JP4774201B2 - Package molded body and semiconductor device - Google Patents

Description

  The present invention relates to a package molded body and a semiconductor device, and more particularly to a package molded body capable of suppressing deterioration of a resin when a light emitting element is mounted as a semiconductor element, and a semiconductor device using the package molded body.

  Conventionally, as a surface-mounted light-emitting diode, which is a semiconductor element, a thermoplastic resin highly reflected by a pigment such as titanium oxide has been used as a housing material. This housing material is integrated with a lead frame material. The package molded body is formed by injection molding. In addition, a package molded body made of a thermoplastic resin, which is bonded to a glass epoxy substrate having a lead pattern or the like is used (Patent Documents 1 and 2).

Such a light emitting diode has a reflector portion made of a highly reflective thermoplastic resin, and covers the surface of the lead frame material with a material having a high visible region reflectance such as silver plating, thereby efficiently emitting light to the front of the die. It can be taken out.
In addition, since an inexpensive material called thermoplastic resin is used and an excellent process called injection molding is performed, the cost of the package can be reduced, and the thermoplastic resin can be recycled. It also has the advantage of.
JP 2000-150966 A JP 2001-168398 A

In general, the thermoplastic resin used for the package molded body is a material known as a heat-resistant polymer such as liquid crystal polymer, polyphenylene sulfide (PPS), polyphthalamide (PPA).
However, as the output of the light emitting diode increases, the generated heat and light increase, and the influence of heat history during the manufacturing process, such as heating when the chip is die-bonded to the package, and when the light emitting diode is mounted on the circuit board Due to the use of lead-free solder, the temperature of the process increases, so that any heat-resistant polymer is not sufficient in light resistance and heat yellowing.

In particular, when a light emitting diode chip having an emission peak of 500 nm or less is packaged, the resin used for the package molded body also has an influence on the original hue of the base resin, although a white pigment is added, In this wavelength region, the reflectance is lowered, and the surface is easily deteriorated by the light due to the increased light absorption.
Further, as the photodegradation of the surface of these thermoplastic resins progresses, it tends to peel off from other materials, leading to a fatal defect in device reliability.

  The present invention has been made in view of the above problems, and provides a package molded body and a semiconductor device capable of improving the light resistance and heat yellowing of the package molded body without causing a decrease in light output of the light emitting diode. For the purpose.

The package molded body of the present invention is a package molded body having a bottom part for mounting a semiconductor element and a side part surrounding the bottom part, and a position away from the outer edge of the mounting area of the semiconductor element in the bottom part And a bottom portion and a side portion outside the wall portion are covered with a coating member.
According to another aspect of the present invention, there is provided a semiconductor device comprising the package molded body and a semiconductor element mounted on a mounting region of the package molded body, wherein the semiconductor element and the coating member are separated from each other. .

  According to the package molded body of the present invention, the wall portion is formed at the bottom portion, and the bottom portion and the side portion outside the wall portion are covered with the coating member, so that the package is formed by the light irradiated from the semiconductor element. It can prevent yellowing and deterioration of the body itself. In addition, since the wall portion is provided at the bottom, the coating member can be reliably prevented from coming into contact with the side surface and the top surface of the semiconductor element. It is possible to prevent a decrease in output.

  In addition, according to the semiconductor device of the present invention, when the semiconductor element is mounted on the package molded body, the side surface and the upper surface of the semiconductor element can be separated from the coating member and disposed so as not to contact the semiconductor element. Light emitted from the side surface and the upper surface of the element can be effectively extracted. Furthermore, the coating member can prevent yellowing and deterioration of the molded package, and can provide a highly reliable and high performance semiconductor device.

The package molded body of the present invention includes a bottom portion for mounting a semiconductor element and a side portion surrounding the bottom portion, and further, an outer side and a side portion at a position away from the outer edge of the semiconductor element mounting region at the bottom portion. Are covered with a coating member.
Here, the semiconductor element mainly means a light-emitting element, but may include any element manufactured using a semiconductor such as a protective element for protecting the light-emitting element from destruction due to overvoltage. .

  The package molded body is usually formed as a container having a bottomed shape or a partial bottomed shape, with side portions extending from the bottom so as to surround the bottom, and a region facing the bottom being opened. ing. The package molded body can be formed by combining one kind or two or more kinds of known materials, usually thermoplastic engineering polymers which are heat-resistant resins, thermosetting resins and the like. Examples thereof include liquid crystal polymer (LCP), polyphenylene sulfide (PPS), aromatic nylon (PPA), epoxy resin, and hard silicone resin. Among these, a thermoplastic engineering polymer is appropriate in terms of cost. These resins include one or two of inorganic fillers such as titanium oxide, zinc oxide, alumina, silica, barium titanate, calcium phosphate, calcium carbonate, white carbon, talc, magnesium carbonate, boron nitride, and glass fiber. More than one species may be added in combination. Furthermore, additives such as an antioxidant, a heat stabilizer, and a light stabilizer may be appropriately added. For example, it is appropriate that 10 to 80 parts by weight, preferably 40 to 80 parts by weight of an inorganic filler is added to 100 parts by weight of the resin.

The package molded body can be formed by a method known in the art such as injection molding, extrusion molding, compression molding, cast molding, transfer molding, vacuum molding, and lamination molding depending on the type of material. .
The shape of the package molded body is not particularly limited, and various shapes such as a circle, an ellipse, a quadrangle, a polygon, or a shape substantially corresponding to these may be used as the projected shape of the bottom. Moreover, the magnitude | size is not specifically limited, For example, 0.05 mm2-100 mm2 is mentioned. The side portion extending from the bottom portion so as to surround the bottom portion does not necessarily have to be formed so as to be clearly distinguishable from the bottom portion, and has an inclination from the bottom portion (for example, about 5 to 90 °) and rises. I just need it. As for the height of a side part, about 100 micrometers-about 10 mm are mentioned, for example.

  Further, the package molded body has a wall portion formed at a position away from the outer edge of the semiconductor element mounting region at the bottom. The wall is suitably provided on the entire periphery of the outer edge, but may be provided on a part thereof. The distance between the wall portion and the outer edge is not particularly limited, and when the semiconductor element is placed on the package molded body, the distance between the semiconductor element and the wall portion is as close as possible. Is preferred. The shape and height of the wall are not particularly limited as long as the coating member can ensure that the coating member does not contact the semiconductor element, as will be described later. For example, (i) a convex portion may be formed on the substantially flat bottom portion as the wall portion, or (ii) a concave portion may be formed on the substantially flat bottom portion, and a side surface of the concave portion may be formed as the wall portion. Alternatively, (iii) a concave portion may be formed on the substantially flat bottom portion, and the wall portion may be formed by disposing the convex portion continuously on the side surface of the concave portion. The constituent material of the wall portion may be a material constituting the package molded body, that is, the above-described heat-resistant resin, or another material, for example, a part of a metal substrate described later. In addition, when a recessed part is formed, it is preferable that the magnitude | size and shape of a recessed part are a shape and a magnitude | size which can accommodate a semiconductor element, especially a light emitting element in a recessed part. Further, the height of the recess is not particularly limited, and may be larger or smaller than the thickness of the semiconductor element.

  In the package molded body of the present invention, when the semiconductor element is placed on the package molded body, a part of the bottom and the entire side are covered with the coating member so as not to contact the semiconductor element, particularly the light emitting element. ing. In order to cover with the coating member in this way, for example, the surface tension and viscosity of the coating member are used, the wettability between the package molded body and the coating member is used, or the wall as described above is used. It is appropriate to use parts. The coating member not only absorbs light emitted from a semiconductor element, particularly a light emitting element, but also has a function of efficiently extracting light to the outside by reflection, scattering, diffusion, and the like. In other words, the provision of this coating member on the bottom and side portions of the outside of the wall portion of the package molded body that does not include the coating member has a function of increasing the reflection of light emitted from the semiconductor element. For example, the reflectance of the coating member is suitably 85% or more, that is, about 85 to 100%.

The coating member is not particularly limited as long as it is translucent and has a heat-resistant resin as a base material. For example, the coating member is a thermosetting resin, specifically, an epoxy resin or an acrylate resin. , Urethane resin, polyimide resin, acrylic resin, polynorbornene resin, silicone resin, modified silicone resin and the like may be used as the substrate.
The coating member may contain, in the base material, one or more of inorganic members and / or fillers shown as the following component (F), and the following other components (a): The additive etc. which are shown as ~ (h) may be contained. Of these, titanium oxide, zinc oxide, alumina, silica, barium titanate, calcium phosphate, calcium carbonate, precipitated silica, talc, magnesium carbonate, boron nitride and the like are suitable. In addition, it is appropriate that the inorganic member and / or filler is contained in an amount of about 5 to 90% with respect to the total weight of the coating member, and preferably about 20 to 50%. As the additive, one or more of dyes, pigments, antioxidants, heat stabilizers and the like are suitable. These additives and the like are suitably contained in an amount of about 0.1 to 10% with respect to the total weight of the coating member.

In addition, the coating member, from the point of light resistance and heat resistance,
(A) an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(B) a silicon compound containing at least two SiH groups in one molecule;
(C) a hydrosilylation catalyst,
(D) a silane coupling agent and / or an epoxy group-containing compound,
(E) You may form with the curable composition containing a silanol condensation catalyst and an essential component. The curable composition preferably further includes (F) an inorganic member.

Ingredient (A)
The organic compound of component (A) is not particularly limited as long as it contains at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule, and C, H, N, It preferably contains only O, S and halogen. Note that organic compounds containing siloxane units (Si—O—Si) such as polysiloxane-organic block copolymers and polysiloxane-organic graft copolymers have problems of gas permeability and repellency.

The organic compound of component (A) can be classified into an organic polymer compound and an organic monomer compound.
Examples of organic polymer compounds include polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based, polyacrylate ester-based, polyamide-based, phenol-formaldehyde-based (phenolic resin). Type) and polyimide type compounds.

Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as straight-chain and alicyclics: heterocyclic compounds, and these A mixture etc. are mentioned.
In the organic compound of component (A), the type of carbon-carbon double bond having reactivity with the SiH group is not particularly limited. For example, the following general formula (II)

（式中、Ｒ²は水素原子又はメチル基を表す。）
で示される基が反応性の点から好適である。なかでも、原料の入手の容易さから、下記式(IIａ)

(In the formula, R ² represents a hydrogen atom or a methyl group.)
Is preferable from the viewpoint of reactivity. Among these, the following formula (IIa)

で示される基が特に好ましい。
さらに、ＳｉＨ基と反応性を有する炭素−炭素二重結合として、下記一般式（III）

Is particularly preferred.
Further, as a carbon-carbon double bond having reactivity with the SiH group, the following general formula (III)

（式中、Ｒ³は水素原子又はメチル基を表す。）
で表される部分構造を環内に有する脂環式の基が、コーティング部材の耐熱性が高いという点から好適である。特に、原料の入手の容易さから、下記式(IIIａ)で表される部分構造を環内に有する脂環式の基が好適である。

(In the formula, R ³ represents a hydrogen atom or a methyl group.)
An alicyclic group having a partial structure represented by the formula is preferable from the viewpoint that the heat resistance of the coating member is high. In particular, an alicyclic group having a partial structure represented by the following formula (IIIa) in the ring is preferable because of easy availability of raw materials.

なお、ＳｉＨ基と反応性を有する炭素−炭素二重結合の位置は特に限定されず、分子内のどこに存在してもよい。つまり、この二重結合は、成分（Ａ）の有機化合物の骨格部分に直接結合していてもよく、２価以上の置換基を介して共有結合していてもよい。

In addition, the position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule. That is, this double bond may be directly bonded to the skeleton portion of the organic compound of component (A), or may be covalently bonded via a divalent or higher substituent.

  The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, and preferably includes only C, H, N, O, S and halogen as constituent elements. Examples of these substituents include

等が挙げられる。また、これらの２価以上の置換基の２つ以上が共有結合によりつながって１つの２価以上の置換基を構成していてもよい。
骨格部分に共有結合する基（以下、「共有結合基」と記することがある）の例としては、ビニル基、アリル基、メタリル基、アクリル基、メタクリル基、２−ヒドロキシ−３−（アリルオキシ）プロピル基、２−アリルフェニル基、３−アリルフェニル基、４−アリルフェニル基、２−（アリルオキシ）フェニル基、３−（アリルオキシ）フェニル基、４−（アリルオキシ）フェニル基、２−（アリルオキシ）エチル基、２、２−ビス（アリルオキシメチル）ブチル基、３−アリルオキシ−２、２−ビス（アリルオキシメチル）プロピル基、

Etc. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.
Examples of the group covalently bonded to the skeleton (hereinafter sometimes referred to as “covalent bond group”) include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy ) Propyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ) Ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group,

等が挙げられる。
成分（Ａ）の有機化合物の具体的な例としては、ジアリルフタレート、トリアリルトリメリテート、ジエチレングリコールビスアリルカーボネート、トリメチロールプロパンジアリルエーテル、ペンタエリスリトールトリアリルエーテル、１，１，２，２−テトラアリロキシエタン、ジアリリデンペンタエリスリット、トリアリルシアヌレート、トリアリルイソシアヌレート、１，２，４−トリビニルシクロヘキサン、ジビニルベンゼン類（純度５０〜１００％のもの、好ましくは純度８０〜１００％のもの）、ジビニルビフェニル、１，３−ジイソプロペニルベンゼン、１，４−ジイソプロペニルベンゼン、およびそれらのオリゴマー、１，２−ポリブタジエン（１、２比率１０〜１００％のもの、好ましくは１、２比率５０〜１００％のもの）、ノボラックフェノールのアリルエーテル、アリル化ポリフェニレンオキサイド、

Etc.
Specific examples of the organic compound of component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetra Allyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably a purity of 80 to 100% ), Divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1) 2 ratio 50-100% Of), allyl ether of novolak phenol, allylated polyphenylene oxide,

等、さらに、従来公知のエポキシ樹脂のグルシジル基の一部又は全部をアリル基に置き換えたもの等が挙げられる。

Furthermore, those in which a part or all of the glycidyl group of a conventionally known epoxy resin is replaced with an allyl group are exemplified.

  The organic compound of component (A) may be a low molecular weight compound that is difficult to express by dividing into a skeleton portion and an alkenyl group as described above. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

From the viewpoint that the heat resistance can be further improved, the organic compound of component (A) contains 0.001 mol or more of carbon-carbon double bond having reactivity with SiH group per 1 g of organic compound of component (A). Those containing 0.005 mol or more per 1 g are more preferable, and those containing 0.008 mol or more are more preferable.
The number of carbon-carbon double bonds having reactivity with the SiH group of the organic compound of component (A) should be at least 2 on average per molecule, but 2 if the mechanical strength is to be improved. It is preferable that the number exceeds 3, and more preferably 3 or more. When the number of carbon-carbon double bonds that are reactive with the SiH group of component (A) is 1 or less per molecule, it becomes a cross-linked structure only by the graft structure even if it reacts with component (B). Hateful.

The organic compound of component (A) preferably contains one or more vinyl groups in one molecule from the viewpoint of good reactivity, and contains two or more vinyl groups in one molecule. More preferably.
Further, from the viewpoint that the storage stability tends to be good, it is preferable that 6 or less vinyl groups are contained in one molecule, and it is more preferable that 4 or less vinyl groups are contained in one molecule.

Furthermore, those having a molecular weight of less than 900 are preferred, and those having a molecular weight of less than 700 are more preferred from the viewpoints of high mechanical heat resistance and less stringiness of the raw material liquid and good moldability, handleability, and coatability. Preferably less than 500 are more preferred.
In order to obtain uniform mixing with other components and good workability, the organic compound of component (A) preferably has a viscosity of less than 1000 poise at 23 ° C., more preferably less than 300 poise, more preferably 30 poise. Even less is more preferred. The viscosity can be measured with an E-type viscometer.

  Further, from the viewpoint of suppression of coloring, particularly yellowing, those having a low content of a compound having a phenolic hydroxyl group and / or a phenolic hydroxyl group derivative are preferable, and a compound having a phenolic hydroxyl group and / or a phenolic hydroxyl group derivative The thing which does not contain is preferable. Here, the phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon exemplified by a benzene ring, naphthalene ring, anthracene ring, etc., and the phenolic hydroxyl group derivative means a hydrogen atom of the above-mentioned phenolic hydroxyl group. Represents a group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, an acyl group such as an acetoxyl group, or the like.

Furthermore, the organic compound of component (A) is vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate, 2,2-bis (4-hydroxycyclohexyl) from the viewpoint that the resulting coating member is less colored and has high light resistance. ) Diallyl ether of propane and 1,2,4-trivinylcyclohexane are preferred, and among them, triallyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinyl More preferred is cyclohexane.
From the viewpoint of reducing the viscosity of the curable composition, vinylcyclohexene, divinylbenzene, 1,2,4-trivinylcyclohexane, and triallyl isocyanurate are particularly preferable.
The organic compound of component (A) may have other reactive groups. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When these functional groups are included, the adhesive property of the resulting curable composition tends to be high, and the strength of the resulting coating member tends to be high. An epoxy group is preferable from the viewpoint that the adhesiveness can be higher. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the resulting coating member tends to be high.
In particular, the organic compound of component (A) has the following general formula (I) from the viewpoint of high heat resistance and light resistance.

（式中、Ｒ¹は炭素数１〜５０の一価の有機基を表し、それぞれのＲ¹は異なっていても同一であってもよい。）
で表されるトリアリルイソシアヌレート及びその誘導体であるか、これを含むものであることが特に好ましい。

(In the formula, R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same.)
It is particularly preferable that it is a triallyl isocyanurate represented by the following formula or a derivative thereof.

As R < ¹ > of general formula (I), it is preferable that it is a C1-C20 monovalent organic group from a viewpoint that the heat resistance of the coating member obtained may become higher, and C1-C10 It is more preferable that it is a monovalent organic group, and it is further more preferable that it is a C1-C4 monovalent organic group.
In addition, from the viewpoint that chemical thermal stability can be improved, it is a monovalent organic group having 1 to 50 carbon atoms containing 2 or less oxygen atoms and containing only C, H and O as constituent elements. It is preferable that it is a monovalent hydrocarbon group having 1 to 50 carbon atoms.

Examples of these preferable R ¹ are methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

等が挙げられる。
さらに、一般式（Ｉ）のＲ¹として、得られるコーティング部材の各種材料との接着性が良好になり得るという観点からは、３つのＲ¹のうち少なくとも１つがエポキシ基を１つ以上含む炭素数１〜５０の一価の有機基であることが好ましく、

Etc.
Furthermore, as R ¹ of the general formula (I), at least one of the three R ^{1 s} contains one or more epoxy groups from the viewpoint that the adhesion of the obtained coating member to various materials can be improved. A monovalent organic group of 1 to 50 is preferable,

で表されるエポキシ基を１個以上含む炭素数１〜５０の一価の有機基であることがより好ましい。これらの好ましいＲ¹の例としては、グリシジル基、

It is more preferable that it is a C1-C50 monovalent organic group containing 1 or more of epoxy groups represented by these. Examples of these preferable R ¹ include a glycidyl group,

等が挙げられる。
また、一般式（Ｉ）のＲ¹として、反応性が良好になるという観点からは、３つのＲ¹のうち少なくとも１つが

Etc.
In addition, as R ¹ in the general formula (I), at least one of the three R ¹ is from the viewpoint of improving the reactivity.

で表される基を１個以上含む炭素数１〜５０の一価の有機基であることが好ましく、下記一般式（ＩＶ）

It is preferable that it is a C1-C50 monovalent organic group containing 1 or more groups represented by general formula (IV) below.

（式中、Ｒ⁴は水素原子又はメチル基を表す。）
で表される基を１個以上含む炭素数１〜５０の一価の有機基であることがより好ましく、３つのＲ¹のうち少なくとも２つが下記一般式（Ｖ）

(In the formula, R ⁴ represents a hydrogen atom or a methyl group.)
More preferably a group represented by the one or more containing monovalent organic group having 1 to 50 carbon atoms, at least two of the three R ¹ following general formula (V)

（式中、Ｒ⁵は結合手又は炭素数１〜４８の二価の有機基であり、Ｒ⁶は水素原子又はメチル基を表す。）
で表される有機化合物（複数のＲ⁵及びＲ⁶はそれぞれ異なっていても同一であってもよい。）がさらに好ましい。

(In the formula, R ⁵ represents a bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group.)
(The plurality of R ⁵ and R ⁶ may be the same or different from each other).

R ^{5 in the} general formula (V) is preferably a bond or a divalent organic group having 1 to 20 carbon atoms from the viewpoint that the resulting coating member can have higher heat resistance. A divalent organic group having 1 to 10 carbon atoms is more preferable, and a bond or a divalent organic group having 1 to 4 carbon atoms is more preferable. Examples of these preferred R ⁵ include

等が挙げられる。
一般式（Ｖ）のＲ⁵は、得られるコーティング部材の化学的な熱安定性が良好になり得るという観点からは、結合手又は２つ以下の酸素原子を含み、かつ構成元素としてＣ、Ｈ及びＯのみを含む炭素数１〜４８の二価の有機基であることが好ましく、結合手又は炭素数１〜４８の二価の炭化水素基であることがより好ましい。これらの好ましいＲ⁵の例としては、

Etc.
From the viewpoint that the chemical thermal stability of the resulting coating member can be improved, R ^{5 in the} general formula (V) contains a bond or two or less oxygen atoms, and C, H as constituent elements And a divalent organic group having 1 to 48 carbon atoms containing only O and more preferably a bond or a divalent hydrocarbon group having 1 to 48 carbon atoms. Examples of these preferred R ⁵ include

等が挙げられる。
一般式（Ｖ）のＲ⁶は、水素原子又はメチル基であるが、反応性が良好であるという観点からは、水素原子が好ましい。

Etc.
R ^{6 in the} general formula (V) is a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of good reactivity.

In addition, in the organic compound represented by general formula (I), it is preferable that the molecule | numerator contains two or more carbon-carbon double bonds which have reactivity with SiH group, and heat resistance is more From the viewpoint that it can be improved, those containing 3 or more per molecule are more preferred.
Preferred specific examples of the organic compound represented by the general formula (I) include triallyl isocyanurate,

等が挙げられる。
硬化性組成物の粘度を低減する観点からは、トリアリルイソシアヌレートが好ましい。
コーティング部材の接着性向上のためには、成分（Ａ）としてはジアリルモノグリシジルイソシアヌレートが好ましい。

Etc.
From the viewpoint of reducing the viscosity of the curable composition, triallyl isocyanurate is preferable.
In order to improve the adhesion of the coating member, the component (A) is preferably diallyl monoglycidyl isocyanurate.

In order to achieve both improved adhesion and light resistance of the coating member, the component (A) is preferably a mixture of triallyl isocyanurate and diallyl monoglycidyl isocyanurate. Since this mixture has an isocyanuric ring skeleton, it is also effective from the viewpoint of heat resistance. The mixing ratio can be selected arbitrarily, for the purpose achieved triallyl isocyanurate / diallyl monoglycidyl isocyanurate = 9 / 1-1 / 9 (molar ratio), more preferably 8 / 2-2 / 8 is more preferable, and 7/3 to 3/7 is particularly preferable.
In addition, a component (A) can be used individually or in mixture of 2 or more types.

Ingredient (B)
The silicon compound of component (B) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule, and examples thereof include compounds described in International Publication WO96 / 15194. It is done.
Among these, from the viewpoint of availability, a chain and / or cyclic organopolysiloxane having at least two SiH groups in one molecule is preferable, and from the viewpoint of good compatibility with the component (A), Formula (VI)

（式中、Ｒ⁷は炭素数１〜６の有機基を表し、ｎは３〜１０の数を表す。）
で表される、１分子中に少なくとも２個のＳｉＨ基を有する環状オルガノポリシロキサンがさらに好ましい。

(In the formula, R ⁷ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10).
A cyclic organopolysiloxane having at least two SiH groups in one molecule represented by the formula is more preferred.

The substituent R ⁷ in the compound represented by the general formula (VI) is preferably composed of C, H and O, more preferably a hydrocarbon group, and further preferably a methyl group.
As the compound represented by the general formula (VI), 1,3,5,7-tetramethylcyclotetrasiloxane is preferable from the viewpoint of availability.
The molecular weight of the silicon compound of component (B) is not particularly limited, and any compound can be suitably used. From the standpoint that the fluidity of the coating member is more easily expressed, those having a low molecular weight are preferred. For example, the molecular weight is 50 or more, 100,000 or less, more preferably 1,000 or less, and still more preferably 700 or less.

From the viewpoint that it has good compatibility with the organic compound of component (A) and the volatility of the silicon compound of component (B), the problem of outgas from the resulting curable composition is less likely to occur. The silicon compound of component (B) comprises an organic compound (α) containing at least one carbon-carbon double bond reactive with SiH group in one molecule and at least two SiH groups in one molecule. The chain and / or cyclic polyorganosiloxane (β) is preferably a compound that can be obtained by subjecting it to a hydrosilylation reaction.
(Component α)
Component α, which is an organic compound containing one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule, is an organic compound (component α1) containing two or more double bonds in one molecule. And an organic compound (component α2) containing one double bond in one molecule.

As the component α1, the same component (A) as the organic compound containing at least two carbon-carbon double bonds reactive with the SiH group in one molecule can be used. When the component α1 is used, the resulting coating member has a high crosslink density and tends to be a coating member having high mechanical strength.
The component α2 is not particularly limited as long as it is an organic compound containing one carbon-carbon double bond having reactivity with the SiH group in one molecule, but the component (B) is compatible with the component (A). In that it does not contain siloxane units (Si—O—Si) like polysiloxane-organic block copolymers, polysiloxane-organic graft copolymers, and C, H, N, O, S and It is preferable that it contains only halogen. ) By using the component α2, the resulting coating member tends to have low elasticity.

The bonding position of the carbon-carbon double bond having reactivity with the SiH group in the component α2 is not particularly limited, and may be present anywhere in the molecule.
The compound of component α2 can be classified into a polymer compound and a monomer compound.
Examples of the polymer compound include polysiloxane, polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde (Phenolic resin type) and polyimide type compounds are mentioned.

Examples of monomeric compounds include, for example, aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic compounds, silicon And compounds of these systems and mixtures thereof.
The carbon-carbon double bond having reactivity with the SiH group of component α2 is not particularly limited, and the group represented by the general formula (II) described above is preferable from the viewpoint of reactivity. Moreover, the group represented by the formula (IIa) described above is particularly preferable from the viewpoint of easy availability of raw materials.

Furthermore, from the viewpoint of high heat resistance of the coating member, an alicyclic group having the partial structure represented by the general formula (III) described above in the ring is preferable. From the viewpoint of easy availability of the raw material, an alicyclic group having a partial structure represented by the above formula (IIIa) in the ring is preferable.
The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the component α2, or may be covalently bonded via a divalent or higher substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms. However, in terms of easy compatibility of the component (B) with the component (A), C, Those containing only H, N, O, S and halogen are preferred. Examples of these substituents are the same as those exemplified in the above “Chemical Formula 5”. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

Examples of the group covalently bonded to the skeleton portion include the same covalent bond groups as exemplified in the component (A).
Specific examples of the component α2 include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-undecene, Idemitsu Petrochemical Co., Ltd. Chains such as linearene, 4,4-dimethyl-1-pentene, 2-methyl-1-hexene, 2,3,3-trimethyl-1-butene, 2,4,4-trimethyl-1-pentene, etc. Aliphatic hydrocarbon compounds, cyclohexene, methylcyclohexene, methylenecyclohexane, norbornylene, ethylidenecyclohexane, vinylcyclohexane, camphene, carene, α pinene, β pinene, etc., cyclic aliphatic hydrocarbon compounds, styrene, α methyl Styrene, indene, phenylacetylene, 4-ethynyltoluene, allylbenzene, 4-phenyl Aromatic hydrocarbon compounds such as 1-butene, allyl ethers such as alkyl allyl ether and allyl phenyl ether, glycerin monoallyl ether, ethylene glycol monoallyl ether, 4-vinyl-1,3-dioxolane-2- Aliphatic compounds such as ON, aromatic compounds such as 1,2-dimethoxy-4-allylbenzene and o-allylphenol, substituted isocyanurates such as monoallyl dibenzyl isocyanurate and monoallyl diglycidyl isocyanurate And silicon compounds such as vinyltrimethylsilane, vinyltrimethoxysilane, and vinyltriphenylsilane. Furthermore, polyether resins such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide, hydrocarbon resins such as one-end allylated polyisobutylene, one-end allylated polybutyl acrylate, one-end allylated polymethyl methacrylate Examples thereof include acrylic resins such as polymers or polymers having a vinyl group at one end, such as acrylic resins.

The structure of the component α2 may be linear or branched, and the molecular weight is not particularly limited, and various structures can be used. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and 1.5 or less in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably.
In the case where a glass transition temperature is present in the component α2, there are no particular limitations and various materials can be used, but the glass point transition temperature is preferably 100 ° C. or less from the viewpoint that the resulting coating member tends to be tough. 50 ° C. or lower is more preferable, and 0 ° C. or lower is further preferable. Examples of the component α2 include polybutyl acrylate.

On the other hand, the glass transition temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, from the viewpoint that the resulting coating member has high heat resistance. Most preferably, it is not lower than ° C. The glass transition temperature can be determined as a temperature at which tan δ exhibits a maximum in the dynamic viscoelasticity measurement.
The component α2 is preferably a hydrocarbon compound from the viewpoint that the resulting coating member has high heat resistance. In this case, the lower limit of the preferred carbon number is 7, and the upper limit is 10.
Component α2 may have other reactive groups. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When these functional groups are included, the adhesive property of the resulting curable composition tends to be high, and the strength of the resulting coating member tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the resulting coating member tends to be high. Specific examples include monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyloxyethyl methacrylate, allyloxyethyl acrylate, and vinyltrimethoxysilane.
A single component α2 may be used, or a plurality of components α2 may be used in combination.

(Component β)
The type of the component β is not particularly limited as long as it includes a linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule. For example,

等が挙げられる。
ここで、成分αとの相溶性が良くなりやすいという観点からは、上述した一般式（VI）の化合物が好ましい。
なお、成分βは、単独又は２種以上のものを混合して用いることができる。

Etc.
Here, from the viewpoint that compatibility with the component α is likely to be improved, the compound of the general formula (VI) described above is preferable.
In addition, component (beta) can be used individually or in mixture of 2 or more types.

(Reaction between component α and component β)
When the component α and the component β are subjected to a hydrosilylation reaction, the mixing ratio thereof is not particularly limited, but the strength of the coating member due to the hydrosilylation of the obtained component (B) and the component (A) is considered. In general, since it is preferable that the component (B) has more SiH groups, the total number (X) of carbon-carbon double bonds having reactivity with SiH groups in the component α to be mixed and the SiH in the component β to be mixed The ratio to the total number of groups (Y) is preferably set so that Y / X ≧ 2, and more preferably Y / X ≧ 3.

Moreover, it is preferable that it is 5> = Y / X from the point that compatibility with the component (A) of a component (B) becomes easy, and it is more preferable that it is 10> = Y / X.
When the component α and the component β are subjected to a hydrosilylation reaction, an appropriate catalyst may be used.
As the catalyst, for example, platinum alone; a support in which solid platinum is supported on a support such as alumina, silica, carbon black; chloroplatinic acid; a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc .; platinum-olefin complex _{(e.g., Pt (CH 2 = CH 2} ) 2 (PPh 3) 2, Pt (CH 2 = CH 2) 2 Cl 2); platinum - vinylsiloxane complex _{(e.g., Pt (ViMe 2 SiOSiMe 2 Vi} ) n, Pt [(MeViSiO) ₄ ] _m ); platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ); platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt _{[P (OBu) 3] 4} ); dicarbonyl dichloroplatinum; Karushuteto (Karstedt) catalyst; U.S. Pat. No. 3,159,601 Ashby (Ashby) and In US Pat. No. 1,596,946; a platinum-hydrocarbon complex described in US Pat. No. 1,596,62; a platinum alcoholate catalyst described in US Pat. No. 3,220,972 to Lamoreaux; in US Pat. No. 3,516,946 to Modic. And platinum chloride-olefin composites described in 1). In the above formulae, Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent integers. In addition, a catalyst other than a platinum compound such as RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl ₄ is used. Also good. These catalysts may be used alone or in combination of two or more. Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity.

The addition amount of the catalyst is not particularly limited, but is preferably 10 ⁻⁸ mol or more with respect to 1 mol of SiH group of component β in order to have sufficient curability and keep the cost of the curable composition relatively low. Is 10 ⁻⁶ mol or more, 10 ⁻¹ mol or less, more preferably 10 ⁻² mol or less.
Further, a cocatalyst may be used in combination with the above catalyst. Examples of promoters include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, acetylene alcohol compounds such as 2-hydroxy-2-methyl-1-butyne, and simple sulfur. Examples thereof include sulfur compounds and amine compounds such as triethylamine.

The amount of the cocatalyst added is not particularly limited, but is 10 ⁻² mol or more, more preferably 10 ⁻¹ mol or more, and 10 ² mol or less, more preferably 10 mol or less, per mol of the hydrosilylation catalyst.
Various methods can be used as a method of mixing the component α, the component β, and the catalyst, and a method of mixing the component α with the catalyst into the component β is preferable. In the case of a method in which a catalyst is mixed with a mixture of component α and component β, it is difficult to control the reaction. In the case of mixing the component α with the component β mixed with the catalyst, the component β may be altered in the presence of the catalyst because the component β has reactivity with the mixed water.

The reaction temperature can be variously set, but is 30 ° C or higher, more preferably 50 ° C or higher, 200 ° C or lower, more preferably 150 ° C or lower. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, or the temperature may be changed in multiple steps or continuously as required.
The reaction time and the pressure during the reaction can be variously set as necessary.

A solvent may be used in the hydrosilylation reaction.
The solvent is not particularly limited as long as it does not inhibit the hydrosilylation reaction. For example, hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl Ether solvents such as ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The amount of solvent used can be adjusted as appropriate. You may use a solvent as a 2 or more types of mixed solvent.

In the hydroxylation reaction, various additives may be used for the purpose of controlling the reactivity.
When component (B) is obtained by reacting component α and component β, the resulting component (B) may be used as a mixture without isolation, or unreacted components and / or solvents may be used. It may be removed. When removing the volatile matter, the resulting component (B) does not have a volatile matter, and therefore, when cured together with the component (A), the problem of voids and cracks due to the volatilization of the volatile matter hardly occurs. Examples of the method for removing volatile components include vacuum devolatilization; treatment with activated carbon, aluminum silicate, silica gel, and the like. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature (for example, 100 ° C. or lower, preferably 60 ° C. or lower). When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

  Examples of component (B) which is a reaction product of component α and component β include a reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, bisphenol A diallyl ether and 1,3,3. Reaction product of 5,7-tetramethylcyclotetrasiloxane, reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, dicyclopentadiene and 1,3,5,7-tetramethylcyclo Reaction product of tetrasiloxane, reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Reaction product of allyl glycidyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane Reaction product of α-methylstyrene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Etc.

Since the resulting curable composition has low viscosity, a reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, α-methylstyrene and 1,3,5,7-tetramethylcyclo A reaction product with tetrasiloxane is preferred.
From the viewpoint of heat resistance and light resistance of the coating member, a reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetra A reaction product with siloxane is preferred.

From the viewpoint of heat resistance, light resistance and adhesiveness, a reaction product of diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, monoallyl diglycidyl isocyanurate and 1,3,5 , 7-tetramethylcyclotetrasiloxane and its reaction product are preferred.
The silicon compound of component (B) can be used alone or in combination of two or more.
Ingredient (C)
The hydrosilylation catalyst of component (C) is not particularly limited as long as it has catalytic activity for hydrosilylation reaction, and examples thereof include the same catalysts as those that can be used for the hydrosilylation reaction of component α and component β. . Examples of preferred catalysts, addition amounts, and promoters are the same as described above.

In addition, a curing retarder is used in combination with the hydrosilylation catalyst of component (C) for the purpose of improving the storage stability of the curable composition or adjusting the reactivity of the hydrosilylation reaction in the production process. May be.
Examples of the curing retarder include one or more compounds such as a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organic phosphorus compound include triorganophosphine, diorganophosphine, organophosphine, and triorganophosphite. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Of these curing retarders, benzothiazole, thiazole, dimethyl maleate, and 3-hydroxy-3-methyl-1-butyne are preferable from the viewpoint of good delay activity and good raw material availability.
Although the addition amount of the curing retarder can be variously set, it is 10 ⁻¹ mol or more, more preferably 1 mol or more, and 10 ³ mol or less, more preferably 50 mol or less with respect to ¹ mol of the hydrosilylation catalyst to be used.

Ingredient (D)
Examples of the silane coupling agent of component (D) include compounds each having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule.
For example, the functional group reactive with the organic group includes at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handleability. From the viewpoint of curability and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable.

As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.
Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxy Methacrylic or acrylic groups such as propyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes or the like for like.

  Examples of the epoxy group-containing compound of component (D) include various epoxy resins. For example, novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4 -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexylene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3- Dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl Examples include those obtained by curing epoxy resins such as glycidyl isocyanurate with aliphatic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and hydrogenated methylnadic anhydride. It is done. These may be used alone or in combination.

  Although the addition amount of the silane coupling agent and / or epoxy group-containing compound of component (D) can be variously set, 0.1 part by weight or more with respect to 100 parts by weight of [component (A) + component (B)] Preferably it is 0.5 weight part or more, 50 weight part or less, More preferably, it is 25 weight part or less. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the coating member may be adversely affected.

In addition, a silanol source compound may be used in combination with the silane coupling agent and / or epoxy group-containing compound of component (D) in order to further enhance the effect of improving adhesiveness.
Examples of the silanol source include silanol compounds such as triphenylsilanol and diphenyldihydroxysilane, and alkoxysilanes such as diphenyldimethoxysilane, tetramethoxysilane, and methyltrimethoxysilane. A silanol source compound may be used independently and may be used together 2 or more types.

  The amount used in the case of using a silanol source compound can be variously set, but is 0.1 parts by weight or more, more preferably 1 part by weight or more, with respect to 100 parts by weight of the silane coupling agent and / or the epoxy group-containing compound, 50 parts by weight or less, more preferably 30 parts by weight or less. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the coating member may be adversely affected.

Furthermore, the silane coupling agent and / or epoxy group-containing compound of component (D) may be used in combination with carboxylic acids and / or acid anhydrides in order to enhance these effects.
Carboxylic acids and acid anhydrides are not particularly limited.

等の化合物、２−エチルヘキサン酸、シクロヘキサンカルボン酸、シクロヘキサンジカルボン酸、メチルシクロヘキサンジカルボン酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、メチルハイミック酸、ノルボルネンジカルボン酸、水素化メチルナジック酸、マレイン酸、アセチレンジカルボン酸、乳酸、リンゴ酸、クエン酸、酒石酸、安息香酸、ヒドロキシ安息香酸、桂皮酸、フタル酸、トリメリット酸、ピロメリット酸、ナフタレンカルボン酸、ナフタレンジカルボン酸、およびそれらの単独あるいは複合酸無水物等が挙げられる。

Such as 2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylheimic acid, norbornene dicarboxylic acid, hydrogenated methylnadic acid, maleic acid, Acetylenedicarboxylic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenecarboxylic acid, naphthalenedicarboxylic acid, and single or complex acids thereof An anhydride etc. are mentioned.

  Among these carboxylic acids and / or acid anhydrides, in terms of having hydrosilylation reactivity, there is little possibility of seeping out from the coating member, and it is difficult to impair the physical properties of the resulting coating member. Those containing reactive carbon-carbon double bonds are preferred. Examples of such carboxylic acids and / or acid anhydrides include:

テトラヒドロフタル酸、メチルテトラヒドロフタル酸およびそれらの単独あるいは複合酸無水物等が挙げられる。これらのカルボン酸類及び／又は酸無水物類は単独で使用してもよく、２種以上併用してもよい。

Examples thereof include tetrahydrophthalic acid, methyltetrahydrophthalic acid, and single or complex acid anhydrides thereof. These carboxylic acids and / or acid anhydrides may be used alone or in combination of two or more.

  The amount used in the case of using carboxylic acids and / or acid anhydrides can be variously set, but is 0.1 parts by weight or more, more preferably 1 with respect to 100 parts by weight of the silane coupling agent and / or epoxy group-containing compound. It is not less than 50 parts by weight, more preferably not more than 10 parts by weight. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the coating member may be adversely affected.

In addition, the silane coupling agent and / or the epoxy group-containing compound of this component (D) are combined with a silanol condensation catalyst which is the following component (E), thereby providing the coating member with adhesiveness to the package resin. It works effectively.
Ingredient (E)
It does not specifically limit as a silanol condensation catalyst of a component (E), An organoaluminum compound, a boric acid ester, a titanium type compound, etc. are mentioned. Of these, boric acid esters are preferred from the viewpoint of low colorability during curing and at high temperatures. In addition, a titanium-based compound can also be used from the viewpoint that adhesion can be improved and / or stabilized.

  Examples of organoaluminum compounds include aluminum alcoholate compounds such as trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum and trinormalpropoxyaluminum; aluminum organic acid salts such as naphthenic acid, stearic acid, octylic acid and benzoic acid; aluminum ethylacetate Examples thereof include aluminum chelate compounds such as acetoacetate diisopropylate, aluminum ethyl acetoacetoacetate diisobutyrate, aluminum tris (ethyl acetoacetate), aluminum bisethyl acetoacetate monoacetylacetonate, and aluminum tris (acetylacetonate). Of these, aluminum chelate and aluminum alcoholate are preferable from the viewpoints of reactivity, adhesion to the substrate and adhesion, and aluminum tris (ethyl acetoacetate) is preferable from the viewpoint of compatibility with the hydrosilylation curing reaction.

As borate ester, the following general formula (VII) and general formula (VIII)
B (OR ⁸ ) ₃ (VII)
B (OCOR ⁸ ) ₃ (VIII)
(In the formula, R ⁸ represents an organic group having 1 to 48 carbon atoms.)
What is shown by can be used suitably.

  Specifically, tri-2-ethylhexyl borate, normal trioctadecyl borate, tri-octal borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, tri-butyl borate, tri-sec-butyl borate, tri-borate triborate -Tert-butyl, triisopropyl borate, trinormalpropyl borate, triallyl borate, triethyl borate, trimethyl borate, boron methoxyethoxide.

From the viewpoint of availability, trimethyl borate, triethyl borate and trinormal butyl borate are preferable, and trimethyl borate is more preferable.
Moreover, from the point which can suppress the volatility at the time of hardening, normal trioctadecyl borate, tri-normal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, tri-normal butyl borate, tri-sec-butyl borate, boric acid Tri-tert-butyl, triisopropyl borate, trinormal propyl borate, triallyl borate, and boron methoxyethoxide are preferable, and normal trioctadecyl borate, tri-tert-butyl borate, triphenyl borate, and trinormal butyl borate are more preferable.

Furthermore, from the viewpoint of suppression of volatility and workability, trinormal butyl borate, triisopropyl borate and trinormal propyl borate are preferable, and trinormal butyl borate is more preferable.
In addition, triethyl borate is preferable and trimethyl borate is more preferable from the viewpoint of low colorability at high temperatures.

Examples of titanium compounds include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium: titanium chelates such as titanium tetraacetylacetonate: general titanate coupling agents having residues such as oxyacetic acid and ethylene glycol Can be illustrated.
The amount used in the case of using a silanol condensation catalyst can be variously set, but it is 0.1 parts by weight or more, more preferably 1 part by weight or more with respect to 100 parts by weight of the silane coupling agent and / or epoxy group-containing compound. It is 30 parts by weight or less, more preferably 30 parts by weight or less. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the coating member may be adversely affected.
In addition, only 1 type may be used for a silanol condensation catalyst, and 2 or more types may be mixed and used for it. Mixing may be performed in advance or may be performed when the coating member is formed.

Ingredient (F)
It is preferable that the inorganic member which is a component (F) is a material which can reflect, scatter, and / or diffuse the light irradiated from the outside by disperse | distributing in a curable composition.
For example, alumina, silica (fume silica, precipitated silica, fused silica, crystalline silica, ultrafine powder amorphous silica, anhydrous silicic acid, etc.), quartz, titanium oxide, tin oxide, zinc oxide, tin monoxide, calcium oxide, magnesium oxide Oxides such as beryllium oxide, metal nitrides such as boron nitride, silicon nitride and aluminum nitride, metal carbides such as SiC, metal carbonates such as calcium carbonate, potassium carbonate, sodium carbonate, magnesium carbonate and barium carbonate, hydroxide Metal hydroxide such as aluminum and magnesium hydroxide, aluminum borate, barium titanate, calcium phosphate, calcium silicate, clay, gypsum, barium sulfate, mica, diatomaceous earth, white clay, inorganic balloon, talc, fluorescent substance, metal piece (silver powder And at least one selected from the group consisting of That.
Although the compounding quantity of the inorganic member in a coating member is not specifically limited, It is 0.1 to 90 weight% of the coating member whole quantity. From the viewpoint of applicability, it is 80% by weight or less, more preferably 70% by weight or less, further preferably 50% by weight or less, particularly preferably 40% by weight or less, and particularly preferably 30% by weight or less. When the blending amount is large, the coating property is lowered, and the reflectance is lowered due to poor coating. From the viewpoint of reflectivity, it is 5% by weight or more, more preferably 10% by weight or more, further preferably 30% by weight or more, particularly preferably 40% by weight or more, and more particularly preferably 50% by weight or more. In order to achieve both coatability and reflectivity, the content is 10% by weight to 80% by weight, more preferably 20% by weight to 70% by weight, and particularly preferably 30% by weight to 60% by weight.
The inorganic member can take various shapes such as a spherical shape, a needle shape, and a flake shape in consideration of dispersibility and reflectivity.

  In particular, titanium oxide is preferable as an inorganic member of the coating member from the viewpoint of high whiteness, hiding power, and excellent durability. From the viewpoint of durability, the crystal form is preferably a rutile type. The particle diameter is preferably 1.0 μm or less, more preferably 0.8 μm or less, and further preferably 0.4 μm or less from the viewpoint of dispersibility. Moreover, from the point of the hiding power, 0.1 μm or more is preferable, and 0.2 μm or more is more preferable. In addition, the average particle diameter of titanium oxide can be measured with an image analyzer (Luzex IIIU) based on an electron micrograph. As the titanium oxide, those produced by either the sulfuric acid method or the chlorine method can be suitably used.

Moreover, in order to improve affinity with resin, what processed the surface by hydrous oxides, such as Al and Si, can also be used suitably. Examples include Ishihara Sangyo Co., Ltd., Taipei R-820, R-680, CR-50-2, CR-97, CR-60, CR-60-2 and the like.
Alumina, silica, boron nitride, aluminum nitride, etc. are strong in weather resistance and can maintain a high reflectance.

Furthermore, it is preferable to use titanium oxide and silica in combination in terms of imparting thixotropy to the curable composition and imparting a thickening effect. Silica has an average primary particle diameter of preferably 3 to 20 nm, particularly preferably 5 to 10 nm. The average particle diameter of silica can be measured based on an electron micrograph.
Silica is preferably not surface-treated from the viewpoint of imparting thixotropy. For example, AEROSIL 300, 130, 200 manufactured by Nippon Aerosil Co., Ltd. can be suitably used. On the other hand, it is preferable that surface treatment is performed from the point of the thickening effect. For example, AEROSIL R812, R972, R974, R976, RX200, RX300 manufactured by Nippon Aerosil Co., Ltd. can be suitably used.

  Further, the fluorescent material has a shielding effect, and further converts visible light and ultraviolet light emitted from the nitride compound semiconductor into other emission wavelengths. Therefore, white light can be emitted when the light emitted from the LED chip and the light from the fluorescent material excited and emitted by the light from the LED chip are in a complementary color relationship, and the characteristics of the light emitting diode are further improved. Can do.

Various fluorescent materials are used depending on the emission wavelength emitted from the light emitting layer used in the LED chip, the desired emission wavelength emitted from the light emitting diode, and the like. Examples include yttrium, aluminum, garnet (so-called YAG) phosphors activated by cerium, perylene derivatives, copper, zinc cadmium sulfide activated by aluminum, magnesium oxide / titanium activated by manganese, etc. Things. These fluorescent materials may be used alone or in combination of two or more. In particular, yttrium-aluminum-garnet fluorescent material activated by cerium (Re ₃ Re ′ ₅ O ₁₂ : Ce, where Re is at least one selected from Y, Gd, Lu, Sc and La, Re ′ Is at least one selected from Al, In, B, and Tl.) Has a garnet structure and is strong against heat, light, and water, and can have an excitation spectrum peak around 450 nm. In addition, the emission peak is in the vicinity of 530 nm and the like, and a broad emission spectrum that extends to 700 nm can be provided. Moreover, the emission wavelength is shifted to the short wavelength side by substituting part of Al of the composition with Ga, and the emission wavelength is shifted to the long wavelength side by substituting part of Y of the composition with Gd. Can do. By changing the composition in this way, various emission wavelengths can be obtained continuously.

In addition, in order to adjust the emission wavelength to the long wavelength or short wavelength side as desired, part of yttrium can be replaced with Lu, Sc, La, or part of aluminum can be replaced with In, B, Tl. It can also be made. Furthermore, in addition to cerium, a small amount of Tb or Cr can be contained to adjust the absorption wavelength.
In particular, the amount of the fluorescent substance used is 5% by weight or more, more preferably 10% by weight or more, still more preferably 30% by weight or more, and particularly preferably 40% by weight of the total amount of the coating member in terms of good conversion. % Or more, more preferably 50% by weight or more.
Directivity can be further increased by including a diffusing agent in addition to the fluorescent substance. Examples of the diffusing agent include inorganic barium titanate, titanium oxide, aluminum oxide, silicon oxide, and organic guanamine resins.

Preparation of curable composition The curable composition comprises the above-described components (A) to (E), optionally (F), and a carbon-carbon double bond reactive with SiH groups in the composition. , And can be prepared by reacting part or all of SiH groups.

  The mixing of the components (A) to (E) and optionally (F) is not particularly limited. After the components (A) to (E) are mixed and reacted at once, the component (F) is added. You may mix, after mixing and reacting a part of component (A)-(E), a component (F) may be added and the remaining component may be mixed and it may be made to react further. Further, for example, in order to control reactivity and / or prevent deterioration during storage, a mixture of component (A), component (C) and component (E), component (B), component (D) It is preferable to mix the component (F) and then the component (F). Furthermore, after mixing arbitrary components, by reacting only a part of the functional groups in the curable composition (B-stage) by utilizing the difference in the reactivity of the control of the reaction conditions and substituents. You may take the process of shaping | molding etc. and taking the further hardening method. According to this method, viscosity adjustment at the time of molding becomes easy.

The components (A) to (E) and the component (F) are, for example, a coating member having excellent dispersibility by kneading using a three-roll, paint mill, ball mill or the like, followed by vacuum defoaming after kneading. Can be obtained. Moreover, if it is a small quantity of 10 g or less, it is also possible to stir with a planetary stirring deaerator.
Components (A) to (E) may be reacted at room temperature or may be reacted by heating. A method of heating and reacting is preferable from the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained. Although various reaction temperatures can be set, for example, a temperature of 30 to 300 ° C can be applied, 50 to 250 ° C is more preferable, and 100 to 200 ° C is more preferable. If the reaction temperature is low, the reaction time for sufficient reaction will be long, and if the reaction temperature is high, molding will tend to be difficult.
The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Various reaction times can also be set. For example, a method of precuring at 60 ° C./1 to 10 minutes and curing at 100 ° C./1 to 60 minutes can be employed. The pressure at the time of reaction can also be set variously as needed, and can be a normal pressure, a high pressure or a reduced pressure state.

Other components (a) to (h)
In addition to the components (A) to (F), the curable composition further includes (a) a thermosetting resin, (b) a thermoplastic resin, (c) a filler, (d) an anti-aging agent, (E) radical inhibitor, (f) UV absorber, (g) colorant, mold release agent, flame retardant, flame retardant aid, surfactant, antifoaming agent, emulsifier, leveling agent, anti-fogging agent, ion Trapping agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity One or more of an imparting agent, an antistatic agent, a radiation shielding agent, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a dye, a pigment, a metal deactivator, a thermal conductivity imparting agent, a physical property modifier, etc. It can add in the range which does not impair the objective and effect of invention. Further, the curable composition may be used after being dissolved in (h) a solvent. These various substances may be used alone or in combination of two or more.

 (A) The thermosetting resin is not particularly limited, and examples thereof include an epoxy resin, a cyanate ester resin, a phenol resin, a polyimide resin, a urethane resin, and a bismaleimide resin. These thermosetting resins may be used alone or in combination. Among these, an epoxy resin is preferable from the viewpoint of excellent practical properties such as adhesiveness. As an epoxy resin, the thing similar to what was illustrated with the epoxy group containing compound of the component (D) is mentioned.

The addition amount of the thermosetting resin is not particularly limited, but is 5% by weight or more, more preferably 10% by weight or more, and 50% by weight or less, more preferably 30% by weight or less of the entire curable composition. If the addition amount is small, it is difficult to obtain the intended effects such as adhesiveness, and if the addition amount is large, the addition tends to be brittle.
The thermosetting resin may be obtained by dissolving a resin raw material and / or a cured product in the component (A) and / or the component (B) and mixing them in a uniform state, or pulverizing them and mixing them in a particle state. Alternatively, it may be dispersed by dissolving in a solvent and mixing. In the point that the obtained coating member tends to become more uniform, it is preferable to melt | dissolve in a component (A) and / or a component (B), and to mix as a uniform state. Also in this case, the thermosetting resin may be directly dissolved in the component (A) and / or the component (B), or may be uniformly mixed using a solvent or the like. It is good also as a dispersed state and / or a mixed state.
When the thermosetting resin is dispersed and used, the average particle diameter can be variously set, but is preferably 10 nm or more and 10 μm or less. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle sizes, but from the viewpoint that the viscosity of the coating member is low and the applicability is likely to be good, The coefficient of variation is preferably 10% or less.

 (B) The thermoplastic resin is not particularly limited. For example, a methyl methacrylate homopolymer or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and another monomer (for example, Hitachi Chemical) Optretz, etc.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3, A tree obtained by singly or copolymerizing a polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like. A cycloolefin resin such as a resin obtained by ring-opening metathesis polymerization of a norbornene derivative, or a hydrogenated product thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene and maleimide Olefin-maleimide resins such as copolymers of TI-PAS manufactured by Tosoh Corporation, bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, and diols such as diethylene glycol Polyester resins such as polyester obtained by polycondensation of phthalic acids such as terephthalic acid and isophthalic acid and aliphatic dicarboxylic acids (for example, O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins , Polyethylene tree , Polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, natural rubber, rubber-like resins such as EPDM can be exemplified.

The thermoplastic resin may have a carbon-carbon double bond and / or SiH group having reactivity with the SiH group in the molecule. From the point that the resulting coating member is likely to be tougher, it has at least one carbon-carbon double bond and / or SiH group having reactivity with SiH groups in the molecule on average in one molecule. Is preferred.
The thermoplastic resin may have other crosslinkable groups. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the resulting coating member tends to be high, it is preferable to have one or more crosslinkable groups per molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less, and preferably 5000 or less from the viewpoint that compatibility with the component (A) or the component (B) tends to be good. Is more preferable. On the contrary, the number average molecular weight is preferably 10,000 or more, more preferably 100,000 or more from the viewpoint that the resulting coating member tends to be tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, from the viewpoint that the viscosity of the curable composition tends to be low and the coating property tends to be good. More preferably, it is as follows.

The blending amount of the thermoplastic resin is not particularly limited, but is 5% by weight or more, more preferably 10% by weight or more, and 50% by weight or less, more preferably 30% by weight or less based on the entire curable composition. . When the addition amount is small, the resulting coating member tends to be brittle, and when it is large, the heat resistance (elastic modulus at high temperature) tends to be low.
The thermoplastic resin may be dissolved in the component (A) and / or the component (B) and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed. Then, it may be in a dispersed state. From the viewpoint that the resulting coating member tends to be more uniform, it is preferable to dissolve in component (A) and / or component (B) and mix in a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in component (A) and / or component (B), or may be mixed uniformly using a solvent or the like, and then the solvent is removed and uniform dispersion is performed. It is good also as a state and / or a mixed state.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of particle diameters, which may be monodispersed or have a plurality of peak particle diameters, but the viewpoint that the viscosity of the obtained curable composition is low and the coating properties are likely to be good Therefore, it is preferable that the coefficient of variation of the particle diameter is 10% or less.

(C) As a filler, various things are mentioned. For example, it is generally used and / or proposed as a filler for conventional sealing materials such as inorganic fillers such as glass fiber, carbon fiber, carbon black, and graphite, inorganic members of component (F) described above, and epoxy resins. And fillers.
The filler and / or the inorganic member (hereinafter sometimes simply referred to as “filler or the like”) may be appropriately surface-treated. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like. Examples of the coupling agent include the same silane coupling agents as those exemplified in the component (D).

  Further, for example, hydrolyzable silane monomers or oligomers such as alkoxysilanes, acyloxysilanes, halogenated silanes; alkoxides, acyloxides, halides, etc. of metals such as titanium and aluminum are added to the curable composition to be curable. The filler may be produced in the curable composition by reacting in the composition or in a partial reactant of the curable composition.

Of the fillers as described above, silica is preferable from the viewpoint that the curing reaction is hardly inhibited and the effect of reducing the linear expansion coefficient is large.
The average particle size of the filler or the like is preferably 10 μm or less, more preferably 5 μm or less, from the viewpoint that the permeability is likely to be good.
The ratio of particles having a particle size of 50 μm or more such as a filler is preferably 1% by weight or less, and more preferably 0.1% by weight or less from the viewpoint that the permeability tends to be good.

The particle size distribution of the filler and the like can be variously set, including those used and / or proposed as fillers of conventional sealing materials such as epoxy resins. For example, particles of 24 μm or more may be 15% by weight or more and particles of 1 μm or less may be 3% by weight or more.
The average particle diameter of the filler and the proportion of particles having a particle diameter of 50 μm or more such as the filler can be measured using a laser microtrack particle size analyzer.

The specific surface area of the filler and the like can be variously set including those used and / or proposed as fillers for conventional sealing materials such as epoxy resins. For example, the viewpoint of imparting thixotropy with a small amount of addition, 50 m ² / g or more, 500 meters ² / g or less, or a large amount be added from the viewpoint of securing the fluidity, 1 m ² / g or more, 10 m ² / It can be arbitrarily set such as g or less.
The specific surface area can be measured by a BET monosorb specific surface area measuring device.

The vitrification rate of the filler or the like can be set in various ways including those used and / or proposed as fillers for conventional sealing materials such as epoxy. For example, 97% or more.
The shape of the filler or the like is preferably a spherical filler from the viewpoint that the viscosity of the curable composition tends to be low.
The addition amount of the filler and the like is not particularly limited, but from the viewpoint that the effect of reducing the linear expansion coefficient is high and the fluidity of the curable composition is good, 30% by weight or more in the total composition, more preferably It is 50% by weight or more, 80% by weight or less, more preferably 70% by weight or less.

A filler etc. can be mixed similarly to mixing of a component (F). In addition, since the storage stability of the intermediate raw material of the curable composition tends to be good, a method of mixing the component (A) and the component (C) with a filler and the component (B) Is preferred. When the component (A) is mixed with the component (B) mixed with the component (C) and / or filler, the component (B) is added in the presence and / or absence of the component (C). Since it is reactive with moisture and / or fillers in the environment, it may be altered during storage.
(D) As an anti-aging agent, the anti-aging agent generally used, for example, a citric acid, phosphoric acid, a sulfur type anti-aging agent, etc. are mentioned. Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
(E) Examples of radical inhibitors include 2,6-di-t-butyl-4-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (Methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) phenolic radical inhibitors such as methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl Examples thereof include amine radical inhibitors such as -p-phenylenediamine, phenothiazine, N, N'-diphenyl-p-phenylenediamine.
(F) As an ultraviolet absorber, for example, 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidyl) Sebacate etc. are mentioned.
(G) Colorant, mold release agent, flame retardant, flame retardant aid, surfactant, antifoaming agent, emulsifier, leveling agent, anti-fogging agent, ion trap agent, thixotropic agent, tackifier, storage Stabilizer, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, thermal stabilizer, conductivity enhancer, antistatic agent, radiation blocker, nucleating agent, Phosphorus peroxide decomposers, lubricants, dyes, pigments, metal deactivators, thermal conductivity-imparting agents, physical property modifiers, metal pieces, fluorescent materials (eg, YAG fluorescent materials), etc. are known in the art. Any of these can be used.
(H) The solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as benzene, toluene, hexane and heptane, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and diethyl ether. Suitable solvents are ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane. Of these, toluene, tetrahydrofuran, 1,3-dioxolane, and chloroform are preferable.

The amount of solvent to be used can be appropriately set, and is, for example, 0.1 mL or more and 10 mL or less with respect to 1 g of the curable composition to be used. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a viscosity reduction. If the amount used is large, the solvent remains in the resulting coating member, which is likely to cause problems such as thermal cracks. This is disadvantageous and the industrial utility value decreases.
In particular, the coating member is preferably white. Here, white means the color of the white region described in “General chromaticity classification of system color names in JIS Z8110-1995 Reference FIG. 1”.

  The film thickness of the coating member is not particularly limited. For example, the coating member may have a uniform film thickness from the bottom to the side, or may be changed so as to be thickened or thinned in stages. The film thickness is preferably a taper shape. That is, it is preferable to arrange the coating member so that it is thin in the vicinity of the upper end portion of the side portion of the package molded body and gradually becomes a thick film as it approaches the bottom portion. By providing the coating member, it is possible to reflect, scatter, and diffuse the light irradiated from the light emitting element in the lateral direction or in the oblique direction, and it is possible to increase the light extraction efficiency to the outside. Further, by providing the coating member in a tapered shape, light scattering, diffusion, and reflection can be further enhanced in a portion closer to the light emitting element. Therefore, more light can be efficiently extracted outside, and light can be emitted with higher luminance. Furthermore, since the coating member does not come into contact with the semiconductor element, light irradiated from the side surface or the upper surface of the light emitting element is not absorbed by the coating member, and the light output can be increased.

  The package molded body of the present invention preferably has a metal substrate on the bottom side. Although the number of metal substrates may be one, it is preferable to arrange at least two and three more. The metal substrate is called a so-called lead, lead frame, lead electrode or the like, and functions as a pair of conductors for supplying power to the semiconductor element or a heat sink. The metal substrate may be arranged in any manner as long as it is provided in a state where it can be electrically connected to a semiconductor element placed on the bottom of the package molded body or can be in direct contact with the semiconductor element. Good. For example, it is preferable that one end is inserted into the package molded body and exposed at the bottom of the package molded body, and the other end is provided to extend outside the package molded body. It is appropriate that the package molded body and the metal substrate are formed by integral molding.

  The metal substrate that functions as a lead electrode can be formed of a high thermal conductor made of an alloy such as copper or iron. The surface of these alloys may be plated with silver, aluminum, gold or the like. In particular, silver plating is preferable. For example, the thermal conductivity as the lead electrode is preferably in the range of 10 to 100 W / m · K, in the range of 15 to 80 W / m · K, and more preferably in the range of 15 to 50 W / m · K. With such a structure, a highly reliable semiconductor device can be obtained even when a large current is dropped for a long time. The outer lead portion of the lead electrode, that is, the outer portion of the package molded body, the back surface, that is, the surface corresponding to the back side of the semiconductor element mounting region of the package molded body is the semiconductor element mounting region of the package molded body It is appropriate to form a positive and negative connection terminal by processing it into a gull wing type, a J-bend type or the like so as to be flush with the back side of the metal substrate and optionally the back side of the metal base.

  The metal substrate that functions as a heat sink is preferably formed of the same material as the lead electrode. Furthermore, it is preferable that the back surface of the metal base is formed to be flush with the back side of the package molded body and the back surface of the lead electrode. With such a configuration, the heat generated from the light emitting element can be directly radiated to the mounting substrate, the amount of current dropped on the light emitting element can be increased, and the output can be improved.

  A semiconductor element may be placed on the metal base on the exposed surface of the bottom of the package molded body. Therefore, the exposed surface may be processed so as to have a recess at the center of the package molded body so that the semiconductor element can be easily placed. Further, in order to enhance the heat sink function, the portion on which the semiconductor element is placed may be formed in a thick film. Thereby, the light emitted from the four side surfaces of the light emitting element can be favorably reflected by the inner wall of the concave portion in the front direction and extracted. In addition, by providing the metal base in this way, the heat dissipation of the semiconductor element, particularly the light emitting element is improved, and deterioration of the package molded body, coating member, sealing member, etc. due to large current drop can be suppressed, Good optical properties can be obtained.

  Moreover, as described above, the wall portion at the bottom of the package molded body may be formed by the metal base. In that case, the metal substrate is usually exposed at the bottom of the package molded body, and the semiconductor element is placed on the exposed metal substrate. Therefore, on the metal substrate, at a position away from the outer edge of the semiconductor element, the entire periphery or part of the outer edge of the semiconductor element by pressing, punching, or the like from the metal substrate, or punch holes from the back surface side. A wall portion can be formed in a part of the periphery of the outer edge of the semiconductor element by forming or the like.

  The light emitting element, which is a semiconductor element in the present invention, is not particularly limited in its configuration, characteristics, etc. As described above, a pair of lead electrodes and optionally a metal substrate are insert-molded together with a package molded body. In this case, a light emitting element in which a pair of positive and negative electrodes is formed on the same surface side is preferable. In addition, a phosphor layer may be formed on the surface of the light-emitting element. In that case, a light-emitting element having a light-emitting layer capable of emitting a light emission wavelength capable of exciting the used fluorescent substance is preferable. Examples of such light emitting elements include those using various semiconductors such as ZnSe and GaN. Among these, a nitride semiconductor (InXAlYGa1-X-YN, 0 ≦ X, 0 ≦ Y, X + Y ≦ 1) that can emit a short wavelength and can efficiently excite a fluorescent material is preferable. Further, this nitride semiconductor may optionally contain boron or phosphorus. Note that the emission wavelength can be appropriately adjusted depending on the semiconductor material and the degree of mixed crystal thereof. The semiconductor constituting the light emitting element may have a homo structure, a hetero structure, or a double hetero structure having a MIS junction, a PIN junction, a pn junction, or the like. Moreover, it is good also as a single quantum well structure or multiple quantum well structure which formed the light emitting layer in the thin film which produces a quantum effect.

  In the case of using a nitride semiconductor, materials for forming a light emitting element include materials such as sapphire, spinel, SiC, Si, ZnO, and GaN. In order to form a nitride semiconductor with good crystallinity with high productivity, it is preferable to use a sapphire substrate. Note that a buffer layer of GaN, AlN, GaAIN, or the like may be formed on the sapphire substrate. A nitride semiconductor can be formed on the sapphire substrate by MOCVD or the like.

  In particular, as an example of a light emitting device having a pn junction using a nitride semiconductor, a first contact layer formed of n-type gallium nitride and a first clad formed of n-type aluminum gallium nitride on a buffer layer A double hetero structure in which a layer, an active layer formed of indium gallium nitride, a second cladding layer formed of p-type aluminum nitride / gallium, and a second contact layer formed of p-type gallium nitride are sequentially stacked. Can be mentioned. After laminating the metal layer on the p-type layer, the semiconductor substrate may be removed.

The light emitting device of the present invention preferably emits white light, and for that purpose, the emission wavelength is preferably about 365 to 530 nm, about 420 to 490 nm, and more preferably about 450 to 475 nm.
Examples of the protective element include a Zener diode and a capacitor.
The Zener diode has a p-type semiconductor region having a positive electrode and an n-type semiconductor region having a negative electrode, and the negative electrode and the positive electrode of the protective element are opposite to the p-side electrode and the n-side electrode of the light emitting element. They are connected in parallel. Thus, by using a Zener diode as the protective element, even if an excessive voltage is applied between the positive and negative electrodes, the positive and negative electrodes of the light emitting element are held at the Zener voltage. Can be prevented and the occurrence of element destruction and performance deterioration can be prevented.

  As the capacitor, a chip component for surface mounting can be used. The capacitor having such a structure is provided with strip-shaped electrodes on both sides, and these electrodes are connected in parallel to the positive electrode and the negative electrode of the light emitting element. When an overvoltage is applied between the positive and negative electrodes, the charging current flows to the capacitor due to this overvoltage, and the terminal voltage of the capacitor is instantaneously reduced, so that the applied voltage to the light emitting element does not increase, thereby protecting the light emitting element from overvoltage. can do. Further, even when noise including a high frequency component is applied, the capacitor functions as a bypass capacitor, so that external noise can be eliminated.

In addition, the semiconductor device of the present invention is configured by mounting a semiconductor element on the bottom of the above-described package molded body, but the above-described light emitting element and a semiconductor element such as a protective element are separately mounted on the package molded body. Alternatively, it may be mounted as an integrated composite element. In addition, the light emitting element may not be in contact with the coating member, and other semiconductor elements may be in contact with the coating member.

The mounting of the semiconductor element on the package molded body may be a method known in the art, for example, a method of directly mounting the semiconductor element on the up face, or a submount substrate (silicon, aluminum nitride, etc.) on the down face. Alternatively, a method using an appropriate adhesive (such as the above-described resin or silver paste) may be used.
In the semiconductor device of the present invention, the upper surface of the semiconductor element is sealed with a sealing member. The sealing member is suitably a resin having heat resistance, light resistance, and transparency, and the above-described resin or curable composition may be used alone or in combination of two or more to form a single layer structure or a laminated structure. Can be used. Here, as described above, the curable composition means one containing components (A) to (E) as essential components.

  Moreover, you may make the sealing member contain the additive etc. which were mentioned as a component (F) and other components (a)-(h). Among them, it is appropriate to contain a fluorescent substance, a diffusing agent, and a filler, and it is appropriate to add a dye or a pigment in order to exert a specific filter effect on the light from the light emitting element. . It is preferable that the sealing member has a curved surface with a central portion protruding on the upper surface thereof, that is, on the outside air side. Thereby, the light irradiated from the light emitting element can be efficiently converged in the front direction, and the luminous intensity in the front direction can be increased.

Embodiments of a package molded body and a semiconductor device according to the present invention will be described below in detail with reference to the drawings.
(Example 1 and Comparative Examples 1 and 2)
First, as a semiconductor element, a nitride semiconductor layer including an n-type layer, an active layer, and a p-type layer is sequentially formed on a sapphire substrate, and a part of the active layer and the p-type layer are removed to remove a part of the n-type layer. To expose. A gallium nitride compound semiconductor LED capable of emitting 475 nm blue light with a monochromatic emission peak of visible light by forming an n-electrode on the exposed n-type layer and a p-electrode on the p-type layer. Formed.

In addition, three types of package molded bodies were prepared using a thermoplastic resin (polyphenylene sulfide) highly reflected by a pigment such as titanium oxide as a housing material.
In other words, 100 parts by weight of resin, 40 parts by weight of glass fiber as a reinforcing material, and 20 parts by weight of titanium oxide as a pigment are kneaded with a slight amount of heat stabilizer, and injected into a silver-plated lead frame material in an integrated manner. Molded.

  As shown in FIG. 1, the obtained package molded body 10 has a pair of lead electrodes formed such that one end is inserted into the package molded body 10 and the other end projects from the outer wall surface of the package molded body 10. 11 and 12. The package molded body 10 has a two-stage structure having a first recess 13 and a second recess 14 inside thereof, and a side surface of the second recess 14 is formed as a wall portion. A part of the main surface of the lead electrodes 11 and 12 is exposed at the bottom surface of the second recess 14.

Further, as shown in FIG. 2, the obtained molded package 20 has the same structure as the package shown in FIG. 1 except that a wall portion 29 is provided in a step shape between the first recess 23 and the second recess 24. This is the same as the molded body 10.
Further, as shown in FIG. 3, the obtained package molded body 30 does not have the second concave portion provided inside the first concave portion 33, and the lead electrode 31 has a region in which the light emitting element 15 is placed by punching. 1 is the same as the package molded body 10 of FIG. 1 except that a wall 39 is provided on the outer periphery.

The light emitting element 15 was fixed by die bonding using epoxy resin in these package molded bodies 10, 20, 30.
An Au wire 16 as a conductive wire was electrically connected to each electrode of the light emitting element 15 and each lead electrode 11, 12, 31 by wire bonding.
Subsequently, as the coating member 17, the coating resins A to C shown below are applied only to the first concave portion 13 of the two-stage structure of the package molded bodies 10, 20, and 30 so as not to contact the light emitting element 15, or Only the outside of the walls 29 and 39 was applied, dried and cured under the following conditions.
・ Coating resin A (white epoxy resin)
One-part cation curable epoxy resin 100 parts by weight Ishihara Sangyo Tybak R-820 100 parts by weight Nippon Aerosil manufactured by Aerosil # 380 5 parts by weight PGMEA * 25 parts by weight Cured at 90 ° C. for 3 hours and then at 150 ° C. for 4 hours.
・ Coating resin B (white silicone resin)
Silicone resin 100 parts by weight Ishihara Sangyo Tybak R-820 100 parts by weight Nippon Aerosil manufactured by Aerosil # 380 1 part by weight Hexane 12 parts by weight Decane 28 parts by weight Cured at 40 ° C. for 1 hour and then at 150 ° C. for 4 hours.
・ Coating resin C (white modified silicone resin)
Modified silicone resin 100 parts by weight Ishihara Sangyo Tybak R-820 100 parts by weight Aerosil # 380 made by Nippon Aerosil 1 part by weight PGMEA * 2 parts by weight Cured at 60 ° C. for 3 hours and then at 100 ° C. for 1 hour.

PGMEA refers to propylene glycol monomethyl ether acetate (1-methoxy-2-acetoxypropane).
Further, a sealing resin was injected and cured as a sealing member in the following combinations from above the package molded bodies 10, 20, and 30, and light emitting diodes were produced as the semiconductor devices 18, 28, and 38, respectively.

-Sealing resin A (white epoxy resin)
One-part cation curable epoxy resin 100 parts by weight Cured at 90 ° C. for 3 hours and then at 150 ° C. for 4 hours.
The sealing resin A was applied to the one using the coating resin A.
-Sealing resin B (white silicone resin)
100 parts by weight of silicone resin Cured at 40 ° C. for 1 hour and then at 150 ° C. for 4 hours.
The sealing resin B was applied to the one using the coating resin B.
・ Sealing resin C (white modified silicone resin)
Modified silicone resin 100 parts by weight Cured at 60 ° C. for 3 hours, then at 100 ° C. for 1 hour, and further at 150 ° C. for 1 hour.

The sealing resin C was applied to the one using the coating resin C.
Further, as Comparative Example 1, among the above-described examples, as the package molded body 40, as shown in FIG. 4, the bottom 41 is flat and does not have a wall, and no coating member is formed. A light emitting diode 42 similar to that of the above example was manufactured.
Further, as Comparative Example 2, as shown in FIG. 5, in the light emitting diode 42 of Comparative Example 1, the coating member 17 is formed so as to cover the entire surface of the light emitting element 15 mounted on the package molded body 40. A light emitting diode 45 similar to the example was manufactured.

When the light output of the obtained light emitting diode was measured, the light output of about 45 mW was obtained when energizing 100 mA for Example 1 (Coating Resin A) in FIG. It was confirmed that the initial light output was halved in comparison with the light emitting diode of Example 1. In addition, in the light emitting diodes of FIGS. 1 to 3, the same results as in Example 1 were obtained when any of the coating resins B and C was used.
(Example 2 and Comparative Example 3)
The light emitting element was die-bonded and wire-bonded to the package molded body having the same two-stage structure as in Example 1 in the same manner as in Example 1.

Subsequently, as a coating member, a white silicone resin (high reflection paste / coating resin B) mixed with 100 phr of titanium oxide is applied only to the upper stage of the two-stage structure of the package molded body so as not to cover the light emitting element, and then dried and cured. (1 hour at 40 ° C., then 4 hours at 150 ° C.).
Further, a silicone resin was injected as a sealing member from above the packaged body and cured (1 hour at 40 ° C., then 4 hours at 150 ° C.) to produce a light emitting diode.

Further, as a comparative example, a similar light emitting diode was produced except that the coating member was not formed in the above-described examples.
The light output of the obtained light emitting diode at the time of 100 mA energization was measured. The results are shown below.

表１から、実施例２では、コーティング部材の形成により、リフレクター部における高反射が実現され、光出力の向上が確認された。
（実施例３及び比較例４）
実施例２及び比較例３で作製した発光ダイオードを、２６０℃でリフロー実装を繰り返し、初期の光出力を１００としたときの光出力の低下をそれぞれ測定した。その結果を以下に示す。

From Table 1, in Example 2, the high reflection in a reflector part was implement | achieved by formation of the coating member, and the improvement of the light output was confirmed.
(Example 3 and Comparative Example 4)
The light emitting diodes manufactured in Example 2 and Comparative Example 3 were repeatedly subjected to reflow mounting at 260 ° C., and the decrease in light output when the initial light output was set to 100 was measured. The results are shown below.

表２から、実施例３においては、コーティング部材の形成により、リフロー時の熱によるリフレクター部の黄変が抑制され、出力低下が抑制されたことが確認された。
（実施例４及び比較例５）
実施例２及び比較例３で作製した発光ダイオードについて、８５℃、８５％ＲＨ条件下で３２０時間、２００ｍＡ通電し、素子寿命を測定した。その結果を以下に示す。

From Table 2, in Example 3, it was confirmed that the yellowing of the reflector part due to heat during reflowing was suppressed and the output reduction was suppressed by forming the coating member.
(Example 4 and Comparative Example 5)
The light emitting diodes manufactured in Example 2 and Comparative Example 3 were energized at 200 mA for 320 hours under the conditions of 85 ° C. and 85% RH, and the element lifetime was measured. The results are shown below.

表３から、実施例４においては、コーティング部材の形成により、素子寿命が格段に向上していることが確認された。
（実施例５）
合成例１：トリアリルイソシアヌレートと１，３，５，７−テトラメチルシクロテトラシロキサンとの反応物Ｂ１（成分（Ｂ））の合成
５Ｌのセパラブルフラスコに、トルエン１．８ｋｇ、１，３，５，７−テトラメチルシクロテトラシロキサン１．４４ｋｇを加えて、内温が１０４℃になるように加熱した。そこに、トリアリルイソシアヌレート２００ｇ、白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）１．４４ｍＬ、トルエン２００ｇの混合物を滴下した。１２０℃のオイルバス中で７時間加熱還流させた。さらに、１−エチニル−１−シクロヘキサノール１．７ｇを加えた。

From Table 3, in Example 4, it was confirmed that the element lifetime was remarkably improved by forming the coating member.
(Example 5)
Synthesis Example 1: Synthesis of reaction product B1 (component (B)) of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Into a 5 L separable flask, 1.8 kg of toluene, 1,3 , 5,7-tetramethylcyclotetrasiloxane 1.44 kg was added, and the internal temperature was heated to 104 ° C. A mixture of 200 g of triallyl isocyanurate, 1.44 mL of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum) and 200 g of toluene was added dropwise. The mixture was heated to reflux in an oil bath at 120 ° C. for 7 hours. Furthermore, 1.7 g of 1-ethynyl-1-cyclohexanol was added.

Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure.
When ¹ H-NMR of the obtained product was measured, a reaction product in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane represented by the following structural formula reacted with triallyl isocyanurate. It was confirmed that B1 (SiH value: 8.2 mmol / g, allyl value: 0.12 mmol / g) was contained as a main component. In addition, this product contains a platinum vinylsiloxane complex which is a hydrosilylation catalyst (component (C)).

コーティング組成物Ｄの製造
成分（Ａ）としてトリアリルイソシアヌレート５４．５１ｇとジアリルモノグリシジルイソシアヌレート８７．０３ｇとの混合物、成分（Ｂ）として合成例１の反応物Ｂ1を１６２．６４ｇ、成分（Ｃ）として白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）９１３ｍｇ、成分（Ｄ）としてγ−グリシドキシプロピルトリメトキシシラン７．６０ｇ、成分（Ｅ）としてほう酸トリメチル１．５２ｇを用いる。
成分（Ａ）、成分（Ｃ）及び成分（Ｅ）をあらかじめ混合、攪拌し、混合物Ａ液を調製した。
また、（Ｂ）成分、（Ｄ）成分及び１−エチニル−１−シクロヘキサノール９１３ｍｇをあらかじめ混合、攪拌し、混合物Ｂ液を調製した。
混合物Ａ液と混合物Ｂ液とを混合し、攪拌・脱泡を行い、一液混合物とした。
この一液混合物２．５ｇに成分（Ｆ）である酸化チタン（石原産業（株）、タイペークＲ−８２０）２．５ｇを混合し、攪拌・脱泡を行い、コーティング組成物Ｄを得た。
コーティング組成物Ｅの製造
コーティング組成物Ｄのために調製した成分（Ａ）〜（Ｅ）の一液混合物２．５ｇに、成分（Ｆ）である酸化チタン（石原産業（株）、タイペークＲ−８２０）２．５ｇを混合し、さらにシリカ（日本アエロジル（株）、アエロジル３００）７５ｍｇを混合し、攪拌・脱泡を行い、コーティング組成物Ｅを得た。
コーティング組成物Ｆの製造
成分（Ａ）としてトリアリルイソシアヌレート１２．０４ｇ、成分（Ｂ）として合成例１で得られた反応物Ｂ１を１７．９６ｇ、成分（Ｃ）として白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）９０ｍｇ、成分（Ｄ）としてγ−グリシドキシプロピルトリメトキシシラン７５０ｍｇ、成分（Ｅ）としてほう酸トリメチル１５０ｍｇを用いる。

As a production component (A) of coating composition D, a mixture of 54.51 g of triallyl isocyanurate and 87.03 g of diallyl monoglycidyl isocyanurate, as component (B), 162.64 g of reactant B1 of Synthesis Example 1 As C), a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) 913 mg, 7.60 g of γ-glycidoxypropyltrimethoxysilane as component (D), and 1.52 g of trimethyl borate as component (E) are used.
Component (A), component (C) and component (E) were mixed and stirred in advance to prepare a mixture A solution.
In addition, (B) component, (D) component and 913 mg of 1-ethynyl-1-cyclohexanol were mixed and stirred in advance to prepare a mixture B solution.
The mixture A and the mixture B were mixed, stirred and degassed to obtain a one-component mixture.
To 2.5 g of this one-part mixture, 2.5 g of titanium oxide (Ishihara Sangyo Co., Ltd., Tyco R-820) as component (F) was mixed, stirred and degassed to obtain a coating composition D.
Manufacture of coating composition E To 2.5 g of one-component mixture of components (A) to (E) prepared for coating composition D, titanium oxide (Ishihara Sangyo Co., Ltd., Type R) was added to component (F). 820) 2.5 g was mixed, and further 75 mg of silica (Nippon Aerosil Co., Ltd., Aerosil 300) was mixed, stirred and degassed to obtain a coating composition E.
Production component (A) of coating composition F: 12.04 g of triallyl isocyanurate, 17.96 g of reaction product B1 obtained in Synthesis Example 1 as component (B), and xylene of a platinum vinylsiloxane complex as component (C) 90 mg of a solution (containing 3 wt% as platinum), 750 mg of γ-glycidoxypropyltrimethoxysilane as component (D), and 150 mg of trimethyl borate as component (E) are used.

Component (A), component (C), and component (E) were mixed and stirred in advance to prepare a mixture C solution.
Further, component (B), component (D) and 90 mg of 1-ethynyl-1-cyclohexanol were mixed and stirred in advance to prepare a mixture D solution.
The mixture C liquid and the mixture D liquid were mixed, stirred and degassed to obtain a one-liquid mixture.

2.5 g of this one-component mixture is mixed with 2.5 g of titanium oxide (Ishihara Sangyo Co., Ltd., Typaque R-820) as component (F), and 125 mg of silica (Nippon Aerosil Co., Ltd., Aerosil 300) is further mixed. Then, stirring and defoaming were performed to obtain a coating composition F.
(Evaluation of coating composition)
Preparation of Adhesive 12.04 g of triallyl isocyanurate, 90 mg of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum) and 150 mg of trimethyl borate are previously mixed and stirred to prepare a mixture E solution.

Further, 17.96 g of the reactant B1 of Synthesis Example 1, 750 mg of γ-glycidoxypropyltrimethoxysilane, and 90 mg of 1-ethynyl-1-cyclohexanol are mixed and stirred in advance to prepare a mixture F solution.
The obtained mixture E liquid and mixture F liquid were mixed, stirred and degassed to obtain an adhesive.
Preparation of die for die shear test The mixture E solution and the mixture F solution obtained above were mixed, stirred and degassed to obtain a one-component mixture.

This one-part mixture was poured into a cell prepared by sandwiching a 3 mm-thick silicone rubber sheet between two glass plates as a spacer, and was heated in a hot air dryer at 60 ° C./6 hours, 70 ° C./1 hour, 80 ° C. / Heating was performed for 1 hour, 120 ° C./1 hour, 150 ° C./1 hour, 180 ° C./30 minutes, and cured to form a transparent molded body.
The obtained transparent molded body was cut to 3 mm (length) × 3 mm (width) × 1 mm (thickness) using a diamond cutter to obtain a die.
Preparation of Test Pieces Coating compositions D to F were respectively applied onto a polyphthalamide resin molded article while controlling the film thickness using a tape as a spacer, and cured at 100 ° C./1 hour to form a coating layer. .

On top of that, a die for die shear test was adhered with an adhesive. The adhesive was heated at 60 ° C./6 hours, 70 ° C./1 hour, 80 ° C./1 hour, 120 ° C./1 hour, 150 ° C./1 hour, heated at 180 ° C./30 minutes and cured to obtain a test piece. It was.
Separately from this, as a comparative example, a die for die shear test was bonded to the polyphthalamide resin molded body with an adhesive. The adhesive was heated at 60 ° C./6 hours, 70 ° C./1 hour, 80 ° C./1 hour, 120 ° C./1 hour, 150 ° C./1 hour, heated at 180 ° C./30 minutes and cured to obtain a test piece. It was.
Die shear test and light resistance test About each test piece obtained above, adhesiveness was evaluated by the die shear test.

The die shear tester used was a universal bond tester 2400 manufactured by Daisy Corporation. A 50 kgf load cell was used, and the test speed was 83 μm / sec.
Moreover, about each test piece obtained above, the light resistance test was implemented in the state which irradiated the light to the adhesion surface through die | dye, and the die share test was done similarly to the above after the light resistance test. In addition, the light resistance test is a super xenon weather meter manufactured by Suga Test Instruments Co., Ltd., with an irradiance of 0.18 kW / m ² , irradiation for 1 hour and 42 minutes, followed by 18 minutes rainfall cycle test, black panel temperature 63 ° C, humidity 50% test The conditions were 330 hours.

  These results are shown in Table 4. The test was performed with n = 5. In Table 4, the maximum and minimum values were cut and the average value of n = 3 was shown.

表４の結果から、耐光性試験の前後において、接着性の低下は見られず、反射能を有していることが明らかとなった。また、耐光性試験後も着色がなく高耐光性を有していた。
半導体装置の作製
図１〜図３に示したパッケージ成形体１０、２０、３０に、コーティング組成物Ｄ〜Ｆを、それぞれ塗布し、乾燥させて、半導体装置１８、２８、３８として発光ダイオードをそれぞれ作製し、実施例１と同様に光出力を測定した。

From the results in Table 4, it was clarified that the adhesiveness was not deteriorated before and after the light resistance test, and that it had reflectivity. Moreover, there was no coloring after the light resistance test, and it had high light resistance.
Manufacturing of Semiconductor Device Coating compositions D to F are respectively applied to package molded bodies 10, 20, and 30 shown in FIGS. 1 to 3 and dried to form light emitting diodes as semiconductor devices 18, 28, and 38, respectively. The light output was prepared and measured in the same manner as in Example 1.

  In any of the semiconductor devices, the coating compositions D to F were excellent in reflectivity and had high light resistance, and a high light output was obtained as in Example 1.

  The package molded body and the semiconductor device of the present invention can be used for various light sources such as signals, illumination, displays, indicators, and backlights of mobile phones.

It is a schematic sectional drawing which shows embodiment of the package molded object and semiconductor device of this invention. It is a schematic sectional drawing which shows another embodiment of the package molded object and semiconductor device of this invention. It is a schematic sectional drawing which shows another embodiment of the package molded object and semiconductor device of this invention. It is a schematic sectional drawing which shows the comparative example with respect to the package molded object and semiconductor device of this invention. It is a schematic sectional drawing which shows another comparative example with respect to the package molded object and semiconductor device of this invention.

Explanation of symbols

10, 20, 30 Package molded body 11, 12, 31 Lead electrode 13, 23, 33 First concave portion 14, 24 Second concave portion 15 Light emitting element 16 Au wire 17 Coating member 18, 28, 38 Semiconductor device 29, 39 Wall

Claims (32)

Disposed on the first base and said first bottom on including mounting region for mounting the semiconductor light emitting element, a molded package and a side surrounding the pre-described depositing area,
In the first bottom, said has a wall portion at a position apart from the outer edge of the mounting area of the semiconductor light-emitting device, and place the second bottom Oite outside of the wall portion,
The wall is convex with respect to the first bottom and the second bottom;
The second bottom portion and the side portion outside the wall portion are covered with a coating member, and the coating member becomes thicker toward the second bottom portion at the side portion. Package molded body. 2. The metal substrate according to claim 1, wherein one end portion is inserted into the package molded body and exposed at a first bottom portion in the package molded body, and the other end portion includes at least two metal bases extending outside the package molded body. Package molded body. The package molded body according to claim 2, wherein the wall portion is formed by the metal base exposed at a first bottom portion in the package molded body. The package molded body according to claim 1 or 2, wherein the wall portion is a side surface of a recess formed on a first bottom portion in the package molded body. The said coating member has a function which raises the reflection of the light irradiated from the said semiconductor light-emitting element in the 2nd bottom part and side part in the outer side of the wall part of the said package molded object. Package molded body as described in 1.   The package molded body according to claim 5, wherein the coating member has a reflectance of 85% or more with respect to light irradiated from the semiconductor light emitting element.   The said coating member is formed by at least 1 sort (s) selected from the group which consists of an epoxy resin, an acrylate resin, a urethane resin, a polyimide resin, an acrylic resin, a polynorbornene resin, a silicone resin, and a modified silicone resin. The package molding as described in any one of these.   The coating member contains (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) containing at least two SiH groups in one molecule. A silicon compound, (C) a hydrosilylation catalyst, (D) a silane coupling agent and / or an epoxy group-containing compound, and (E) a curable composition containing a silanol condensation catalyst as essential components. The package molded body according to any one of 6.   The package molded body according to claim 8, wherein the curable composition further contains (F) an inorganic member. The component (A) is represented by the following general formula (I)

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same), and includes an organic compound represented by The package molded body according to claim 8 or 9. The component (A) is triallyl isocyanurate or a mixture of triallyl isocyanurate and diallyl monoglycidyl isocyanurate,
The package molded body according to any one of claims 8 to 10, wherein the component (B) is a reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and triallyl isocyanurate.   The component (D) has at least one functional group selected from the group consisting of an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group in the molecule and a hydrolyzable silicon group. The package molded article according to any one of claims 8 to 11, which is a silane coupling agent having   The package molded article according to claim 12, wherein the component (D) is a silane coupling agent having an epoxy group and a hydrolyzable silicon group in the molecule.   The package molded body according to any one of claims 8 to 13, wherein the component (E) is an organoaluminum compound and / or a borate ester.   The package molded body according to claim 14, wherein the component (E) is an aluminum chelate compound or an aluminum alcoholate compound.   The component (E) comprises aluminum ethyl acetoacetate diisopropylate, aluminum ethyl acetoacetate diisobutyrate, aluminum tris (ethyl acetoacetate), aluminum bisethyl acetoacetate monoacetylacetonate and aluminum tris (acetylacetonate). The package molded article according to claim 14, which is at least one selected from the group.   The component (E) is at least one selected from the group consisting of tri-normal octadecyl borate, tri-normal octyl borate, tri-normal butyl borate, triisopropyl borate, tri-normal borate, triethyl borate and trimethyl borate. The package molding as described in 1.   The package formed body according to any one of claims 9 to 17, wherein the component (F) is titanium oxide.   The package molded body according to claim 18, wherein the titanium oxide is of a rutile type and has an average particle diameter of 0.1 to 1.0 µm. The coating member contains at least one selected from the group consisting of titanium oxide, zinc oxide, alumina, silica, barium titanate, calcium phosphate, calcium carbonate, white carbon, talc, magnesium carbonate, and boron nitride. The package molded body according to any one of 1 to 8 and 10 to 19 . The package molded body according to any one of claims 1 to 20 , and a semiconductor light emitting device described in a mounting region of the package molded body,
The semiconductor device, wherein the semiconductor light emitting element and the coating member are separated from each other. The upper surface of the semiconductor light emitting device is selected from the group consisting of epoxy resin, acrylate resin, urethane resin, polyimide resin, acrylic resin, polycarbonate resin, polynorbornene resin, silicone resin, modified silicone resin, amorphous polyamide resin, and fluorine resin The semiconductor device according to claim 21 , wherein the semiconductor device is sealed with at least one kind. The top surface of the semiconductor light emitting device is (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) at least two SiH groups in one molecule. A cured product obtained by curing a curable composition containing, as essential components, a silicon compound containing (C) a hydrosilylation catalyst, (D) a silane coupling agent and / or an epoxy group-containing compound, and (E) a silanol condensation catalyst The semiconductor device according to claim 21 , wherein the semiconductor device is sealed. The component (A) is represented by the following general formula (I)

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same), and includes an organic compound represented by The semiconductor device according to claim 23 . The component (A) is triallyl isocyanurate or a mixture of triallyl isocyanurate and monoglycidyl diallyl isocyanurate,
The semiconductor device according to claim 23 or 24 , wherein the component (B) is a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and triallyl isocyanurate. The component (D) has at least one functional group selected from the group consisting of an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group in the molecule and a hydrolyzable silicon group. The semiconductor device according to claim 23 , wherein the semiconductor device is a silane coupling agent having 27. The semiconductor device according to claim 26 , wherein the component (D) is a silane coupling agent having an epoxy group and a hydrolyzable silicon group in the molecule. The semiconductor device according to any one of claims 23 to 27 , wherein the component (E) is an organoaluminum compound and / or a borate ester. 29. The semiconductor device according to claim 28 , wherein the component (E) is an aluminum chelate compound or an aluminum alcoholate compound. The component (E) comprises aluminum ethyl acetoacetate diisopropylate, aluminum ethyl acetoacetate diisobutyrate, aluminum tris (ethyl acetoacetate), aluminum bisethyl acetoacetate monoacetylacetonate and aluminum tris (acetylacetonate). 29. The semiconductor device according to claim 28 , wherein the semiconductor device is at least one selected from the group. The ingredients (E), boric acid tri-n-octadecyl borate tri-n-octyl borate, tri-n-butyl borate, triisopropyl borate tri-n-propyl, at least one kind of claim 28 selected from the group consisting of boric acid, triethyl and trimethyl borate A semiconductor device according to 1. One end portion is inserted into the package molded body and exposed at the first bottom portion in the package molded body, and the other end portion includes at least two metal bases extending outside the package molded body, and the semiconductor light emitting device includes: the semiconductor device according to claim 21 to 31, which is placed on the first bottom exposed to the metal substrate on the molded package body comprising.

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