JP5960613B2 - Manufacturing method of semiconductor device - Google Patents

Description

  The present invention relates to a semiconductor device coated with a silicone resin composition that can be made stressless and can be applied under various conditions.

  In relation to electronic materials, miniaturization of substrate used, fine patterning, high heat resistance, high shock resistance, and the like are required, and various resins are currently used.

Along with the minimization of the base material, minute dust contained in the sealing material and the coating material is one of the causes of discoloration due to poor conductivity, heat, etc., poor reliability, and yield reduction. As a generation source of dust, SiO _3/2 units contained inside the silicone resin and microgels derived from SiO ₂ units are mainly considered, such as linear or fibrous foreign matters from outside, powdery foreign matters due to friction between metals, etc. Is mentioned. In addition, with optical sensors such as photocouplers, CCDs, and CMOSs, particle management has become very strict with the miniaturization of sensors, and in particular, image sensors and the like have poor image quality when foreign objects are placed on individual fine sensors. Therefore, it is managed very strictly.

  In patent document 1, the penetration | invasion of the dust from an electronic device is prevented by apply | coating a silicone rubber composition to the electronic device surface and the whole. However, the silicone resin composition may vary in thickness before and after curing, which may lead to intrusion of water vapor, corrosive gas, etc., or stickiness before curing, which may cause dust to adhere. It was. In Patent Document 2, an epoxy-containing silicone resin is cured after spin coating by UV irradiation. However, since it contains an epoxy group, it has low heat resistance and light resistance, and is difficult to use in electronic material applications that require high reliability.

  Patent Document 3 has conventionally developed a coating material made of a photocurable resin such as an acrylic resin, and Patent Document 4 has conventionally developed an adhesive material for a semiconductor made of a thermosetting resin such as an epoxy resin. Since the resin is greatly deteriorated by light and light, discoloration and cracks of electronic devices occur, and high reliability has been lost in places where strong heat and light are applied. Moreover, since it will whiten by adding a filler etc. in order to maintain reliability, it could not be used in the field where translucency is required.

JP 2002-164480 A Japanese Patent No. 4651935 Japanese Patent No. 4935833 Japanese Patent No. 5003855

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a semiconductor device coated with a silicone resin composition that can be made stressless and can be applied under various conditions.

In order to solve the above problems, according to the present invention,
A step of microfiltration of the silicone resin composition composed of the following components (A) to (E) with a pressure of 0.1 to 0.3 MPa using a filter having a pore size of 0.2 μm or less;
(A) Silicone resin which is represented by the following average composition formula (1) and contains at least two alkenyl groups in one molecule and is solid at room temperature: 30 to 95 parts by mass R ¹ _a R ² _b R ³ _c (OX) _d SiO _{(4-abccd) / 2} (1)
Wherein R ¹ is an aryl group having 6 to 20 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ is 2 to 8 carbon atoms. A, b, c and d are arbitrary numbers, provided that a> 0, b> 0, c> 0, d> 0, and a + b + c + d = 1.0 to 2.0. X is an unsubstituted monovalent hydrocarbon group or a hydrogen atom.)
(B) A silicone resin which is represented by the following average composition formula (2) and has hydrogen bonded to at least one silicon atom in one molecule and which is solid at room temperature: 5 to 70 parts by mass R ¹ _e R ² _{f H g (OX) h SiO} (4-e-f-g-h) / 2 (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 = 1. 0 to 2.0. )
(C) addition reaction catalyst appropriate amount (D) adhesion imparting agent appropriate amount (E) organic solvent appropriate amount applying the composition on a semiconductor device, heating the organic solvent to volatilize by heating, and forming a silicone resin film There is provided a method for producing a semiconductor device coated with a silicone resin composition, comprising the step of heat-curing the silicone resin composition to form a cured film.

  With such a semiconductor device manufacturing method, it becomes a semiconductor device that is excellent in durability against luminance deterioration and discoloration resistance due to degradation of phosphors and the like without dust generation.

  The step of applying the silicone resin composition is preferably at least one of brush coating, spray coating, roll coating, impregnation coating, electrostatic coating, powder coating, screen printing, and spin coating.

  By using such a method, the silicone resin composition can be uniformly applied.

  The formed cured film preferably has a film thickness of 1 mm or less and a transmittance of 95% or more in a wavelength range of 400 to 800 nm.

  If it is such a film thickness, invasion of water vapor or corrosive gas can be suppressed, and if it has such a transmittance, it can be suitably used in a field where permeability is required.

In the present invention, a silicone resin composition,
(A) Silicone resin which is represented by the following average composition formula (1) and contains at least two alkenyl groups in one molecule and is solid at room temperature: 30 to 95 parts by mass R ¹ _a R ² _b R ³ _c (OX) _d SiO _{(4-abccd) / 2} (1)
Wherein R ¹ is an aryl group having 6 to 20 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ is 2 to 8 carbon atoms. A, b, c and d are arbitrary numbers, provided that a> 0, b> 0, c> 0, d> 0, and a + b + c + d = 1.0 to 2.0. X is an unsubstituted monovalent hydrocarbon group or a hydrogen atom.)
(B) A silicone resin which is represented by the following average composition formula (2) and has hydrogen bonded to at least one silicon atom in one molecule and which is solid at room temperature: 5 to 70 parts by mass R ¹ _e R ² _{f H g (OX) h SiO} (4-e-f-g-h) / 2 (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 = 1. 0 to 2.0. )
(C) Addition reaction catalyst Appropriate amount (D) Adhesion imparting agent Appropriate amount (E) Organic solvent Containing an appropriate amount, the number of foreign matters having a particle size of 0.2 μm is 10 or less per ml as measured by a particle counter A silicone resin composition is provided.

  If it is such a silicone resin composition, it will become a stressless silicone resin composition which can be applied under various conditions.

  According to the method for producing a semiconductor device of the present invention, a dustless silicone resin composition can be obtained by a step of microfiltration by adding an organic solvent to the silicone resin specified in the present invention, and the semiconductor device is coated with the composition. Thus, a highly reliable semiconductor device can be provided.

Hereinafter, the present invention will be described in more detail.
As described above, a semiconductor device excellent in durability against luminance deterioration and discoloration resistance due to deterioration of a phosphor coated with an optical semiconductor element (such as a high-intensity LED) with the silicone resin composition having very little foreign matter. Development was desired.

  Therefore, as a result of intensive studies to achieve the above object, the present inventors have obtained a silicone resin composition having a property of being solid at room temperature, and by adding a solvent to make a solution and performing microfiltration It was found that the cured product obtained can be made dustless and the hygroscopicity can be suppressed. Furthermore, it has been found that by covering an optical semiconductor element (such as a high-brightness LED) with the silicone molded body, it is possible to provide a semiconductor device having excellent durability against luminance deterioration and discoloration resistance due to deterioration of the phosphor. It came to complete.

That is, the present invention
A step of microfiltration of the silicone resin composition composed of the following components (A) to (E) with a pressure of 0.1 to 0.3 MPa using a filter having a pore size of 0.2 μm or less;
(A) Silicone resin which is represented by the following average composition formula (1) and contains at least two alkenyl groups in one molecule and is solid at room temperature: 30 to 95 parts by mass R ¹ _a R ² _b R ³ _c (OX) _d SiO _{(4-abccd) / 2} (1)
Wherein R ¹ is an aryl group having 6 to 20 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ is 2 to 8 carbon atoms. A, b, c and d are arbitrary numbers, provided that a> 0, b> 0, c> 0, d> 0, and a + b + c + d = 1.0 to 2.0. X is an unsubstituted monovalent hydrocarbon group or a hydrogen atom.)
(B) A silicone resin which is represented by the following average composition formula (2) and has hydrogen bonded to at least one silicon atom in one molecule and which is solid at room temperature: 5 to 70 parts by mass R ¹ _e R ² _{f H g (OX) h SiO} (4-e-f-g-h) / 2 (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 = 1. 0 to 2.0. )
(C) addition reaction catalyst appropriate amount (D) adhesion imparting agent appropriate amount (E) organic solvent appropriate amount applying the composition on a semiconductor device, heating the organic solvent to volatilize by heating, and forming a silicone resin film A method for producing a semiconductor device coated with a silicone resin composition, comprising a step of heat-curing the silicone resin composition to form a cured film.

Hereinafter, the present invention will be described in detail.
A silicone-containing solution having a foreign matter management particle size of 0.2 μm according to the pressure condition of the silicone solution and 10 or less foreign matters per ml can be removed by passing the filter having a pore size of 0.2 μm or less. The number of foreign matters is preferably 0.2 to 0.4 [mu] m, more preferably 0.1 to 0.5 [mu] m, and even more preferably 0.1 to 1.0 [mu] m. Can be obtained. Filters used for removing foreign substances are preferably 0.05 to 0.2 μm, more preferably 0.05 to 0.1 μm, and finer foreign substances can be removed. The pressure is 0.1 to 0.3 MPa, preferably 0.1 to 0.28 MPa, more preferably 0.1 to 0.25 MPa. If the pressurization is higher than 0.3 MPa, the soft microgel is deformed by the pressure and passes through the filter diameter, which is not preferable. If the pressurization is lower than 0.1, it takes time for filtration, so that sedimentation occurs. This is not preferable because the foreign matter deposited on the filter may be unable to be filtered. An example of a device that counts the number of foreign objects is a particle counter.

(A) Silicone resin The component (A) is a silicone resin having at least two alkenyl groups bonded to silicon atoms in one molecule, and particularly bonded to at least one silicon atom in one molecule. It is preferable that the silicone resin has a cycloalkyl group. The silicone resin is a silicone resin represented by the following average composition formula (1).

_{^{R 1 a R 2 b R 3}} c (OX) d SiO (4-a-b-c-d) / 2 (1)
Wherein R ¹ is an aryl group having 6 to 20 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ is 2 to 8 carbon atoms. A, b, c and d are arbitrary numbers, provided that a> 0, b> 0, c> 0, d> 0, and a + b + c + d = 1.0 to 2.0. X is an unsubstituted monovalent hydrocarbon group or a hydrogen atom.)

  In the above formula (1), a is preferably a number from 0.3 to 0.98, more preferably from 0.4 to 0.95, even more preferably from 0.4 to 0.8, and b is preferably 0.00. 05 to 0.75, more preferably 0.05 to 0.6, and even more preferably 0.05 to 0.1, and c is preferably 0.02 to 0.6, more preferably 0.03 to 0.03. 0.5 is a number of 0.05 to 0.3, and d is preferably a number of 0.001 to 0.2, more preferably 0.001 to 0.1. a + b + c + d = 1.0 to 2.0, preferably 1.1 to 1.9.

In the above formula (1), R ¹ is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Of these, a phenyl group is preferable.

In the above formula (1), R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which is not an aryl group or an alkenyl group, preferably a monovalent hydrocarbon having 1 to 6 carbon atoms. It is a group. Examples of such R ² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, and decyl group. An alkyl group; an aralkyl group such as a benzyl group, a phenylethyl group or a phenylpropyl group, and a hydrogen atom of these groups partially or entirely substituted with a halogen atom such as fluorine, bromine or chlorine, or a cyano group, for example, Examples thereof include halogen-substituted alkyl groups such as chloromethyl group, chloropropyl group, bromoethyl group and trifluoropropyl group, and cyanoethyl group. Of these, a methyl group and a phenyl group are preferable.

In the above formula (1), R ³ is an alkenyl group having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms. Examples of such R ³ include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, and an octenyl group, and a vinyl group or an allyl group is particularly preferable.

  In the above formula (1), X is an unsubstituted, monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, or a hydrogen atom. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, and octyl group. X is preferably a methyl group or a hydrogen atom.

The silicone resin represented by the above formula (1) is an organopolysiloxane having a resin structure (that is, a three-dimensional network structure). The organopolysiloxane is preferably an organopolysiloxane comprising R ⁶ SiO _3/2 units, R ⁵ _k R ⁶ _p SiO _2/2 units and R ⁵ _q R ⁶ _r SiO _1/2 units. In the above formula, R ⁵ is the same group as R ^3, and R ⁶ is the same group as R ¹ or R ² , or a hydroxyl group or an alkoxy group. k is 0 or 1, p is an integer of 1 or 2, provided that k + p = 2, q is 1 to 3, and r is an integer of 0 to 2, provided that q + r = 3. R ⁶ is preferably an aryl group. However, at least one of R ⁶ is preferably a hydroxyl group or an alkoxy group. If the silicone resin does not have a hydroxyl group or an alkoxy group, the adhesion of the molded product to the substrate is lowered, which is not preferable.

Resin-structured organopolysiloxane has R ⁶ SiO _3/2 units as a ′ units, R ⁵ _k R ⁶ _p SiO _2/2 units as b ′ units, and R ⁵ _q R ⁶ _r SiO _1/2 units as c ′ units. When the unit is used, the molar ratio of (b ′ + c ′) / a ′ = 0.01 to 1, preferably 0.1 to 0.5, c ′ / a ′ = 0.05 to 3, preferably 0. It is preferable that the amount is 1 to 0.5. The organopolysiloxane has a weight average molecular weight of 2,000 to 100,000, preferably 6,000 to 50,000.

In the present invention, the weight average molecular weight is a weight average molecular weight based on polystyrene by gel permeation chromatography (GPC), and can be measured under the following conditions.
[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 amount: 20 μL (THF solution with a concentration of 0.1% by weight)

  In addition to the a ′ unit, b ′ unit, and c ′ unit, the organopolysiloxane having the resin structure further contains a bifunctional siloxane unit or a trifunctional siloxane unit (that is, an organosilsesquioxane unit). May be.

  The above-mentioned organopolysiloxane having a resin structure is a combination of compounds that are unit sources of the a ′ unit, the b ′ unit, and the c ′ unit so as to have the above molar ratio, and, for example, performs a cohydrolysis reaction in the presence of an acid. Can be easily synthesized.

  As the a ′ unit source, for example, phenyltrichlorosilane, methyltrimethoxysilane, cyclohexyltriethoxysilane, or the like can be used.

  As the b ′ unit source, for example, dimethyldichlorosilane, methylvinyldichlorosilane, methylcyclohexyldimethoxysilane, methylvinyldimethoxysilane, dicyclohexyldimethoxysilane, octamethylcyclotetrasiloxane, 1,3,5,7-tetramethyl1,3 , 5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl 1,3,5,7-tetraallylcyclotetrasiloxane can be used.

Furthermore, the following compound can be illustrated as a raw material of b 'unit.

（ここで、ｐ’、ｑ’及びｒ’は０〜５０の数（平均値）であり、ｐ’＋ｑ’＋ｒ’＝５〜５０を満たす数（平均値）である。

(Here, p ′, q ′ and r ′ are numbers (average value) of 0 to 50, and are numbers (average value) satisfying p ′ + q ′ + r ′ = 5 to 50.

As the c ′ unit source, for example, the following can be used.

The organopolysiloxane shown below is preferable.
^{_{(PhSiO u '/ 2) s}} [(CH 3) 2 SiO v' / 2] t [CH 3 ViSiO] u [(CH 3) 2 ViSiO 1/2] w (OX) z
In the above formula, Ph represents a phenyl group, X is as described above, s, t, u, w, and z represent the molar ratio of each unit, s is 0.1 to 0.9, and t is 0. 0.01 to 0.8, u is a number from 0.01 to 0.3, w is a number from 0.01 to 0.2, and z is a number from 0.001 to 0.3. u ′ is a number from 1 to 3, and v ′ is a number from 1 to 2. In OX, an oxygen atom is bonded to any Si atom in the formula, and the bonding position is not particularly limited.

  The component (A) of the present invention may be a mixture of the above-described organopolysiloxane having a resin structure and a linear organopolysiloxane. When it is set as a mixture, it is good to mix | blend with the quantity from which organopolysiloxane of a resin structure is 20-100 mass% in a mixture, More preferably, it is 40-100 mass%. If the compounding amount of the organopolysiloxane having a resin structure is too small, the physical strength of the molded product is lowered, and there is a possibility that tack will occur on the surface of the molded product.

  As the linear organopolysiloxane, those having a viscosity at 25 ° C. of 10 to 1,000,000 mPa · s, preferably 1,000 to 50,000 mPa · s are preferable from the viewpoints of workability and curability. The viscosity can be measured with a rotational viscometer or the like. In addition, the value of the viscosity shown by this invention represents the measured value in 25 degreeC measured by rotation speed 6, 12, 30 or 60 rpm using the BM type | mold viscometer.

  In particular, a linear organopolysiloxane represented by the following general formula (3) having at least one vinyl group on each silicon atom at both ends of the molecular chain can be used. The following organopolysiloxane may contain a small amount of a branched structure (trifunctional siloxane unit) in the molecular chain.

（式中、Ｒ^１及びＲ^２は上述したとおりであり、Ｒ^４はＲ^１またはＲ^２であり、Ｒ^４の一部は水酸基またはアルコキシ基であってよい。ｗは１、２又は３の整数であり、ｘ、ｙ及びｚは０又は正の整数であり、但し、１≦ｘ＋ｙ＋ｚ≦１，０００を満足する数であり、ｘまたはｙの少なくとも１つは１以上である。）

(Wherein R ¹ and R ² are as described above, R ⁴ is R ¹ or R ² , a part of R ⁴ may be a hydroxyl group or an alkoxy group. W is 1, 2 or 3) And x, y, and z are 0 or a positive integer, provided that 1 ≦ x + y + z ≦ 1,000, and at least one of x or y is 1 or more.)

  In the above formula (3), x, y and z are 0 or a positive integer satisfying 1 ≦ x + y + z ≦ 1,000, preferably 5 ≦ x + y + z ≦ 500, more preferably 30 ≦ x + y + z ≦ 500. However, it is an integer satisfying 0.5 <(x + y) / (x + y + z) ≦ 1.0.

（上記式において、ｘ、ｙ、ｚは上述の通りである） Examples of the organopolysiloxane represented by the above formula (3) include the following.

(In the above formula, x, y, and z are as described above.)

（上記式において、ｚ及びｙは上述した通りである。）

(In the above formula, z and y are as described above.)

(B) Organohydrogenpolysiloxane Organohydrogenpolysiloxane acts as a crosslinking agent, and includes a hydrogen atom bonded to a silicon atom in the component (hereinafter referred to as SiH group) and an alkenyl group in component (A). Is cured to form a cured product. Such organohydrogenpolysiloxane, Ri organohydrogenpolysiloxane der having hydrogen bonded to at least one silicon atom in a molecule, at least two SiH groups in one molecule, preferably having 3 or more Those are preferably used. In particular, the organohydrogenpolysiloxane of the present invention preferably has a cycloalkyl group bonded to at least one silicon atom in one molecule.

The organohydrogenpolysiloxane is a siloxane represented by the following average composition formula (2).

^{_{R 1 e R 2 f H g}} (OX) h SiO (4-e-f-g-h) / 2 (2)
(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) The position of the SiH group in the molecule is not particularly limited, and may be at the end of the molecular chain or in the middle.)

  In the above formula (2), e is preferably a number from 0.3 to 0.98, more preferably a number from 0.4 to 0.95, even more preferably a number from 0.4 to 0.8, and f is preferably The number is from 0.05 to 0.8, more preferably from 0.05 to 0.6, and even more preferably from 0.05 to 0.1, and g is preferably from 0.02 to 0.5, more preferably from 0.00. The number is from 05 to 0.3, and h is preferably from 0.001 to 0.2, more preferably from 0.001 to 0.1. e + f + g + h = 1.0 to 2.0, preferably 1.0 to 1.5. The position of the SiH group in the molecule is not particularly limited, and may be at the end of the molecular chain or in the middle.

The organohydrogenpolysiloxane represented by the above formula (2) has a resin structure (that is, a three-dimensional network structure). Such ^{organohydrogenpolysiloxane,} _(R 7) 2 _HSiO copolymer comprising a _1/2 units and _{SiO 4/2} units, ^and, _(R 7) 2 _{HSiO 1/2} units and _{SiO 4/2} units, and And a copolymer composed of (R ⁷ ) SiO _3/2 units. In the formula, R ⁷ is R ¹ or R ² described above, and a part of R ⁷ may be a hydroxyl group or an alkoxy group.

Such an organohydrogenpolysiloxane can be prepared by a known method, and usually R ⁷ SiCl ₃ , R ⁷ SiHCl ₂ , (R ⁷ ) ₃ SiCl, (R ⁷ ) ₂ SiCl ₂ , (R ⁷ ) Chlorosilane such as ₂ SiHCl, or (R ⁷ ) ₃ Si (OR ⁸ ), (R ⁷ ) ₂ Si (OR ⁸ ) ₂ , R ⁷ Si (OR ⁸ ) ₃ (wherein R ⁷ is R ¹ above) Or R ² , R ⁸ is a monovalent hydrocarbon group having 1 to ⁸ carbon atoms), or equilibrates a siloxane obtained by hydrolysis using a strong acid catalyst. Can be obtained.

Moreover, the organohydrogensiloxane shown by the following structure can be used as a unit source.

The organohydrogenpolysiloxane represented by the above formula (2) is particularly preferably a polysiloxane represented by the following structural formula.
(PhSiO _{s ′ / 2} ) _i [(CH ₃ ) ₂ SiO _{t ′ / 2} ] _j [CH ₃ HSiO] _k (OX) _l
In the above formula, Ph represents a phenyl group, X is as described above, i, j, k, and l represent the molar ratio of each unit, i is 0.1 to 0.9, and j is 0.01 -0.8, k is a number from 0.03 to 0.3, and l is a number from 0.01 to 0.2. s ′ is a number from 1 to 3, and t ′ is a number from 1 to 2. In OX, an oxygen atom is bonded to any Si atom in the formula, and the bonding position is not particularly limited.

  The component (B) of the present invention may be a mixture of the above-described organohydrogenpolysiloxane having a resin structure and a linear and / or branched organohydrogenpolysiloxane. In the case of preparing a mixture, the organohydrogenpolysiloxane having a resin structure is preferably added to the mixture in an amount of 10 to 100% by mass, more preferably 50 to 100% by mass. If the amount of the resin-structured organohydrogenpolysiloxane is too small, the physical strength of the molded product is lowered, and the surface of the molded product may be tucked.

  Examples of the linear or branched organohydrogenpolysiloxane include tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, phenyl-containing branched siloxane, terminal hydrogenphenylmethylpolysiloxane, 1,1, 3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends phenyldimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends Trimethylsiloxy-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends phenyldimethylsiloxy-blocked dimethylsiloxane / methylhydrogensiloxane copolymer Both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, Both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, Both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, Both ends Examples thereof include trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer.

（式中、ｎは１〜１０の整数）

The following organohydrogen (poly) siloxanes can also be used.

(Where n is an integer from 1 to 10)

  (B) The compounding quantity of a component is 5-70 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 30-60 mass parts. In particular, the blending amount of the component (B) should be a curing effective amount by a crosslinking reaction with the component (A), and the number of SiH groups in the component (B) is the alkenyl group 1 in the component (A). It is preferable that 0.5 to 4.0, preferably 0.8 to 2.0, and more preferably 0.9 to 1.5 is added to each. If the amount is less than the lower limit, the curing reaction may not proceed and it may be difficult to obtain a cured product. If the amount exceeds the upper limit, unreacted SiH groups remain in the cured product in a large amount, and thus sheet physical properties are reduced. There is a risk of changing over time.

(C) The addition reaction catalyst catalyst is blended to promote the addition reaction, and a platinum-based, palladium-based, rhodium-based or other metal-based catalyst can be used, but a platinum group metal-based catalyst is preferable from the viewpoint of cost and the like. Examples of the platinum group metal catalyst 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, PtO ₂ · mH ₂ O (m is a positive integer). In addition, a complex of the platinum group metal catalyst with a hydrocarbon such as an olefin, an alcohol, or a vinyl group-containing organopolysiloxane can be used. The catalyst may be used alone or in combination of two or more.

  What is necessary is just to mix | blend a catalyst with what is called a catalyst amount, 0.0001-0.5 mass part in metal conversion (mass) which is an active ingredient with respect to 100 mass parts of total amounts of the said (A) and (B) component, Preferably it is used in an amount of 0.001 to 0.3 parts by mass.

(D) Adhesion imparting agent The adhesion imparting agent is used for the purpose of imparting adhesiveness to a package material such as LCP of the silicone resin composition in the present invention, a metal substrate, and a semiconductor device. Adhesive agents include phenyltrimethylsilane, phenyltriethylsilane, phenylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyl. Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldi Ethoxysilane, 3-methacryloxypropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxylane, 3-mercaptopropyltri Examples include methoxysilane and the like, trimethoxysilane, tetramethoxysilane and oligomers thereof. These adhesion-imparting agents may be used alone or in combination of two or more. It is preferable to mix | blend this adhesion | attachment imparting agent with the quantity used as 0.1-10 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, especially 0.1-10 mass parts.

(E) Organic solvent The organic solvent is used to improve the applicability of the mixture of components (A) to (D) because component (A) and component (B) are solid at room temperature. . Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy. Alcohols such as 2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3 Examples include esters such as ethyl ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyl lactone, one of these alone or two Although the above can be mixed and used, it is not limited to these. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, cyclopropanone, cyclohexanone, and mixed solvents thereof, which are most excellent in solubility with the silicone resin composition, are used. Preferably used.

  The compounding quantity of the organic solvent is 0.1-80 mass% with respect to the mass of the whole silicone resin composition, Preferably it is 1-30 mass%. If the blending amount of the organic solvent exceeds the above upper limit, there may be a large amount of solvent remaining after heat drying, or the resin thickness after heat drying may become uneven. Moreover, if it is less than the said lower limit, the viscosity as a coating material may be too high.

  The silicone resin composition of this invention can mix | blend well-known various additives as needed other than the (A)-(E) component mentioned above. As various additives, reinforcing inorganic fillers such as fumed silica and fumed titanium dioxide, non-reinforcing inorganic fillers such as calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, and zinc oxide, Examples include photodegradation inhibitors such as hindered amines, and reactive diluents such as vinyl ethers, vinyl amides, epoxy resins, oxetanes, allyl phthalates, and vinyl adipate. These various additives can be appropriately blended depending on the purpose.

Preparation of Silicone Resin Composition The silicone resin composition is prepared by stirring, dissolving, mixing, and dispersing the above-described components simultaneously or separately while applying heat treatment as necessary. The components (A) and (C) and the component (B) can be stored separately in two liquids so that the curing reaction does not proceed before use, and the two liquids can be mixed and cured at the time of use. . If component (B) and component (C) are stored in a single solution, there is a risk of causing a dehydrogenation reaction. Therefore, it is preferable to store component (B) and component (C) separately. Further, a small amount of a curing inhibitor such as acetylene alcohol can be added and used as one liquid.

  Although the apparatus used for operations, such as stirring, is not specifically limited, A raikai machine provided with stirring and a heating apparatus, 3 rolls, a ball mill, a planetary mixer etc. can be used. Moreover, you may combine these apparatuses suitably. In addition, it is preferable that the viscosity in 25 degreeC measured with the rotational viscometer of the obtained silicone resin composition is about 100-10,000,000 mPa * s, especially about 300-500,000 mPa * s. Moreover, the silicone resin composition after removing the solvent is in a solid state having no fluidity at room temperature.

Method for Applying Silicone Coating Material The present invention can provide a coating material that is solid at room temperature by coating the above-described silicone resin composition on an electronic material by various methods and then drying by heating. The film thickness of the heat-dried silicone resin composition should be 0.1 μm or more, preferably 0.5 μm to 500 μm, more preferably 0.8 μm to 200 μm. As a coating method, a conventionally known method may be used. For example, a roll coater or a spin coater can be used. The drying conditions are not particularly limited, but are usually 50 to 150 ° C., preferably 60 to 150 ° C., and 10 seconds to 30 minutes, preferably 30 seconds to 10 minutes.

  In the present invention, the curing conditions of the silicone resin composition are not particularly limited, but are usually 40 to 250 ° C., preferably 60 to 200 ° C., 5 minutes to 10 hours, preferably 30 minutes to 6 hours. It can be cured. The silicone resin composition can be immediately cured to form a silicone coating material. The molded product is free from dust on the electronic material and adheres very well to package materials such as LCP, metal substrates and semiconductor devices.

  Moreover, the sheet-like molded product of the present invention can be used as a covering sheet that covers the surface of a semiconductor element or the entire surface of a semiconductor device. For example, the sheet-like molded product is cut into small pieces according to the size of the surface of the semiconductor element or the entire surface of the semiconductor device, and the obtained sheet piece is arranged and brought into contact with the surface to be coated, followed by heat forming. Can be coated.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to these.
In the examples, the weight average molecular weight is a weight average molecular weight based on polystyrene by gel permeation chromatography (GPC), and is measured under the above-mentioned conditions.

[Synthesis Example 1]
1142.1 g (87.1 mol%) of phenyltrichlorosilane, ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 529 g (3.2 mol%), and 84.6 g (9.7 mol%) of methylvinyldichlorosilane were added to the toluene solvent. After being dissolved in the solution, it was dropped into water and cohydrolyzed, and further neutralized and dehydrated by washing with water and alkali, and then the solvent was stripped to obtain a phenyl group-containing vinyl silicone resin. The vinyl group content was 0.032 mol / 100 g. The weight average molecular weight in terms of polystyrene as measured by GPC using THF as a solvent was 62,000. The SiOH content was 2.1 mol% as measured using ²⁹ Si-NMR.

[Synthesis Example 2]
After dissolving 1142.1 g (87.1 mol%) of phenyltrichlorosilane, ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 529 g (3.2 mol%), and 69 g of methyldichlorosilane (9.7 mol%) in a toluene solvent. The solution was dropped into water, co-hydrolyzed, further neutralized by water washing and alkali washing, dehydrated, and then the solvent was stripped to obtain a phenyl group-containing hydrogen silicone resin. The amount of hydrogen gas generated was 0.032 mol / 100 g. The weight average molecular weight in terms of polystyrene as measured by GPC using THF as a solvent was 58,000. The amount of SiOH measured by ²⁹ Si-NMR was 2.0 mol%.

[Example 1]
100 g of an aryl group-containing vinyl resin prepared in Synthesis Example 1, 100 g of an aryl group-containing hydrogen silicone resin prepared in Synthesis Example 2, 0.2 g of a chloroplatinic acid vinyl silicone-modified solution (platinum concentration 1% by mass), acetylene alcohol-based reaction As an inhibitor, 0.6 g of ethynylcyclohexanol and 6.0 g of an adhesion-imparting agent represented by [Chemical Formula 12] were added and mixed to prepare a silicone resin composition. Further, cyclopentanone was added to the silicone resin composition as a solvent to adjust the non-volatile content to 80%, and particle microfiltration was performed with a filter having a pore size of 0.2 μm or less. The pressing condition at that time was 0.25 MPa. The silicone resin composition was applied onto a silicon wafer with a spin coater at 2000 rpm × 1 minute, and then heated in an oven at 100 ° C. for 5 minutes to evaporate the solvent, thereby producing a coating material having 300 mmφ × 0.05 mm thickness. .

[Example 2]
A coating material was produced on a silicon wafer in the same manner as in Example 1 except that microfiltration was performed under a pressure condition of 0.3 MPa.

[Example 3]
A coating material was produced on a silicon wafer in the same manner as in Example 1 except that microfiltration was performed under a pressure condition of 0.1 MPa.

（２）ビニルメチルシロキサン（ＶＭＱ）：ＳｉＯ_２単位５０モル％、（ＣＨ_３）_３ＳｉＯ_０．５単位４２．５モル％及びＶｉ_３ＳｉＯ_０．５単位７．５モル％からなるレジン構造を有するビニルメチルシロキサン。
（３）ハイドロジェンポリシロキサン（ＨＤＭ）：

上記ポリシロキサン（ＶＦ）２５ｇ、ビニルメチルシロキサン（ＶＭＱ）７５ｇ、ハイドロジェンポリシロキサン（ＨＤＭ）１．５ｇを用い、反応抑制剤としてアセチレンアルコール系のエチニルシクロヘキサノール０．６ｇ、[化１２]で示される接着付与剤６．０ｇを加えて混合してシリコーン樹脂組成物を調製した。得られた樹脂組成物は常温で流動性を有するペースト状であった。この樹脂組成物を用い、実施例１と同じ方法によりウエハ上にコート材料を硬化させた。 [Comparative Example 1]
(1) Polysiloxane (VF):

(2) Vinylmethylsiloxane (VMQ): Resin structure comprising 50 mol% of SiO ₂ units, 42.5 mol% of (CH ₃ ) ₃ SiO _0.5 units and 7.5 mol% of Vi ₃ SiO _0.5 units. Vinylmethylsiloxane having.
(3) Hydrogen polysiloxane (HDM):

Using 25 g of the above polysiloxane (VF), 75 g of vinylmethylsiloxane (VMQ), 1.5 g of hydrogen polysiloxane (HDM), 0.6 g of acetylenic alcohol ethynylcyclohexanol as a reaction inhibitor, represented by [Chemical Formula 12] A silicone resin composition was prepared by adding and mixing 6.0 g of the adhesion-imparting agent. The obtained resin composition was a paste having fluidity at room temperature. Using this resin composition, the coating material was cured on the wafer by the same method as in Example 1.

[Comparative Example 2]
100 parts by mass of epoxy resin (triphenolmethane skeleton-containing polyfunctional solid epoxy (manufactured by Japan Epoxy Resin Co., Ltd., trade name “EP1032H60”)), curing agent (2-phenyl-4,5-dihydroxymethylimidazole (Shikoku Kasei Co., Ltd.) Product name “2PHZ-PW”)) 7.5 parts by mass and a mixed solvent of toluene and ethyl acetate (mass ratio 1: 1) so that the solid content is 60% by mass to obtain a resin varnish. . The obtained resin varnish was subjected to the same operation as in Example 1 to produce a coating material on a silicon wafer.

[Comparative Example 3]
A coating material was produced on a silicon wafer in the same manner as in Example 1 except that microfiltration was performed at a filtration pressure of 0.35 MPa.

[Comparative Example 4]
An attempt was made to produce a coating material on a silicon wafer by the same method as in Example 1 except that microfiltration was performed at a filtration pressure of 0.05 MPa. Since it was clogged, it was judged that it would not be put to practical use, and no further examination was conducted.

[Comparative Example 5]
Compounding was performed with the same composition as in Example 1, and microfiltration was performed with a filter pore size of 0.45 μm.

[Comparative Example 6]
A coating material was produced on a silicon wafer in the same manner as in Example 1 except that microfiltration was performed with a filter pore size of 0.25 μm.

[Evaluation test]
The following evaluation was performed on each wafer processed in the above-described Examples and Comparative Examples. The results are shown in Table 1.
(1) Tackiness A wafer including a coating material layer was cut into a 3 cm square, touched with a dry index finger, and tackiness was observed depending on whether it was lifted by sticking to the finger when leaving.

(2) Thin Film Stability The standard deviation σ of the film thickness measured for the coating material layer was determined. And it was considered good if the film thickness was in the range of 3σ ± 2 μm.

(3) Dicing characteristics A wafer having an underfill agent layer in a B-stage state was subjected to dicing, and blade reduction was evaluated. Five 8-inch wafers were continuously diced, and the reduction was ranked as follows.
○: Reduction is 5% or less.
Δ: Decrease is more than 5% and 10% or less.
X: The reduction exceeded 10%.

(4) Appearance inspection The number of foreign matters of 0.2 μm per ml was counted with a particle counter.

(5) Endurance of connection The device after being subjected to the test (2) was subjected to a thermal cycle test (TCT) under the following conditions.
-1 cycle: -55 ° C x 10 minutes, 125 ° C x 10 minutes.
・ Number of cycles: 1000
The presence or absence of cracks, peeling and discoloration of the wafer after the test was confirmed.

  From the results of Table 1, it was found that the tackiness and thin film stability were excellent in the examples, and the dicing characteristics and reliability were also excellent. Further, it has been shown that the manufacturing method of the present invention can manufacture a highly reliable semiconductor device.

  The present invention relates to a silicone resin composition that is extremely free of foreign matter and is solid at room temperature in an uncured state when the solvent is volatilized, and is a semiconductor device coated with a coating material having good heat resistance, light resistance and particle management Therefore, it has high reliability and can be used for various applications in the field of electronic materials.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Claims (4)

A step of microfiltration of the silicone resin composition composed of the following components (A) to (E) with a pressure of 0.1 to 0.3 MPa using a filter having a pore size of 0.2 μm or less;
(A) Silicone resin which is represented by the following average composition formula (1) and contains at least two alkenyl groups in one molecule and is solid at room temperature: 30 to 95 parts by mass R ¹ _a R ² _b R ³ _c (OX) _d SiO _{(4-abccd) / 2} (1)
Wherein R ¹ is an aryl group having 6 to 20 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ is 2 to 8 carbon atoms. A, b, c and d are arbitrary numbers, provided that a> 0, b> 0, c> 0, d> 0, and a + b + c + d = 1.0 to 2.0. X is an unsubstituted monovalent hydrocarbon group or a hydrogen atom.)
(B) A silicone resin which is represented by the following average composition formula (2) and has hydrogen bonded to at least one silicon atom in one molecule and which is solid at room temperature: 5 to 70 parts by mass R ¹ _e R ² _{f H g (OX) h SiO} (4-e-f-g-h) / 2 (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 = 1. 0 to 2.0. )
(C) addition reaction catalyst appropriate amount (D) adhesion imparting agent appropriate amount (E) organic solvent appropriate amount applying the composition on a semiconductor device, heating the organic solvent to volatilize by heating, and forming a silicone resin film A method for producing a semiconductor device coated with a silicone resin composition, comprising a step of heat-curing the silicone resin composition to form a cured film.   The step of applying the silicone resin composition is at least one of brush coating, spray coating, roll coating, impregnation coating, electrostatic coating, powder coating, screen printing, and spin coating. 2. A method for producing a semiconductor device according to 1.   The semiconductor device according to claim 1 or 2, wherein the formed cured film has a film thickness of 1 mm or less and a transmittance of 95% or more in a wavelength range of 400 to 800 nm. Method. A silicone resin composition comprising:
(A) Silicone resin which is represented by the following average composition formula (1) and contains at least two alkenyl groups in one molecule and is solid at room temperature: 30 to 95 parts by mass R ¹ _a R ² _b R ³ _c (OX) _d SiO _{(4-abccd) / 2} (1)
(In the formula, R ¹ is an aryl group having 6 to 20 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ has 2 to 8 carbon atoms. An alkenyl group, a, b, c and d are arbitrary numbers, provided that a> 0, b> 0, c> 0, d> 0, and a + b + c + d = 1.0 to 2.0. X is an unsubstituted monovalent hydrocarbon group.)
(B) A silicone resin which is represented by the following average composition formula (2) and has hydrogen bonded to at least one silicon atom in one molecule and which is solid at room temperature: 5 to 70 parts by mass R ¹ _e R ² _{f H g (OX) h SiO} (4-e-f-g-h) / 2 (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 = 1. 0 to 2.0. )
(C) Addition reaction catalyst Appropriate amount (D) Adhesion imparting agent Appropriate amount (E) Organic solvent An appropriate amount is contained, and the number of foreign matters having a particle size of 0.2 μm is 10 or less per ml as measured with a particle counter. There is a silicone resin composition characterized by that.