterns, have high heat resistance, and have high impact resistance, and various resins are currently used. With the minimization of the base material, a small amount of metal catalyst contained in the encapsulant and the coating material is one of the causes of discoloration and deterioration of reliability due to heat and light. In addition, for optical sensors such as photocouplers, CCDs, and CMOS, reliability such as heat resistance, light resistance, and impact resistance is also emphasized as the sensors become finer and higher in performance, and conventional sensors are sealed with glass. There are also problems such as cracks occurring just by doing so.

Patent Document 4 describes a method of molding and manufacturing a material such as a sensor by compression molding or the like using a layered hot melt silicone composition. However, in reality, an addition reaction catalyst is used, and it is difficult to further improve the heat resistance and light resistance characteristics. Patent Document 5 describes that a gas barrier layer is provided by containing polysilazane and being subjected to vacuum ultraviolet irradiation treatment, but the gas barrier layer cannot be made so thick, and there is a problem in the flexibility of the polymer. rice field. Patent Document 6 describes a method for manufacturing a chip-sized package in which a chip is mounted on an adhesive layer containing thermally expandable microspheres, coated with a protective substance, the adhesive layer is peeled off, and dicing is performed. However, an adhesive layer is required, and the thermosetting resin always contains a catalyst, making it difficult to improve heat resistance.

Japanese Unexamined Patent Publication No. 2013-159003 Japanese Patent Publication No. 2014-516964 Japanese Patent Publication No. 2015-511164 Special Table 2016-508290 Publication No. Japanese Unexamined Patent Publication No. 2015-186922 WO2013 / 01185 50

Like the thermosetting silicone resin composition described in Patent Document 1, the conventional thermosetting silicone resin composition contains a metal catalyst. Therefore, the metal catalyst remains in the obtained cured product. It was found that the cured product did not have sufficient heat discoloration property and reliability, and these problems depended on the amount of catalyst remaining in the cured product. Therefore, it is an issue to reduce the amount of metal catalyst contained in the thermosetting silicone resin composition which is a raw material of the cured product. Further, in the case of the one-component type, the silicone resin composition containing a metal catalyst has poor storage stability because its reactivity gradually changes and changes with time. Further, in the case of the two-component type, there is a problem that voids are likely to occur when the mixture is mixed and formed into a film.
Further, the compound using polysilazane or acrylate having low gas permeability has a problem in the flexibility of the resin and the heat-resistant discoloration property.

In view of the above circumstances, the present invention provides a method for producing a film by curing a curable silicone resin composition which does not contain a metal catalyst and has high storage stability in an uncured state, and has heat resistance and reliability. It is an object of the present invention to provide a silicone resin film having enhanced properties. Further, an object of the present invention is to provide a silicone-containing device having improved heat resistance and reliability, which comprises a step of adhering the silicone resin composition to a substrate and curing it.

In Japanese Patent Application Laid-Open No. 2014-516964 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2015-511164 (Patent Document 3), a catalyst having a catalytic activity in which a metal catalyst is immobilized on the surface and inside of an inorganic / organic polymer hybrid material. Materials, especially catalyst films, are described. It is stated that the catalyst membrane is permeable to solvents and gases and can be used to catalyze chemical reactions in solution or in liquid / gas two-phase systems. Patent Documents 2 and 3 do not describe that the catalyst membrane is used for a reaction in a solid, or is used for a reaction in which the reaction system solidifies as the reaction proceeds.

The present inventors have diligently studied the use of a film having catalytic activity (hereinafter referred to as a catalyst film) in which a metal catalyst as described above is fixed, as a catalyst for curing a thermosetting organopolysiloxane composition. However, it has been found that when a curable organopolysiloxane composition containing no catalyst is formed into a film, bonded to a catalyst film and cured by heating, the organopolysiloxane composition is cured to give a film-like molded product. Furthermore, they have found that a silicone resin film containing an extremely small amount of metal catalyst can be provided by peeling the catalyst film from the film-shaped molded product, and have achieved the present invention.
Furthermore, the present inventors mold a curable organopolysiloxane composition containing no catalyst into a film shape, attach it to a catalyst film, and then attach the surface of the curable organopolysiloxane composition to a semiconductor device and heat-cure it. Then, by peeling the catalyst film from the film-shaped molded product and dicing it, it was found that a semiconductor device containing an extremely small amount of metal catalyst can be provided, and the present invention has been completed.

That is, the present invention is (B) a method for producing a silicone resin film by curing a curable organopolysiloxane composition containing an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule. The organopolysiloxane composition does not contain a metal catalyst.
The manufacturing method includes the following steps 1) to 3).
1) A step of forming the organopolysiloxane composition into a film on or between two films having catalytic activity, or at least the organopolysiloxane composition formed into a film. The process of bonding one surface and a film having catalytic activity,
2) Next, a step of curing the organopolysiloxane composition to obtain a silicone resin film, and 3) a step of peeling the obtained silicone resin film from the film. Alternatively, the above-mentioned manufacturing method is provided, which comprises having a catalyst on the surface and inside of the film.

Further, the present invention is (B) a method for producing a semiconductor device including a cured product of a curable organopolysiloxane composition containing an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule. The organopolysiloxane composition does not contain a metal catalyst.
The manufacturing method includes the following steps 1) to 4).
1) A step of forming the organopolysiloxane composition into a film on one film having catalytic activity, or one surface of the organopolysiloxane composition formed into a film and a film having catalytic activity. The process of laminating to obtain a film-like laminate,
2) Next, the composition surface of the film-like laminate obtained in the step 1) and the semiconductor chip mounting surface of the substrate on which the semiconductor chip is mounted are bonded together, and the semiconductor chip is coated with the organopolysiloxane composition. Process,
3) Next, a step of curing the organopolysiloxane composition, and 4) Next, a step of peeling the cured product from the catalyst membrane to obtain a semiconductor device in which the semiconductor chip is coated with the cured product.
Provided is a method for manufacturing a semiconductor device, wherein the film having catalytic activity has a catalyst on the surface of the film or on the surface and inside of the film.
The manufacturing method can further include a step of dicing the obtained semiconductor device into individual pieces after the above step 4).

Further, in the present invention, the cured organopolysiloxane composition further comprises (A) an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule, and the number of alkenyl groups in the component (A). Provided is a method for producing the silicone resin film and the semiconductor device, which comprises the ratio of the number of SiH groups in the component (B) to the above in an amount of 0.5 to 8.

Further, the present invention (B) is a silicone comprising a cured product of an organopolysiloxane composition containing an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule and containing no metal catalyst. Provided is a silicone resin film, wherein the amount of a metal catalyst that may be contained in the cured product is less than 0.1 ppm in terms of metal mass with respect to the total mass of the cured product.
Further, the present invention includes (B) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule, and (A) at least two alkenyl groups bonded to a silicon atom in one molecule. The organopolysiloxane having each is contained in an amount such that the ratio of the number of SiH groups in the component (B) to the number of alkenyl groups in the component (A) is 0.5 to 8, and does not contain a metal catalyst. A silicone resin film made of a cured product of an organopolysiloxane composition, wherein the amount of metal catalyst that may be contained in the cured product is less than 0.1 ppm in terms of metal mass with respect to the total mass of the cured product. Provide resin film.

In the production method of the present invention, since the organopolysiloxane composition does not contain a metal catalyst, physical properties are unlikely to change over time when the composition is cured or when the composition is stored in an uncured state. Therefore, the storage stability of the composition is improved. Further, since the amount of the metal catalyst contained in the obtained silicone resin film is extremely small, and in particular, the metal catalyst is substantially not contained, the silicone resin film is less likely to change with time even if it is stored for a long period of time, and is reliable. A high resin film can be provided. Further, the resin film can have high heat resistance. Further, the semiconductor device provided with the film-like cured product of the organopolysiloxane composition also has excellent heat resistance and can provide a highly reliable semiconductor device.

It is a schematic diagram of the laminate which consists of the film-like molded article of the curable organopolysiloxane composition and the catalyst film. It is a schematic diagram which shows the mode of sealing the semiconductor device which mounted the flip chip with the organopolysiloxane composition of this invention. It is a schematic diagram which shows the mode of sealing the semiconductor device with a wire with the organopolysiloxane composition of this invention. It is a schematic diagram which shows an example of the semiconductor device manufacturing method of this invention.

Hereinafter, the present invention will be described in detail.

The present invention is a method for producing a resin film by curing a curable organopolysiloxane composition, wherein the organopolysiloxane composition does not contain a metal catalyst, and a film having catalytic activity as a curing catalyst (hereinafter referred to as a film). , Called a catalyst film). The catalyst membrane has a hydrosilylation reaction catalyst on the surface of the membrane or on the surface and inside of the membrane. Hereinafter, the catalyst membrane will be described in detail.

[Catalyst membrane]
The catalyst membrane used in the production method of the present invention is a membrane having catalytic activity in which the catalyst is fixed to the surface of the membrane or fixed to the surface of the membrane and embedded inside the membrane. be. The catalyst is fixed by a supporting material constituting the membrane, and for example, a membrane based on an organic polymer such as polyvinyl alcohol (PVA) or a derivative thereof, polyimide, polyethylene, or regenerated cellulose can be used. Particularly preferred is a membrane containing a hybrid compound of an inorganic oxide and an organic polymer having a hydroxyl group. The inorganic oxide can be chemically bonded to the organic polymer via a hydroxyl group, and the catalyst is immobilized on the hybrid compound. As the catalyst membrane, those described in JP-A-2014-516964 (Patent Document 2) and JP-A-2015-511164 (Patent Document 3) can be used in particular. Hereinafter, it will be described in more detail.

The inorganic oxide constituting the hybrid compound is preferably a silicic acid compound or a zirconate acid compound. Silicic acid compound means silicic acid and its derivatives, or any compound containing silicic acid as a main component. The zirconate compound means zirconate and its derivatives, or any compound containing zirconate as a main component. Particularly preferably, it is a zirconate acid compound. Further, the silicic acid compound and the zirconate compound may contain other elements and / or may contain additives as long as their properties are not impaired.

The organic polymer having a hydroxyl group is preferably a water-soluble polymer, and particularly preferably polyvinyl alcohol. Other polymers include, for example, polyolefin polymers such as polyethylene and polypropylene, polyacrylic polymers, polyether polymers such as polyethylene oxide and polypropylene oxide, polyester polymers such as polyethylene terephthalate and polybutylene terephthalate, polytetrafluoroethylene and polyvinylidene fluoride. Fluoropolymers, sugar chain compounds such as methylcellulose, polyvinyl acetate polymers, polystyrene polymers, polycarbonate polymers, epoxy resin polymers and the like. These may be mixed and used. Further, other organic and inorganic additives may be mixed with the hybrid compound as long as the characteristics of the catalyst membrane are not impaired.

The catalyst is a simple substance of metal or a metal compound. For example, platinum-based, palladium-based, and rhodium-based catalysts which are platinum group metals or platinum group metal compounds and which are platinum group metal-based catalysts can be preferably used. From the viewpoint of cost and the like, platinum-based or palladium-based catalysts are often used, and metal fine particle catalysts of these metals or metal compound catalysts containing these metal elements can be used. More specifically, examples of the platinum group metal compound include H ₂ PtCl ₆ · mH ₂ O, K ₂ PtCl ₆ , KH PtCl ₆ · mH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ · mH ₂ O, PtO. _2. mH ₂ O (m is a positive integer). In addition to these, a complex of the platinum group metal compound and a hydrocarbon such as an olefin, an alcohol or a vinyl group-containing organopolysiloxane can be used, and examples of the palladium catalyst include PdCl ₂ . The catalyst may be used alone or in combination of two or more. In the catalyst membrane, the amount of the catalyst is preferably 0.0001 to 10 wt%, preferably 0.1 to 10 wt%, based on the total weight of the catalyst membrane in terms of metal. The metal particle catalyst preferably has a diameter of 0.5 to 500 nm.

The method for producing the catalyst membrane may be, for example, according to the methods described in JP-A-2014-516964 (Patent Document 2) and JP-A-2015-511164 (Patent Document 3). Further, as a commercially available product, for example, a catalyst membrane in which palladium is immobilized on an inorganic oxide / polyvinyl alcohol hybrid compound (trade name: Pd-iObrane (registered trademark), manufactured by Nippon Kodoshi Paper Industry Co., Ltd.) can be used.

The present invention uses the catalyst membrane to cure a curable organopolysiloxane composition that does not contain a catalyst. By molding the organopolysiloxane composition into a film shape, contacting it with the catalyst film, and heating it, a curing reaction is promoted on the surface of the catalyst film to give a cured product. During the reaction, the use of a catalyst in a film state prevents the agglutination of the catalytic metal particles and makes the catalytic activity constant. Further, since the catalyst is strongly fixed to the catalyst membrane, the transfer of the catalyst into the composition during the reaction is suppressed. Therefore, by peeling off the catalyst film after curing, the amount of metal catalyst contained in the cured product can be made extremely low. That is, according to the production method of the present invention, it is possible to provide a silicone resin film in which the amount of metal catalyst contained in the cured product is less than 0.1 ppm in terms of metal mass, and in particular, silicone containing substantially no metal catalyst. A resin film can be given.

[Organopolysiloxane composition]
The organopolysiloxane composition cured by the production method of the present invention has two aspects. The first aspect is a composition containing the following component (B) alone and cured by dehydrogenation condensation. The second aspect is a composition containing the following components (A) and (B) and cured by an addition reaction. The organopolysiloxane composition of the present invention does not contain a metal catalyst as described above.
(A) Organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule (B) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule The following components Will be described in detail.

（式中、Ｒ^１は炭素数６～１０の１価芳香族炭化水素基であり、Ｒ^２は置換もしくは非置換の、炭素数１～１０の鎖状脂肪族炭化水素基または炭素数３～１０の環状脂肪族炭化水素基であり、Ｒ^３は炭素数２～８のアルケニル基であり、ａ、ｂ、ｃおよびｄは、それぞれａ≧０、ｂ＞０、ｃ＞０、及びｄ＞０であり、ａ＋ｂ＋ｃ＋ｄ＝１～２を満たす数であり、但し、ケイ素原子に結合したアルケニル基を少なくとも２個有し、Ｘは、置換もしくは非置換の、炭素数１～８の一価炭化水素基、または水素原子である） [(A) Alkenyl group-containing organopolysiloxane]
The component (A) is an organopolysiloxane having at least two, preferably three or more alkenyl groups bonded to a silicon atom in one molecule. The component (A) may be a conventionally known alkenyl group-containing organopolysiloxane.
It is preferably an organopolysiloxane represented by the following average composition formula (1).

(In the formula, R ¹ is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ² is a substituted or unsubstituted chain aliphatic hydrocarbon group having 1 to 10 carbon atoms or 3 to 3 carbon atoms. 10 cyclic aliphatic hydrocarbon groups, R ³ is an alkenyl group having 2 to 8 carbon atoms, and a, b, c and d are a ≧ 0, b> 0, c> 0, and d>, respectively. It is 0 and is a number satisfying a + b + c + d = 1 to 2, but has at least two alkenyl groups bonded to a silicon atom, and X is a substituted or unsubstituted monovalent hydrocarbon having 1 to 8 carbon atoms. Group or hydrocarbon atom)

In the above formula (1), as the monovalent aromatic hydrocarbon group having R ¹ : 6 to 10 carbon atoms, an aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group, a benzyl group, a phenylethyl group or a phenylpropi. Examples include an aralkyl group such as a le group. Among them, a phenyl group, a benzyl group and the like are preferable, and a phenyl group is particularly preferable. R ² : As the chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group and a hexyl group. , Octyl group, nonyl group, decyl group and other alkyl groups. R ² : Examples of the cyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Of these, a methyl group, an ethyl group, a cyclopentyl group, and a cyclohexyl group are preferable, and a methyl group and a cyclohexyl group are particularly preferable. Further, as R ² , a part or all of the hydrogen atoms of these hydrocarbon groups may be substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group or the like, and for example, a chloromethyl group or a chloro may be used. Examples thereof include a halogen-substituted alkyl group such as a propyl group, a bromoethyl group and a trifluoropropyl group, and a cyanoethyl group. R ³ : Examples of the alkenyl group having 2 to 8 carbon atoms include a vinyl group, an allyl group, a 3-butenyl group, a 4-pentenyl group and the like. Of these, a vinyl group and an allyl group are preferable, and a vinyl group is particularly preferable. Examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms in X include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. It is preferably a methyl group or a hydrogen atom.

The alkenyl group-containing organopolysiloxane preferably has at least one monovalent aromatic hydrocarbon group, and is particularly monovalent with respect to the total number of R ¹ , R ² and R ³ in the formula (1). The ratio of the number of aromatic hydrocarbon groups (R ¹ ) is preferably 20 to 50%, more preferably 30 to 50%. It is preferable that the monovalent aromatic hydrocarbon group is in this range because the obtained composition becomes a solid or semi-solid state at 25 ° C. In the present invention, the semi-solid has the property of having plasticity but not fluidity at a temperature of 15 to 30 ° C., and is a liquid or solid due to external stress such as temperature, stress, and distortion. It is a state of exhibiting properties.

Further, in the above formula (1), a is preferably a number of 0 to 0.5, more preferably 0.05 to 0.5, and further 0.1 to 0.5, and b is preferably 0. The number is 1 to 0.7, more preferably 0.15 to 0.65, c is preferably 0.01 to 0.5, more preferably 0.015 to 0.5, and even 0.02 to 0.02. It is a number of 0.5, and d is preferably a number of 0.001 to 0.2, more preferably a number of 0.001 to 0.15. However, a + b + c + d = 1 to 2.

The component (A) may have any of a linear, branched, annular, and mesh-like structure, and has R ₂ SiO _2/2 units (D units) and R ₃ SiO _1/2 units (M units). , RSiO _3/2 unit (T unit), and SiO _4/2 unit (Q unit). R is an ^R1 , ^R2 , R3 ^, or OX group. In order for the resulting composition to have a semi-solid or solid form at 25 ° C., it should have at least T or Q units. In particular, a silicone resin composed of T units, M units, and D units and having a linear structure (continuous D units) is preferable. The organopolysiloxane may contain a small amount of Q units. In the component (A), 30 mol% or more and 99 mol% or less, preferably 50 mol% or more and 99 mol% or less of the siloxane unit (D unit) represented by R ₂ SiO _2/2 are continuous, and the continuation thereof. The number of siloxane units formed is preferably 5 to 50, preferably 5 to 40, and more preferably 8 to 40. As a result, the composition which is in a solid or semi-solid state at 25 ° C. is melted at an appropriate temperature, so that it becomes easy to handle when the film-like molded product made of the composition is bonded to the catalyst film. In the molecule, the position of the silicon atom to which the alkenyl group is bonded is not particularly limited.

The organopolysiloxane preferably has a weight average molecular weight of 2,000 to 100,000, and particularly preferably 5,000 to 80,000. The weight average molecular weight referred to in the present invention is a weight average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC). The weight average molecular weight is particularly measured under the following conditions.
[Measurement condition]
Developing solvent: Tetrahydrofuran (THF)
Flow rate: 0.6 mL / min
Detector: Differential Refractometer Detector (RI)
Column: TSK Guardcolomn SuperH-L
TSKgel SuperH4000 (6.0mm ID x 15cm x 1)
TSKgel SuperH3000 (6.0mm ID x 15cm x 1)
TSKgel SuperH2000 (6.0 mm ID x 15 cm x 2)
(Both manufactured by Tosoh)
Column temperature: 40 ° C
Sample injection volume: 20 μL (THF solution with a concentration of 0.5 wt%)

[(B) Organohydrogenpolysiloxane]
The component (B) is an organohydrogenpolysiloxane having a hydrogen atom bonded to at least two or more silicon atoms in one molecule. Organohydrogenpolysiloxane acts as a cross-linking agent and is cured by an addition reaction between a hydrogen atom (hereinafter, SiH group) bonded to a silicon atom in the component and an alkenyl group in the component (A). .. The organohydrogenpolysiloxane may have at least two SiH groups in one molecule, and those having three or more SiH groups are preferably used.

（式中、Ｒ^１、Ｒ^２及びＸは上記のとおりであり、ｅ、ｆ、ｇおよびｈは、それぞれｅ≧０、ｆ＞０、ｇ＞０、及びｈ＞０であり、ｅ＋ｆ＋ｇ＋ｈ＝１～２を満たす数であり、但し、ケイ素原子に結合した水素原子を少なくとも２個有する） The component (B) is preferably represented by the following average composition formula (2).

(In the equation, R ¹ , R ² and X are as described above, e, f, g and h are e ≧ 0, f> 0, g> 0, and h> 0, respectively, and e + f + g + h = 1. A number that satisfies ~ 2, but has at least two hydrogen atoms bonded to silicon atoms)

In the above formula (2), R ¹ is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and examples thereof can be mentioned for the above (A). Examples thereof include a phenyl group, a tolyl group, a xylyl group and a naphthyl group, and a phenyl group is preferable. In the above formula (2), R ² is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms. Examples of such R ² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group and the like. Alkyl groups; examples thereof include halogen-substituted alkyl groups such as chloromethyl group, chloropropyl group, bromoethyl group and trifluoropropyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and cyanoethyl groups. Of these, the methyl group is preferable. The organohydrogenpolysiloxane preferably has at least one monovalent aromatic hydrocarbon group, and in particular, a monovalent aromatic hydrocarbon group with respect to the total number of all R ¹ and R ² in the formula (2). The ratio of the number of (R ¹ ) is preferably 20 to 50%, more preferably 30 to 50%. It is preferable that the monovalent aromatic hydrocarbon group is in this range because the obtained composition becomes a solid or semi-solid state at 25 ° C.

In the above formula (2), e is preferably a number from 0 to 1.5, f is preferably a number of 0 <f≤0.85, and g is preferably a number of 0 <g≤0.5. H is preferably a number of 0 <h ≦ 0.1, but is a number satisfying e + f + g + h = 1 to 2. The position of the hydrosilyl group in the molecule is not particularly limited and may be at the end or in the middle of the molecular chain.

The component (B) may have any of a linear, branched, annular, and mesh-like structure, and has R ₂ SiO _2/2 units (D units) and R ₃ SiO _1/2 units (M units). , RSiO _3/2 unit (T unit), and SiO _4/2 unit (Q unit). R is R ¹ , R ² , a hydrogen atom, or an OX group. In order for the resulting composition to have a semi-solid or solid form at 25 ° C., it should have at least T or Q units. In particular, a silicone resin composed of T units, M units, and D units and having a linear structure (continuous D units) is preferable. The organopolysiloxane may contain a small amount of Q units. In the component (B), 30 mol% or more and 99 mol% or less, preferably 50 mol% or more and 99 mol% or less of the siloxane unit (D unit) represented by R ₂ SiO _2/2 are continuous, and the continuation thereof. The number of siloxane units formed is preferably 5 to 50, preferably 5 to 40, and more preferably 8 to 40.

Examples of other organohydrogenpolysiloxanes include tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1,1,3,3-tetramethyldisiloxane, 1,3,5. 7-Tetramethylcyclotetrasiloxane, both-ended trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both-ended trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both-ended dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydro Gensiloxane copolymer, double-ended trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, double-ended trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, (CH ₃ ) ₂ HSiO ₁ A copolymer consisting of _{2 units and 4/2 units} of SiO, a polymer consisting of _1/2 unit of (CH ₃ ) ₂ HSiO, _4/2 units of SiO and _3/2 units of (C ₆ H ₅ ) SiO And so on.

The organohydrogenpolysiloxane preferably has a weight average molecular weight of 1,000 to 200,000, and particularly preferably 2,000 to 100,000. The weight average molecular weight is a weight average molecular weight using polystyrene as a standard material by gel permeation chromatography (GPC). The measurement conditions are as described above.

The component (B) can be cured by a dehydrogenation condensation reaction alone in the presence of the catalyst membrane. When the component (B) is used together with the component (A), that is, when the organopolysiloxane composition is an addition reaction curing type, the amount of the component (B) in the composition is in the above component (A). The ratio of the number of SiH groups in the component (B) to the number of alkenyl groups in (B) is usually 0.5 to 8, preferably 0.7 to 5.

[(C) Adhesive aid]
The organopolysiloxane composition of the present invention may contain an adhesive aid in addition to the above-mentioned components (A) and (B) in order to impart adhesiveness. As the adhesion aid, for example, one or more substituents selected from a hydrogen atom bonded to a silicon atom and an alkenyl group in one molecule, and a substituent containing a hydroxysilyl group, an alkoxy group, an epoxy group or a nitrogen atom. Examples thereof include an organosiloxane oligomer having one or more of the above. The organosiloxane oligomer preferably has 4 to 50 silicon atoms, more preferably 4 to 20 silicon atoms. The components (A) and (B) are different from each other in that they contain a substituent containing a hydroxysilyl group, an alkoxy group, an epoxy group or a nitrogen atom.

Examples of the adhesion aid include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyl. Diethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane , N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxy Silane coupling agents such as silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxylane, 3-mercaptopropyltrimethoxysilane, trimethoxysilane, tetra. Examples thereof include methoxysilane and its oligomers.

Further, as another adhesive, an organooxysilyl-modified isocyanurate compound represented by the following general formula (3) and a hydrolyzed condensate thereof (organosiloxane-modified isocyanurate compound) can be used.

（式中、Ｒ⁵は水素原子又は炭素数１～６のメチル基、エチル基等の一価炭化水素基であり、ｔは２～１０の整数であり、好ましくは１～６の整数であり、好ましくは１～４の整数である。） In the above formula (3), R ⁴ is a monovalent aliphatic unsaturated hydrocarbon group which may have an organic group represented by the following general formula (4) or an oxygen atom independently of each other. However, at least one of R ⁴ is a group represented by the following formula (4).

(In the formula, R ⁵ is a hydrogen atom or a monovalent hydrocarbon group such as a methyl group or an ethyl group having 1 to 6 carbon atoms, and t is an integer of 2 to 10, preferably an integer of 1 to 6. , Preferably an integer of 1 to 4.)

（ｍは２～１０の整数である） In the above formula (4), the monovalent aliphatic unsaturated hydrocarbon group which may have an oxygen atom represented by R ⁴ is preferably a monovalent aliphatic unsaturated hydrocarbon group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. More preferably, a linear or branched alkenyl group having 2 to 6 carbon atoms, for example, a vinyl group, an allyl group, a 1-butenyl group, a 1-hexenyl group, a 2-methylpropenyl group, or a (meth) acrylic group. And so on. For example, it can be expressed by the following formula.

(M is an integer from 2 to 10)

（式（５’）中、Ｒ^６は互いに独立に、炭素数１～３の一価炭化水素基であり、ｖは２～７の整数である。好ましくは、Ｒ^６が全てメチル基であり、ｖが３である化合物である）

（式（６）中、Ｒ^５は置換もしくは非置換の、炭素数１～１０の鎖状脂肪族炭化水素基または炭素数３～１０の環状脂肪族炭化水素基であり、上記（Ａ）の為に記載したＲ^２で示される基の選択肢が挙げられる、ｋは１～３であり、ｊは１～２である。ｓ、ｐ、及びｑは合計１となる正数であり、例えばｓ＝０．２、ｐ＝０．５、及びｑ＝０．３である。該化合物は重量平均分子量１，０００～８，０００を有する） Other adhesion aids include organopolysiloxanes having at least one epoxy group in the molecule. The organopolysiloxane may be any conventionally known compound. For example, an organosiloxane represented by the following general formula (5) or average formula (6) can be mentioned. Above all, the composition containing the compound represented by the following general formula (5) is preferable because the peelability from the catalyst film after curing is better than that of other adhesive aids.

(In the formula (5'), R ⁶ is a monovalent hydrocarbon group having 1 to 3 carbon atoms independently of each other, and v is an integer of 2 to 7. Preferably, R ⁶ is all a methyl group. , V is 3)

(In the formula ( ⁶ ), R5 is a substituted or unsubstituted chain aliphatic hydrocarbon group having 1 to 10 carbon atoms or a cyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms, and is the above-mentioned (A). The alternatives of the groups represented by R ² described above are given, where k is 1 to 3 and j is 1 to 2. s, p, and q are positive numbers totaling 1, for example s. = 0.2, p = 0.5, and q = 0.3. The compound has a weight average molecular weight of 1,000 to 8,000).

When the adhesive auxiliary is blended, the blending amount is preferably 10 parts by mass or less, more preferably 0.1 to 8 parts by mass, and particularly preferably 0.1 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). It is 0.2 to 5 parts by mass. If the blending amount is not more than the above upper limit, the hardness of the cured product is high and the surface tackiness is suppressed.

In addition, as the blending amount when the adhesive aid is blended, the ratio of the total number of hydrosilyl groups in the total composition to the total number of alkenyl groups in the total composition containing the present adhesive aid is 0.4. The amount of up to 4 is preferable, the amount of up to 0.6 to 3 is more preferable, and the amount of up to 0.8 to 2 is even more preferable.

Further, the ratio of the adhesive auxiliary component to the total of 100 parts by mass of the components (A) and (B) is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. Within this range, the adhesive strength can be improved without impairing the effect of the present invention.

In addition to the above-mentioned components (A), (B) and (C), the organopolysiloxane composition of the present invention may contain a fluorescent substance, an inorganic filler, a curing inhibitor and the like, if necessary. .. Hereinafter, each component will be described.

[Fluorescent material]
The fluorescent substance is not particularly limited, and a conventionally known fluorescent substance may be used. For example, it is preferable to absorb light from a semiconductor element, particularly a semiconductor light emitting diode having a nitride semiconductor as a light emitting layer, and convert the wavelength into light having a different wavelength. Examples of such a phosphor include a nitride-based phosphor / oxynitride-based phosphor that is mainly activated by a lanthanoid-based element such as Eu and Ce, a lanthanoid-based phosphor such as Eu, and a transition metal-based such as Mn. Alkaline earth metal halogen apatite phosphors, alkaline earth metal boron borate phosphors, alkaline earth metal aluminate phosphors, alkaline earth metal silicate phosphors, alkaline earth metals mainly activated by elements Rare earth aluminate phosphors, rare earths that are mainly activated by sulfide phosphors, alkaline earth metal thiogalate phosphors, alkaline earth metal silicon nitride phosphors, germanate phosphors, or lanthanoid elements such as Ce. One or more selected from organic and organic complex phosphors mainly activated by silicate phosphors or lanthanoid elements such as Eu, Ca-Al-Si-ON oxynitride glass phosphors, and the like. Is preferable.

The nitride-based phosphor mainly activated by lanthanoid-based elements such as Eu and Ce is M ₂ Si ₅ N ₈ : Eu (M is at least one selected from Sr, Ca, Ba, Mg and Zn. There is.). Further, MSi ₇ N ₁₀ : Eu, M _1.8 Si ₅ O _0.2 N ₈ : Eu, and M _0.9 Si ₇ O _0.1 N ₁₀ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn). It is.) And so on.

As the oxynitride-based phosphor mainly activated by lanthanoid-based elements such as Eu and Ce, at least one selected from MSi ₂ O ₂ N ₂ : Eu (M is Sr, Ca, Ba, Mg, Zn). Is mentioned.).

Alkaline earth metal halogen apatite phosphors mainly activated by lanthanoid-based elements such as Eu and transition metal-based elements such as Mn include M ₅ (PO ₄ ) ₃ X': R'(M is Sr, Ca). , Ba, Mg, Zn. X'is at least one selected from F, Cl, Br, I. R'is one or more of Eu and Mn.) Can be mentioned.

The alkaline earth metal halide halogen phosphor is M ₂ B ₅ O ₉ X': R'(M is at least one selected from Sr, Ca, Ba, Mg and Zn. X'is F. , Cl, Br, and at least one selected from I. R'is one or more of Eu and Mn).

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

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

Rare earth aluminate phosphors mainly activated by lanthanoid elements such as Ce include Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al _0.8 Ga). _0.2 ) ₅ O ₁₂ : A YAG-based phosphor represented by the composition formula of Ce and (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ can be mentioned. Further, there are also Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which a part or all of Y is replaced with Tb, Lu, or the like.

Examples of other phosphors include ZnS: Eu, Zn ₂ GeO ₄ : Mn, Mga ₂ S ₄ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, and Zn). Be done.

The above phosphor should contain at least one selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni and Ti in place of Eu or in addition to Eu, if desired. Can be done.

The Ca-Al-Si-ON-based oxynitride glass phosphor is mol%, CaCO ₃ is converted into CaO, 20 to 50 mol%, Al ₂ O ₃ is 0 to 30 mol%, and SiO is The base material is oxynitride glass in which 25 to 60 mol%, AlN is 5 to 50 mol%, rare earth oxide or transition metal oxide is 0.1 to 20 mol%, and the total of the five components is 100 mol%. It is a phosphor. In a phosphor made of oxynitride glass as a base material, the nitrogen content is preferably 15 mol% or less, and in addition to rare earth oxide ions, other rare earth element ions serving as sensitizers are used as rare earth oxides. It is preferable to include the content in the fluorescent glass in the range of 0.1 to 10 mol% as a coactivator.

Further, a fluorescent substance other than the above-mentioned fluorescent substance, which has the same performance and effect, can also be used.

The phosphor used in the present invention preferably has an average particle size of 10 nm or more, more preferably 10 nm to 10 μm, and even more preferably 10 nm to 1 μm. The average particle size is measured by measuring the particle size distribution by a laser light diffraction method such as a Cirrus laser measuring device.

When the fluorescent substance is blended, the blending amount is preferably 0.1 to 2,000 parts by mass, more preferably 0.1 to 2,000 parts by mass, based on 100 parts by mass of the total of the components other than the fluorescent substance, for example, the components (A) and (B). It is 0.1 to 100 parts by mass. When the cured product of the organopolysiloxane composition of the present invention is used as a fluorophore-containing wavelength conversion film, the fluorophore content is preferably 10 to 2,000 parts by mass.

[Inorganic filler]
Examples of the inorganic filler include silica, fumed silica, fumed titanium dioxide, alumina, calcium carbonate, calcium silicate, titanium dioxide, ferrous oxide, zinc oxide and the like. These can be used alone or in combination of two or more.

The blending amount when blending the inorganic filler is not particularly limited, but it is preferable that the blending amount is such that the silicone resin film of the present invention does not lose its transparency. 20 parts by mass or less, preferably 0.1 to 10 parts by mass, may be appropriately blended per 100 parts by mass of the components (A) and (B).

[Other additives]
In addition to the above components, other additives can be added to the organopolysiloxane composition of the present invention. Other additives include, for example, radical inhibitors, flame retardants, surfactants, light stabilizers, thickeners, plasticizers, antioxidants, heat stabilizers, conductivity-imparting agents, antistatic agents, radiation blocking agents. Examples thereof include agents, nucleating agents, phosphorus-based peroxide decomposing agents, lubricants, pigments, metal inactivating agents, physical property adjusting agents, organic solvents and the like. These optional components may be used alone or in combination of two or more.

The simplest embodiment of the organopolysiloxane composition of the present invention is a composition consisting of only the component (B) or the components (A) and (B). In addition, in order to obtain a cured product having high transparency, it is preferable that the inorganic filler is not contained. The method for preparing the organopolysiloxane composition of the present invention is not particularly limited, and conventionally known methods may be followed, and the above components (A), (B), and other optional components may be mixed by any method. And prepare it. For example, it can be prepared by putting it in a commercially available stirrer (THINKY CONDITIONING MIXER Co., Ltd., manufactured by Shinky Co., Ltd.) and mixing it uniformly for about 1 to 5 minutes.

The properties of the organopolysiloxane composition of the present invention may be liquid, semi-solid, or solid, but if it is solid at 25 ° C, the fluidity of the resin is very low even before curing, so before and after curing. It is preferable because it is easy to maintain the shape of the product.

The organopolysiloxane composition of the present invention can provide a cured product having high light transmittance. Therefore, the organopolysiloxane composition of the present invention is useful for encapsulating LED elements, particularly for encapsulating blue LEDs and ultraviolet LEDs. The method for sealing the LED element or the like with the organopolysiloxane composition of the present invention may follow a conventionally known method. For example, a dispense method, a compression mold method, and the like can be used.

[Manufacturing method I. Silicone resin film manufacturing method]
Hereinafter, the method for producing the silicone resin film will be described in more detail.
The manufacturing method of the present invention I. Includes the following steps (1) to (3).
(1) A step of forming the organopolysiloxane composition into a film, or an organopolysiloxane composition formed into a film, on or between two films having catalytic activity. A step of bonding at least one surface and a film having catalytic activity,
(2) Next, a step of curing the organopolysiloxane composition to obtain a silicone resin film, and (3) a step of peeling the obtained silicone resin film from the film.

Process of manufacturing method I. (1)
As a method for forming the organopolysiloxane composition into a film, a conventionally known method may be followed, and for example, a film coater, a heat press machine or the like can be used. Film coaters include direct gravure coater, chamber doctor coater, offset gravure coater, roll kiss coater, reverse kiss coater, bar coater, die coater, reverse roll coater, slot die, air doctor coater, forward rotation roll coater, blade coater, etc. There are knife coaters, impregnation coaters, MB coaters, and MB reverse coaters. Of these, direct gravure coaters, offset gravure coaters, die coaters and the like are preferable. When a hot press machine is used, the step of laminating the catalyst membrane may be before or after molding the composition. When a film coater is used, it is preferable to bond the catalyst film after molding into a film.

Further, another catalyst film may be further attached to the surface to which the catalyst film of the organopolysiloxane composition formed into a film is not attached.

The thickness of the organopolysiloxane composition formed into a film is preferably 10 to 2,000 μm, more preferably 50 to 1,000 μm. Within this range, the composition can be sufficiently cured by the catalyst contained in the catalyst membrane, and curing failure does not occur.

When a hot press is used, it is usually at a temperature of 60 to 150 ° C., preferably 80 to 120 ° C., and under a pressure of 0.1 to 20 MPa, preferably 0.3 to 15 MPa for 1 to 40 minutes, preferably 1 to 1 to 1. Perform compression molding for 20 minutes. A catalyst membrane may be arranged on one side or both sides of the organopolysiloxane composition, and compression molding may be performed using a hot press machine. When a hot press machine is used, the film forming thickness is 0.01 to 3 mm, preferably 0.015 to 2 mm as the thickness of the obtained cured product.

When a film coater is used, it may be formed into a sheet or the like in a solvent-free state, or the composition may be dissolved in an organic solvent to form a varnish.

The organic solvent is not particularly limited, and for example, a hydrocarbon solvent such as benzene, toluene, and xylene; an ether solvent such as tetrahydrofuran, 1,4-dioxane, and diethyl ether; a ketone solvent such as methyl ethyl ketone; chloroform, and the like. Halogen-based solvents such as methylene chloride, 1,2-dichloroethane; alcohol-based solvents such as methanol, ethanol, isopropyl alcohol and isobutyl alcohol; octamethylcyclotetrasiloxane, hexamethyldisiloxane and the like, and further, cellosolve acetate, cyclohexanone, etc. It is a solvent such as butyrocellosolve, methylcarbitol, carbitol, butylcarbitol, diethylcarbitol, cyclohexanol, diglime, and triglime. These organic solvents may be used alone or in combination of two or more. The varnished composition is heated with a film coater at a temperature of 60 to 150 ° C., preferably 80 to 120 ° C. for 1 to 20 minutes, preferably 3 to 10 minutes to process it into a sheet. When a film coater is used, the film forming thickness is 0.01 to 1 mm, preferably 0.015 to 0.5 mm as the thickness of the obtained cured product.

Further, the release film may be attached to the surface to which the catalyst film of the organopolysiloxane composition formed into a film is not attached. Examples of the release film include a PET film coated with a fluororesin, a PET film coated with a silicone resin, and a fluororesin film.

Process of manufacturing method I. (2)
The curing conditions of the organopolysiloxane composition of the present invention are not particularly limited to either the dehydrogenation condensation type or the addition reaction curing type, and conventionally known methods may be followed. For example, it can be cured at 60 to 180 ° C. for about 1 to 12 hours. In particular, it is preferable to cure by step curing. Step cure can be performed, for example, through the following two steps. First, the organopolysiloxane composition is heated at a temperature of 60 to 100 ° C. for 0.5 to 2 hours to sufficiently defoam. The organopolysiloxane composition is then heat-cured at a temperature of 120-180 ° C. for 1-10 hours. By going through these steps, it is sufficiently cured, no bubbles are generated, and a colorless and transparent cured product can be obtained. In the present invention, the colorless and transparent cured product means a product having a light transmittance of 80% or more, preferably 85% or more, particularly preferably 90% or more at 450 nm at a thickness of 1 mm.

Process of manufacturing method I. (3)
A silicone resin film can be obtained by peeling off the cured product (silicone resin film) formed by the above step and the catalyst film. According to the production method of the present invention, the amount of the metal catalyst contained in the silicone resin film is less than 0.1 ppm in terms of metal mass, preferably less than 0.05 ppm. If it exceeds the above upper limit, the storage stability of the composition is lowered in the uncured state, and the heat resistance and reliability of the obtained silicone resin film may be lowered, which is not preferable.

[Manufacturing method II. Manufacturing method of semiconductor device]
Hereinafter, a method for manufacturing a semiconductor device using the film-shaped molded product made of the organopolysiloxane composition of the present invention (meaning the molded product made of the uncured composition) will be described in more detail.
The production method of the present invention II. Includes the following steps (1) to (4).
(1) A step of forming the organopolysiloxane composition into a film on one film having catalytic activity, or one surface of the organopolysiloxane composition formed into a film and a film having catalytic activity. (2) The composition surface of the film-like laminate obtained in the above step (1) and the semiconductor chip mounting surface of the substrate on which the semiconductor chip is mounted are bonded together to obtain a film-like laminate. Step of coating the semiconductor chip with the organopolysiloxane composition (3) Step of curing the organopolysiloxane composition (4) The cured product and the catalyst film are peeled off, and the semiconductor chip is coated with the cured product. Step of obtaining the semiconductor device of the present invention Further, the manufacturing method of the present invention II. Can further include the step (5) after the step (4) of dicing and disassembling the obtained semiconductor device.

The manufacturing method II. FIG. 4 shows a schematic diagram for explaining a method of manufacturing a semiconductor device according to the above. Each step (1) to (5) shown in FIG. 4 corresponds to the above steps (1) to (5). Hereinafter, each step will be described in more detail.
Process of manufacturing method II. (1)
In the step (1), the curable organopolysiloxane composition is formed into a film, and a film-like laminate composed of the film-like molded product and the catalyst film is obtained (step (1) in FIG. 4). The method of forming into a film and the method of attaching to the catalyst film are described in the above-mentioned manufacturing method I. It is as described in the step (1) of.

Step of manufacturing method II. (2)
The composition surface of the film-like laminate obtained in the step (1) is bonded to the semiconductor chip mounting surface of the substrate on which the semiconductor chip is mounted, and the semiconductor chip is coated with the organopolysiloxane composition (the semiconductor chip is coated with the organopolysiloxane composition). Step (2) of FIG. The step may follow a conventionally known method, and a hot press, a vacuum laminator, compression molding, or the like can be used, and a vacuum laminator is particularly desirable from the viewpoint of followability. More specifically, for example, a substrate on which a semiconductor chip is mounted is adhered to a metal plate of an upper mold of a molding apparatus via an adhesive film or the like, and a catalyst surface of the laminate is formed on a lower mold of the molding apparatus. Placed on the side, with a vacuum laminator (V-130 manufactured by Nikko Materials), the molding temperature is 50 to 150 ° C, the degree of vacuum in the system is 0.1 to 10 hPa, the vacuum is 10 seconds to 1 minute, and the pushing pressure is It can be molded at 0.05 to 0.5 MPa.

Process of manufacturing method II. (3)
The semiconductor device in which the semiconductor chip is coated with the organopolysiloxane composition obtained in the step (2) is cured (step (3) in FIG. 4).

The curing conditions of the curable organopolysiloxane composition of the present invention are the above-mentioned production method I. It is as described in the step (2) of. For example, it can be cured by heating at a temperature of 60 to 180 ° C. for 1 to 12 hours. It is preferable to heat at 120 to 180 ° C. for 1 to 4 hours. In particular, it is preferable to cure by step curing. The step cure is as described above. When heated at a curing temperature of more than 180 ° C. (for example, 200 ° C.) for a long time (for example, 4 hours or more), the obtained cured product and the catalyst membrane may not be easily peeled off. By laminating the composition surface of the film-like molded product made of the organopolysiloxane composition of the present invention and the film-like laminate made of the catalyst film and the semiconductor device, molding can be performed without causing voids or the like. The manufacturing method of the present invention can be formed by either a flip-chip type semiconductor device as shown in FIG. 2 or a semiconductor device having a wire-attached chip as shown in FIG.

Step of manufacturing method II. (4)
In the semiconductor device obtained in the step (3), the cured product and the catalyst membrane are peeled off to obtain a semiconductor device in which the semiconductor chip is coated with the cured product (step (4) in FIG. 4). The cured product of the organopolysiloxane composition of the present invention and the catalyst membrane can be easily peeled off by hand.

Step of manufacturing method II. (5)
In the step (5), the semiconductor device manufactured in the above step is diced and individualized in order to package it (step (5) in FIG. 4). Dicing is a dicing machine manufactured by DISCO, etc., and dicing can be performed without generating burrs.

When the production method of the present invention is used, as described above, the amount of the metal catalyst contained in the cured product is less than 0.1 ppm in terms of metal mass, preferably less than 0.05 ppm, and thus has excellent heat resistance and reliability. Can provide semiconductor devices.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

In the following examples, the weight average molecular weight is the weight average molecular weight using polystyrene as a standard material by gel permeation chromatography (GPC). The measurement conditions are as follows.
[Measurement condition]
Developing solvent: THF
Flow rate: 0.6 mL / min
Detector: Differential Refractometer Detector (RI)
Column: TSK Guardcolomn SuperH-L
TSKgel SuperH4000 (6.0mm ID x 15cm x 1)
TSKgel SuperH3000 (6.0mm ID x 15cm x 1)
TSKgel SuperH2000 (6.0 mm ID x 15 cm x 2)
(Both manufactured by Tosoh)
Column temperature: 40 ° C
Sample injection volume: 20 μL (THF solution with a concentration of 0.5 wt%)

[Synthesis Example 1]
Synthesis of alkenyl group-containing organopolysiloxane
Phenyltrichlorosilane 1142.1 g (87.1 mol%), ClMe ₂ SiO (Me ₂ SiO) ₃₃ Sime ₂ Cl 529 g (3.2 mol%), and dimethylvinylchlorosilane 72.4 g (9.7 mol%) as a toluene solvent After dissolution, it was dropped into water, co-hydrolyzed, neutralized by washing with water and washed with alkali, dehydrated, and then stripped of the solvent to obtain a solid phenyl group-containing vinyl silicone resin A1 at 25 ° C. The polystyrene-equivalent weight average molecular weight measured by GPC using THF as a solvent was 63,000.

[Synthesis Example 2]
Synthesis of alkenyl group-containing organopolysiloxane
Toluene phenyltrichlorosilane 1142.1 g (84.4 mol%), ClMe ₂ SiO (Me ₂ SiO) ₁₃ Sime ₂ Cl 466.6 g (6.3 mol%), and dimethylvinylchlorosilane 72.4 g (9.4 mol%). After being dissolved in a solvent, it was dropped into water, co-hydrolyzed, neutralized by washing with water and washed with alkali, dehydrated, and then stripped of the solvent to obtain a solid phenyl group-containing vinyl silicone resin A2 at 25 ° C. The polystyrene-equivalent weight average molecular weight measured by GPC using THF as a solvent was 22,000.

[Synthesis Example 3]
Synthesis of alkenyl group-containing organopolysiloxane
After dissolving 1142.1 g (87.4 mol%) of phenyltrichlorosilane, HO- (PhMeSiO) ₃₅ -H 869.7 g (2.9 mol%), and 72.3 g (9.7 mol%) of dimethylvinylchlorosilane in a toluene solvent. , Dropped into water, co-hydrolyzed, neutralized by washing with water and washed with alkali, dehydrated, and then stripped of the solvent to obtain a solid phenyl group-containing vinyl silicone resin A3 at 25 ° C. The polystyrene-equivalent weight average molecular weight measured by GPC using THF as a solvent was 23,000.

[Synthesis Example 4]
Synthesis of Organohydrogen Polysiloxane
After dissolving 1142.1 g (87.1 mol%) of phenyltrichlorosilane, 529 g (3.2 mol%) of _{ClMe 2} SiO (Me ₂ SiO) ₃₃ , and 69 g (9.7 mol%) of methyldichlorosilane in a toluene solvent. , Dropped into water, co-hydrolyzed, neutralized by washing with water and washed with alkali, dehydrated, and then stripped of the solvent to obtain a solid phenyl group-containing hydrogen silicone resin B1 at 25 ° C. The polystyrene-equivalent weight average molecular weight measured by GPC using THF as a solvent was 58,000.

[Synthesis Example 5]
Synthesis of Organohydrogen Polysiloxane
Toluene phenyltrichlorosilane 1142.1 g (84.4 mol%), ClMe ₂ SiO (Me ₂ SiO) ₁₃ Sime ₂ Cl 466.6 g (6.3 mol%), and methyldichlorosilane 69.0 g (9.4 mol%). After being dissolved in a solvent, it was dropped into water, co-hydrolyzed, neutralized by washing with water and washed with alkali, dehydrated, and then stripped of the solvent to obtain a solid phenyl group-containing hydrogen silicone resin B2 at 25 ° C. .. The polystyrene-equivalent weight average molecular weight measured by GPC using THF as a solvent was 11,000.

[Synthesis Example 6]
Synthesis of Organohydrogen Polysiloxane
After dissolving 1142.1 g (87.4 mol%) of phenyltrichlorosilane, HO- (PhMeSiO) ₃₅ -H 869.7 g (2.9 mol%), and 69 g (9.7 mol%) of methyldichlorosilane in a toluene solvent, It was dropped into water, co-hydrolyzed, neutralized by washing with water and washed with alkali, dehydrated, and then stripped of the solvent to obtain a solid phenyl group-containing hydrogen silicone resin B3 at 25 ° C. The polystyrene-equivalent weight average molecular weight measured by GPC using THF as a solvent was 8,000.

[Catalyst membrane]
The catalyst film used in the following examples is a catalyst film in which palladium is immobilized on an inorganic oxide / polyvinyl alcohol hybrid compound (trade name: Pd-iObrane (registered trademark), manufactured by Nippon Kodoshi Kogyo Co., Ltd., Pd loading amount 7 wt%. ).

I. Production of Silicone Resin Film [Example 1]
100 g of the vinyl silicone resin A1 synthesized in Synthesis Example 1 and 100 g of the hydrogen silicone resin B1 synthesized in Synthesis Example 4 were mixed to prepare an organopolysiloxane composition 1. Using the automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.), the organopolysiloxane composition 1 was applied onto the catalyst membrane Pd-iObrane (registered trademark), and the length 150 mm × width 150 mm and thickness. It was formed into a film having a thickness of 0.1 mm (molded product F1).

[Example 2]
An organopolysiloxane composition 2 was prepared by mixing 100 g of the vinyl silicone resin A2 synthesized in Synthesis Example 2 and 100 g of the hydrogen silicone resin B2 synthesized in Synthesis Example 5. Example 1 was repeated except that the organopolysiloxane composition 2 was used instead of the organopolysiloxane composition 1, and the film was formed into a film having a length of 150 mm × width of 150 mm and a thickness of 0.1 mm (molded product F2).

[Example 3]
An organopolysiloxane composition 3 was prepared by mixing 100 g of the vinyl silicone resin A3 synthesized in Synthesis Example 3 and 100 g of the hydrogen silicone resin B3 synthesized in Synthesis Example 6. Example 1 was repeated except that the organopolysiloxane composition 3 was used instead of the organopolysiloxane composition 1, and the film was formed into a film having a length of 150 mm × width of 150 mm and a thickness of 0.1 mm (molded product F3).

上記式（３’）中、Ｒ’’は、下記式（ａ）又は（ｂ）で表される基であり、（ａ）と（ｂ）は２：１の比で存在する。

[Example 4]
100 g of the vinyl silicone resin A1 synthesized in the synthesis example 1, 100 g of the hydrogen silicone resin B1 synthesized in the synthesis example 4, and 6 g of the adhesive-imparting agent 2 represented by the following formula (3') are mixed. To prepare an organopolysiloxane composition 4. Example 1 was repeated except that the organopolysiloxane composition 4 was used instead of the organopolysiloxane composition 1, and the film was formed into a film having a length of 150 mm × width of 150 mm and a thickness of 0.1 mm (molded product F4).

In the above formula (3'), R'' is a group represented by the following formula (a) or (b), and (a) and (b) exist in a ratio of 2: 1.

[Example 5]
100 g of the vinyl silicone resin A2 synthesized in Synthesis Example 2, 100 g of the hydrogen silicone resin B2 synthesized in Synthesis Example 5, and 6 g of the adhesion-imparting agent represented by the above formula (3') are mixed to form an organo A polysiloxane composition 5 was prepared. Example 1 was repeated except that the organopolysiloxane composition 5 was used instead of the organopolysiloxane composition 1, and the film was formed into a film having a length of 150 mm × width of 150 mm and a thickness of 0.1 mm (molded product F5).

[Example 6]
100 g of the vinyl silicone resin A3 synthesized in Synthesis Example 3, 100 g of the hydrogen silicone resin B3 prepared in Synthesis Example 6, and 6 g of the adhesion-imparting agent represented by the above formula (3') are mixed. Organopolysiloxane composition 6 was prepared. Example 1 was repeated except that the organopolysiloxane composition 6 was used instead of the organopolysiloxane composition 1, and the film was formed into a film having a length of 150 mm × width of 150 mm and a thickness of 0.1 mm (molded product F6).

[Example 7]
Except for changing the thickness of the applied organopolysiloxane composition to 0.4 mm, the above-mentioned Example 1 was repeated to form a film having a length of 150 mm × a width of 150 mm and a thickness of 0.4 mm (molded product F7).

[Example 8]
The organopolysiloxane composition 1 prepared in Example 1 is sandwiched between two catalyst films Pd-iObrane (registered trademark) and compression-molded to form a film having a length of 150 mm × width of 150 mm and a thickness of 0.1 mm. did. For 10 of the film-shaped molded products, the process of peeling off the catalyst film on one side one by one and bonding them together at a temperature of 80 ° C. using a pressurized vacuum laminator V130 (manufactured by Nichigo Morton Co., Ltd.) was repeated for 10 molded products. To produce a 1.0 mm film-shaped molded product F8 having catalyst films on both sides.
In the evaluation test described later, the catalyst film on one side was peeled off and the molded product was attached to the slide glass.

[Example 9]
Example 1 was repeated except that the organopolysiloxane composition 1 prepared in Example 1 was used and a PET film was used instead of the palladium nanoparticle-supported polyvinyl alcohol film, and the length was 150 mm × width 150 mm and the thickness was 0.1 mm. It was molded into a film shape. For 10 of the film-shaped molded products, the PET film was peeled off, bonded using a pressurized vacuum laminator V130 (manufactured by Nichigo Morton Co., Ltd.), and laminated at a temperature of 80 ° C., and one side of the obtained molded product was obtained. The PET film in the above was peeled off and the catalyst film Pd-iObrane was attached. A 1.0 mm film-shaped molded product F9 having a catalyst film on one side and a PET film on the other side was produced.

[Comparative Example 1]
100 g of vinyl silicone resin A1 synthesized in Synthesis Example 1, 100 g of hydrogen silicone resin B1 synthesized in Synthesis Example 4, 0.2 g of vinyl silicone modified solution of platinum chloride acid (platinum concentration 1% by mass) as a hydrosilylation reaction catalyst. , 0.6 g of acetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor and 6.0 g of an adhesion-imparting agent represented by the above formula (3') as an adhesion-imparting agent are mixed to obtain an organopolysiloxane composition C'1. Prepared. Using the automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.), the organopolysiloxane composition C'1 is coated on a PET film to obtain a length of 150 mm x a width of 150 mm and a thickness of 0.1 mm. It was molded into a film shape (molded product F'1).

[Comparative Example 2]
In Comparative Example 1, Comparative Example 1 was repeated except that the amount of the hydrosilylation reaction catalyst was 0.004 g and the amount of ethynylcyclohexanol was 0.006 g, and the hydrosilylation reaction catalyst had a length of 150 mm × a width of 150 mm and a thickness of 0.1 mm. It was molded into a film (molded product F'2).

[Comparative Example 3]
Comparative Example 1 was repeated except that 100 g of vinyl silicone resin A2 was used instead of vinyl silicone resin A1 and 100 g of hydrogen silicone resin B2 was used instead of hydrogen silicone resin B1, and the length was 150 mm × width 150 mm and the thickness was 0. It was molded into a film having 1 mm (molded product F'3).

[Comparative Example 4]
Comparative Example 1 was repeated except that 100 g of vinyl silicone resin A3 was used instead of vinyl silicone resin A1 and 100 g of hydrogen silicone resin B3 was used instead of hydrogen silicone resin B1, and the length was 150 mm × width 150 mm and the thickness was 0. It was molded into a film having 1 mm (molded product F'4).

[Comparative Example 5]
The organopolysiloxane composition 1 prepared in Example 1 was applied onto a PET film using an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.) and formed into a film. The composition melted when heated and could not maintain its conventional shape.

[Comparative Example 6]
The organopolysiloxane composition 2 prepared in Example 2 was applied onto a PET film using an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.) and formed into a film. The composition melted when heated and could not maintain its conventional shape.

[Comparative Example 7]
The organopolysiloxane composition 3 prepared in Example 3 was applied onto a PET film using an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.) and formed into a film. The composition melted when heated and could not maintain its conventional shape.

[Comparative Example 8]
The PET film was peeled off from 10 pieces of the molded product F'1 molded in Comparative Example 1, bonded together using a pressurized vacuum laminator V130 (manufactured by Nichigo Morton Co., Ltd.), laminated at a temperature of 80 ° C., and 1. A 0 mm film-shaped molded product F'8 was produced.

[Measurement of residual metal catalyst]
For the molded products formed in Examples 1 to 8 and Comparative Examples 1 to 7, the surfaces to which the catalyst film was not bonded were bonded to a slide glass, and the molded products were heated at 150 ° C. for 4 hours to be cured. Then, the catalyst membrane was peeled off from the cured product to obtain a film. For each film, the amount of metal catalyst remaining in the cured product was measured using ICP-AES (Inductively Coupled Plasma-Emission Spectroscopy). The results are shown in Tables 1 and 2.

[Measurement of minute hardness]
For the molded products formed in Examples 1 to 8 and Comparative Examples 1 to 7, the surfaces to which the catalyst film was not bonded were bonded to a slide glass, and the molded products were heated at 150 ° C. for 4 hours to be cured. Then, the catalyst membrane was peeled off from the cured product to obtain a film. Each film was subjected to a load / unloading test using a dynamic ultrafine hardness tester SHIMADZU DUH-211SR (manufactured by Shimadzu Corporation). After a test force of 1 gf, a load rate of 0.0298 gf / sec, and a load and unloading holding time of 2 seconds each, the minute hardness (MPa) was measured. The average micro-hardness (MPa) of 5 tests is shown in Tables 1 and 2.

[Heat resistance test (change in transmittance)]
For the molded products formed in Examples 1 to 8 and Comparative Examples 1 to 7, the surfaces to which the catalyst film was not bonded were bonded to a slide glass, and the molded products were heated at 150 ° C. for 4 hours to be cured. Then, the catalyst membrane was peeled off from the cured product to obtain a film. The transmittance of the film at 400 nm was measured according to JIS R 3106: 1998 (initial transmittance). Then, the film was placed at 180 ° C. for 1000 hours, and then the transmittance was measured. The transmittance (%) when the initial transmittance was 100% was calculated.
Transmittance change (%) = (180 ° C x transmittance after leaving for 1,000 hours) / (initial transmittance)
The results are shown in Tables 1 and 2.

[Long-term storage stability test]
The molded products of Example 9 and Comparative Example 8 were subjected to a load / unloading test using a dynamic ultrafine hardness tester SHIMADZU DUH-211SR (manufactured by Shimadzu Corporation). After a test force of 1 gf, a load rate of 0.0298 gf / sec, and a load and unloading holding time of 2 seconds each, the minute hardness (MPa) was measured. The average micro-hardness (MPa) of 5 tests is shown in Table 3 (micro-hardness before curing (initial value)). Then, the molded articles of Example 9 and Comparative Example 8 were stored at 25 ° C. for 6 months. The molded product after storage was subjected to a loading / unloading test in the same manner as described above, and the average micro-hardness (MPa) was measured (micro-hardness before curing (after storage)). Further, each molded product before and after storage was heat-cured at 150 ° C. for 4 hours to produce a film, and the micro-hardness after curing was measured. The results are shown in Table 3.

As shown in Tables 1 to 3, the silicone resin film obtained by curing an organopolysiloxane composition containing no catalyst using a catalyst membrane is transparent and has excellent heat resistance. Further, the organopolysiloxane composition molded on the catalyst membrane does not easily change with time even if it is stored for a long period of time in an uncured state, and is excellent in long-term storage stability.

II. Manufacturing of Semiconductor Devices [Example 10]
The same organopolysiloxane composition 1 as in Example 1 was prepared. The organopolysiloxane composition 1 (FIG. 1 in FIG. 1) is placed on a catalyst membrane Pd-iObrane (registered trademark) (reference numeral 1 in FIG. 1) using an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.). Reference numeral 2) was applied, and the film was formed into a film having length × width × thickness = 100 mm × 100 mm × 0.2 mm. FIG. 1 shows a schematic diagram of a laminate composed of the film-shaped molded product and the catalyst film. Using a pressurized vacuum laminator V130 (manufactured by Nichigo Morton Co., Ltd.), the composition surface of the film-like laminate (reference numeral 2 in FIG. 2) and the semiconductor chip mounting substrate (semiconductor chip (reference numeral 3 in FIG. 2) are 500 μm. A flip-chip type LED chip having × 500 μm and a height of 150 μm and a substrate (the size of reference numeral 4 in FIG. 2 is 10 cm × 10 cm) were bonded together (a schematic diagram of the process is shown in FIG. 2). .. Next, the organopolysiloxane composition 1 was cured by heating at 150 ° C. for 4 hours without peeling off the catalyst membrane. After curing, the cured product and the catalyst film were peeled off to obtain a semiconductor device in which the semiconductor chip was coated with the film-like cured product. In this step, the cured product and the catalyst membrane layer were easily peeled off. The semiconductor device was diced to obtain a semiconductor device having a length of 3.5 mm and a width of 3.5 mm and having a semiconductor chip sealed with a cured product having a thickness of 0.2 mm (semiconductor device 1).

[Example 11]
The same organopolysiloxane composition 2 as in Example 2 was prepared. The same method as in Example 10 was repeated except that the organopolysiloxane composition 2 was used instead of the organopolysiloxane composition 1, and the cured product had a length of 3.5 mm and a width of 3.5 mm and a thickness of 0.2 mm. A semiconductor device in which a semiconductor chip was sealed with an object was obtained (semiconductor device 2).

[Example 12]
The same organopolysiloxane composition 3 as in Example 3 was prepared. The same method as in Example 10 was repeated except that the organopolysiloxane composition 3 was used instead of the organopolysiloxane composition 1, and the cured product had a length of 3.5 mm and a width of 3.5 mm and a thickness of 0.2 mm. A semiconductor device in which a semiconductor chip was sealed with an object was obtained (semiconductor device 3).

で表される接着助剤１を２ｇ混合して、オルガノポリシロキサン組成物７を調製した。オルガノポリシロキサン組成物１に変えてオルガノポリシロキサン組成物７を用いた他は実施例１０と同じ方法を繰り返して、縦３．５ｍｍ×横３．５ｍｍを有し、厚さ０．２ｍｍの硬化物で半導体チップが封止された半導体デバイスを得た（半導体デバイス４）。 [Example 13]
The vinyl silicone resin A1 synthesized in Synthesis Example 1 was 100 g, the hydrogen silicone resin B1 synthesized in Synthesis Example 4 was 100 g, and the following formula (5').

2 g of the adhesive aid 1 represented by the above was mixed to prepare an organopolysiloxane composition 7. The same method as in Example 10 was repeated except that the organopolysiloxane composition 7 was used instead of the organopolysiloxane composition 1 , and the length was 3.5 mm × the width was 3.5 mm, and the thickness was 0.2 mm. A semiconductor device in which a semiconductor chip was sealed with a cured product was obtained (semiconductor device 4).

[Example 14]
100 g of the vinyl silicone resin A2 synthesized in the synthesis example 2, 100 g of the hydrogen silicone resin B2 synthesized in the synthesis example 5, and 2 g of the adhesive aid 1 represented by the above formula (5') are mixed to form an organo A polysiloxane composition 8 was prepared. The same method as in Example 10 was repeated except that the organopolysiloxane composition 8 was used instead of the organopolysiloxane composition 1, and the cured product had a length of 3.5 mm and a width of 3.5 mm and a thickness of 0.2 mm. A semiconductor device in which a semiconductor chip was sealed with an object was obtained (semiconductor device 5).

[Example 15]
100 g of the vinyl silicone resin A3 synthesized in Synthesis Example 3, 100 g of the hydrogen silicone resin B3 prepared in Synthesis Example 6, and 2 g of the adhesive aid 1 represented by the above formula (5') are mixed. Organopolysiloxane composition 9 was prepared. The same method as in Example 10 was repeated except that the organopolysiloxane composition 9 was used instead of the organopolysiloxane composition 1, and the cured product had a length of 3.5 mm and a width of 3.5 mm and a thickness of 0.2 mm. A semiconductor device in which a semiconductor chip was sealed with an object was obtained (semiconductor device 6).

[Example 16]
The organopolysiloxane composition 10 was prepared by repeating Example 6 except that the amount of the adhesive aid 2 represented by the formula (3') in Example 6 was 2 g. The same method as in Example 10 was repeated except that the organopolysiloxane composition 10 was used instead of the organopolysiloxane composition 1, and the cured product had a length of 3.5 mm and a width of 3.5 mm and a thickness of 0.2 m. A semiconductor device in which a semiconductor chip was sealed with an object was obtained (semiconductor device 7).

（式中、Ｒ^５はメチル基またはイソプロピル基であり、重量平均分子量は２，５００である） [Example 17]
A mixture of 100 g of the vinyl silicone resin A3 synthesized in Synthesis Example 3, 100 g of the hydrogen silicone resin B3 prepared in Synthesis Example 6, and 2 g of the adhesive aid 3 represented by the following average formula (6') is mixed. , Organopolysiloxane composition 11 was prepared. The same method as in Example 10 was repeated except that the organopolysiloxane composition 11 was used instead of the organopolysiloxane composition 1, and the cured product had a length of 3.5 mm and a width of 3.5 mm and a thickness of 0.2 mm. A semiconductor device in which a semiconductor chip was sealed with an object was obtained (semiconductor device 8).

( ^In the formula, R5 is a methyl group or an isopropyl group, and the weight average molecular weight is 2,500.)

[Example 18]
The same method as in Example 10 above was repeated except that the thickness of the applied organopolysiloxane composition was changed to 0.4 mm, and the film had a length of 3.5 mm × a width of 3.5 mm and was cured to a thickness of 0.4 mm. A semiconductor device in which a semiconductor chip was sealed with an object was obtained (semiconductor device 9).

[Example 19]
In Example 10, the semiconductor chip mounting substrate is a semiconductor chip mounting substrate with a wire (the semiconductor chip is an LED chip (with a wire) having a height of 500 μm × 500 μm, and the wire height is 250 μm, and the size of the substrate is large. The size is 10 cm × 10 cm. A schematic diagram is shown in FIG. 3), and the same method as in Example 10 is repeated to have a length of 3.5 mm × a width of 3.5 mm and a thickness of 0.4 mm. A semiconductor device in which a semiconductor chip was sealed with the cured product of the above was obtained (semiconductor device 10).

[Example 20]
In Example 10, the one-step curing condition of heating at 160 ° C. × 4 hours was changed to the two-step curing condition of heating at 100 ° C. × 1 hour and then heating at 150 ° C. × 4 hours. By repeating the same method as above, a semiconductor device having a length of 3.5 mm and a width of 3.5 mm and having a semiconductor chip sealed with a cured product having a thickness of 0.2 mm was obtained (semiconductor device 11).

[Comparative Example 9]
100 g of vinyl silicone resin A1 synthesized in Synthesis Example 1, 100 g of hydrogen silicone resin B1 synthesized in Synthesis Example 4, 0.2 g of vinyl silicone modified solution of platinum chloride acid (platinum concentration 1% by mass) as a hydrosilylation reaction catalyst. The organopolysiloxane composition C'2 was prepared by mixing 0.6 g of an acetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor and 2 g of an adhesion-imparting agent represented by the above formula (5') as an adhesion-imparting agent. .. Using the automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.), the organopolysiloxane composition C'2 is applied onto a PET film, and length x width x thickness = 100 mm x 100 mm x 0. It was formed into a film having a thickness of .2 mm. Using a pressurized vacuum laminator V130 (manufactured by Nichigo Morton Co., Ltd.), the composition surface of the film-shaped molded product and the same semiconductor chip mounting substrate as in Example 10 were bonded together. The PET film was peeled off and heated at 150 ° C. for 4 hours to cure the organopolysiloxane composition C'2. The obtained semiconductor device was diced to obtain a semiconductor device having a length of 3.5 mm × a width of 3.5 mm and having a semiconductor chip sealed with a cured product having a thickness of 0.2 mm (semiconductor device 1'). ..

[Comparative Example 10]
In Comparative Example 9, the same method as in Comparative Example 9 was repeated except that the amount of the hydrosilylation reaction catalyst was 0.004 g and the amount of ethynylcyclohexanol was 0.006 g, and the length was 3.5 mm × the width was 3.5 mm. A semiconductor device having a semiconductor chip sealed with a cured product having a thickness of 0.2 mm was obtained (semiconductor device 2').

[Comparative Example 11]
The same method as in Comparative Example 9 was repeated except that 100 g of vinyl silicone resin A2 was used instead of vinyl silicone resin A1 and 100 g of hydrogen silicone resin B2 was used instead of hydrogen silicone resin B1. A semiconductor device having a thickness of 0.5 mm and having a semiconductor chip sealed with a cured product having a thickness of 0.2 mm was obtained (semiconductor device 3').

[Comparative Example 12]
The same method as in Comparative Example 9 was repeated except that 100 g of vinyl silicone resin A3 was used instead of vinyl silicone resin A1 and 100 g of hydrogen silicone resin B3 was used instead of hydrogen silicone resin B1. A semiconductor device having a thickness of 0.5 mm and having a semiconductor chip sealed with a cured product having a thickness of 0.2 mm was obtained (semiconductor device 4').

[Comparative Example 13]
The organopolysiloxane composition 1 prepared in Example 10 was applied onto a PET film using an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.) and formed into a film. The composition melted when heated and could not maintain its pre-heated shape. Therefore, no further evaluation was performed.

[Comparative Example 14]
100 g of the vinyl silicone resin A1 synthesized in Synthesis Example 1, 100 g of the hydrogen silicone resin B1 synthesized in Synthesis Example 4, and 0.2 g of a vinyl silicone modified solution of platinum chloride acid (platinum concentration 1% by mass) as a hydrosilylation reaction catalyst. , 0.6 g of acetylene alcohol-based ethynylcyclohexanol was mixed as a reaction inhibitor to prepare an organopolysiloxane composition C'3. The method of Comparative Example 9 was repeated except that the organopolysiloxane composition C'3 was applied onto the catalyst membrane Pd-iObrane (registered trademark), and the film had a length of 3.5 mm × a width of 3.5 mm and a thickness of 0. A semiconductor device in which a semiconductor chip was sealed with a film-like cured product having a thickness of 2 mm was obtained (semiconductor device 5').

Organopolysiloxane compositions 7-11 were prepared in the same manner as in each of Examples 13-17. Each organopolysiloxane composition is coated on the catalyst membrane Pd-iObrane (registered trademark) using an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.), and has a length of 100 mm and a width of 100 mm. , Formed into a film having a thickness of 0.2 mm. The film obtained by curing the film-like molded product and peeling off the catalyst film was subjected to measurement of the residual amount of the metal catalyst, measurement of the minute hardness, and heat resistance test (change in transmittance). Each test method is as described above. The results are shown in Table 4.

[Removability from catalyst membrane]
The releasability of the organopolysiloxane compositions 1 to 3 and 7 to 11 from the catalyst membrane was evaluated.
Each organopolysiloxane composition was applied onto the catalyst film Pd-iObrane (registered trademark) according to the same method as in each of Examples 10 to 17, and molded into a film shape. The surface to which the catalyst membrane was not bonded was bonded to a slide glass and cured by heating at 150 ° C. for 4 hours. Then, the catalyst membrane was peeled off from the cured product. The cured products obtained from the organopolysiloxane compositions 1 to 3 and 7 to 9 could be peeled off from the catalyst membrane very easily, and no silicone film remained on the catalyst membrane. The cured products obtained from the organopolysiloxane compositions 10 and 11 were slightly inferior in peelability as compared with the former, but could be easily peeled off from the catalyst membrane.

The semiconductor devices manufactured in Examples 10 to 20 and Comparative Examples 9 to 12 and 14 were subjected to a heat resistance test (luminance change) according to the following method. The results are shown in Tables 5 and 6.
[Heat resistance test (change in brightness)]
For each semiconductor device, after an HTOL test ( high temperature drive test test condition 180 ° C., applied current 500 mA) was allowed for 1,000 hours, the change in brightness from the initial stage was measured. The brightness (%) when the initial brightness was 100% was calculated by the following formula.
Luminance change (%) = (180 ° C x brightness after leaving for 1,000 hours) / (initial brightness)

As shown in Table 5, the semiconductor device obtained by encapsulating the semiconductor chip with a film-like material made of a cured product of an organopolysiloxane composition containing no catalyst according to the production method of the present invention has excellent heat resistance.

The production method of the present invention is excellent in heat resistance and permeability, does not easily change with time even when stored for a long period of time, and can provide a highly reliable silicone resin film. In addition, it can have long-term storage stability even in an uncured state. The silicone resin film of the present invention can be applied to various materials that require heat resistance while taking advantage of transparency. Further, according to the method for manufacturing a semiconductor device of the present invention, the obtained device has excellent heat resistance and can provide a highly reliable semiconductor device.

1 Catalyst film 2 Organopolysiloxane composition 2'Cured product of organopolysiloxane composition 3 Semiconductor chip 4 Semiconductor substrate 5 Wire 6 Membrane-like laminate 7 Semiconductor device

Claims (21)

(B) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, and (A) Organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule. A) A curable organopolysiloxane composition containing an amount in which the ratio of the number of SiH groups in the component (B) to the number of alkenyl groups in the component is 0.5 to 8 is cured to produce a silicone resin film. In a method, the curable organopolysiloxane composition does not contain a metal catalyst and
The manufacturing method includes the following steps 1) to 3).
1) A step of forming the cured organopolysiloxane composition into a film on or between two films having catalytic activity, or
A step of laminating at least one surface of the cured organopolysiloxane composition formed into a film and a film having catalytic activity.
2) Next, a step of curing the curable organopolysiloxane composition to obtain a silicone resin film, and 3) a step of peeling the obtained silicone resin film from the film. The production method, which comprises having a hydrosilylation reaction catalyst on the surface or on the surface and inside of the film. The production method according to claim 1, wherein the membrane having catalytic activity is composed of a hybrid compound of an organic polymer having a hydroxyl group and an inorganic oxide, and the hydrosilylation reaction catalyst is immobilized on the hybrid compound. The production method according to claim 1 or 2, wherein the hydrosilylation reaction catalyst is a simple substance of a metal or a metal compound. The production method according to claim 3, wherein the hydrosilylation reaction catalyst is a platinum group metal or a platinum group metal compound. The production method according to any one of claims 1 to 4, wherein the thickness of the silicone resin film is 10 to 2000 μm. In the cured organopolysiloxane composition,
(A) The component is represented by the following average composition formula (1). R ¹ _a R ² _b R ³ _c (OX) _d SiO _{(4-a-b-cd) / 2} (1)
(In the formula, R ¹ is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ² is a substituted or unsubstituted chain aliphatic hydrocarbon group having 1 to 10 carbon atoms or 3 carbon atoms. ~ 10 cyclic aliphatic hydrocarbon groups, R ³ is an alkenyl group having 2 to 8 carbon atoms, and a, b, c and d are a ≧ 0, b> 0, c> 0, and d, respectively. > 0, a number satisfying a + b + c + d = 1 to 2, but having at least two alkenyl groups bonded to silicon atoms, where X is a substituted or unsubstituted monovalent hydrocarbon having 1 to 8 carbon atoms. Hydrogen group or hydrogen atom)
The component (B) is represented by the following average composition formula (2).
R ¹ _e R ² _f H _g (OX) _h SiO _{(4-e-f-g-h) / 2} (2)
(In the equation, R ¹ , R ² and X are as described above, e, f, g and h are e ≧ 0, f> 0, g> 0, and h> 0, respectively, and e + f + g + h = 1. A number that satisfies ~ 2, but has at least two hydrogen atoms bonded to silicon atoms)
The silicone resin according to any one of claims 1 to 5, which is contained in an amount such that the ratio of the number of SiH groups in the component (B) to the number of alkenyl groups in the component (A) is 0.5 to 8. How to make a film. The method for producing a silicone resin film according to any one of claims 1 to 6, wherein the cured organopolysiloxane composition is in a solid state at 25 ° C. The method for producing a silicone resin film according to any one of claims 1 to 7, wherein the curable organopolysiloxane composition further contains (C) an adhesive aid. The method for producing a silicone resin film according to claim 8, wherein the (C) adhesive is an organopolysiloxane having one or more epoxy groups in one molecule. (B) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, and (A) Organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule. A) A method for producing a semiconductor device comprising a cured product of a curable organopolysiloxane composition containing an amount such that the ratio of the number of SiH groups in the component (B) to the number of alkenyl groups in the component is 0.5 to 8. The cured organopolysiloxane composition does not contain a metal catalyst.
The manufacturing method includes the following steps 1) to 4).
1) A step of forming the curable organopolysiloxane composition into a film on one film having catalytic activity to obtain a film-like laminate, or
A step of laminating one surface of the cured organopolysiloxane composition formed into a film and a film having catalytic activity to obtain a film-like laminate.
2) Next, the composition surface of the film-like laminate obtained in the step 1) and the semiconductor chip mounting surface of the substrate on which the semiconductor chip is mounted are bonded together to form the semiconductor chip into the cured organopolysiloxane composition. The process of covering with,
3) Next, a step of curing the cured organopolysiloxane composition, and 4) Next, a step of peeling the cured product from the catalyst membrane to obtain a semiconductor device in which the semiconductor chip is coated with the cured product. ,
A method for producing a semiconductor device, wherein the membrane having catalytic activity has a hydrosilylation reaction catalyst on the surface of the membrane or on the surface and inside of the membrane. The method for manufacturing a semiconductor device according to claim 10, further comprising a step of dicing and individualizing the obtained semiconductor device after the step 4). One of claims 10 or 11, wherein the film having catalytic activity is composed of a hybrid compound of an organic polymer having a hydroxyl group and an inorganic oxide, and the hydrosilylation reaction catalyst is immobilized on the hybrid compound. The method for manufacturing a semiconductor device according to the section. The method for manufacturing a semiconductor device according to any one of claims 10 to 12, wherein the hydrosilylation reaction catalyst is a simple substance of a metal or a metal compound. The production method according to claim 13, wherein the hydrosilylation reaction catalyst is a platinum group metal or a platinum group metal compound. The method for manufacturing a semiconductor device according to any one of claims 10 to 14, wherein the cured product has a thickness of 10 to 2,000 μm. The method for manufacturing a semiconductor device according to any one of claims 10 to 15, wherein the multi-step curing is performed in the step 3). In the cured organopolysiloxane composition,
(A) The component is represented by the following average composition formula (1). R ¹ _a R ² _b R ³ _c (OX) _d SiO _{(4-a-b-cd) / 2} (1)
(In the formula, R ¹ is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ² is a substituted or unsubstituted chain aliphatic hydrocarbon group having 1 to 10 carbon atoms or 3 carbon atoms. ~ 10 cyclic aliphatic hydrocarbon groups, R ³ is an alkenyl group having 2 to 8 carbon atoms, and a, b, c and d are a ≧ 0, b> 0, c> 0, and d, respectively. > 0, a number satisfying a + b + c + d = 1 to 2, but having at least two alkenyl groups bonded to silicon atoms, where X is a substituted or unsubstituted monovalent hydrocarbon having 1 to 8 carbon atoms. Hydrogen group or hydrogen atom)
The component (B) is represented by the following average composition formula (2).
R ¹ _e R ² _f H _g (OX) _h SiO _{(4-e-f-g-h) / 2} (2)
(In the equation, R ¹ , R ² and X are as described above, e, f, g and h are e ≧ 0, f> 0, g> 0, and h> 0, respectively, and e + f + g + h = 1. A number that satisfies ~ 2, but has at least two hydrogen atoms bonded to silicon atoms)
The semiconductor according to any one of claims 10 to 16, which is contained in an amount such that the ratio of the number of SiH groups in the component (B) to the number of alkenyl groups in the component (A) is 0.5 to 8. How to make the device. The method for manufacturing a semiconductor device according to any one of claims 10 to 17, wherein the curable organopolysiloxane composition further contains (C) an adhesive aid. The method for manufacturing a semiconductor device according to claim 18, wherein the (C) adhesive is an organopolysiloxane having one or more epoxy groups in one molecule. The method for producing a semiconductor device according to any one of claims 10 to 19, wherein the cured organopolysiloxane composition is in a solid state at 25 ° C. The method for manufacturing a semiconductor device according to any one of claims 10 to 20, wherein the semiconductor chip is an optical semiconductor element.

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