JP2017206678A - Silicone resin film and production method of the same, and method for manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a film by curing a curable organopolysiloxane composition having high storage stability in an uncured state and containing no metal catalyst, and to provide a silicone resin film having increased heat resistance and reliability.SOLUTION: A method for manufacturing a silicone resin film is provided, in which the film is produced by curing a curable organopolysiloxane composition comprising (B) organo-hydrogen polysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule. The organopolysiloxane composition does not contain a metal catalyst. The method includes the following steps (1) to (3). They are steps of: (1) forming the organopolysiloxane composition into a film state on a single film having a catalytic activity or between two films or laminating a film having catalytic activity on at least one surface of the organopolysiloxane composition formed into a film state; (2) then curing the organopolysiloxane composition to obtain a silicone resin film; and (3) peeling the obtained silicone resin film from the above film. The film having the catalytic activity has a catalyst on a surface of the film or on a surface of the film and in the film.SELECTED DRAWING: None

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. Moreover, this invention relates to the silicone resin film which does not contain a metal catalyst substantially.
Furthermore, this invention relates to the manufacturing method of a semiconductor device provided with the film-form hardened | cured material of curable organopolysiloxane which does not contain the said catalyst.

LEDs are used in various fields of modern society, and demand is expanding. In particular, white LEDs are used not only for mobile phones and small lighting but also for general lighting and large displays. As a method of manufacturing this white LED, generally, a blue LED, which uses a phosphor called YAG (yttrium aluminum garnet) that excites 450 nm light, and a red, green, and blue LED called 3in1 emit light simultaneously. The method of making it known is known. Since the method using the blue LED and the phosphor is less expensive than the 3 in 1 method because the number of LEDs and the number of wires can be reduced, this method is used for various LEDs.

However, when the LED device is sealed and thermally cured with a liquid silicone encapsulant mixed with phosphors such as YAG, the viscosity of the liquid encapsulant is reduced by heating, so the phosphor in the encapsulant Has settled and the color variation of the LED becomes a problem. As a countermeasure, it has been proposed to improve color variation by attaching a semi-solid or solid film provided with a phosphor layer and a transparent layer to a chip (Patent Document 1).

  Electronic materials-related materials are required to minimize the base material used, make fine patterns, have high heat resistance, and have high impact resistance, and various resins are currently used. Along with the minimization of the base material, a trace amount of metal catalyst contained in the sealing material or the coating material has become one of the causes of discoloration due to heat or light and a decrease in reliability. In addition, optical sensors such as photocouplers, CCDs, and CMOSs have become more important in terms of reliability such as heat resistance, light resistance, and impact resistance with the miniaturization and performance enhancement of sensors, and conventional sensors are sealed with glass. There are also problems such as cracking if just done.

  Patent Document 4 describes a method for manufacturing a material such as a sensor by compression molding or the like using a layered hot melt silicone composition. However, an addition reaction catalyst is actually used, and it has been difficult to achieve further improvement in heat resistance and light resistance. Patent Document 5 describes that polysilazane is contained and a gas barrier layer is provided by vacuum ultraviolet irradiation treatment. However, the gas barrier layer cannot be made so thick and there is a problem in the flexibility of the polymer. It was. Patent Document 6 describes a chip size package manufacturing method in which a chip is mounted on an adhesive layer containing thermally expandable microspheres, covered with a protective material, and the adhesive layer is peeled off and diced. However, an adhesive layer is required, and the thermosetting resin always contains a catalyst, so that it is difficult to improve heat resistance.

JP2013-159003A Special table 2014-519964 gazette JP-T-2015-511164 JP-T-2006-508290 Japanese Patent Laying-Open No. 2015-186922 WO2013 / 011850

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. The cured product has insufficient heat discoloration and reliability, and it has been found that these problems depend on the amount of catalyst remaining in the cured product. Therefore, reduction of the amount of the metal catalyst contained in the thermosetting silicone resin composition that is a raw material of the cured product has been an issue. In addition, in the case of a one-pack type silicone resin composition containing a metal catalyst, the reactivity gradually changes and changes with time, so that the storage stability is poor. Further, in the case of the two-component type, there is a problem that voids are likely to occur when mixed and formed into a film.
Further, compounds using polysilazane and acrylate having low gas permeability have problems in resin flexibility and heat discoloration.

  In view of the above circumstances, the present invention provides a method for producing a film by curing a curable silicone resin composition that does not contain a metal catalyst and has high storage stability in an uncured state, and heat resistance and reliability. It aims at providing the silicone resin film which improved the property. Furthermore, this invention aims at providing the silicone containing device which improved the heat resistance and reliability including the process of bonding the said silicone resin composition to a board | substrate, and hardening.

JP-A-2014-519964 (Patent Document 2) and JP-A-2015-511164 (Patent Document 3) disclose a catalyst having a catalytic activity in which a metal catalyst is fixed on the surface and inside of an inorganic / organic polymer hybrid material. Materials, in particular catalyst membranes, are described. The catalyst membrane is described as being 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 the use of the catalyst film for a reaction in a solid or a reaction in which a reaction system is solidified as the reaction proceeds.

As a catalyst for curing the thermosetting organopolysiloxane composition, the present inventors diligently studied to use a film having catalytic activity (hereinafter referred to as catalyst film) to which the above metal catalyst is fixed. However, it has been found that when a curable organopolysiloxane composition not containing a catalyst is formed into a film shape, bonded to the catalyst film and cured by heating, the organopolysiloxane composition is cured to give a film-shaped molded product. Furthermore, the present inventors 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-like molded product, thereby achieving the present invention.
Furthermore, the present inventors formed a curable organopolysiloxane composition that does not contain a catalyst into a film shape, bonded the catalyst film, and then bonded the surface of the curable organopolysiloxane composition to a semiconductor device and cured by heating. After that, the catalyst film was peeled off from the film-like molded product and diced to find that a semiconductor device containing an extremely small amount of metal catalyst can be provided, and the present invention has been achieved.

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 include a metal catalyst;
The manufacturing method includes the following steps 1) to 3):
1) A step of forming the organopolysiloxane composition into a film form on one or two sheets having catalytic activity, or at least of the organopolysiloxane composition formed into a film form Bonding one surface and a membrane 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 and the membrane. The membrane having the catalytic activity is a surface of the membrane, Alternatively, the present invention provides the above production method, characterized by having a catalyst on the surface and inside of the membrane.

The present invention also provides (B) a method for producing a semiconductor device comprising 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) Forming the organopolysiloxane composition into a film on one sheet having catalytic activity, or one side of the organopolysiloxane composition formed into a film and a film having catalytic activity A step of bonding to obtain a film-like laminate,
2) Next, the composition surface of the film 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 covered with the organopolysiloxane composition. The process of
3) Next, a step of curing the organopolysiloxane composition, and 4) Next, a step of peeling the cured product and the catalyst film to obtain a semiconductor device in which a semiconductor chip is coated with the cured product,
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 may further include a step of dicing the obtained semiconductor device into pieces after step 4).

  In the present invention, the curable organopolysiloxane composition further comprises (A) an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule, and the number of alkenyl groups in the component (A). A method for producing the silicone resin film and the semiconductor device, wherein the SiH group in the component (B) is contained in an amount such that the number ratio of the SiH groups in the component is 0.5-8.

Further, the present invention relates to (B) a silicone comprising a cured product of an organopolysiloxane composition containing at least two hydrogen atoms bonded to silicon atoms in one molecule and containing no metal catalyst. A silicone resin film, which is a resin film and has an 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 mass of the entire cured product.
The present invention also includes (B) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, and (A) at least two alkenyl groups bonded to silicon atoms in one molecule. The number of organopolysiloxanes contained is in an amount such that the number ratio of SiH groups in the component (B) to the number of alkenyl groups in the component (A) is 0.5 to 8, and no metal catalyst is contained. A silicone resin film comprising a cured product of an organopolysiloxane composition, wherein the amount of the metal catalyst that may be contained in the cured product is less than 0.1 ppm in terms of metal mass relative to the total mass of the cured product A resin film is provided.

  In the production method of the present invention, since a metal catalyst is not included in the organopolysiloxane composition, changes in physical properties hardly occur with time when the composition is cured and when the composition is stored in an uncured state. Therefore, the storage stability of the composition is improved. In addition, the amount of metal catalyst contained in the resulting silicone resin film is extremely small, and particularly contains substantially no metal catalyst. A high resin film can be provided. Furthermore, the resin film can have high heat resistance. Furthermore, a semiconductor device provided with a film-like cured product of the organopolysiloxane composition is also excellent in heat resistance and can provide a highly reliable semiconductor device.

It is a schematic diagram of the laminated body which consists of a film-form molding of a curable organopolysiloxane composition, and a catalyst film. It is a schematic diagram which shows the aspect which seals the semiconductor device by which a flip chip is mounted with the organopolysiloxane composition of this invention. It is a schematic diagram which shows the aspect which seals a 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, and that the organopolysiloxane composition does not contain a metal catalyst, and a film having catalytic activity as a curing catalyst (hereinafter referred to as a curing catalyst). And a catalyst membrane). 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 on the surface of the membrane, or fixed on the surface of the membrane and embedded in the inside of the membrane. is there. The catalyst is fixed by a supporting material constituting the membrane. For example, a membrane based on an organic polymer such as polyvinyl alcohol (PVA) or a derivative thereof, polyimide, polyethylene, regenerated cellulose, or the like can be used. Particularly preferred is a film 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 fixed to the hybrid compound. As the catalyst membrane, in particular, those described in JP-T-2014-519964 (Patent Document 2) and JP-T-2015-511164 (Patent Document 3) can be used. This will be described in more detail below.

  The inorganic oxide constituting the hybrid compound is preferably a silicate compound or a zirconate compound. The silicic acid compound means silicic acid and its derivatives, or any compound containing silicic acid as a main component. A zirconic acid compound means any compound containing zirconic acid and its derivatives, or zirconic acid as a main component. Particularly preferred are zirconate compounds. In addition, the silicic acid compound and the zirconic acid compound may contain other elements and / or contain additives as long as the characteristics are not impaired.

  The organic polymer having a hydroxyl group is preferably a water-soluble polymer, particularly preferably polyvinyl alcohol. Examples of other polymers include 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, etc. Fluoropolymers, sugar chain compounds such as methylcellulose, polyvinyl acetate polymers, polystyrene polymers, polycarbonate polymers, and epoxy resin polymers. These may be used as a mixture. In addition, other organic and inorganic additives may be mixed with the hybrid compound as long as the characteristics of the catalyst film are not impaired.

The catalyst is a simple metal or a metal compound. For example, platinum group metals or platinum group metal compounds, and platinum group metal catalysts such as platinum, palladium, and rhodium catalysts can be suitably used. From the viewpoint of cost and the like, the catalyst is preferably a platinum-based or palladium-based catalyst, and a metal fine particle catalyst of these metals or a metal compound catalyst 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 , KHPtCl ₆ · mH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ · mH ₂ O, and PtO. ₂ · mH ₂ O (m is a positive integer). In addition to these, complexes of the platinum group metal compound with hydrocarbons such as olefins, alcohols, or vinyl group-containing organopolysiloxanes can be used, and PdCl ₂ can be used as a palladium catalyst. The catalyst may be used alone or in combination of two or more. In the catalyst film, the amount of the catalyst is 0.0001 to 10 wt%, preferably 0.1 to 10 wt%, based on the weight of the entire catalyst film in terms of metal. The metal particle catalyst preferably has a diameter of 0.5 to 500 nm.

  The manufacturing method of a catalyst film should just follow the method described in the Japanese translations of PCT publication No. 2014-519964 (patent document 2) and the special table 2015-511164 (patent document 3), for example. Further, as a commercial product, for example, a catalyst film (trade name: Pd-iObrane (registered trademark), manufactured by Nippon Kogyo Paper Industries Co., Ltd.) in which palladium is fixed to an inorganic oxide / polyvinyl alcohol hybrid compound can be used.

  The present invention uses the catalyst film to cure a curable organopolysiloxane composition that does not contain a catalyst. The organopolysiloxane composition is formed into a film shape, brought into contact with the catalyst film and heated, whereby the curing reaction is accelerated on the surface of the catalyst film to give a cured product. During the reaction, the catalyst in the form of a membrane is used to prevent the agglomeration of the catalytic metal particles, and the catalytic activity becomes constant. Moreover, since the catalyst is strongly fixed to the catalyst membrane, the catalyst is prevented from moving into the composition during the reaction. Therefore, the amount of metal catalyst contained in the cured product can be made extremely low by peeling off the catalyst film after curing. 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 the metal catalyst contained in the cured product is less than 0.1 ppm in terms of metal mass, and in particular, a silicone substantially free of metal catalyst. A resin film can be provided.

[Organopolysiloxane composition]
There are two embodiments of the organopolysiloxane composition cured by the production method of the present invention. A 1st aspect is a composition which contains the following (B) component independently and hardens | cures by dehydrogenation condensation. A 2nd aspect is a composition which hardens | cures by addition reaction including the following (A) component and (B) component. 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 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]
Component (A) is an organopolysiloxane having at least 2, preferably 3 or more alkenyl groups bonded to silicon atoms in one molecule. The component (A) may be any conventionally known alkenyl group-containing organopolysiloxane.
An organopolysiloxane represented by the following average composition formula (1) is preferable.

(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 is a cyclic aliphatic hydrocarbon group, 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, provided that it 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 hydrogen atom)

In the above formula (1), R ¹ : monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms includes aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropylene. And an aralkyl group such as a ru group. Of these, a phenyl group, a benzyl group and the like are preferable, and a phenyl group is particularly preferable. R ^2: The chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, tert- butyl group, a pentyl group, a neopentyl group, a hexyl group , Alkyl groups such as octyl group, nonyl group and decyl group. R ² : Examples of the cyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Among 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. R ² may be a hydrocarbon group in which part or all of the hydrogen atoms are substituted with a halogen atom such as fluorine, bromine or chlorine, or a cyano group. Examples thereof include halogen-substituted alkyl groups such as propyl group, bromoethyl group and trifluoropropyl group, and 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, and a 4-pentenyl group. Among 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 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Preferably, they are a methyl group or a hydrogen atom.

The alkenyl group-containing organopolysiloxane preferably has at least one monovalent aromatic hydrocarbon group, and in particular, 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 for the monovalent aromatic hydrocarbon group to fall within this range since the resulting composition will be in a solid or semi-solid state at 25 ° C. In the present invention, the semi-solid means that the temperature of 15 to 30 ° C. is a room temperature, has a property of having plasticity but not fluidity, and is liquid or solid due to external stress such as temperature, stress, and distortion. A state of exhibiting properties.

  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 0.00. 1 to 0.7, more preferably 0.15 to 0.65, and c is preferably 0.01 to 0.5, more preferably 0.015 to 0.5, and even more preferably 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 0.001 to 0.15. However, a + b + c + d = 1-2.

The component (A) may have any of linear, branched, cyclic, and network structures, R ₂ SiO _2/2 unit (D unit), R ₃ SiO _1/2 unit (M unit). , RSiO _3/2 unit (T unit) and SiO _4/2 unit (Q unit). R is R ¹ , R ² , R ³ , or an OX group. In order for the resulting composition to be semi-solid or solid at 25 ° C., it is preferable to have at least T units or Q units. In particular, a silicone resin having a linear structure (continuous D units) composed of T units, M units, and D units is preferred. 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 is continuous. It is preferable that the number of siloxane units obtained is 5 to 50, preferably 5 to 40, and more preferably 8 to 40. As a result, the composition that 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 a film-shaped 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 more preferably 5,000 to 80,000. In addition, the weight average molecular weight mentioned 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: 0.6mL / min
Detector: Differential refractive index detector (RI)
Column: TSK Guardcolom SuperH-L
TSKgel SuperH4000 (6.0 mm ID × 15 cm × 1)
TSKgel Super H3000 (6.0 mm ID × 15 cm × 1)
TSKgel SuperH2000 (6.0 mm ID × 15 cm × 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 20 μL (0.5% by weight THF solution)

[(B) Organohydrogenpolysiloxane]
The component (B) is an organohydrogenpolysiloxane having hydrogen atoms bonded to at least two silicon atoms in one molecule. Organohydrogenpolysiloxane acts as a cross-linking agent, and is cured by an addition reaction between a hydrogen atom bonded to a silicon atom in the component (hereinafter referred to as SiH group) and an alkenyl group in component (A). . Such organohydrogenpolysiloxanes only need to 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).

(Wherein 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 satisfying ˜2, with 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 include those exemplified for the above (A). Examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, and among them, a phenyl group is preferable. In the above formula (2), R ² may be 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 group; 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 group. Of these, a methyl group is preferred. The organohydrogenpolysiloxane preferably has at least one monovalent aromatic hydrocarbon group, and in particular, a monovalent aromatic hydrocarbon group based on 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%, and more preferably 30 to 50%. It is preferable for the monovalent aromatic hydrocarbon group to fall within this range since the resulting composition will be in a solid or semi-solid state at 25 ° C.

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

The component (B) may have any of linear, branched, cyclic, and network structures, R ₂ SiO _2/2 unit (D unit), R ₃ SiO _1/2 unit (M unit). , 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 be semi-solid or solid at 25 ° C., it is preferable to have at least T units or Q units. In particular, a silicone resin composed of a T unit, an M unit, and a D unit and having a linear structure (continuous D unit) 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 is continuous. It is preferable that the number of siloxane units obtained is 5 to 50, preferably 5 to 40, and more preferably 8 to 40.

Other organohydrogenpolysiloxanes include tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1,1,3,3-tetramethyldisiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydro Gensiloxane copolymer, trimethylsiloxy group-capped methylhydrogensiloxane / diphenylsiloxane copolymer, both-end trimethylsiloxy group-capped methylhydrogensiloxane Down-diphenylsiloxane-dimethylsiloxane _{copolymer, (CH} 3) 2 _{HSiO 1/2} copolymer comprising units and _{SiO 4/2 units, (CH} 3) 2 _{HSiO 1/2} units and _{SiO 4/2} units And a copolymer comprising (C ₆ H ₅ ) SiO _3/2 units.

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

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

[(C) Adhesion aid]
The organopolysiloxane composition of the present invention may contain an adhesion assistant in addition to the above-described components (A) and (B) in order to impart adhesiveness. Examples of the adhesion assistant include 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. And organosiloxane oligomers having one or more of the following. The organosiloxane oligomer preferably has 4 to 50 silicon atoms, more preferably 4 to 20 silicon atoms. The components (A) and (B) are different in that they include a hydroxysilyl group, an alkoxy group, an epoxy group, or a substituent containing a nitrogen atom.

  Examples of the adhesion assistant 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, -Silane coupling agents such as aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxylane, 3-mercaptopropyltrimethoxysilane, trimethoxysilane, tetramethoxysilane and The oligomer is mentioned.

Moreover, the organooxysilyl modified isocyanurate compound represented by the following general formula (3) and its hydrolysis condensate (organosiloxane modified isocyanurate compound) can be used as other adhesion assistants.

（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 independently of each other is an organic group represented by the following general formula (4) or a monovalent aliphatic unsaturated hydrocarbon group which may have an oxygen atom. 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 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 optionally having an oxygen atom represented by R ⁴ is preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, More preferably, it is a C2-C6 linear or branched alkenyl group such as a vinyl group, allyl group, 1-butenyl group, 1-hexenyl group, 2-methylpropenyl group, or (meth) acryl group. Etc. For example, it can be represented by the following formula.

(M is an integer of 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 assistants include organopolysiloxanes having at least one epoxy group in the molecule. The organopolysiloxane may be a conventionally known compound. Examples thereof include organosiloxanes represented by the following general formula (5) or average formula (6). Among these, a composition containing a compound represented by the following general formula (5) is preferable because it has better peelability from the cured catalyst film than other adhesion aids.

(In Formula (5 ′), R ⁶ is independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, and v is an integer of 2 to 7. Preferably, all R ⁶ are methyl groups. , V is 3)

(In the formula (6), R ⁵ 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. include options group represented by ^{R 2} described for, k is 1 to 3, j is .s is 1 to 2, p, and q are positive numbers as the sum 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)

  The blending amount in the case of blending the adhesion assistant is preferably 10 parts by mass or less, more preferably 0.1 to 8 parts by mass, particularly preferably 100 parts by mass in total of the components (A) and (B). 0.2 to 5 parts by mass. If the blending amount is less than or equal to the above upper limit value, the cured product hardness is high, and surface tackiness is also suppressed.

  Further, as a blending amount in the case of blending the adhesion assistant, the ratio of the total number of hydrosilyl groups in the whole composition to the total number of alkenyl groups in the whole composition containing the adhesion assistant is 0.4. The amount of ˜4 is preferred, the amount of 0.6˜3 is more preferred, and the amount of 0.8˜2 is even more preferred.

  Furthermore, it is preferable that the ratio of an adhesion assistant component is 0.01-10 mass parts with respect to a total of 100 mass parts of (A) and (B) component, More preferably, it is 0.1-5 mass parts. Within this range, the adhesive force can be improved without impairing the effects of the present invention.

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

[Phosphor]
The phosphor is not particularly limited, and a conventionally known phosphor may be used. For example, it is preferable to absorb light from a semiconductor element, particularly a semiconductor light emitting diode having a nitride-based semiconductor as a light emitting layer, and convert the light to light having a different wavelength. Examples of such phosphors include nitride-based phosphors / oxynitride-based phosphors mainly activated by lanthanoid elements such as Eu and Ce, lanthanoid-based substances such as Eu, and transition metal-based substances such as Mn. Alkaline earth metal halogen apatite phosphor, alkaline earth metal borate phosphor, alkaline earth metal aluminate phosphor, alkaline earth metal silicate phosphor, alkaline earth metal activated mainly by elements Sulfide phosphor, alkaline earth metal thiogallate phosphor, alkaline earth metal silicon nitride phosphor, germanate phosphor, rare earth aluminate phosphor mainly activated by lanthanoid elements such as Ce, rare earth Organic and organic complex phosphors mainly activated by lanthanoid elements such as silicate phosphors or Eu, Ca—Al—Si—O—N oxynitride glass phosphors It is preferably at least one member selected from.

As a nitride-based phosphor mainly activated by a lanthanoid element such as Eu or Ce, M ₂ Si ₅ N ₈ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, 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 Sr, Ca, Ba, Mg, and Zn And the like.

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

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 X ′ is at least one selected from F, Cl, Br and I. R ′ is any one or more of Eu and Mn.) Is mentioned.

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

Alkaline earth metal aluminate phosphors include SrAl ₂ O ₄ : R ′, Sr ₄ Al ₁₄ O ₂₅ : R ′, CaAl ₂ O ₄ : R ′, BaMg ₂ Al ₁₆ O ₂₇ : R ′, BaMg ₂ Al ₁₆ O ₁₂ : R ′ and BaMgAl ₁₀ O ₁₇ : R ′ (R ′ is any 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.

As rare earth aluminate phosphors mainly activated by lanthanoid elements such as Ce, Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al _0.8 Ga) _0.2 ) ₅ O ₁₂ : Ce, and (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ YAG phosphors represented by the composition formulas. Further, there are Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which a part or all of Y is substituted with Tb, Lu, or the like.

Other phosphors include ZnS: Eu, Zn ₂ GeO ₄ : Mn, MGa ₂ S ₄ : Eu (M is at least one selected from Sr, Ca, Ba, Mg and Zn). It is done.

  The phosphor contains at least one selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, Ti instead of Eu or in addition to Eu as desired. Can do.

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

  Moreover, it is also possible to use a phosphor other than the above phosphors and having the same performance and effect.

  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, still more preferably 10 nm to 1 μm. The average particle diameter is measured by particle size distribution measurement by a laser light diffraction method such as a cirrus laser measuring apparatus.

  The blending amount when the phosphor is blended is preferably 0.1 to 2,000 parts by mass, more preferably 100 parts by mass in total of components other than the phosphor, for example, the components (A) and (B). 0.1 to 100 parts by mass. When the cured product of the organopolysiloxane composition of the present invention is a phosphor-containing wavelength conversion film, the phosphor 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, ferric oxide, and zinc oxide. These can be used individually by 1 type or in combination of 2 or more types.

  The blending amount in the case of blending the inorganic filler is not particularly limited, but is preferably such an amount that the silicone resin film of the present invention does not lose transparency. What is necessary is just to mix | blend suitably in the range of 20-10 mass parts per 100 mass parts in total of (A) and (B) component, Preferably 0.1-10 mass parts.

[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, thermal stabilizers, conductivity enhancers, antistatic agents, radiation shielding Agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, physical property modifiers, 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 comprising only the component (B) or the components (A) and (B). In addition, in order to obtain the hardened | cured material which has high transparency, it is preferable not to contain the said inorganic filler. The method for preparing the organopolysiloxane composition of the present invention is not particularly limited, and may be a conventionally known method. The above components (A) and (B) and other optional components are mixed by any method. To be prepared. For example, it can be prepared by putting it in a commercially available stirrer (THINKY CONDITIONING MIXER Co., Ltd., manufactured by Shinky Co., Ltd.) or the like and mixing uniformly for about 1 to 5 minutes.

  The property of the organopolysiloxane composition of the present invention may be liquid, semi-solid, or solid, but if it is solid at 25 ° C., the flowability of the resin is very low even before curing. It is preferable because the shape can be easily maintained.

  The organopolysiloxane composition of the present invention can give a cured product having high light transmittance. Therefore, the organopolysiloxane composition of the present invention is useful for LED element sealing, particularly for blue LED and ultraviolet LED element sealing. A method for sealing an LED element or the like with the organopolysiloxane composition of the present invention may be a conventionally known method. For example, a dispensing method and a compression molding method can be used.

[Production Method I. Manufacturing method of silicone resin film]
Hereinafter, the manufacturing method of a silicone resin film is demonstrated in detail.
Production method of the present invention Includes the following steps (1) to (3).
(1) A step of forming the organopolysiloxane composition into a film form on one film having catalytic activity or between two sheets, or an organopolysiloxane composition formed into a film form 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 separating the obtained silicone resin film and the membrane.

Process (1) of production method I.
The method of forming the organopolysiloxane composition into a film may be in accordance with a conventionally known method, and for example, a film coater, a hot press machine or the like can be used. As film coater, 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, There are knife coaters, impregnation coaters, MB coaters, and MB reverse coaters. Of these, a direct gravure coater, an offset gravure coater, a die coater and the like are preferable. In the case of using a hot press, the step of bonding the catalyst film may be before or after molding the composition. When a film coater is used, it is preferable that the catalyst film is bonded after being formed into a film.

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

  The thickness of the organopolysiloxane composition formed into a film is preferably 10 to 2,000 μm, more preferably 50 to 1,000 μm. If it is this range, a composition can fully harden | cure with the catalyst which a catalyst film has, and does not raise | generate a curing failure.

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

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

  Examples of the organic solvent include, but are not limited to, hydrocarbon solvents such as benzene, toluene, and xylene; ether solvents such as tetrahydrofuran, 1,4-dioxane, and diethyl ether; ketone solvents such as methyl ethyl ketone; chloroform, Halogen solvents such as methylene chloride and 1,2-dichloroethane; alcohol solvents such as methanol, ethanol, isopropyl alcohol and isobutyl alcohol; octamethylcyclotetrasiloxane, hexamethyldisiloxane and the like, and cellosolve acetate, cyclohexanone, Solvents such as butyrocellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, cyclohexanol, diglyme and triglyme. These organic solvents may be used alone or in combination of two or more. The composition in a varnish state is heated to 60 to 150 ° C., preferably 80 to 120 ° C. with a film coater for 1 to 20 minutes, preferably 3 to 10 minutes to be processed into a sheet. When a film coater is used, the film molding thickness is 0.01 to 1 mm, preferably 0.015 to 0.5 mm, as the thickness of the obtained cured product.

  Furthermore, a release film may be bonded to the surface where the catalyst film of the organopolysiloxane composition formed into a film is not bonded. Examples of the release film include a fluororesin-coated PET film, a silicone resin-coated PET film, and a fluororesin film.

Step (2) of production method I.
The curing conditions for the organopolysiloxane composition of the present invention are not particularly limited for both the dehydrogenative condensation type and the addition reaction curing type, and may be a conventionally known method. 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 cure. In step cure, for example, the following two steps can be performed. First, the organopolysiloxane composition is heated at a temperature of 60 to 100 ° C. for 0.5 to 2 hours to sufficiently degas it. Next, the organopolysiloxane composition is heat-cured at a temperature of 120 to 180 ° C. for 1 to 10 hours. By passing through these steps, it is sufficiently cured, and there is no generation of bubbles, and a colorless and transparent cured product can be obtained. In the present invention, the colorless and transparent cured product means that the light transmittance at 450 nm with a thickness of 1 mm is 80% or more, preferably 85% or more, particularly preferably 90% or more.

Step (3) of production method I.
A silicone resin film can be obtained by peeling the cured product (silicone resin film) and catalyst film formed by the above process. If the manufacturing method of this invention is used, the quantity of the metal catalyst contained in a silicone resin film will be less than 0.1 ppm in conversion of metal mass, Preferably it will be less than 0.05 ppm. Exceeding the upper limit is not preferable because the storage stability of the composition in an uncured state is lowered, and the heat resistance and reliability of the resulting silicone resin film may be lowered.

[Production Method II. Manufacturing method of semiconductor device]
Hereinafter, a method for producing a semiconductor device using a film-like molded article made of the organopolysiloxane composition of the present invention (meaning a molded article made of a composition before curing) will be described in more detail.
Production method II. Includes the following steps (1) to (4).
(1) A step of forming the organopolysiloxane composition into a film shape on one film having catalytic activity, or one surface of the organopolysiloxane composition formed into a film shape and a film having catalytic activity (2) Bonding the composition surface of the film laminate obtained in the step (1) and the semiconductor chip mounting surface of the substrate on which the semiconductor chip is mounted, The step of coating a semiconductor chip with the organopolysiloxane composition (3) The step of curing the organopolysiloxane composition (4) The cured product and the catalyst film are peeled off and the semiconductor chip is covered with the cured product Step of obtaining a manufactured semiconductor device Furthermore, the manufacturing method II. Can further include a step of dicing and dividing the obtained semiconductor device after the step (4).

Production method II. FIG. 4 is a schematic diagram for explaining a method for manufacturing a semiconductor device according to the above. Each process (1)-(5) shown by FIG. 4 respond | corresponds to the said process (1)-(5). Hereinafter, each process is demonstrated in detail.
Step (1) of production method II.
In the step (1), the curable organopolysiloxane composition is formed into a film to obtain a film-shaped laminate composed of the film-shaped molded product and a catalyst film (step (1) in FIG. 4). The method of forming into a film and the method of pasting with a catalyst membrane are described in the above-mentioned production methods I. As described in step (1).

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

Step (3) of production method II.
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 for the curable organopolysiloxane composition of the present invention are as described in the above-described production method I.I. As described in step (2). 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 cure. Step cure is as described above. When heated at a curing temperature exceeding 180 ° C. (for example, 200 ° C.) for a long time (for example, 4 hours or more), there is a possibility that peeling between the obtained cured product and the catalyst film may not be easy. By bonding the composition surface of the film-shaped laminate composed of the organopolysiloxane composition of the present invention and the catalyst film to the semiconductor device, it can be molded without causing voids or the like. The manufacturing method of the present invention can form either a flip chip type semiconductor device as shown in FIG. 2 or a semiconductor device having a chip with a wire as shown in FIG.

Step (4) of production method II.
In the semiconductor device obtained in the step (3), the cured product and the catalyst film 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 film can be easily peeled off by hand.

Step (5) of production method II.
In step (5), the semiconductor device manufactured in the above step is diced to form a package (step (5) in FIG. 4). Dicing can be performed with a DISCO dicer or the like without causing burrs.

  If 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, and preferably less than 0.05 ppm, so that it has excellent heat resistance and reliability. A semiconductor device can be provided.

  Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

In the following examples, the weight average molecular weight is a weight average molecular weight based on polystyrene by gel permeation chromatography (GPC). The measurement conditions are as follows.
[Measurement condition]
Developing solvent: THF
Flow rate: 0.6mL / min
Detector: Differential refractive index detector (RI)
Column: TSK Guardcolom SuperH-L
TSKgel SuperH4000 (6.0 mm ID × 15 cm × 1)
TSKgel Super H3000 (6.0 mm ID × 15 cm × 1)
TSKgel SuperH2000 (6.0 mm ID × 15 cm × 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 20 μL (0.5% by weight THF solution)

[Synthesis Example 1]
Synthesis of alkenyl group-containing organopolysiloxane 1142.1 g (87.1 mol%) of phenyltrichlorosilane, 529 g of ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl (3.2 mol%), and 72 dimethylvinylchlorosilane .4 g (9.7 mol%) dissolved in a toluene solvent, dropped into water, co-hydrolyzed, neutralized by water washing and alkali washing, dehydrated, stripped of the solvent, and solid phenyl at 25 ° C. A group-containing vinyl silicone resin A1 was obtained. The weight average molecular weight in terms of polystyrene by GPC measurement using THF as a solvent was 63,000.

[Synthesis Example 2]
Alkenyl group-containing organopolysiloxane synthesized <br/> phenyltrichlorosilane _{1142.1g (84.4mol%), ClMe 2} SiO (Me 2 SiO) 13 SiMe 2 Cl 466.6g (6.3mol%), and dimethyl vinyl Dissolve 72.4 g (9.4 mol%) of chlorosilane in a toluene solvent, drop it into water, co-hydrolyze, neutralize and dehydrate with water, alkali wash, strip the solvent, and solid at 25 ° C The phenyl group-containing vinyl silicone resin A2 was obtained. The weight average molecular weight in terms of polystyrene as measured by GPC using THF as a solvent was 22,000.

[Synthesis Example 3]
Synthesis of alkenyl group-containing organopolysiloxane 1142.1 g (87.4 mol%) of phenyltrichlorosilane, 869.7 g (2.9 mol%) of HO- (PhMeSiO) _35- H, and 72.3 g of dimethylvinylchlorosilane. (9.7 mol%) dissolved in a toluene solvent, dropped into water, co-hydrolyzed, neutralized with water and alkali washed, dehydrated, stripped of the solvent, and containing a solid phenyl group at 25 ° C Vinyl silicone resin A3 was obtained. The weight average molecular weight in terms of polystyrene as measured by GPC using THF as a solvent was 23,000.

[Synthesis Example 4]
Organohydrogen synthesis of the polysiloxane <br/> phenyltrichlorosilane _{1142.1g (87.1mol%), ClMe 2} SiO (Me 2 SiO) 33 SiMe 2 Cl 529g (3.2mol%), and methyl dichlorosilane 69 g ( 9.7 mol%) was dissolved in a toluene solvent, dropped into water, co-hydrolyzed, neutralized by water washing and alkali washing, dehydrated, stripped of the solvent, and a solid phenyl group-containing hydrogel at 25 ° C. Gen silicone resin B1 was obtained. The weight average molecular weight in terms of polystyrene as measured by GPC using THF as a solvent was 58,000.

[Synthesis Example 5]
Organohydrogenpolysiloxane synthetic <br/> phenyltrichlorosilane _{1142.1g (84.4mol%), ClMe 2} SiO (Me 2 SiO) 13 SiMe 2 Cl 466.6g (6.3mol%), and methyl dichlorosilane 69.0 g (9.4 mol%) was dissolved in a toluene solvent, dropped into water, co-hydrolyzed, neutralized by water washing and alkali washing, dehydrated, stripped of the solvent, and solidified at 25 ° C. A phenyl group-containing hydrogen silicone resin B2 was obtained. The weight average molecular weight in terms of polystyrene as measured by GPC using THF as a solvent was 11,000.

[Synthesis Example 6]
Synthesis of organohydrogenpolysiloxane 1142.1 g (87.1 mol%) of phenyltrichlorosilane, 869.7 g (2.9 mol%) of HO— (PhMeSiO) ₃₅ and 69 g of methyldichlorosilane (9. 7 mol%) is dissolved in a toluene solvent, dropped into water, co-hydrolyzed, neutralized and dehydrated with water and alkali, stripped of the solvent, and a phenyl group-containing hydrogen silicone that is solid at 25 ° C. Resin B3 was obtained. The weight average molecular weight in terms of polystyrene as measured by GPC using THF as a solvent was 8,000.

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

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

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

[Example 3]
100 g of vinyl silicone resin A3 synthesized in Synthesis Example 3 and 100 g of hydrogen silicone resin B3 synthesized in Synthesis Example 6 were mixed to prepare organopolysiloxane composition 3. Example 1 was repeated except that the organopolysiloxane composition 3 was used instead of the organopolysiloxane composition 1, and a film having a length of 150 mm × width of 150 mm and a thickness of 0.1 mm was formed (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 vinyl silicone resin A1 synthesized in Synthesis Example 1, 100 g of hydrogen silicone resin B1 synthesized in Synthesis Example 4, and 6 g of adhesion-imparting agent 2 represented by the following formula (3 ′) were mixed. Thus, an organopolysiloxane composition 4 was prepared. Example 1 was repeated except that the organopolysiloxane composition 1 was used instead of the organopolysiloxane composition 1, and a film having a length of 150 mm × width of 150 mm and a thickness of 0.1 mm was formed (molded product F4).

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

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

[Example 6]
100 g of vinyl silicone resin A3 synthesized in Synthesis Example 3, 100 g of hydrogen silicone resin B3 prepared in Synthesis Example 6, and 6 g of an 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 a film having a length of 150 mm × width of 150 mm and a thickness of 0.1 mm was formed (molded product F6).

[Example 7]
Example 1 was repeated except that the thickness of the coated organopolysiloxane composition was changed to 0.4 mm, and formed into a film having a length of 150 mm × 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 membranes Pd-iObrane (registered trademark), compression-molded, and molded into a membrane having a length of 150 mm × width of 150 mm and a thickness of 0.1 mm. did. For 10 sheets of the film-shaped molded product, the catalyst film on one side was peeled off one by one and the process of pasting at a temperature of 80 ° C. using a pressure-type vacuum laminator V130 (manufactured by Nichigo-Morton Co., Ltd.) was repeated for 10 molded products. Was laminated 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 bonded to a 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 formed into a film shape. About 10 sheets of the film-shaped molded product, the PET film was peeled off, and bonded using a pressure type vacuum laminator V130 (manufactured by Nichigo Morton Co., Ltd.), laminated at a temperature of 80 ° C., and one side of the obtained molded product The PET film on the surface was peeled off, and a 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 a chloroplatinic acid vinyl silicone modified solution (platinum concentration 1 mass%) as a hydrosilylation reaction catalyst Then, 0.6 g of acetylenic 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 prepare an organopolysiloxane composition C′1. Prepared. Using an automatic coating apparatus PI-1210 (manufactured by Tester Sangyo Co., Ltd.), the organopolysiloxane composition C′1 is applied on a PET film, and the length is 150 mm × width 150 mm and the thickness is 0.1 mm. It was formed 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 hydrosilylation reaction catalyst was 0.004 g and the amount of ethynylcyclohexanol was 0.006 g, and the length was 150 mm × 150 mm and the thickness was 0.1 mm. 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. The film was formed 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. Molded into a film having 1 mm (molded product F′4).

[Comparative Example 5]
Using an automatic coating apparatus PI-1210 (manufactured by Tester Sangyo Co., Ltd.), the organopolysiloxane composition 4 prepared in Example 4 was applied onto a PET film and molded into a film shape. The composition melted when heated, and the conventional shape could not be maintained.

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

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

[Comparative Example 8]
About 10 molded articles F′1 molded in Comparative Example 1, the PET film was peeled off and bonded using a pressure type vacuum laminator V130 (manufactured by Nichigo Morton Co., Ltd.), laminated at a temperature of 80 ° C. A 0 mm film-like molded product F′8 was produced.

[Measurement of remaining amount of metal catalyst]
About the molding formed in Examples 1-8 and Comparative Examples 1-7, the surface where the catalyst film was not bonded together was bonded together to the slide glass, respectively, and it was made to harden by heating at 150 degreeC for 4 hours. Thereafter, the catalyst film was peeled 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 (High Frequency Inductively Coupled Plasma-Emission Spectroscopy). The results are as shown in Tables 1 and 2.

[Measurement of micro hardness]
About the molding formed in Examples 1-8 and Comparative Examples 1-7, the surface where the catalyst film was not bonded together was bonded together to the slide glass, respectively, and it was made to harden by heating at 150 degreeC for 4 hours. Thereafter, the catalyst film was peeled from the cured product to obtain a film. Each film was subjected to a load / unload test using a dynamic ultra-small hardness meter SHIMADZU DUH-211SR (manufactured by Shimadzu Corporation). After a test force of 1 gf, a loading speed of 0.0298 gf / second, a load and an unloading holding time of 2 seconds each, the microhardness (MPa) was measured. Tables 1 and 2 show the average microhardness (MPa) of the test of 5 times.

[Heat resistance test (change in transmittance)]
About the molding formed in Examples 1-8 and Comparative Examples 1-7, the surface in which the catalyst film was not bonded together was bonded together to the slide glass, respectively, and it was made to harden by heating at 150 degreeC for 4 hours. Thereafter, the catalyst film was peeled 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). Subsequently, the transmittance was measured after the film was placed at 180 ° C. for 1000 hours. The transmittance (%) was calculated when the initial transmittance was 100%.
Change in transmittance (%) = (transmittance after leaving at 180 ° C. × 1,000 hours) / (initial transmittance)
The results are as shown in Tables 1 and 2.

[Long-term storage stability test]
For the molded products of Example 9 and Comparative Example 8, a load / unloading test was performed using a dynamic ultra-micro hardness meter SHIMADZU DUH-211SR (manufactured by Shimadzu Corporation). After a test force of 1 gf, a loading speed of 0.0298 gf / second, a load and an unloading holding time of 2 seconds each, the microhardness (MPa) was measured. Table 3 shows the average microhardness (MPa) of 5 tests (microhardness before curing (initial value)). Next, the molded products of Example 9 and Comparative Example 8 were stored at 25 ° C. for 6 months. The molded product after storage was subjected to a load / unloading test as described above, and the average microhardness (MPa) was measured (microhardness before curing (after storage)). Each molded product before and after storage was cured by heating at 150 ° C. for 4 hours to produce a film, and the microhardness after curing was measured. The results are as shown in Table 3.

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

II. Manufacturing of Semiconductor Device [Example 10]
The same organopolysiloxane composition 1 as in Example 1 was prepared. Using an automatic coating apparatus PI-1210 (manufactured by Tester Sangyo Co., Ltd.), the organopolysiloxane composition 1 (of FIG. 1) is formed on the catalyst film Pd-iObrane (registered trademark) (reference numeral 1 of FIG. 1). 2) was applied and formed into a film shape 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 a catalyst film. Using a pressure-type vacuum laminator V130 (manufactured by Nichigo Morton Co., Ltd.), the composition side 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 a size of 500 μm and a height of 150 μm was bonded to a substrate (reference numeral 4 in FIG. 2 is 10 cm × 10 cm) (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 film. After curing, the cured product and the catalyst film were peeled off to obtain a semiconductor device in which the semiconductor chip was covered with the film-like cured product. In this step, the cured product and the catalyst film layer were easily separated. The semiconductor device was diced to obtain a semiconductor device having a length of 3.5 mm × width 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 procedure as in Example 10 was repeated except that the organopolysiloxane composition 2 was used instead of the organopolysiloxane composition 1, and the product had a length of 3.5 mm × width of 3.5 mm and a thickness of 0.2 mm. A semiconductor device in which a semiconductor chip was sealed with a product was obtained (semiconductor device 2).

[Example 12]
The same organopolysiloxane composition 3 as in Example 3 was prepared. The same procedure as in Example 10 was repeated except that the organopolysiloxane composition 3 was used instead of the organopolysiloxane composition 1, and it had a length of 3.5 mm × width of 3.5 mm and a thickness of 0.2 mm. A semiconductor device having a semiconductor chip sealed with a product 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１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]
100 g of vinyl silicone resin A1 synthesized in Synthesis Example 1, 100 g of hydrogen silicone resin B1 synthesized in Synthesis Example 4, and the following formula (5 ′)

2 g of the adhesion assistant 1 represented by the following formula was mixed to prepare an organopolysiloxane composition 7. The same procedure as in Example 1 was repeated except that the organopolysiloxane composition 7 was used instead of the organopolysiloxane composition 1, and it had a length of 3.5 mm × width of 3.5 mm and a thickness of 0.2 mm. A semiconductor device having a semiconductor chip sealed with a product was obtained (semiconductor device 4).

[Example 14]
100 g of vinyl silicone resin A2 synthesized in Synthesis Example 2 and 100 g of hydrogen silicone resin B2 synthesized in Synthesis Example 5 and 2 g of adhesion assistant 1 represented by the above formula (5 ′) were mixed, Polysiloxane composition 8 was prepared. Except that the organopolysiloxane composition 8 was used in place of the organopolysiloxane composition 1, the same method as in Example 10 was repeated, and the curing had a length of 3.5 mm × width of 3.5 mm and a thickness of 0.2 mm. A semiconductor device having a semiconductor chip sealed with a product 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 adhesion assistant 1 represented by the above formula (5 ′) were mixed, Organopolysiloxane composition 9 was prepared. Except that the organopolysiloxane composition 9 was used in place of the organopolysiloxane composition 1, the same method as in Example 10 was repeated, and the curing had a length of 3.5 mm × width 3.5 mm and a thickness of 0.2 mm. A semiconductor device in which the semiconductor chip was sealed with a product was obtained (semiconductor device 6).

[Example 16]
An organopolysiloxane composition 10 was prepared by repeating Example 6 except that the amount of the adhesion assistant 2 represented by the formula (3 ′) in Example 6 was changed to 2 g. Except that the organopolysiloxane composition 10 was used in place of the organopolysiloxane composition 1, the same method as in Example 10 was repeated, and the curing had a length of 3.5 mm × width of 3.5 mm and a thickness of 0.2 m. A semiconductor device having a semiconductor chip sealed with a product 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]
100 g of vinyl silicone resin A3 synthesized in Synthesis Example 3 and 100 g of hydrogen silicone resin B3 prepared in Synthesis Example 6 and 2 g of Adhesive Aid 3 represented by the following average formula (6 ′) were mixed. An organopolysiloxane composition 11 was prepared. The same procedure as in Example 10 was repeated except that the organopolysiloxane composition 11 was used in place of the organopolysiloxane composition 1, and the cured product had a length of 3.5 mm × width of 3.5 mm and a thickness of 0.2 mm. A semiconductor device having a semiconductor chip sealed with a product was obtained (semiconductor device 8).

(In the formula, R ⁵ is a methyl group or an isopropyl group, and the weight average molecular weight is 2,500)

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

[Example 19]
In Example 10, the semiconductor chip mounting substrate is a semiconductor chip mounting substrate with wires (the semiconductor chip is an LED chip (with a wire) of 500 μm × 500 μm and a height of 150 μm, the wire height is 250 μm, and the size of the substrate) The thickness is 10 cm × 10 cm (schematic diagram is shown in FIG. 3), except that the same method as in Example 10 is repeated to have a length of 3.5 mm × width of 3.5 mm and a thickness of 0.4 mm. A semiconductor device in which the semiconductor chip was sealed with the cured product was obtained (semiconductor device 10).

[Example 20]
In Example 10, except that the one-stage curing condition of heating at 160 ° C. × 4 hours was changed to two-stage curing of heating at 100 ° C. × 1 hour and then heating at 150 ° C. × 4 hours, Example 10 The same method was repeated to obtain a semiconductor device having a length of 3.5 mm × width 3.5 mm and having a semiconductor chip sealed with a cured product having a thickness of 0.2 mm (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 a chloroplatinic acid vinyl silicone modified solution (platinum concentration 1 mass%) as a hydrosilylation reaction catalyst An organopolysiloxane composition C′2 was prepared by mixing 0.6 g of an acetylenic alcohol-based ethynylcyclohexanol as a reaction inhibitor and 2 g of an adhesion promoter represented by the above formula (5 ′) as an adhesion promoter. . Using an automatic coating apparatus PI-1210 (manufactured by Tester Sangyo Co., Ltd.), the organopolysiloxane composition C′2 is applied onto a PET film, and length × width × thickness = 100 mm × 100 mm × 0. Molded into a film having a thickness of 2 mm. Using a pressure-type 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 × width of 3.5 mm and 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 hydrosilylation reaction catalyst was 0.004 g and the amount of ethynylcyclohexanol was 0.006 g. 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, and the length was 3.5 mm × width 3 A semiconductor device having a thickness of 0.5 mm and 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, and the length was 3.5 mm × width 3 A semiconductor device having a thickness of 0.5 mm and a semiconductor chip sealed with a cured product having a thickness of 0.2 mm was obtained (semiconductor device 4 ′).

[Comparative Example 13]
Using an automatic coating apparatus PI-1210 (manufactured by Tester Sangyo Co., Ltd.), the organopolysiloxane composition 1 prepared in Example 10 was applied onto a PET film and formed into a film shape. The composition melted when heated, and the shape before heating could not be maintained. For this reason, subsequent evaluation was not performed.

[Comparative Example 14]
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 a chloroplatinic acid vinyl silicone modified solution (platinum concentration 1 mass%) as a hydrosilylation reaction catalyst Then, 0.6 g of acetylenic 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 on the catalyst film Pd-iObrane (registered trademark), and had a length of 3.5 mm × width of 3.5 mm and a thickness of 0 A semiconductor device in which a semiconductor chip was sealed with a 2 mm film-like cured product was obtained (semiconductor device 5 ′).

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

[Peelability from catalyst film]
The organopolysiloxane compositions 1 to 3 and 7 to 11 were evaluated for peelability from the catalyst film.
According to the same method as in each of Examples 10 to 17, each organopolysiloxane composition was applied onto a catalyst film Pd-iObrane (registered trademark) and formed into a film shape. The surface on which the catalyst film was not bonded was bonded to a slide glass and cured by heating at 150 ° C. for 4 hours. Thereafter, the catalyst film was peeled 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 film very easily, and no silicone film remained on the catalyst film. Although the cured products obtained from the organopolysiloxane compositions 10 and 11 were slightly inferior to the former, they could be easily separated from the catalyst film.

About the semiconductor device manufactured in Examples 10-20 and Comparative Examples 9-12 and 14, the heat resistance test (luminance change) was done according to the following method. The results are shown in Tables 5 and 6.
[Heat resistance test (brightness change)]
About each semiconductor device, the HTOL test (high temperature drive test test conditions 150 degreeC, applied current 500mA) was left for 1000 hours, Then, the luminance change with an initial stage was measured. The luminance (%) when the initial luminance was 100% was calculated by the following formula.
Luminance change (%) = (180 ° C. × luminance after standing for 1,000 hours) / (initial luminance)

  As shown in Table 5, the semiconductor device obtained is excellent in heat resistance by sealing the semiconductor chip with a film-like product comprising a cured product of an organopolysiloxane composition not containing a catalyst according to the production method of the present invention.

  The production method of the present invention is excellent in heat resistance and permeability, hardly changes with time even after long-term storage, and can provide a highly reliable silicone resin film. Moreover, 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 utilizing transparency. Furthermore, according to the method for manufacturing a semiconductor device of the present invention, the resulting device has excellent heat resistance and can provide a highly reliable semiconductor device.

DESCRIPTION OF SYMBOLS 1 Catalyst film 2 Organopolysiloxane composition 2 'Cured product of organopolysiloxane composition 3 Semiconductor chip 4 Semiconductor substrate 5 Wire 6 Film-like laminate 7 Semiconductor device separated into pieces

Claims (28)

(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 polysiloxane 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 form on one or two sheets having catalytic activity, or at least of the organopolysiloxane composition formed into a film form Bonding one surface and a membrane 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 and the membrane. The membrane having the catalytic activity is a surface of the membrane, Or the said manufacturing method characterized by having a catalyst in the surface and the inside of a film | membrane.   The curable organopolysiloxane composition further comprises (A) an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule, the above (B) with respect to the number of alkenyl groups in the component (A). The production method according to claim 1, wherein the SiH group number ratio in the component is contained in an amount of 0.5 to 8.   The production method according to claim 1 or 2, 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 catalyst is fixed to the hybrid compound.   The manufacturing method of any one of Claims 1-3 whose catalyst is a metal single-piece | unit or a metal compound.   The manufacturing method of Claim 4 whose catalyst is a platinum group metal or a platinum group metal compound.   The manufacturing method of any one of Claims 1-5 whose thickness of a silicone resin film is 10-2000 micrometers. In the organopolysiloxane composition,
(A) component is 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 carbon atoms. Is a cycloaliphatic hydrocarbon group having 1 to 10, 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, provided that it has at least two alkenyl groups bonded to silicon atoms, and X is a substituted or unsubstituted monovalent carbon atom having 1 to 8 carbon atoms. A hydrogen group or a hydrogen atom)
The component (B) is represented by the following average composition formula (2):

(Wherein 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 satisfying ˜2, with at least two hydrogen atoms bonded to silicon atoms)
The silicone resin according to any one of claims 2 to 6, which is contained in an amount such that the number ratio of SiH groups in component (B) to the number of alkenyl groups in component (A) is 0.5 to 8. A method for producing a film.   The method for producing a silicone resin film according to any one of claims 1 to 7, wherein the organopolysiloxane composition is solid at 25 ° C.   The method for producing a silicone resin film according to claim 1, wherein the organopolysiloxane composition further contains (C) an adhesion aid.   The method for producing a silicone resin film according to claim 9, wherein the (C) adhesion assistant is an organopolysiloxane having one or more epoxy groups in one molecule.   (B) A silicone resin film comprising a cured product of an organopolysiloxane composition containing an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, wherein the metal catalyst in the cured product The silicone resin film whose quantity is less than 0.1 ppm as metal mass conversion with respect to the mass of the whole hardened | cured material.   In the component (B), the organopolysiloxane composition comprises (A) an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule, relative to the number of alkenyl groups in the component (A). The silicone resin film according to claim 11, which is contained in an amount such that the number ratio of SiH groups is 0.5 to 8. The component (A) is 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 carbon atoms. Is a cycloaliphatic hydrocarbon group having 1 to 10, 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, provided that it has at least two alkenyl groups bonded to silicon atoms, and X is a substituted or unsubstituted monovalent carbon atom having 1 to 8 carbon atoms. A hydrogen group or a hydrogen atom)
The component (B) is represented by the following average composition formula (2):

(Wherein 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, e + f + g + h = It is a number satisfying 1-2, provided that it has at least two hydrogen atoms bonded to silicon atoms)
The silicone resin film of Claim 12 whose number ratio of the SiH group in (B) component with respect to the number of the alkenyl group in said (A) component is 0.5-8.   The silicone resin film according to claim 11, wherein the metal catalyst is a platinum group metal or a platinum group metal compound.   The silicone resin film according to any one of claims 11 to 14, wherein the organopolysiloxane composition is solid at 25 ° C. (B) A method for producing a semiconductor device comprising 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 siloxane composition does not contain a metal catalyst,
The manufacturing method includes the following steps 1) to 4):
1) Forming the organopolysiloxane composition into a film on one sheet having catalytic activity, or one side of the organopolysiloxane composition formed into a film and a film having catalytic activity A step of bonding to obtain a film-like laminate,
2) Next, the composition surface of the film 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 covered with the organopolysiloxane composition. The process of
3) Next, a step of curing the organopolysiloxane composition, and 4) Next, a step of peeling the cured product and the catalyst film to obtain a semiconductor device in which a semiconductor chip is coated with the cured product,
The 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 method of manufacturing a semiconductor device according to claim 16, further comprising a step of dicing and separating the obtained semiconductor device after the step 4).   The curable organopolysiloxane composition further comprises (A) an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule, the above (B) with respect to the number of alkenyl groups in the component (A). The method for manufacturing a semiconductor device according to claim 17, wherein the number ratio of SiH groups in the component is included in an amount of 0.5 to 8.   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 catalyst is fixed to the hybrid compound. A method for manufacturing a semiconductor device.   The method for manufacturing a semiconductor device according to any one of claims 16 to 19, wherein the catalyst is a simple metal or a metal compound.   The production method according to claim 20, wherein the 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 16 to 21, wherein a thickness of the cured product is 10 to 2,000 µm.   The method for manufacturing a semiconductor device according to any one of claims 16 to 22, wherein in the step 3), multistage curing is performed. In the curable organopolysiloxane composition,
(A) component is 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 carbon atoms. Is a cycloaliphatic hydrocarbon group having 1 to 10, 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, provided that it has at least two alkenyl groups bonded to silicon atoms, and X is a substituted or unsubstituted monovalent carbon atom having 1 to 8 carbon atoms. A hydrogen group or a hydrogen atom)
The component (B) is represented by the following average composition formula (2):

(Wherein 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 satisfying ˜2, with at least two hydrogen atoms bonded to silicon atoms)
The semiconductor according to any one of claims 16 to 23, which is contained in an amount such that the number ratio of SiH groups in the component (B) to the number of alkenyl groups in the component (A) is 0.5 to 8. Device manufacturing method.   The method for producing a semiconductor device according to any one of claims 16 to 24, wherein the curable organopolysiloxane composition further contains (C) an adhesion assistant.   26. The method for producing a semiconductor device according to claim 25, wherein (C) the adhesion assistant is an organopolysiloxane having one or more epoxy groups in one molecule.   27. The method of manufacturing a semiconductor device according to any one of claims 16 to 26, wherein the curable organopolysiloxane composition is solid at 25 [deg.] C.   The method for manufacturing a semiconductor device according to any one of claims 16 to 27, wherein the semiconductor chip is an optical semiconductor element.

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