KR20190129001A - Primer composition and optical semiconductor device using the same - Google Patents

Abstract

The present invention provides a primer composition and an optical semiconductor device using the primer composition. In particular, the primer composition can improve adhesion with a cured material of an addition-curable silicone composition encapsulating a substrate on which an optical semiconductor device is mounted and the optical semiconductor device; can prevent corrosion of a metal electrode formed on a substrate; and can improve the heat resistance and flexibility of a primer itself. The primer composition is for bonding a cured material of an addition-curable silicone composition encapsulating a substrate on which an optical semiconductor device is mounted and the optical semiconductor device, and comprises: (A) a copolymer comprising at least one of acrylate ester and methacrylate ester having one or more SiH groups per molecule, at least one of acrylate ester and methacrylate ester having one or more alkoxy groups per molecule, and at least one of acrylate ester and methacrylate ester not containing SiH groups and alkoxy groups; and (B) a solvent.

Description

Primer composition and optical semiconductor device using the same {PRIMER COMPOSITION AND OPTICAL SEMICONDUCTOR DEVICE USING THE SAME}

This invention relates to the primer composition which adhere | attaches the board | substrate which mounted the optical semiconductor element, the hardened | cured material of the addition reaction curable silicone composition which seals the said optical semiconductor element, and the optical semiconductor device using this primer composition.

The light emitting diode (LED) lamp known as an optical semiconductor device is a structure which sealed the LED mounted on the board | substrate with the sealing material containing transparent resin. As this sealing material, the composition of the epoxy resin base was conventionally used.

However, in the epoxy resin-based sealing material, cracking and yellowing are liable to occur due to the increase in the amount of heat generated due to the recent miniaturization of the semiconductor package, the high brightness of the LED, and the short wavelength of the light, resulting in a decrease in reliability.

Therefore, a silicone composition is used as a sealing material from the point which has the outstanding heat resistance (patent document 1). In particular, since an addition reaction hardening type silicone composition hardens in a short time by heating, productivity is favorable and it is suitable as a sealing material of LED (patent document 2).

However, the adhesiveness between the board | substrate (resin and electrode) which mounts LED, and the sealing material containing hardened | cured material of an addition reaction hardening type silicone composition is not necessarily sufficient.

Moreover, since a silicone composition is generally excellent in gas permeability, it is easy to be influenced from an external environment. When the LED lamp is exposed to sulfur compounds, exhaust gases and the like in the atmosphere, sulfur compounds and the like penetrate the cured product of the silicone composition, and the metal electrode on the substrate sealed with the cured product, in particular, the Ag electrode is corroded over time and blackened. As a countermeasure, by using a polymer of acrylate ester containing SiH, a copolymer of acrylate ester, a copolymer of methacrylate ester, a copolymer of acrylate ester and methacrylic acid ester or a polysilazane compound Primers (Patent Documents 3 to 5) for suppressing black stools have been developed. However, when the acrylic polymer containing SiH is used, the heat resistance of a primer film is inadequate, and resin deteriorates around the semiconductor element through which the high electric current flows in recent years. On the other hand, although polysilazane compound is excellent in heat resistance, since the film formed is hard, a film | membrane tends to be broken when apply | coated on the mounting board | substrate with which many optical semiconductor elements called multichips are mounted.

Japanese Patent Laid-Open No. 2000-198930 Japanese Patent Laid-Open No. 2004-292714 Japanese Patent Laid-Open No. 2010-168496 Japanese Patent Laid-Open No. 2012-144652 Japanese Patent Publication No. 2014-157849

The present invention has been made to solve the above problems, and improves the adhesion between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition for sealing the optical semiconductor element, and is formed on the substrate. An object of the present invention is to provide a primer composition which prevents corrosion of a metal electrode and further improves heat resistance and flexibility of the primer itself, and an optical semiconductor device using the primer composition.

In order to achieve the above object, in the present invention,

As a primer composition which adhere | attaches the board | substrate which mounted the optical semiconductor element, and the hardened | cured material of the addition reaction curable silicone composition which seals the said optical semiconductor element,

(A) At least one of the acrylic acid ester and methacrylic acid ester which has one or more SiH groups in 1 molecule, and at least one of the acrylic acid ester and methacrylic acid ester which has one or more alkoxy groups in 1 molecule, and does not have a SiH group and an alkoxy group A copolymer comprising at least one of an acrylic acid ester and a methacrylic acid ester,

(B) solvent

It provides a primer composition containing.

Such primer composition improves the adhesion between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition for sealing the optical semiconductor element, and prevents corrosion of the metal electrode formed on the substrate. In addition, the heat resistance and flexibility of the primer itself are improved.

Moreover, it is preferable that the compounding quantity of the said (B) component is 70 mass% or more of the said primer composition.

By containing 70 mass% or more of (B) components, it becomes a primer composition with more workability | operativity.

In addition, the primer composition,

(C) silane coupling agent

It is preferable to contain more.

Thus, by containing a silane coupling agent, it becomes a primer composition which improves the adhesiveness of the board | substrate and the hardened | cured material of an addition reaction curable silicone composition further.

Moreover, this invention provides the optical semiconductor device by which the board | substrate which mounted the optical semiconductor element and the hardened | cured material of the addition reaction hardening type silicone composition which seals the said optical semiconductor element are adhere | attached with the said primer composition.

In such an optical semiconductor device using the primer composition of the present invention, since the substrate and the cured product of the addition reaction curable silicone composition are firmly adhered to each other and corrosion of the metal electrode formed on the substrate can be prevented, it has high reliability. It becomes.

The optical semiconductor element may be a light emitting diode.

Thus, the optical semiconductor device of this invention can be used suitably for light emitting diodes.

Moreover, the constituent material of the said board | substrate can be made into polyamide, fiber reinforced plastics, ceramics, silicone, a silicone modified polymer, or a liquid crystal polymer.

In the optical semiconductor device of the present invention, since the adhesion of the primer is excellent, even such a substrate can be used without impairing the adhesion.

Moreover, it is preferable that the hardened | cured material of the said addition reaction curable silicone composition is rubbery.

If it is the hardened | cured material of such an addition reaction hardening type silicone composition, it has more firm adhesiveness and can prevent the corrosion of the metal electrode, especially Ag electrode formed on the board | substrate more effectively.

As described above, the primer composition of the present invention improves the adhesion between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition for sealing the optical semiconductor element, and the metal electrode formed on the substrate. It is possible to prevent corrosion of the primer and to improve the heat resistance and flexibility of the primer itself, and the optical semiconductor device using the primer composition has high reliability.

1 is a cross-sectional view of an LED lamp showing an example of an optical semiconductor device according to the present invention.
It is a perspective view explaining the test piece for adhesive tests in an Example and a comparative example.

As described above, the adhesion between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction curable silicone composition for sealing the optical semiconductor element is improved, and the corrosion of the metal electrode formed on the substrate is prevented, Moreover, development of the primer composition which can improve the heat resistance and flexibility of the primer itself was calculated | required.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined about the said subject, As a result, at least one of the acrylic acid ester and methacrylic acid ester which has one or more SiH groups in one molecule, and the acrylic acid ester and methacrylic acid ester which have one or more alkoxy groups in one molecule If it is a primer composition containing the copolymer containing at least one of these, and the copolymer containing at least one of the acrylic acid ester and methacrylic acid ester which do not have a SiH group and an alkoxy group, The board | substrate which mounted the optical semiconductor element, and the addition which seals this optical semiconductor element The present invention was completed by finding that the cured product of the reaction curable silicone composition can be firmly adhered to a primer composition capable of preventing corrosion of a metal electrode, particularly an Ag electrode, formed on a substrate.

That is, the present invention,

As a primer composition which adhere | attaches the board | substrate which mounted the optical semiconductor element, and the hardened | cured material of the addition reaction curable silicone composition which seals the said optical semiconductor element,

(A) At least one of the acrylic acid ester and methacrylic acid ester which has one or more SiH groups in 1 molecule, and at least one of the acrylic acid ester and methacrylic acid ester which has one or more alkoxy groups in 1 molecule, and does not have a SiH group and an alkoxy group A copolymer comprising at least one of an acrylic acid ester and a methacrylic acid ester,

(B) solvent

It is a primer composition containing.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail, this invention is not limited to these.

<Primer Composition>

The primer composition of this invention contains the (A) component and (B) component mentioned later as an essential component.

Hereinafter, each component of the primer composition of this invention is demonstrated.

[(A) component]

(A) component contained in the primer composition of this invention is an acrylic acid ester and methacrylic acid ester which has at least one of the acrylic acid ester and methacrylic acid ester which has one or more SiH groups in one molecule, and one or more alkoxy groups in one molecule. It is a copolymer containing at least one and at least one of acrylic acid ester and methacrylic acid ester which do not have a SiH group and an alkoxy group.

(A) component which is a copolymer can be obtained by superposing | polymerizing the corresponding monomer (ester mentioned later) using radical polymerization initiators, such as 2,2'- azobisisobutyronitrile (AIBN).

The primer composition containing the component (A) provides sufficient adhesion to the substrate and the electrode on which the optical semiconductor element is mounted, and forms a flexible film on the substrate, thereby providing a metal electrode (especially an Ag electrode). It is to suppress corrosion over time.

Although the compounding quantity of (A) component will not be specifically limited if it is a quantity melt | dissolved with respect to (B) component mentioned later, It is preferable that it is 30 mass% or less of the whole composition (total of (A), (B) component, etc.), and more Preferably it is 0.01-20 mass%, More preferably, it is 0.1-10 mass%. When content is 30 mass% or less, generation | occurrence | production of the unevenness | corrugation of the surface of the film | membrane obtained can be prevented, and sufficient performance as a primer can be obtained.

Acrylic esters and methacrylic esters having at least one SiH group in one molecule

As acrylic acid ester and methacrylic acid ester which have one or more SiH groups in 1 molecule, the compound containing the structure represented by following formula (1) is mentioned.

(Wherein R is a hydrogen atom or a methyl group, R ¹ represents a monovalent organic group, and R ² represents a divalent organic group. N is 0, 1 or 2).

Moreover, the compound which has a structure represented by following formula (2) or following formula (3) in diorganopolysiloxane can also be illustrated.

(Wherein R, R ¹ and R ² have the same meaning as above. L is 0 or a positive integer and m is a positive integer. The order of the units of each siloxane in parentheses is not constant.)

(Wherein R, R ¹ and R ² have the same meaning as described above. O and p are positive integers. The order of the units of siloxane units with parentheses is not constant.)

Here, as a monovalent organic group represented by R <^1> , a C1-C10, especially C1-C3 unsubstituted or substituted monovalent hydrocarbon group is preferable. Examples of the monovalent hydrocarbon group include an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and octyl group and cyclohexyl group Alkenyl groups such as cycloalkyl groups, vinyl groups, allyl groups, propenyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, naphthyl groups, aralkyl groups such as benzyl groups, phenylethyl groups, and phenylpropyl groups; A part or all of the hydrogen atoms of which are substituted with halogen atoms such as fluorine, bromine, chlorine, cyano group, etc., for example, chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl group, etc. Can be mentioned. As R <^1> , a methyl group, an ethyl group, and a phenyl group are preferable, and a methyl group is especially preferable.

As a divalent organic group represented by R <^2> , a C1-C10, especially a C1-C3 unsubstituted or substituted bivalent hydrocarbon group is preferable. Examples of the divalent hydrocarbon group include alkylene groups such as methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, cyclohexylene group and n-octylene group, phenylene group, Arylene groups, such as a naphthylene group, are mentioned. As R <^2> , an ethylene group and n-propylene group are preferable and n-propylene group is especially preferable.

Acrylic acid ester and methacrylic acid ester which has one or more SiH groups in 1 molecule may use together single 1 type or 2 types or more.

Acrylic esters and methacrylic acid esters having at least one alkoxy group in one molecule

As acrylic acid ester and methacrylic acid ester which have one or more alkoxy groups in 1 molecule, the compound containing the structure represented by following formula (4) is mentioned.

(In formula, R, R <^1> , R <^2> shows the same meaning as the above. R <^3> represents a C1-C4 monovalent hydrocarbon group. Q is 0, 1 or 2.)

Moreover, the compound which has a structure represented by following formula (5) or following formula (6) in diorganopolysiloxane can also be illustrated.

(Wherein R, R ¹ , R ² , and R ³ represent the same meaning as described above. R is 0 or a positive integer and s is a positive integer. The order of the units of siloxane in parentheses is not constant.) .)

(Wherein, R, R ¹ , R ² , and R ³ represent the same meanings as above. T and u are positive integers. The order of the units of each siloxane unit in parentheses is not constant.)

Here, the thing similar to the above is mentioned as an organic group represented by R <^1> , R <^2> . As a C1-C4 monovalent hydrocarbon group represented by R <^3> , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert- butyl group, etc. are mentioned, A methyl group or an ethyl group is preferable. .

Acrylic acid ester and methacrylic acid ester which has one or more alkoxy groups in 1 molecule may use together 1 type individually or 2 types or more.

Acrylic esters and methacrylic esters having no SiH and alkoxy groups

As acrylic acid ester which does not have a SiH group and an alkoxy group, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isopentyl acrylate, n-hexyl acrylate, isooctyl acrylate and 2-ethylhexyl acrylate , Acrylic acid n-octyl, isononyl acrylate, acrylic acid n-decyl, isodecyl acrylate and the like.

As methacrylic acid ester which does not have a SiH group and an alkoxy group, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isopentyl methacrylate, and methacrylic acid- n-hexyl, isooctyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid-n-octyl, isononyl methacrylate, methacrylic acid-n-decyl, isodecyl methacrylate, etc. are mentioned. have.

Among the above examples, acrylic acid alkyl esters and methacrylic acid alkyl esters having 1 to 12 carbon atoms, particularly 1 to 4 carbon atoms in the alkyl group, are preferable, and one type alone or two or more types may be used in combination.

[(B) component]

As (B) component which is a solvent, if it melt | dissolves the said (A) component and the optional component mentioned later which comprise the primer composition of this invention, it will not specifically limit, A well-known organic solvent can be used.

Examples of the solvent include aromatic hydrocarbon solvents such as xylene, toluene and benzene, aliphatic hydrocarbon solvents such as heptane and hexane, halogenated hydrocarbon solvents such as trichloroethylene, perchloroethylene and methylene chloride, ethyl acetate and 1-. Ester solvents such as propylene glycol methyl ether acetate, ketone solvents such as methyl isobutyl ketone and methyl ethyl ketone, alcohol solvents such as ethanol, isopropanol and butanol, ligroin, cyclohexanone, diethyl ether, rubber volatiles, silicone A solvent etc. are mentioned. Among these, ethyl acetate, 1-propylene glycol methyl ether acetate, hexane, and acetone are used suitably.

(B) A component may be used individually by 1 type or in combination of 2 or more types as a mixed solvent according to the evaporation rate at the time of primer composition application | coating operation.

Although the compounding quantity of (B) component is not specifically limited, It is preferable that it is 70 mass% or more of the whole primer composition (total of (A), (B) component, etc.), More preferably, it is 80-99.99 mass%, More preferably, Is 90 to 99.9 mass%. When the compounding quantity of (B) component is 70 mass% or more, it becomes a primer composition with more favorable workability at the time of application | coating and drying, for example, can be made uniform when forming a primer film on the board | substrate mentioned later, There is no cracking of the film due to unevenness, and it gives sufficient performance as a primer.

[(C) component]

A silane coupling agent can further be mix | blended with the primer composition of this invention as (C) component.

As a silane coupling agent, a general silane coupling agent may be sufficient, and epoxy group containing silane coupling agents, such as vinyl group containing silane coupling agents, such as vinyl trimethoxysilane and vinyl triethoxysilane, and glycidoxy propyl trimethoxysilane, for example. Mercapto group-containing silane coupling agents such as (meth) acryloxy group-containing silane coupling agents such as methacryloyloxypropyltrimethoxysilane and acryloyloxypropyltrimethoxysilane, and mercaptopropyltrimethoxysilane Can be mentioned. Among these, vinyl trimethoxysilane and methacryloyloxypropyl trimethoxysilane are preferable.

As a compounding quantity at the time of using (C) component, it is preferable that it is 0.05-10 mass% of the whole primer composition (total of (A)-(C) component etc.), More preferably, it is 0.1-3 mass%. When the compounding quantity of (C) component is 0.05 mass% or more, an adhesive improvement effect will become enough, and even if it mix | blends the value exceeding 10 mass%, since the further adhesive improvement effect is not obtained, it is preferable that it is 10 mass% or less. .

[Other Ingredients]

In addition to the said component, other arbitrary components can be mix | blended with the primer composition of this invention as needed. For example, as the metal corrosion inhibitor, benzotriazole, butylhydroxytoluene, hydroquinone or derivatives thereof can be blended.

As for benzotriazole, dibutylhydroxytoluene, hydroquinone or derivatives thereof, an LED lamp is exposed to a harsh external environment, for example, the sulfur compound in air | atmosphere is a sealing material (hardened | cured material of an addition reaction hardening type silicone composition) of an optical semiconductor device. In the case of passing through, it is a component that more effectively suppresses corrosion of metal electrodes, particularly Ag electrodes, on the substrate sealed with the sealing material.

It is preferable that it is 0.005-1 mass part with respect to a total of 100 mass parts of (A) and (B) component, and, as for the compounding quantity at the time of adding a metal corrosion inhibitor, it is especially preferable that it is 0.01-0.5 mass part.

Moreover, you may add fluorescent substance, a reinforcing filler, dye, a pigment, a heat resistance improver, antioxidant, an adhesion promoter, etc. as other arbitrary components.

[Method for Producing Primer Composition]

As a manufacturing method of the primer composition of this invention, the method of mixing uniformly the said (A), (B) component and the said arbitrary component as needed with a mixing stirrer under normal temperature or heating as needed.

<Optical semiconductor device>

Moreover, this invention provides the optical semiconductor device by which the board | substrate which mounted the optical semiconductor element and the hardened | cured material of the addition reaction hardening type silicone composition which seals the said optical semiconductor element are adhere | attached with the said primer composition.

EMBODIMENT OF THE INVENTION Hereinafter, one form of the optical semiconductor device of this invention is demonstrated with reference to drawings.

1 is a cross-sectional view of an optical semiconductor device (LED lamp) showing an example of the optical semiconductor device according to the present invention. The optical semiconductor device (LED lamp) 1 describes the substrate 4 on which the LED 3 is mounted as the optical semiconductor element, and the cured product 5 of the addition reaction curable silicone composition sealing the LED 3. It adhere | attaches by one primer composition (2). Among them, a metal electrode 6 such as an Ag electrode is formed on the substrate 4, and an electrode terminal (not shown) of the LED 3 and the metal electrode 6 are electrically connected to each other by the bonding wire 7. Connected.

As a material which comprises the board | substrate 4, polyamide, various fiber reinforced plastics, ceramics, silicone, a silicone modified polymer, a liquid crystal polymer, etc. are mentioned.

The hardened | cured material 5 of an addition reaction hardening type silicone composition is obtained by hardening an addition reaction hardening type silicone composition, It is preferable that it is a transparent hardened | cured material, and it is preferable that it is rubbery. As said addition reaction hardening type silicone composition, what contains at least the conventionally well-known vinyl group containing organopolysiloxane, the organohydrogen polysiloxane which is a crosslinking agent, and the platinum-type catalyst which is an addition reaction catalyst can be used, Moreover, in the said addition reaction hardening type silicone composition, As other optional components, a reaction inhibitor, a coloring agent, a flame retardant imparting agent, a heat resistance improving agent, a plasticizer, a reinforcing silica, an adhesive imparting agent or the like may be added.

The following method can be illustrated as a manufacturing method of the optical semiconductor device (LED lamp) 1 shown in FIG.

An optical semiconductor element such as the LED 3 is bonded to the substrate 4 on which the metal electrode 6 such as the Ag electrode is formed by Ag plating in advance with an adhesive, and the electrode terminal of the LED 3 is bonded by the bonding wire 7. (Not shown) and the metal electrode 6 are electrically connected to each other, and then the substrate 4 on which the LED 3 is mounted is cleaned as necessary, and then the primer is applied with a coating device such as a spinner, a sprayer, or the like. After apply | coating the composition 2 to the board | substrate 4, the solvent in the primer composition 2 is volatilized by heating, air drying, etc., Preferably it is 10 micrometers or less, More preferably, the film of the thickness of 0.1-5 micrometers is Form. After the coating of the primer is formed, the addition reaction curable silicone composition is applied by a dispenser or the like, and is left to stand at room temperature or heat cured to seal the LED 3 with the rubbery cured product 5.

Thus, by using the primer composition of this invention containing the above-mentioned (A) and (B) component, the board | substrate which mounted optical semiconductor elements, such as LED, and the hardened | cured material of an addition reaction curable silicone composition adhere firmly, It is possible to provide a high reliability optical semiconductor device, in particular an LED lamp.

In addition, even when an LED lamp is exposed to a harsh external environment and sulfur compounds in the atmosphere are permeated into the cured product of the silicone composition, the use of the primer composition of the present invention suppresses corrosion of metal electrodes, particularly Ag electrodes, on a substrate. can do.

In addition, the optical semiconductor device of this invention can be used suitably for LED, The above-mentioned aspect demonstrated using LED as an example of an optical semiconductor element, In addition, For example, a photo transistor, a photodiode, a CCD, It can also be applied to solar cell modules, EPROMs, photocouplers and the like.

EXAMPLE

Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to a following example.

Synthesis Example 1

40 parts by mass of methyl methacrylate, 10 parts by mass of SiH-containing methacrylic acid ester represented by the following formula (7), 6 parts by mass of methoxy group-containing methacrylic acid ester represented by the following formula (8), 1-propylene glycol methyl 230 mass parts of ether acetate and 0.25 mass parts of AIBN were heated and stirred at 90 degreeC for 6 hours, and the solution containing a copolymer was produced.

Synthesis Example 2

40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylic acid ester represented by formula (7), 4 parts by mass of methoxy group-containing methacrylic acid ester represented by formula (8), 1-propylene glycol methyl 230 mass parts of ether acetate and 0.25 mass parts of AIBN were heated and stirred at 90 degreeC for 6 hours, and the solution containing a copolymer was produced.

Synthesis Example 3

40 parts by mass of methyl methacrylate, 19 parts by mass of SiH-containing methacrylic acid ester represented by formula (7), 1 part by mass of methoxy group-containing methacrylic acid ester represented by formula (8), 1-propylene glycol methyl 230 mass parts of ether acetate and 0.25 mass parts of AIBN were heated and stirred at 90 degreeC for 6 hours, and the solution containing a copolymer was produced.

Synthesis Example 4

40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylic acid ester represented by the formula (7), 5 parts by mass of methoxy group-containing methacrylic acid ester represented by the following formula (9), 1-propylene glycol methyl 230 mass parts of ether acetate and 0.25 mass parts of AIBN were heated and stirred at 90 degreeC for 6 hours, and the solution containing a copolymer was produced.

Synthesis Example 5

40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing acrylate ester represented by the following formula (10), 4 parts by mass of methoxy group-containing methacrylate ester represented by the formula (8), 1-propylene glycol methyl ether acetate 230 mass parts and 0.25 mass parts of AIBN were heat-stirred at 90 degreeC for 6 hours, and the solution containing a copolymer was produced.

Synthesis Example 6

40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylic acid ester represented by the formula (7), 4 parts by mass of methoxy group-containing acrylate ester represented by the following formula (11), 1-propylene glycol methyl ether acetate 230 mass parts and 0.25 mass parts of AIBN were heat-stirred at 90 degreeC for 6 hours, and the solution containing a copolymer was produced.

Comparative Synthesis Example 1

40 parts by mass of methyl methacrylate, 14 parts by mass of SiH-containing methacrylic acid ester represented by the formula (7), 230 parts by mass of 1-propylene glycol methyl ether acetate, and 0.25 parts by mass of AIBN were heated and stirred at 90 ° C. for 6 hours, A solution containing a copolymer was prepared.

[Examples 1 to 6 and Comparative Example 1]

The copolymers synthesized in Synthesis Examples 1 to 6 and Comparative Synthesis Example 1 were diluted with 1-propylene glycol methyl ether acetate so as to have a nonvolatile content of 8% to obtain a primer composition (Examples 1 to 6 and Comparative Example 1). .

Using the obtained primer composition, various physical properties (appearance, transmittance, adhesiveness (adhesive strength), and corrosiveness) were measured by the evaluation method shown below, and the results are shown in Tables 1 and 2. In addition, the physical property shown in Table 1, 2 is the value measured at 23 degreeC.

[Exterior]

The obtained primer composition was brush-coated so that it might become thickness of 2 micrometers on slide glass, it was left to stand at 60 degreeC for 30 minutes, and it dried at 180 degreeC for 30 minutes. On this primer composition, an addition reaction curable silicone rubber composition (manufactured by Shin-Etsu Chemical Co., Ltd., KER-2600) was applied to a thickness of 2 mm, cured at 150 ° C for 1 hour, and the appearance thereof was observed.

[Transmittance test]

The obtained primer composition was brush-coated so that it might become 2 micrometers in thickness on slide glass, it was left to stand at 60 degreeC for 30 minutes, and it dried, and the primer composition film was formed. Transmittance) was measured with a slide glass as a blank, and this was made into 100%. Subsequently, the slide glass in which the said primer composition film was formed was heat-processed 180 degreeCx500 hours, the transmittance | permeability after heat processing was measured similarly to the above, and the change with respect to initial stage transmittance | permeability was calculated | required.

[Adhesion (Adhesion Strength) Test]

The test piece 11 for adhesion tests as shown in FIG. 2 was produced. That is, the primer composition obtained is apply | coated to each single side | surface of two Al board | substrates 12 and 13 (made by Cadence Ltd., width 25mm) by thickness 0.01mm, it is left to stand at 60 degreeC for 30 minutes, and also it is dried at 180 degreeC. The primer composition films 14 and 15 were formed. These Al substrates face the surface on which the primer composition films 14 and 15 are formed so that their ends overlap 10 mm, and an addition reaction curable silicone rubber composition (manufactured by Shin-Etsu Chemical Co., Ltd., KER) therebetween. -2600) to be sandwiched at a thickness of 2 mm, and heated at 150 ° C. for 30 minutes to cure the addition reaction curable silicone rubber composition, and adhered by the cured product 16 of the silicone rubber composition (adhesive area 25 mm × 10 mm = 250 mm). ² ) a test piece comprising two Al substrates.

Each end of each of the Al substrates 12 and 13 of this test piece was pulled at a tensile speed of 50 mm / min using a tensile tester (manufactured by Shimadzu Seisakusho, Autograph) in the opposite direction (arrow direction in Fig. 2), The adhesive strength (MPa) per unit area was calculated | required.

[Corrosion Resistance Test]

After filling the obtained primer composition into the LED package which has a silver electrode in the bottom part, it was left to stand at 60 degreeC for 30 minutes, and it dried at 180 degreeC, and the addition reaction hardening type silicone rubber composition (made by Shin-Etsu Chemical Co., Ltd. on this), KER-2600) was applied to a thickness of 1 mm, and cured at 150 ° C. for 2 hours to prepare a test piece having a silicone rubber layer. The test piece was placed in a 100 cc glass bottle with 0.1 g of sulfur crystals, sealed, and left to stand at 70 ° C. The degree of corrosion of silver plating after 1 day and 7 days was visually observed and evaluated according to the following criteria.

○: no corrosion (discoloration)

△: slight corrosion (discoloration)

×: black side

Comparative Example 2

The adhesiveness (adhesive strength) test and the corrosion resistance test were done similarly to Examples 1-6 and Comparative Example 1 except not using a primer composition.

As apparent from the results shown in Table 1, in Examples 1 to 6 using the primer composition of the present invention, Al and the cured product of the addition reaction curable silicone rubber composition are firmly adhered. Moreover, in the heat resistance test of the primer composition film apply | coated to the slide glass, there was no discoloration, there was no change of the film itself, and it was excellent also in heat resistance. In the corrosion resistance test using the LED package equipped with the silver electrode, all of Examples 1 to 6 had no discoloration even after 7 days had elapsed, and a high corrosion inhibitory effect was observed.

On the other hand, the comparative example 1 using the primer composition different from the primer composition of this invention was inferior to adhesiveness and corrosion resistance compared with Examples 1-6. In Comparative Example 2, in which the primer composition itself was not used, the adhesion and the corrosion resistance were significantly inferior to those of Examples 1 to 6.

In addition, this invention is not limited to the said embodiment. The said embodiment is an illustration, It has the structure substantially the same as the technical idea described in the claim of this invention, and what exhibits the same effect is contained in the technical scope of this invention.

One… Optical semiconductor device (LED lamp)
2… Primer composition
3... LED
4… Board
5... Cured product of the addition reaction curable silicone composition
6... Metal electrode
7... Bonding wire
11... Test piece
12, 13... Al substrate
14, 15... Primer composition film
16... Cured product of an addition reaction curable silicone rubber composition

Claims (7)

As a primer composition which adhere | attaches the board | substrate which mounted the optical semiconductor element, and the hardened | cured material of the addition reaction curable silicone composition which seals the said optical semiconductor element,
(A) At least one of the acrylic acid ester and methacrylic acid ester which has one or more SiH groups in 1 molecule, and at least one of the acrylic acid ester and methacrylic acid ester which has one or more alkoxy groups in 1 molecule, and does not have a SiH group and an alkoxy group A copolymer comprising at least one of an acrylic acid ester and a methacrylic acid ester,
(B) solvent
A primer composition comprising a. The primer composition of Claim 1 whose compounding quantity of the said (B) component is 70 mass% or more of the said primer composition. The method according to claim 1 or 2, wherein the primer composition,
(C) silane coupling agent
A primer composition further comprising. The board | substrate which mounted the optical semiconductor element, and the hardened | cured material of the addition reaction curable silicone composition which seals the said optical semiconductor element were adhere | attached with the primer composition of Claim 1 or 2, The optical semiconductor device characterized by the above-mentioned. The optical semiconductor device according to claim 4, wherein the optical semiconductor element is a light emitting diode. The optical semiconductor device according to claim 4, wherein the constituent material of the substrate is polyamide, fiber reinforced plastic, ceramics, silicon, silicon modified polymer, or liquid crystal polymer. The optical semiconductor device according to claim 4, wherein the cured product of the addition reaction curable silicone composition is rubbery.

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