JP5368379B2 - Curable organopolysiloxane composition and semiconductor device using the same - Google Patents

Description

  The present invention relates to a curable organopolysiloxane composition and a semiconductor device, and in particular, has a low viscosity, a good filling property, a good curability, a cured, a high refractive index, a high light transmittance, and a substrate. TECHNICAL FIELD The present invention relates to a curable organopolysiloxane composition that forms a cured product having high adhesion to the surface, excellent in crack resistance and gas barrier properties, and a semiconductor device excellent in reliability, in which a semiconductor element is coated with a cured product of the composition. .

  A curable organopolysiloxane composition that is cured by a hydrosilylation reaction is used as a protective coating agent for semiconductor elements in optical semiconductor devices such as photocouplers, light-emitting diodes, and solid-state imaging elements. Such a protective coating agent for a semiconductor element is required not to absorb or scatter light because the element emits light or receives light.

  Examples of the curable organopolysiloxane composition that is cured by a hydrosilylation reaction to form a cured product having a large refractive index and high light transmittance include, for example, organos containing a silicon atom-bonded phenyl group and a silicon atom-bonded alkenyl group. A curable organopolysiloxane composition comprising a polysiloxane, an organohydrogencyclosiloxane, and a hydrosilylation reaction catalyst (see Patent Document 1), a viscosity containing a silicon atom-bonded phenyl group and a silicon atom-bonded alkenyl group has a viscosity of 10,000 cp (25 C.) or higher liquid or solid organopolysiloxane, an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and a hydrosilylation catalyst (patent) Reference 2) Organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and having an aryl group bonded to silicon atoms, and organopolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule Curable organopolysiloxane composition comprising siloxane and platinum aryl group-containing organosiloxane oligomer complex (see Patent Document 3), organopolysiloxane in which both molecular chain ends are blocked with silicon atom-bonded hydrogen atoms via siloxane bonds A composition (refer patent document 4) etc. are mentioned.

  However, these curable organopolysiloxane compositions have high viscosity, poor filling properties, poor adhesion of cured products obtained by curing, and are easy to peel off from the substrate, and have a siloxane bond ratio. The increase in gas permeability has a problem in that gas permeability is high and the substrate is easily corroded.

JP-A-8-176447 Japanese Patent Laid-Open No. 11-1619 JP 2003-128922 A JP 2005-105217 A

  The present invention has been made in view of the above circumstances, and has a low viscosity, a good filling property, a good curability, a curing, a high refractive index, a high light transmittance, a high adhesion to a substrate, and a high resistance. To provide a curable organopolysiloxane composition that forms a cured product having excellent cracking properties and low gas permeability, and a semiconductor device that has a semiconductor element coated with a cured product of the composition and that has excellent reliability. Objective.

（式中、Ｒ^１は同一又は異なっていても良い、二価の置換又は非置換のメチレン基、エチレン基、プロピレン基、フェニレン基から選ばれる有機基であり、Ｒ^２は同一又は異なっていても良い、一価の置換又は非置換でアリール基、アルキル基、アラルキル基、ハロゲン化アルキル基から選ばれる炭素数１〜１０の有機基である。ｐは同一又は異なっていても良い１〜３の整数、ｍは０〜５の整数、ｎは０〜２の整数である。）
及び
（Ｄ）ヒドロシリル化反応用触媒：触媒量、
からなる硬化性オルガノポリシロキサン組成物を提供する。
In order to solve the above problems, the present invention provides at least
(A) an organopolysiloxane represented by the following average unit formula (1):
(RSiO _3/2 ) _a (R ₂ SiO _2/2 ) _b (R ₃ SiO _1/2 ) _c (XO _1/2 ) _d (1)
{Wherein R may be the same or different, a substituted or unsubstituted monovalent hydrocarbon group (provided that 0.1 to 50 mol% of R is an alkenyl group, and 10 mol% or more of R is aryl) X is a hydrogen atom or an alkyl group. a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, and (b + c + d) / a is 0-3. }
(B) Linear organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule, and at least 10 mol% of all substituents bonded to silicon atoms being aryl groups: (A ) An amount of 10/90 to 70/30 by mass ratio with respect to the component,
(C) An organosilicon compound represented by the following general formula (2) or the following general formula (3): an amount of 1 to 100 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B),

(In the formula, R ¹ may be the same or different, and is an organic group selected from a divalent substituted or unsubstituted methylene group, ethylene group, propylene group, and phenylene group, and R ² is the same or different. Or a monovalent substituted or unsubstituted organic group having 1 to 10 carbon atoms selected from an aryl group, an alkyl group, an aralkyl group, and a halogenated alkyl group, and p may be the same or different. , M is an integer of 0 to 5, and n is an integer of 0 to 2.)
And (D) catalyst for hydrosilylation reaction: catalytic amount,
A curable organopolysiloxane composition is provided.

  Such a curable organopolysiloxane composition of the present invention has low viscosity, good filling properties, and good curability. Further, when cured, the cured product has a high refractive index, high light transmittance, high adhesion to the substrate, excellent crack resistance, and low gas permeability.

で表される単位構造を１０モル％以上含むオルガノポリシロキサンであることが好ましい。 In addition, the component (B) is

It is preferable that it is organopolysiloxane containing 10 mol% or more of the unit structure represented by these.

  Thus, if (B) component contains the said unit structure 10 mol% or more, the hardened | cured material which was more excellent in crack resistance and transparency can be obtained.

  The present invention also provides a semiconductor device wherein a semiconductor element is coated with a cured product of the curable organopolysiloxane composition.

  Such a semiconductor device of the present invention is a curable organopolysiloxane composition of the present invention having a large refractive index, high light transmittance, high adhesion to a substrate, excellent crack resistance, and low gas permeability. Since it is coated with the cured product, it is excellent in reliability.

  As described above, the curable organopolysiloxane composition of the present invention has low viscosity, good filling properties, good curability, cures, has a high refractive index, high light transmittance, and high adhesion. The semiconductor device according to the present invention is characterized by forming a cured product that is high, excellent in crack resistance, and low in gas permeability, and the semiconductor device of the present invention is reliable because the semiconductor element is covered with the cured product of the above composition. It is characterized by being excellent.

It is a schematic sectional drawing of LED which is an example of the semiconductor device of this invention.

Hereinafter, the present invention will be described in more detail.
As described above, the conventional curable organopolysiloxane composition has high gas permeability due to its high viscosity and poor filling, poor adhesion of the cured product and easy peeling from the substrate, and a high proportion of siloxane bonds. It has a problem that it becomes high and corrodes the substrate, and the crack resistance is poor.

  Therefore, as a result of intensive studies to solve the above problems by the present inventors, if a curing agent having many divalent organic bonds in the component is used, the gas permeability can be lowered, or the thermal shock test. It has become possible to improve the durability and the like, and found that the above problems can be solved, thereby completing the present invention.

（式中、Ｒ^１は同一又は異なっていても良い、二価の置換又は非置換の炭素数１〜１０の有機基であり、Ｒ^２は同一又は異なっていても良い、一価の置換又は非置換で炭素数１〜１０の有機基である。ｐは同一又は異なっていても良い１〜３の整数、ｍは０〜５の整数、ｎは０〜２の整数である。）
及び
（Ｄ）ヒドロシリル化反応用触媒：触媒量、
からなることを特徴とする。 That is, the curable organopolysiloxane composition of the present invention has at least
(A) an organopolysiloxane represented by the following average unit formula (1):
(RSiO _3/2 ) _a (R ₂ SiO _2/2 ) _b (R ₃ SiO _1/2 ) _c (XO _1/2 ) _d (1)
{Wherein R may be the same or different, a substituted or unsubstituted monovalent hydrocarbon group (provided that 0.1 to 50 mol% of R is an alkenyl group, and 10 mol% or more of R is aryl) X is a hydrogen atom or an alkyl group. a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, and (b + c + d) / a is 0-3. }
(B) Linear organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule, and at least 10 mol% of all substituents bonded to silicon atoms being aryl groups: (A ) An amount of 5/95 to 95/5 in mass ratio to the component,
(C) Organosilicon compound represented by the following general formula (2) or the following general formula (3): an amount of 1 to 200 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B),

Wherein R ¹ is the same or different divalent substituted or unsubstituted organic group having 1 to 10 carbon atoms, and R ² may be the same or different, monovalent substituted or An unsubstituted organic group having 1 to 10 carbon atoms, p may be the same or different, m is an integer of 1 to 3, m is an integer of 0 to 5, and n is an integer of 0 to 2.)
And (D) catalyst for hydrosilylation reaction: catalytic amount,
It is characterized by comprising.

Hereinafter, each component of the present invention will be described in detail.
<(A) component>
The component (A) is an organopolysiloxane represented by the following average unit formula (1).
(RSiO _3/2 ) _a (R ₂ SiO _2/2 ) _b (R ₃ SiO _1/2 ) _c (XO _1/2 ) _d (1)
{Wherein R may be the same or different, a substituted or unsubstituted monovalent hydrocarbon group (provided that 0.1 to 50 mol% of R is an alkenyl group, and 10 mol% or more of R is aryl) X is a hydrogen atom or an alkyl group. a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, and (b + c + d) / a is 0-3. }

  Examples of the alkenyl group in R include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, and a vinyl group is particularly preferable. The alkenyl group in R is 0.1 to 50 mol%, preferably 1 to 40 mol%, particularly preferably 5 to 30 mol%. If it is less than 0.1 mol%, the curability of the composition becomes insufficient, and if it exceeds 50 mol%, the cured product becomes brittle and the crack resistance decreases.

  Examples of the aryl group in R include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, and a phenyl group is particularly preferable. Content of the aryl group in R is 10 mol% or more, Preferably it is 40-99.9 mol%, Most preferably, it is 45-95 mol%. The light transmittance of hardened | cured material falls that it is less than 10 mol%.

Examples of silicon-bonded organic groups other than alkenyl and aryl groups in R include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl; benzyl and phenethyl Aralkyl groups such as chloromethyl group, 3-chloropropyl group, substituted or unsubstituted monovalent hydrocarbon groups such as halogenated alkyl groups such as 3,3,3-trifluoropropyl group, etc. A methyl group is preferred.
Moreover, in said average unit formula (1), X is a hydrogen atom or an alkyl group, As this alkyl group, the group similar to the above is illustrated, and it is especially preferable that they are a methyl group and an ethyl group.

A is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, and (b + c + d) / a is 0 to 3 ((RSiO _{3 / 2} ) Unit content of 25 mol% or more), preferably 0 to 2 ((RSiO _3/2 ) unit content of 33.3 mol% or more), particularly preferably 0 to 1 ((RSiO _3/2 ) The unit content is 50 mol% or more). When the content of the (RSiO _3/2 ) unit is less than 25 mol%, the crack resistance and the like are insufficient. The molecular weight of such component (A) is not limited, but the weight average molecular weight (Mw) by GPC measurement (in terms of standard polystyrene) using a THF solvent is preferably 500 to 10,000, more preferably 700 to 5,000, particularly preferably 1,000 to 3,000.

<(B) component>
Component (B) is a component for imparting flexibility to a cured product obtained by curing the present composition, and is bonded to at least two silicon-bonded alkenyl groups and at least silicon atoms in one molecule. A straight chain having 10 mol% or more, preferably 10 to 99.9 mol%, more preferably 20 to 60 mol% of a silicon atom-bonded aryl group of all substituents (excluding oxygen atoms forming a siloxane bond). It is an organopolysiloxane. (B) As an alkenyl group in a component, the group similar to what was illustrated by R of (A) component is illustrated, and it is especially preferable that it is a vinyl group. Moreover, as an aryl group in (B) component, the group similar to what was illustrated by R of (A) component is illustrated, and it is especially preferable that it is a phenyl group. Examples of the substituent other than the alkenyl group and the aryl group include the same groups as those exemplified for R of the component (A), and a methyl group is particularly preferable.
If the content of silicon-bonded aryl group is less than 10 mol%, the refractive index and transparency will be insufficient.

で表されるジフェニルシロキサン単位構造を１０モル％以上、特に２０〜６０モル％含んでいることが好ましい。この単位の含有量が１０モル％以上であると、屈折率、透明性に優れると共に、耐クラック性もより優れたものとなる。 In particular, the component (B)

It is preferable that 10 mol% or more, especially 20 to 60 mol% is contained. When the content of this unit is 10 mol% or more, the refractive index and transparency are excellent, and the crack resistance is also excellent.

  The viscosity of the component (B) at 25 ° C. is not limited, but is preferably in the range of 10 to 1,000,000 mPa · s, particularly 100 to 50,000 mPa · s as measured by a rotational viscometer. It is preferable to be within the range. When the viscosity of the component (B) is within the above range, the resulting cured product has better mechanical strength, and the resulting composition has better handling workability.

  The content of the component (B) is such that the ratio of the mass of the component (B) to the component (A) {the mass of the component (B) / the mass of the component (A)} is 5/95 to 95/5. The amount is preferably within the range of 10/90 to 70/30. This is because if the content of the component (B) is less than the lower limit of the above range, the flexibility of the resulting cured product is reduced, whereas if it exceeds the upper limit of the above range, the workability of the resulting composition is handled. This is because the cured product obtained is extremely soft.

（式中、Ｒ^１は同一又は異なっていても良い、二価の置換又は非置換の炭素数１〜１０の有機基であり、Ｒ^２は同一又は異なっていても良い、一価の置換又は非置換で炭素数１〜１０の有機基である。ｐは同一又は異なっていても良い１〜３の整数、ｍは０〜５、好ましくは０〜２の整数、ｎは０〜２の整数である。） <(C) component>
Component (C) is a curing agent of the present composition, and is an organosilicon compound blocked with a silicon atom-bonded hydrogen atom represented by the following general formula (2) or the following general formula (3).

Wherein R ¹ is the same or different divalent substituted or unsubstituted organic group having 1 to 10 carbon atoms, and R ² may be the same or different, monovalent substituted or An unsubstituted organic group having 1 to 10 carbon atoms, p is an integer of 1 to 3 which may be the same or different, m is an integer of 0 to 5, preferably 0 to 2, and n is an integer of 0 to 2. .)

  In this way, the component has many divalent organic bonds, preferably alkylene bonds, so that the gas permeability can be lowered or the thermal shock can be reduced as compared with the commonly used organohydrogenpolysiloxane curing agents. Durability during testing can be improved.

Examples of R ¹ in the general formulas (2) and (3) include substituted or unsubstituted divalent organic groups such as a methylene group, an ethylene group, a propylene group, and a phenylene group, and preferably have 1 to 3 carbon atoms. And particularly preferably an ethylene group.
R ² in the general formulas (2) and (3) is a substituted or unsubstituted monovalent organic group excluding an alkenyl group such as the aryl group, the alkyl group, the aralkyl group, and the halogenated alkyl group. Examples thereof include a methyl group and a phenyl group.

  Moreover, m in the above formula is an integer of 0 to 5, preferably 0 to 2, particularly preferably an integer of 0 or 2. This is because if the value of m exceeds the upper limit of the above range, the gas barrier property of the obtained cured product is lowered, or the adhesiveness of the cured product is deteriorated.

The viscosity of component (C) at 25 ° C. is not limited, but is preferably in the range of 1 to 100,000 mPa · s, and particularly preferably in the range of 2 to 20,000 mPa · s. This is because when the viscosity of the component (C) is in the above range, it is difficult to volatilize, the composition of the resulting composition is more stable, and the handling workability of the resulting composition is further improved.
Moreover, since handling is easy, what is represented by the said General formula (3) as (C) component is used more preferable.

As such (C) component, the organosilicon compound represented by a following formula is mentioned preferably, for example.

  The content of the component (C) is an amount that falls within the range of 1 to 200 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). It is the quantity which becomes an inside, Especially preferably, it is the quantity which becomes in the range of 1-50 mass parts. This is because if the content of the component (C) is less than 1 part by mass, the curability of the resulting composition will be insufficient, and if it exceeds 200 parts by mass, the heat resistance of the resulting cured product will decrease. is there.

  Further, in order to improve the curability and heat resistance of the composition, the content of the component (C) is in this component with respect to 1 mol of the total alkenyl groups contained in the components (A) and (B). It is preferable that the amount of silicon atom-bonded hydrogen atoms is in the range of 0.1 to 10 mol, more preferably 0.2 to 5 mol, and particularly 0.5 to 5 mol. The amount is preferably 2 mol.

<(D) component>
The (D) component hydrosilylation reaction catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group in the (A) component and the (B) component and the silicon atom-bonded hydrogen atom in the (C) component. is there. Examples of such component (D) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferred because they can significantly accelerate the curing of the composition. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex, and in particular, a platinum-alkenylsiloxane complex. It is preferable. Examples of the alkenyl siloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples include alkenyl siloxanes in which a part of the methyl groups of these alkenyl siloxanes are substituted with groups such as ethyl groups and phenyl groups, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with groups such as allyl groups and hexenyl groups. . In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because the stability of this platinum-alkenylsiloxane complex is good.

  Further, since the stability of this platinum-alkenylsiloxane complex can be improved, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1 can be added to this complex. , 3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, , 3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane is preferably added, and alkenylsiloxane such as dimethylsiloxane oligomer is preferably added. It is preferable.

  The content of the component (D) is not limited as long as it is an amount (catalytic amount) that accelerates the curing (hydrosilylation reaction) of the composition. Specifically, the content of the component in the component is The amount of metal atoms is preferably in an amount in the range of 0.01 to 500 ppm, more preferably in an amount in the range of 0.01 to 100 ppm, particularly 0.01 to 500 ppm. The amount is preferably within the range of 50 ppm. This is because when the content of the component (D) is in the above range, the present composition is sufficiently cured, and there is no possibility of causing problems such as coloring in the obtained cured product, and it is economical. is there.

<Optional component>
In this composition, as other optional components, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, etc. Alkyne alcohols; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5 , 7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, benzotriazole, and other reaction inhibitors may be contained. Although content of this reaction inhibitor is not limited, It is preferable to exist in the range of 0.0001-5 mass parts with respect to a total of 100 mass parts of (A) component and (B) component.

  In addition, the composition may contain an adhesion-imparting agent for improving the adhesion. The adhesion-imparting agent is preferably an organosilicon compound having at least one, preferably two or more alkoxy groups bonded to silicon atoms in one molecule. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group is particularly preferable. The group other than the alkoxy group bonded to the silicon atom of the organosilicon compound includes substituted or unsubstituted monovalent groups such as the alkyl group, the alkenyl group, the aryl group, the aralkyl group, and the halogenated alkyl group. Hydrocarbon group; glycidoxyalkyl group such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) Epoxy cyclohexyl alkyl group such as propyl group; Epoxy group-containing monovalent organic group such as oxiranylalkyl group such as 4-oxiranylbutyl group and 8-oxiranyloctyl group; Acrylic such as 3-methacryloxypropyl group Group-containing monovalent organic group; a hydrogen atom is exemplified. Specific examples include silane coupling agents such as epoxy group-containing silane coupling agents and (meth) acryl group-containing silane coupling agents, and partial hydrolysis condensates thereof (oligomers of silane coupling agents).

  More specifically, silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane; silicon atoms in one molecule Siloxane compound having at least one bonded alkenyl group or silicon atom bonded hydrogen atom and silicon atom bonded alkoxy group, silane compound having at least one silicon atom bonded alkoxy group or siloxane compound and silicon atom bonded hydroxy in one molecule Examples thereof include a mixture of a group and a siloxane compound each having at least one silicon-bonded alkenyl group, methyl polysilicate, ethyl polysilicate, and epoxy group-containing ethyl polysilicate.

The adhesion-imparting agent is preferably a low-viscosity liquid, and the viscosity is not limited, but is preferably in the range of 1 to 500 mPa · s at 25 ° C. An adhesion-imparting material as shown in the following formula may be added.

Moreover, in the said composition, although content of this adhesion imparting agent is not limited, It is preferable that it is 0.01-10 mass parts with respect to a total of 100 mass parts of (A) component and (B) component.
Further, in the present composition, as long as the object of the present invention is not impaired, as other optional components, inorganic fillers such as silica, glass, alumina and zinc oxide; fine organic resin powders such as polymethacrylate resin; You may contain dye, a pigment, a flame-retarding agent, a solvent, etc.

Further, the composition is preferably cured to form a cured product having a hardness specified by JIS of 30 or more, particularly 30 to 90, according to JIS.
In this way, when cured, for example, if a cured product of 30 or more is formed by Shore D, even when used in a semiconductor device, it is hardly affected by external stress, and dust and the like are hardly adhered. Become.

  Moreover, in order to give sufficient reliability to the semiconductor device which has the semiconductor element coat | covered with the hardened | cured material of the composition, this composition is the refractive index (25 nm) of the hardened | cured material obtained by hardening | curing. ° C) is 1.45 or more, and the light transmittance (25 ° C) of the cured product is preferably 80% or more.

  This refractive index can be measured by, for example, an Abbe refractometer. At this time, the refractive index at an arbitrary wavelength can be measured by changing the wavelength of the light source in the Abbe refractometer. Moreover, this light transmittance can be calculated | required by measuring the hardened | cured material of optical path length 2.0mm with a spectrophotometer, for example.

  Moreover, it is preferable that the ultraviolet-ray transmittance (25 degreeC) in the wavelength of 200 nm-250 nm of the hardened | cured material obtained by hardening | curing this composition is 10% or less. This is because when a semiconductor device in which a semiconductor element is coated with a cured product of the composition receives ultraviolet rays having a short wavelength of 200 nm to 250 nm, deterioration of the material constituting the semiconductor device can be prevented. It is because there is a risk of disappearing. This ultraviolet transmittance can be determined, for example, by measuring a cured product having an optical path length of 2.0 mm with a spectrophotometer.

  The composition is cured at room temperature or by heating, but is preferably heated to cure quickly. The heating temperature is preferably in the range of 50 to 200 ° C.

  A cured product obtained by curing the present composition can be obtained from an elastomer, for example, a gel or a flexible rubber to an elastic resin. Such a composition can be used as an electrical / electronic adhesive, a potting agent, a protective coating agent, and an underfill agent. In particular, since it has a high light transmittance, it can adhere to semiconductor elements for optical applications. Suitable as an agent, potting agent, protective coating agent, and underfill agent.

The present invention further provides a semiconductor device using such a curable organopolysiloxane composition of the present invention.
Hereinafter, the semiconductor device of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.
FIG. 1 is a schematic sectional view showing an example (in this case, LED) of the semiconductor device of the present invention.
In the semiconductor device 1 of the present invention, a semiconductor chip 4 is die-bonded on a package 3 on which a silver-plated substrate 2 is formed, and the semiconductor chip 4 is wire-bonded by a bonding wire 5.

And the semiconductor chip 4 is coat | covered with the hardened | cured material 6 of the curable organopolysiloxane composition of this invention mentioned above.
The semiconductor chip 4 is coated by applying the curable organopolysiloxane composition 6 of the present invention described above and curing the curable organopolysiloxane composition 6 by heating.

  In this case, the curable organopolysiloxane composition 6 has a hardness specified by JIS of 30 or more in Shore D by curing from the viewpoint of being hardly affected by external stress and suppressing adhesion of dust and the like as much as possible. It is preferable to form a cured product.

  The curable organopolysiloxane composition of the present invention has a large refractive index, high light transmittance, high adhesion to the substrate, excellent crack resistance, and forms a cured product with low gas permeability. The semiconductor device of the present invention using such a composition of the present invention has excellent reliability, and is particularly suitable as a diode, a light emitting diode (LED) or the like.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example etc.
In addition, the viscosity in an Example is the value measured in 25 degreeC. Moreover, the characteristic of the curable organopolysiloxane composition and the cured product thereof was measured as follows.

Oxygen gas permeable curable organopolysiloxane composition of curable organopolysiloxane composition A cured product having a thickness of 1 mm obtained by curing the curable organopolysiloxane composition by heating in a hot-air circulating oven at 150 ° C. for 3 hours is used to transmit oxygen gas. Measurements were made using the instrument.

Sulfur Corrosion Test of Curable Organopolysiloxane Composition Obtained by pouring the curable organopolysiloxane composition into a package on which a silver-plated substrate is formed and curing it by heating in a hot air circulation oven at 150 ° C. for 3 hours. The package (Fig. 1) covered with a hardened material is put inside a glass bottle containing sulfur powder and sealed, and it is visually checked if the silver plating is corroded over time. A substrate that did not change by comparison was indicated by ◯, a substrate that slightly changed was indicated by Δ, and a substrate that changed black was indicated by ×.

Hardness of Cured Product A cured product was prepared by heating the curable organopolysiloxane composition in a hot air circulation oven at 150 ° C. for 3 hours. The hardness of the cured product was measured using a Shore D hardness meter.

Refractive index curable organopolysiloxane composition of the cured product was cured by heating in a hot air circulation oven at 150 ° C. for 3 hours, and the refractive index at 25 ° C. of the cured product was measured using an Abbe refractometer. It was measured. In addition, visible light (589 nm) was used as a light source used for the measurement.

Light transmittance of cured product Cured organopolysiloxane composition was cured by heating in a hot air circulation oven at 150 ° C. for 3 hours. The light transmittance was measured.

Heat resistance of cured product The result obtained in the above [Light transmittance of cured product] is 100, and this cured product is heated in a hot air circulation oven at 150 ° C. for 500 hours, and then the cured product is taken out and light transmittance is 100. It was measured how much it fell compared.

Crack after the endurance of the cured product The package prepared as shown in Fig. 1 is put into a thermal shock tester with {-40 ° C (30 minutes), 100 ° C (30 minutes)} as one cycle, and 100 cycles have passed. Thereafter, the package was observed with a magnifying microscope. The case where there was a crack in the cured product was indicated as “X”, the case where there was no crack was indicated as “◯”, and the case where there was no crack was indicated as “Δ”.

[Example 1]
Average unit formula:
(C ₆ H ₅ SiO _3/2 ) _0.75 [(CH ₂ ═CH) (CH ₃ ) SiO] _0.25
Branched-organopolysiloxane represented by the following formula: {characteristic = solid (25 ° C.), silicon atom-bonded vinyl group content in silicon atom-bonded all organic groups = 12.5 mol%, silicon atom-bonded all organic groups Content of silicon atom-bonded phenyl group in the mixture = 75 mol%, weight average molecular weight in terms of standard polystyrene = 2400}, 50 parts by mass, viscosity 700 mPa · s, linear molecular chain dimethylvinylsiloxy group-blocked diphenyl 25 parts by mass of dimethylpolysiloxane (content of silicon atom-bonded vinyl group = 0.055 mol%, content of silicon atom-bonded phenyl group in all silicon atom-bonded organic groups = 30 mol%), formula:
_{H (CH 3) 2 SiCH 2} CH 2 (C 6 H 5) 2 SiCH 2 CH 2 Si (CH 3) 2 H
23 parts by mass of a dimethylhydrogensilethynyl group-blocked organosilicon compound represented by the following formula: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (in this composition, The amount of platinum metal in the complex is 30 ppm by mass), and 1.0 mass part of a SiH-containing compound of the following structural formula is uniformly mixed as an adhesion promoter, and the viscosity is 2,700 mPa · s. A siloxane composition was prepared.

  The characteristics of this curable organopolysiloxane composition and its cured product were measured. These results are shown in Table 1. Moreover, LED was produced using this curable organopolysiloxane composition. Table 1 shows the evaluation results of the reliability of these semiconductor devices.

で表されるシラン化合物２．０質量部、白金の１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体（本組成物において、本錯体中の白金金属が質量単位で２．５ｐｐｍとなる量）、粘度３，５００ｍＰａ・ｓである硬化性オルガノポリシロキサン組成物を調製した。 [Example 2]
Average unit formula:
(C ₆ H ₅ SiO _3/2 ) _0.8 [(CH ₂ ═CH) (CH ₃ ) ₂ SiO _1/2 ] _0.2
A branched-chain organopolysiloxane represented by the formula {characteristic = solid (25 ° C.), silicon atom-bonded vinyl group content in silicon atom-bonded all organic groups = 10 mol%, silicon atom-bonded all organic groups in Content of silicon atom-bonded phenyl group = 80 mol%, standard polystyrene equivalent weight average molecular weight = 1,600} 55 parts by mass, viscosity 700 mPa · s, linear molecular chain both ends dimethylvinylsiloxy group-capped diphenyl 25 parts by mass of dimethylpolysiloxane (content of silicon atom-bonded vinyl group = 0.055 mol%, content of silicon atom-bonded phenyl group in all silicon atom-bonded organic groups = 30 mol%),
formula:
_{H (CH 3) 2 SiCH 2} CH 2 (CH 3) 2 SiCH 2 CH 2 Si (CH 3) 2 H
As the adhesion-imparting agent, 15 parts by mass of a dimethylhydrogen ethynyl group-blocked organosilicon compound at both molecular chains represented by

2.0 parts by mass of a silane compound represented by the formula: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (in the present composition, platinum metal in the complex is 2 by mass unit) A curable organopolysiloxane composition having a viscosity of 3,500 mPa · s was prepared.

  The characteristics of this curable organopolysiloxane composition and its cured product were measured. These results are shown in Table 1. Moreover, LED was produced using this curable organopolysiloxane composition. Table 1 shows the evaluation results of the reliability of these semiconductor devices.

[Comparative Example 1]
Viscosity is 3,500 mPa · s, linear molecular chain both ends dimethylvinylsiloxy group-blocked methylphenylpolysiloxane (content of silicon atom-bonded vinyl group = 0.20 mass%, in silicon atom-bonded all organic groups) (Content of silicon atom-bonded phenyl group = 49 mol%) 60 parts by mass, average unit formula:
(C ₆ H ₅ SiO _3/2 ) _0.75 [(CH ₂ ═CH) (CH ₃ ) ₂ SiO _1/2 ] _0.25
Branched-organopolysiloxane represented by the following formula: {characteristic = solid (25 ° C.), silicon atom-bonded vinyl group content in silicon atom-bonded all organic groups = 12.5 mol%, silicon atom-bonded all organic groups Content of silicon-bonded phenyl group in the content = 75 mol%, weight average molecular weight in terms of standard polystyrene = 1,600} 40 parts by mass, formula:
H (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] ₄ Si (CH ₃ ) ₂ H
24 parts by mass of dimethylpolysiloxane represented by the formula: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (in the present composition, platinum metal in the complex is 30 ppm by mass) Were uniformly mixed to prepare a curable organopolysiloxane composition having a viscosity of 2,460 mPa · s.

  The characteristics of this curable organopolysiloxane composition and its cured product were measured. These results are shown in Table 1. Moreover, LED was produced using this curable organopolysiloxane composition. Table 1 shows the evaluation results of the reliability of these semiconductor devices.

[Comparative Example 2]
Average unit formula:
(C ₆ H ₅ SiO _3/2 ) _0.75 [(CH ₂ ═CH) (CH ₃ ) ₂ SiO _1/2 ] _0.25
Branched-organopolysiloxane represented by the following formula: {characteristic = solid (25 ° C.), silicon atom-bonded vinyl group content in silicon atom-bonded all organic groups = 12.5 mol%, silicon atom-bonded all organic groups Content of silicon-bonded phenyl group in the content = 75 mol%, weight average molecular weight in terms of standard polystyrene = 1,600} 55 parts by mass, viscosity 950 mPa · s, average unit formula:
(C ₆ H ₅ SiO _3/2 ) _0.60 [(CH ₃ ) ₂ HSiO _1/2 ] _0.40
Branched chain organopolysiloxane (content of silicon atom-bonded hydrogen atoms in all silicon atom-bonded groups = 22 mol%, content of silicon atom-bonded phenyl groups in all silicon atom-bonded groups = 33 mol) %, Standard polystyrene equivalent weight average molecular weight = 1,100) 12 parts by mass, viscosity 3,500 mPa · s, linear molecular chain dimethylvinylsiloxy group-blocked methylphenylpolysiloxane (silicon atom-bonded vinyl group) Content = 0.20 mass%, silicon atom-bonded phenyl group content in all silicon-bonded organic groups = 49 mol%) 50 parts by mass, platinum 1,3-divinyl-1,1,3,3 -Tetramethyldisiloxane complex (in this composition, the amount of platinum metal in the complex is 2.5 ppm by mass) is uniformly mixed, and the viscosity is 3,500 mPa · s. That was a curable organopolysiloxane composition was prepared.

  The characteristics of this curable organopolysiloxane composition and its cured product were measured. These results are shown in Table 1. Moreover, LED was produced using this curable organopolysiloxane composition. Table 1 shows the evaluation results of the reliability of these semiconductor devices.

[Comparative Example 3]
Average unit formula:
(C ₆ H ₅ SiO _3/2 ) _0.75 [(CH ₂ ═CH) (CH ₃ ) ₂ SiO _1/2 ] _0.25
Branched-organopolysiloxane represented by the following formula: {characteristic = solid (25 ° C.), silicon atom-bonded vinyl group content in silicon atom-bonded all organic groups = 12.5 mol%, silicon atom-bonded all organic groups The content of silicon atom-bonded phenyl group is 75 mol%, the weight average molecular weight in terms of standard polystyrene is 1,600} 45 parts by mass, the viscosity is 3,500 mPa · s, and both ends of the linear molecular chain are dimethylvinyl Siloxy group-blocked methylphenyl polysiloxane (content of silicon atom-bonded vinyl group = 0.20 mass%, content of silicon atom-bonded phenyl group in all silicon atom-bonded organic groups = 49 mol%) 55 parts by mass, formula:
H (CH ₃ ) ₂ SiO [CH ₃ (C ₆ H ₅ ) SiO] ₄ Si (CH ₃ ) ₂ H
Dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane 24 parts by weight of a molecular chain represented by the following formula: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (in this composition, The amount of platinum metal in the complex was 2.5 ppm by mass) was uniformly mixed to prepare a curable organopolysiloxane composition having a viscosity of 1,700 mPa · s.

  The characteristics of this curable organopolysiloxane composition and its cured product were measured. These results are shown in Table 1. Moreover, LED was produced using this curable organopolysiloxane composition. Table 1 shows the evaluation results of the reliability of these semiconductor devices.

[Comparative Example 4]
The branched organopolysiloxane of Example 1 is represented by the average unit formula:
(C ₆ H ₅ SiO _3/2 ) _0.05 (CH ₃ SiO _3/2 ) _0.70 [(CH ₂ ═CH) (CH ₃ ) ₂ SiO _1/2 ] _0.25 {Property = Solid ( 25 ° C.), content of silicon atom-bonded vinyl group in all silicon atom-bonded organic groups = 12.5 mol%, content of silicon atom-bonded phenyl group in all silicon atom-bonded organic groups = 5 mol%, standard polystyrene A curable organopolysiloxane composition having a viscosity of 2,300 mPa · s was prepared in the same manner as in Example 1 except that the converted weight average molecular weight was 2,100}.

  The characteristics of this curable organopolysiloxane composition and its cured product were measured. These results are shown in Table 1. Moreover, LED was produced using this curable organopolysiloxane composition. Table 1 shows the evaluation results of the reliability of these semiconductor devices.

  As shown in Table 1, Examples 1 and 2 have low oxygen gas permeability, no corrosion due to sulfur, sufficient hardness of the cured product, and good refractive index, light transmittance and heat resistance of the cured product. Thus, no cracks were observed in the cured product.

On the other hand, in Comparative Examples 1-3, although the refractive index and light transmittance of the cured product were good and the hardness was sufficient, the oxygen gas transmittance was very high and there was corrosion due to sulfur.
Moreover, in Comparative Examples 2 and 3, the occurrence of cracks was observed, and Comparative Example 1 in which the presence or absence of cracks was unclear was also inferior in heat resistance.
In Comparative Example 4, although the heat resistance was good, the oxygen gas permeability was high, corrosion due to sulfur was slightly observed, and the refractive index and light transmittance of the cured product were slightly inferior to those of other examples. .

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

  In the above examples, the curable organopolysiloxane composition of the present invention was used as a potting agent for semiconductor elements. However, the curable organopolysiloxane composition of the present invention has a particularly high light transmittance. Is also suitable as an adhesive, protective coating agent, underfill agent, etc. for semiconductor elements for optical applications, and of course, also used as an adhesive for electric and electronic, potting agent, protective coating agent, underfill agent, etc. be able to.

DESCRIPTION OF SYMBOLS 1 ... Semiconductor device, 2 ... Silver plating board | substrate, 3 ... Package, 4 ... Semiconductor chip,
5 ... bonding wire, 6 ... polyorganosiloxane composition (curing agent).

Claims (3)

at least,
(A) an organopolysiloxane represented by the following average unit formula (1):
(RSiO _3/2 ) _a (R ₂ SiO _2/2 ) _b (R ₃ SiO _1/2 ) _c (XO _1/2 ) _d (1)
{Wherein R may be the same or different, a substituted or unsubstituted monovalent hydrocarbon group (provided that 0.1 to 50 mol% of R is an alkenyl group, and 10 mol% or more of R is aryl) X is a hydrogen atom or an alkyl group. a is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is 0 or a positive number, and (b + c + d) / a is 0-3. }
(B) Linear organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule, and at least 10 mol% of all substituents bonded to silicon atoms being aryl groups: (A ) An amount of 10/90 to 70/30 by mass ratio with respect to the component,
(C) An organosilicon compound represented by the following general formula (2) or the following general formula (3): an amount of 1 to 100 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B),

(In the formula, R ¹ may be the same or different, and is an organic group selected from a divalent substituted or unsubstituted methylene group, ethylene group, propylene group, and phenylene group, and R ² is the same or different. Or a monovalent substituted or unsubstituted organic group having 1 to 10 carbon atoms selected from an aryl group, an alkyl group, an aralkyl group, and a halogenated alkyl group, and p may be the same or different. , M is an integer of 0 to 5, and n is an integer of 0 to 2.)
And (D) catalyst for hydrosilylation reaction: catalytic amount,
A curable organopolysiloxane composition comprising: The component (B) is

The curable organopolysiloxane composition according to claim 1, which is an organopolysiloxane containing 10 mol% or more of a unit structure represented by the formula:   A semiconductor device, wherein a semiconductor element is coated with a cured product of the curable organopolysiloxane composition according to claim 1.

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