JP2010278411A - White coating agent, substrate for mounting optical semiconductor element using the same, and optical semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a white coating agent capable of forming a substrate for mounting an optical semiconductor element capable of sufficiently suppressing the generation of cracks caused by stress applied in a manufacturing process or the like of a printed circuit board. <P>SOLUTION: The white coating agent includes a thermosetting resin, a white pigment, a curing agent, a curing catalyst, and elastomer. Whiteness when leaving cured materials composed of the white coating agent for 24 hours at 200°C is preferably 75 or more. Preferably, the thermosetting resin is an epoxy resin. Preferably, the elastomer is at least one kind selected from a group composed of an acrylic resin, an urethane resin, a polybutadiene resin, a polyester resin, a silicone resin, and modified resins thereof. Preferably, the white pigment is at least one kind selected from a group composed of titanium oxide, silica, alumina, magnesium oxide, antimony oxide, aluminum hydroxide, barium sulfate, magnesium carbonate, barium carbonate, and magnesium hydroxide. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a white coating agent, an optical semiconductor element mounting substrate and an optical semiconductor device using the white coating agent, and more specifically, a white coating agent used between conductor members, an optical semiconductor element mounting substrate and an optical semiconductor using the white coating agent. Relates to the device.

  Conventionally, as a printed wiring board for mounting a light emitting diode (LED), a glass woven cloth impregnated with an epoxy resin containing titanium dioxide and then heat-cured laminated board or an epoxy containing alumina in addition to titanium dioxide. It is known to use a laminate using a resin (for example, see Patent Documents 1 to 3).

JP-A-10-202789 JP 2003-060321 A JP 2008-001880 A

  However, the conventional epoxy resin laminate as described in the above-mentioned patent document is cracked by the heat treatment in the manufacturing process of the printed wiring board and the LED mounting process, or the heating at the time of use after the LED mounting. Sometimes. Therefore, deformation due to heat generation occurs at the time of use after LED mounting, and there is a concern about a decrease in reliability when used as an optical semiconductor device, and further improvement is necessary.

  The present invention has been made in view of the above-described problems of the prior art, and can form a substrate such as a substrate for mounting an optical semiconductor element that can sufficiently suppress the generation of cracks due to stress applied in a manufacturing process of a printed wiring board. It is another object of the present invention to provide a white coating agent, an optical semiconductor element mounting substrate and an optical semiconductor device using the white coating agent.

  In order to achieve the above object, the present invention provides a white coating agent containing a thermosetting resin, a white pigment, a curing agent, a curing catalyst, and an elastomer.

  According to such a white coating agent, by having the above-described composition, it is possible to form a substrate such as an optical semiconductor element mounting substrate that can sufficiently suppress generation of cracks due to stress applied in a manufacturing process of a printed wiring board. .

  The white coating agent of the present invention preferably has a whiteness of 75 or more when a cured product made of the white coating agent is left at 200 ° C. for 24 hours.

  According to such a white coating agent, it has excellent heat resistance and excellent light reflectance in the visible light region by having the above-described composition and satisfying the above-described whiteness condition. It is possible to form a substrate such as a substrate for mounting an optical semiconductor element that can sufficiently suppress a decrease in light reflectivity due to irradiation treatment and can sufficiently suppress generation of cracks due to stress applied in a manufacturing process of a printed wiring board.

  Moreover, it is preferable that the white coating agent of this invention is what is used between conductor members. Since the effect mentioned above is acquired, the white coating agent of this invention is used suitably between conductor members.

  In the white coating agent of the present invention, the thermosetting resin is preferably an epoxy resin. According to such a white coating agent, a substrate such as a substrate for mounting an optical semiconductor element having better heat resistance can be formed.

  In the white coating agent of the present invention, the elastomer is preferably at least one selected from the group consisting of acrylic resins, urethane resins, polybutadiene resins, polyester resins, silicone resins, and modified resins thereof. . According to such a white coating agent, it is possible to form a substrate such as a substrate for mounting an optical semiconductor element that can sufficiently suppress the occurrence of cracks. Moreover, since generation | occurrence | production of a crack can be suppressed further fully, it is more preferable that the said elastomer is a dendritic polyester resin.

  In the white coating agent of the present invention, the white pigment is selected from the group consisting of titanium oxide, silica, alumina, magnesium oxide, antimony oxide, aluminum hydroxide, barium sulfate, magnesium carbonate, barium carbonate, and magnesium hydroxide. It is preferable that at least one selected. By using these white pigments, it is possible to form a substrate such as a substrate for mounting an optical semiconductor element having better light reflectance in the visible light region.

  Moreover, in the white coating agent of this invention, it is preferable that the average particle diameter of the said white pigment is 0.1-50 micrometers. By using a white pigment having an average particle diameter within the above range, a substrate such as an optical semiconductor element mounting substrate having a better light reflectance in the visible light region can be formed.

  Furthermore, in the white coating agent of the present invention, the content of the white pigment is preferably 10 to 85% by volume based on the total solid content of the white coating agent. By setting the content of the white pigment within the above range, it is possible to form a substrate such as a substrate for mounting an optical semiconductor element having better light reflectance in the visible light region.

  The present invention also includes a substrate, a plurality of conductor members formed on the surface of the substrate, and a white resin layer formed between the plurality of conductor members and made of the white coating agent of the present invention. Provided is a substrate for mounting an optical semiconductor element. In the substrate for mounting an optical semiconductor element in which a white resin layer made of a white coating agent is formed between a plurality of conductor members, generation of cracks due to stress applied in a manufacturing process of a printed wiring board is sufficiently suppressed.

  The present invention further provides an optical semiconductor device comprising an optical semiconductor element mounted on the optical semiconductor element mounting substrate of the present invention. Since the optical semiconductor device includes the optical semiconductor element mounting substrate of the present invention, the generation of cracks due to stress applied in the manufacturing process of the printed wiring board is sufficiently suppressed.

  According to the present invention, a white coating agent capable of forming a substrate such as a substrate for mounting an optical semiconductor element that can sufficiently suppress the occurrence of cracks due to stress applied in a manufacturing process of a printed wiring board, etc., and an optical semiconductor device using the same A mounting substrate and an optical semiconductor device can be provided.

It is the schematic which shows a suitable example of the optical semiconductor device of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

(White coating agent)
The white coating agent of the present invention contains a thermosetting resin, a white pigment, a curing agent, a curing catalyst, and an elastomer. The white coating agent of the present invention preferably has a whiteness of 75 or more when a cured product made of the white coating agent is left at 200 ° C. for 24 hours.

The whiteness is determined by the following formula (1). Whiteness can be measured using a spectrocolorimeter.
W = 100−sqr [(100−L) ² + (a ² + b ² )] (1)
(W: whiteness, L: lightness, a: hue, b: saturation)

  Further, the curing condition of the cured product composed of the white coating agent is a condition capable of sufficiently curing the white coating agent, more specifically, a mixture of the thermosetting resin and the curing agent can be sufficiently cured. The conditions may be sufficient, and it is preferable to set the conditions at 130 to 180 ° C. for 0.5 to 10 hours.

  In the white coating agent of the present invention, the whiteness is preferably 75 or more, more preferably 80 or more, and still more preferably 90 or more.

  According to the white coating agent having the above composition and satisfying the above whiteness degree, it is used between the conductor members, has excellent heat resistance and excellent light reflectance in the visible light region, and is heated. Forming a substrate for mounting an optical semiconductor element capable of sufficiently suppressing a decrease in light reflectivity due to a processing or a light irradiation process and capable of sufficiently suppressing a crack caused by a stress applied in a manufacturing process of a printed wiring board, etc. Can do.

  Hereinafter, each component used for the white coating agent of this invention is demonstrated.

  Examples of the thermosetting resin used in the present invention include epoxy resins, urethane resins, silicone resins, polyester resins, and modified resins thereof. Among these, an epoxy resin is preferable, and an alicyclic epoxy resin and an epoxy resin having an isocyanurate skeleton are more preferable.

  By using an alicyclic epoxy resin or an epoxy resin having an isocyanurate skeleton as an epoxy resin, a substrate such as an optical semiconductor element mounting substrate that can more sufficiently suppress a decrease in light reflectance due to heating or light irradiation. Can be formed.

  Moreover, it is preferable that an epoxy resin does not have an aromatic ring as much as possible from a viewpoint which suppresses the fall of the light reflectivity by light irradiation more fully. Further, the thermosetting resin is preferably one with relatively little coloring.

  Examples of the alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate [trade names: Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2081 (above, Daicel Chemical Industries Ltd.) ERL 4221, ERL 4221D, ERL 4221E (above, manufactured by Dow Chemical Japan Co., Ltd.), bis (3,4-epoxycyclohexylmethyl) adipate Ink Chemical Industries, Ltd.)], 1-epoxyethyl-3,4-epoxycyclohexane, Epicoat YX8000, Epicoat YX8034, Epicoat YL7170 (above, Japan Epoxy Resin) Made by formula companies), Celloxide 2081, CELLOXIDE 3000, Epolead GT301, Epolead GT401, EHPE3150 (or more, include Daicel Chemical Industries, Ltd.), and the like.

  Preferred alicyclic epoxy resins include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, Epikote YX8000, Epicote YX8034, Eporide GT301, Epolide GT401 and EHPE3150 are mentioned.

  Examples of the epoxy resin having an isocyanurate skeleton include triglycidyl isocyanurate (trade name: TEPIC-S, manufactured by Nissan Chemical Industries, Ltd.).

  Examples of the epoxy resin other than the above include bisphenol A type epoxy resin and bisphenol S type epoxy resin. Specifically, for example, Epicoat 828, YL980 (manufactured by Japan Epoxy Resin Co., Ltd.), YLSV120TE (Toto Kasei Co., Ltd.) and the like can be mentioned.

  A thermosetting resin can be used individually by 1 type or in mixture of 2 or more types as appropriate.

  Moreover, it is preferable to use a thermosetting resin having a molecular weight of less than about 500.

  The content of the thermosetting resin in the white coating agent is preferably 5 to 30% by mass and more preferably 10 to 20% by mass based on the total solid content of the white coating agent. When this content is less than 5% by mass, the fluidity tends to be lowered and a uniform cured product tends to be hardly obtained, and when it exceeds 30% by mass, the reflectance tends to decrease.

  The curing agent used in the present invention can be used without particular limitation as long as it reacts with the thermosetting resin, but a curing agent with relatively little color is preferable. Examples of the curing agent include an acid anhydride curing agent, an isocyanuric acid derivative, and a phenol curing agent.

  Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride. Acid, dimethyl glutaric anhydride, diethyl glutaric anhydride, succinic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, norbornene dicarboxylic anhydride, methyl norbornene dicarboxylic anhydride, norbornane dicarboxylic anhydride, methyl norbornane And dicarboxylic acid anhydride.

  Isocyanuric acid derivatives include 1,3,5-tris (1-carboxymethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3-carboxypropyl) ) Isocyanurate, 1,3-bis (2-carboxyethyl) isocyanurate and the like.

  In the present invention, among the curing agents described above, phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, dimethyl anhydride It is preferable to use glutaric acid, diethyl glutaric anhydride, or 1,3,5-tris (3-carboxypropyl) isocyanurate.

  The curing agent preferably has a molecular weight of 100 to 400, and is preferably colorless or light yellow.

  A hardening | curing agent can be used individually by 1 type or in combination of 2 or more types.

  The content of the curing agent in the white coating agent is preferably 50 to 200 parts by mass and more preferably 100 to 150 parts by mass with respect to 100 parts by mass of the thermosetting resin. When this content is less than 50 parts by mass, curing tends not to proceed sufficiently, and when it exceeds 200 parts by mass, the cured product tends to be brittle and easily colored.

  The elastomer used in the present invention is one or two selected from the group consisting of acrylic resins, urethane resins, polybutadiene resins, polyester resins, silicone resins, silicone-caprolactone block copolymers, and modified resins thereof. A combination of more than one species is preferred.

  Moreover, it is preferable to use an elastomer having a weight average molecular weight of about 500 to 1,000,000. If the weight average molecular weight is less than 500, the crack suppressing effect may not be sufficiently exhibited. If the weight average molecular weight exceeds 1,000,000, the viscosity of the white coating agent increases, and it is applied when applied by screen printing or the like. There is a tendency to deteriorate.

  In the present invention, it is preferable to use a dendritic polymer as the elastomer. As the dendritic polymer, it is preferable to use a dendritic polyester resin from the viewpoint of exhibiting the effects of less coloring and excellent strength and transparency such as crack resistance and the like.

  The dendritic polyester resin is a polyester resin in which at least one dihydroxymonocarboxylic acid of 1 to 50 generations, preferably 1 to 10 generations, is added to a core having at least one reactive epoxy group or hydroxyl group. More preferably.

  Preferred nuclei include alcohols such as neopentyl glycol, trimethylolpropane, pentaerythritol, 2-butyl-2-ethyl-1,3-propanediol, epoxides such as glycidyl esters of monocarboxylic acids, glycidyl ethers of monoalcohols, etc. And the like.

  Examples of the dihydroxymonocarboxylic acid include 2,2-bis (hydroxymethyl) propionic acid and 2,2-bis (hydroxymethyl) butanoic acid.

  There is no restriction | limiting in particular in the manufacturing method of the dendritic polymer used for this invention, A well-known method is applicable.

  In the white coating agent of the present invention, the elastomer such as a dendritic polymer is preferably contained in an amount of 1 to 60 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the curing agent. When the content of the elastomer is less than 1 part by mass, the toughness of the obtained cured product is not sufficient, and crack resistance may be reduced. On the other hand, when the content of the elastomer exceeds 60 parts by mass, the white coating agent becomes highly viscous and difficult to handle, and the glass transition temperature of the resulting cured product may be remarkably lowered, which is not preferable in practice.

  The curing catalyst (curing accelerator) used in the present invention is not particularly limited. For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, tri-2,4, Tertiary amines such as 6-dimethylaminomethylphenol, imidazoles such as 2-ethyl-4-methylimidazole and 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o , O-diethyl phosphorodithioate, tetra-n-butylphosphonium-tetrafluoroborate, phosphorus compounds such as tetra-n-butylphosphonium-tetraphenylborate, quaternary ammonium salts, organometallic salts and derivatives thereof It is done. These can be used individually by 1 type or in combination of 2 or more types. Among these curing accelerators, it is preferable to use tertiary amines, imidazoles, and phosphorus compounds.

  The content of the curing catalyst (curing accelerator) in the white coating agent is preferably 0.01 to 8 parts by mass, and 0.1 to 3 parts by mass with respect to 100 parts by mass of the thermosetting resin. Is more preferable. If the content of the curing accelerator is less than 0.01 parts by mass, a sufficient curing acceleration effect may not be obtained, and if it exceeds 8 parts by mass, discoloration may be seen in the resulting molded product. .

  Examples of the white pigment used in the present invention include silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, barium carbonate, and inorganic hollow particles. It is done. These can be used individually by 1 type or in combination of 2 or more types.

  Among these, white pigments include silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, and magnesium hydroxide in terms of thermal conductivity, light reflection characteristics, moldability, and flame retardancy. , One or a mixture of two or more selected from the group consisting of barium sulfate, magnesium carbonate and barium carbonate is preferred.

  Examples of the inorganic hollow particles include sodium silicate glass, aluminum silicate glass, borosilicate soda glass, and shirasu.

  By using the white pigment described above, it is possible to form a substrate such as an optical semiconductor element mounting substrate that has a better light reflectance in the visible light region.

  The average particle diameter of the white pigment is preferably in the range of 0.1 to 50 μm, and more preferably in the range of 0.1 to 10 μm. If the average particle size is less than 0.1 μm, the particles tend to aggregate and the dispersibility tends to deteriorate, and if it exceeds 50 μm, the reflection characteristics tend to be difficult to obtain sufficiently.

  By using a white pigment having an average particle diameter within the above range, a substrate such as an optical semiconductor element mounting substrate having a better light reflectance in the visible light region can be formed. The average particle diameter of the white pigment is measured by a laser beam type particle size distribution analyzer, for example, a Beckman Coulter LS 13 320.

  Further, from the viewpoint of the flame retardant effect, the white pigment is preferably aluminum hydroxide or magnesium hydroxide. These flame retardants are preferable in that they are white and do not affect the reflectance. Furthermore, from the viewpoint of moisture resistance reliability, aluminum hydroxide and magnesium hydroxide with less ionic impurities are preferable. For example, a Na compound content of 0.2% by mass or less is preferable.

  The average particle diameter of aluminum hydroxide or magnesium hydroxide is not particularly limited, but is preferably 0.1 to 50 μm and more preferably 0.1 to 10 μm from the viewpoint of flame retardancy and fluidity. preferable.

  The content of aluminum hydroxide or magnesium hydroxide in the white coating agent is preferably 10 to 30% by mass, more preferably 20 to 30% by mass based on the total amount of the white pigment. If the content is less than 10% by mass, the flame-retardant effect tends to be hardly obtained, and if it exceeds 30% by mass, the fluidity and curability tend to be adversely affected. By setting the content of aluminum hydroxide or magnesium hydroxide within the above range, a substrate such as a substrate for mounting an optical semiconductor element having excellent light reflectivity in the visible light region and excellent flame retardancy can be obtained. Can be formed.

  The white pigment content (filling amount) in the white coating agent is preferably 10 to 85% by volume, more preferably 15 to 70% by volume, based on the total solid content of the white coating agent, and 20 It is particularly preferred that it is ˜50% by volume. If this content is less than 10% by volume, the light reflection characteristics tend to be reduced, and if it exceeds 85% by volume, the moldability tends to be poor and the production of the substrate tends to be difficult. By setting the content of the white pigment within the above range, it is possible to form a substrate such as a substrate for mounting an optical semiconductor element having better light reflectance in the visible light region.

  Moreover, you may add a coupling agent to the white coating agent of this invention in order to improve the dispersibility of a white pigment. Examples of the coupling agent include a silane coupling agent and a titanate coupling agent. From the viewpoint of coloring, an epoxy silane coupling agent is preferable.

  Epoxysilane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

  The content of the coupling agent in the white coating agent is preferably 5 parts by mass or less with respect to 100 parts by mass of the white pigment.

  In addition, the white coating agent of the present invention includes, as other additives, an antioxidant, a light stabilizer, an ultraviolet absorber, a release agent, an ion scavenger, a flexible agent, a leveling agent, an antifoaming agent, and the like. It may be added. As the leveling agent and antifoaming agent, a dimethylsiloxane resin is suitable.

  Furthermore, a solvent may be added to the white coating agent of the present invention. Examples of the solvent include acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, ethyl carbitol acetate, propylene glycol monomethyl ether acetate and the like. However, the white coating agent of the present invention having the above composition is liquid even without a solvent, and can be formed without adding a solvent.

  In the case of a solvent-free process, the B-stage process can be omitted at the time of film formation, so that the process can be simplified and problems such as a decrease in light reflectivity associated with the B-stage process can be solved. Can do.

  The white coating agent of the present invention preferably has a viscosity at 25 ° C. of 5 to 200 Pa · s, and more preferably 10 to 50 Pa · s. The viscosity of the white coating agent is measured with an E-type viscometer. If the viscosity is less than 5 Pa · s, unevenness tends to occur in the film thickness of the resulting cured product, and if it exceeds 200 Pa · s, the printability of the white coating agent tends to decrease.

(Optical semiconductor element mounting substrate and optical semiconductor device)
The substrate for mounting an optical semiconductor element of the present invention is a white resin layer made of the white coating agent of the present invention formed between a base material and a plurality of conductor members (connection terminals) formed on the surface of the base material, Is provided. The optical semiconductor device of the present invention is obtained by mounting an optical semiconductor element on the optical semiconductor element mounting substrate of the present invention.

  In the optical semiconductor element mounting substrate in which the white resin layer made of the white coating agent of the present invention is formed between a plurality of conductor members, generation of cracks due to stress applied in the manufacturing process of the printed wiring board is sufficiently suppressed. .

  In addition, since the optical semiconductor device includes the optical semiconductor element mounting substrate of the present invention, generation of cracks due to stress applied in the manufacturing process of the printed wiring board is sufficiently suppressed.

  In addition, as a white coating agent for forming a white resin layer, an optical semiconductor element in which a white coating agent having a whiteness of 75 or more when a cured product of the white coating agent is allowed to stand at 200 ° C. for 24 hours is used. The mounting substrate and the optical semiconductor device have excellent heat resistance and excellent light reflectance in the visible light region, and the decrease in light reflectance due to heat treatment or light irradiation treatment is sufficiently suppressed, and printing. Generation of cracks due to stress applied in the manufacturing process of the wiring board is sufficiently suppressed.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the optical semiconductor device of the present invention. As shown in FIG. 1, an optical semiconductor device 100 is formed between a base material 1, a plurality of conductor members 2 formed on the surface of the base material 1, and a plurality of conductor members (connection terminals) 2. An optical semiconductor element 10 is mounted on an optical semiconductor element mounting substrate including the white resin layer 3 made of the white coating agent of the present invention, and a transparent sealing resin so that the optical semiconductor element 10 is sealed 4 is a surface-mount type light emitting diode provided with 4. In the optical semiconductor device 100, the optical semiconductor element 10 is bonded to the conductor member 2 through the adhesive layer 8 and is electrically connected to the conductor member 2 by a wire 9.

  As the base material 1, a base material used for a substrate for mounting an optical semiconductor element can be used without particular limitation, and examples thereof include a resin laminated board such as an epoxy resin laminated board.

  The conductor member 2 functions as a connection terminal, and can be formed by a known method such as a method of photoetching a copper foil.

  The substrate for mounting an optical semiconductor element is produced by applying the white coating agent of the present invention between the plurality of conductor members 2 on the base material 1 and heating and curing to form the white resin layer 3 made of the white coating agent. can do.

  As a method for applying the white coating agent of the present invention to the substrate 1, for example, a coating method such as a printing method, a die coating method, a curtain coating method, a spray coating method, or a roll coating method can be used.

  Although it does not specifically limit as a heating condition at the time of heat-hardening the coating film of a white coating agent, For example, it is preferable to heat on 130-180 degreeC and the conditions for 30 to 600 minutes.

  Thereafter, the resin component excessively attached to the surface of the conductor member 2 is removed by buffing or the like to expose the circuit formed of the conductor member 2 to form an optical semiconductor element mounting substrate.

  Moreover, in order to ensure the adhesiveness between the white resin layer 3 and the conductor member 2, it is also preferable to subject the conductor member 2 to a roughening treatment such as oxidation-reduction treatment or CZ treatment (manufactured by MEC Co., Ltd.).

  Since the surface of the optical semiconductor element mounting substrate of the present invention is formed of only the white resin layer 3 and the conductor member 2, the use of the optical semiconductor element mounting substrate can sufficiently prevent heat and light deterioration. An optical semiconductor device having a suppressed long life can be obtained.

  In the optical semiconductor element mounting substrate of the present invention, since the white resin layer 3 is disposed only between the conductor members 2, for example, the white resin layer 3 is disposed between the base material 1 and the conductor member 2. Compared with the case where it forms on the whole surface of the base material 1, generation | occurrence | production of the curvature of the board | substrate for optical semiconductor element mounting can fully be suppressed.

  As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment.

  EXAMPLES Hereinafter, although an Example explains in full detail this invention, the scope of the present invention is not limited to these Examples.

[Example 1]
100 parts by mass of triglycidyl isocyanurate (trade name: TEPIC-S, manufactured by Nissan Chemical Industries, Ltd.) as a thermosetting resin (epoxy resin), methylhexahydrophthalic anhydride as a curing agent (acid anhydride curing agent) (Trade name: HN-5500E, manufactured by Hitachi Chemical Co., Ltd.) 150 parts by mass, dendritic polyester (trade name: BOLTORN P-1000, manufactured by Perstorp, weight average molecular weight: 1800) as an elastomer, 25 parts by mass, as white pigment 470 parts by mass of titanium oxide (trade name: FTR-700, manufactured by Sakai Chemical Industry Co., Ltd., average particle size: 0.2 μm), and tetra-n-butylphosphonium-o, o- as a curing catalyst (curing accelerator) 1.5 parts by mass of diethyl phosphorodithioate (trade name: PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) , Kneading temperature 20 to 30 ° C., under the conditions of the kneading time of 10 minutes, then kneaded with kneader to prepare a white coating agent. The viscosity of the obtained white coating agent was 30 Pa · s at 25 ° C. The white pigment content based on the total solid content of the white coating agent was 32% by volume.

[Example 2]
As thermosetting resin (epoxy resin), 100 parts by mass of Celoxide 2021P (trade name, manufactured by Daicel Chemical Industries), which is an alicyclic epoxy resin, methylhexahydrophthalic anhydride (trade name: HN-5500E, Hitachi Chemical) 120 parts by mass of Kogyo Co., Ltd., dendritic polyester (trade name: BOLTORN P-1000, manufactured by Perstorp, weight average molecular weight: 1800) as an elastomer, 25 parts by mass, titanium oxide (trade name: FTR-700, Sakai Chemical Industry) 410 parts by mass) and 1.5 parts by mass of tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (trade name: PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) A white coating agent was prepared by kneading with a rough machine under conditions of kneading temperature 20-30 ° C. and kneading time 10 minutes. . The viscosity of the obtained white coating agent was 20 Pa · s at 25 ° C. The white pigment content based on the total solid content of the white coating agent was 32% by volume.

[Example 3]
Cellulose 2021P (trade name, manufactured by Daicel Chemical Industries, Ltd.), an alicyclic epoxy resin, as thermosetting resin (epoxy resin), 100 parts by mass, methyl hexahydrophthalic anhydride (trade name: HN-5500E, Hitachi Chemical) Industrial Co., Ltd.) 120 parts by mass, elastomer as acrylic polymer (trade name: LA2140e, Kuraray Co., Ltd., weight average molecular weight: 80,000) 10 parts by mass, titanium oxide (trade name: FTR-700, Sakai Chemical Industry Co., Ltd.) 410 parts by mass and tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (trade name: PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) 1.5 parts by mass are mixed and kneading temperature The mixture was kneaded with a rough machine under conditions of 20 to 30 ° C. and a kneading time of 10 minutes to prepare a white coating agent. The viscosity of the obtained white coating agent was 50 Pa · s at 25 ° C. The white pigment content based on the total solid content of the white coating agent was 33% by volume.

[Example 4]
Cellulose 2021P (trade name, manufactured by Daicel Chemical Industries, Ltd.), an alicyclic epoxy resin, as thermosetting resin (epoxy resin), 100 parts by mass, methyl hexahydrophthalic anhydride (trade name: HN-5500E, Hitachi Chemical) 120 parts by mass of Kogyo Co., Ltd., 20 parts by mass of dendritic polyester (trade name: BOLTORN P-500, manufactured by Perstorp, weight average molecular weight: 1800) as an elastomer, titanium oxide (trade name: FTR-700, Sakai Chemical Industry) 410 parts by mass) and 1.5 parts by mass of tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (trade name: PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) The mixture was kneaded with a rough machine under conditions of a kneading temperature of 20 to 30 ° C. and a kneading time of 10 minutes to prepare a white coating agent. The viscosity of the obtained white coating agent was 10 Pa · s at 25 ° C. The white pigment content based on the total solid content of the white coating agent was 32% by volume.

[Example 5]
Cellulose 2021P (trade name, manufactured by Daicel Chemical Industries, Ltd.), an alicyclic epoxy resin, as thermosetting resin (epoxy resin), 100 parts by mass, methyl hexahydrophthalic anhydride (trade name: HN-5500E, Hitachi Chemical) 120 parts by mass of Kogyo Co., Ltd., acrylic rubber as an elastomer (trade name: HTR-811-2DR, manufactured by Nagase Chemtech Co., Ltd., weight average molecular weight: 470,000), 1 part by mass, titanium oxide (trade name: FTR- 700, manufactured by Sakai Chemical Industry Co., Ltd.) 410 parts by mass and tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (trade name: PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) 1.5 mass The parts were mixed and kneaded with a roughing machine under conditions of a kneading temperature of 20 to 30 ° C. and a kneading time of 10 minutes to prepare a white coating agent. The viscosity of the obtained white coating agent was 50 Pa · s at 25 ° C. The content of the white pigment based on the total solid content of the white coating agent was 34% by volume.

[Example 6]
Cellulose 2021P (trade name, manufactured by Daicel Chemical Industries, Ltd.), an alicyclic epoxy resin, as thermosetting resin (epoxy resin), 100 parts by mass, methyl hexahydrophthalic anhydride (trade name: HN-5500E, Hitachi Chemical) Kogyo Co., Ltd.) 120 parts by mass, elastomer as acrylic rubber (trade name: HTR-860P-3, manufactured by Nagase Chemtech Co., Ltd., weight average molecular weight: 800,000) 1 part by mass, titanium oxide (trade name: FTR- 700, manufactured by Sakai Chemical Industry Co., Ltd.) 410 parts by mass and tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (trade name: PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) 1.5 mass The parts were mixed and kneaded with a roughing machine under conditions of a kneading temperature of 20 to 30 ° C. and a kneading time of 10 minutes to prepare a white coating agent. The viscosity of the obtained white coating agent was 80 Pa · s at 25 ° C. The content of the white pigment based on the total solid content of the white coating agent was 34% by volume.

[Comparative Example 1]
100 parts by mass of triglycidyl isocyanurate (trade name: TEPIC-S, manufactured by Nissan Chemical Industries, Ltd.) as a thermosetting resin (epoxy resin), methylhexahydrophthalic anhydride as a curing agent (acid anhydride curing agent) (Trade name: HN-5500E, manufactured by Hitachi Chemical Co., Ltd.) 150 parts by mass, titanium oxide as a white pigment (trade name: FTR-700, manufactured by Sakai Chemical Industry Co., Ltd., average particle size: 0.2 μm) 470 parts by mass And 1.5 parts by mass of tetra-n-butylphosphonium-o, o-diethylphosphorodithioate (trade name: PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) as a curing catalyst (curing accelerator) The mixture was kneaded with a rough machine under conditions of a kneading temperature of 20 to 30 ° C. and a kneading time of 10 minutes to prepare a white coating agent. The viscosity of the obtained white coating agent was 8 Pa · s at 25 ° C. The white pigment content based on the total solid content of the white coating agent was 35% by volume.

[Comparative Example 2]
Cellulose 2021P (trade name, manufactured by Daicel Chemical Industries, Ltd.), an alicyclic epoxy resin, as thermosetting resin (epoxy resin), 100 parts by mass, methyl hexahydrophthalic anhydride (trade name: HN-5500E, Hitachi Chemical) Industrial Co., Ltd.) 120 parts by mass, titanium oxide (trade name: FTR-700, Sakai Chemical Industry Co., Ltd.) 410 parts by mass, and tetra-n-butylphosphonium-o, o-diethyl phosphorodithioate (commodity) Name: PX-4ET, manufactured by Nippon Kagaku Kogyo Co., Ltd.) 1.5 parts by mass was mixed and kneaded with a rough machine under conditions of a kneading temperature of 20-30 ° C. and a kneading time of 10 minutes to prepare a white coating agent. . The viscosity of the obtained white coating agent was 6 Pa · s at 25 ° C. The content of the white pigment based on the total solid content of the white coating agent was 34% by volume.

(Measurement of whiteness)
The white coating agents prepared in Examples 1 to 6 and Comparative Examples 1 and 2, respectively, were applied on a mold with an Al foil by a casting method, and heated and cured at 150 ° C. for 120 minutes. A cured film having a thickness of 1 mm made of an agent was prepared. About this cured film, L (lightness), a · b (hue / saturation), whiteness, and reflectance of light having a wavelength of 460 nm after being allowed to stand for 24 hours at 200 ° C. CM-508d, manufactured by Konica Minolta Sensing Co., Ltd.). The results are shown in Table 1 (initial) and Table 2 (after leaving at 200 ° C. for 24 hours).

(Evaluation of light reflectance and coloration after light irradiation)
The cured film produced by measuring the whiteness was visually checked for coloration after irradiation with light having a wavelength of 240 to 380 nm at an irradiation dose of 30 J / cm ² . Evaluation was made as “A” when there was no coloring (white), and as “B” when there was coloring. Moreover, the reflectance of the light of wavelength 460nm of the cured film after light irradiation was measured using the spectrocolorimeter (brand name: CM-508d, Minolta company make). The results are shown in Table 3.

(Production of optical semiconductor device and evaluation of cracks)
After the conductor circuit of the optical semiconductor element mounting substrate on which the conductor circuit made of copper foil is formed by photoetching is roughened by CZ treatment, the white coating agents of Examples 1 to 6 and Comparative Examples 1 and 2 are thickened by the printing method. It apply | coated by 50 micrometers and was heat-hardened at 150 degreeC for 2 hours, and formed the cured film. About the formed cured film, the presence or absence of a crack was observed visually, and the case where there was no crack was evaluated as "A", and the case where there was a crack was evaluated as "B". The evaluation results are shown in Table 3 as the presence or absence of cracks after curing.

  Next, excess resin (cured film) adhering to the surface of the conductor circuit was removed by buffing to expose the conductor circuit, thereby forming a white resin layer between the conductor circuits. The buffing was performed by mechanical polishing using a polishing machine (made by Ishii Co., Ltd.) using buffalo. As the baffle, JP buff monster V3 / V3-D2 (trade name, manufactured by Jaburo Industry Co., Ltd.) for hole filling resin polishing was used. The numbers of the baflor used were # 600, # 800, and # 1000, and these were used in combination in this order. The polishing current was 1.2A. About the white resin layer after grinding | polishing, the presence or absence of a crack was observed visually, and the case where there was no crack was evaluated as "A", and the case where there was a crack was evaluated as "B". The evaluation results are shown in Table 3 as the presence or absence of cracks after polishing.

  Thereafter, nickel and silver plating was applied to the conductor circuit. About the white resin layer after silver plating, the presence or absence of a crack was observed visually, and the case where there was no crack was evaluated as "A", and the case where there was a crack was evaluated as "B". The evaluation results are shown in Table 3 as the presence or absence of cracks after silver plating.

  Thereafter, the optical semiconductor element was die-bonded. Furthermore, the optical semiconductor element and the conductor circuit were electrically connected by wire bonding, and sealed with a transparent sealing resin to produce an optical semiconductor device.

  As shown in Tables 1 to 3, it was confirmed that the white coating agents of Examples 1 to 6 were free from cracks even after the printed wiring board manufacturing process was performed. In addition, it was confirmed that the white coating agents of Examples 1 to 5 were not colored by heat treatment or light irradiation, and the decrease in light reflectance was sufficiently suppressed.

  As is apparent from the above results, according to the substrate for mounting an optical semiconductor element in which the white resin layer made of the white coating agent of the present invention is formed between the conductor members on the substrate surface, the substrate surface is composed of only the white resin layer and the conductor circuit. Therefore, it is possible to obtain a long-life optical semiconductor device in which heat and light degradation are sufficiently suppressed.

  DESCRIPTION OF SYMBOLS 1 ... Base material, 2 ... Conductive member, 3 ... White resin layer, 4 ... Sealing resin, 8 ... Adhesive layer, 9 ... Wire, 10 ... Optical semiconductor element, 100 ... Optical semiconductor device.

Claims (11)

  A white coating agent containing a thermosetting resin, a white pigment, a curing agent, a curing catalyst, and an elastomer.   The white coating agent according to claim 1, wherein the whiteness when the cured product made of the white coating agent is allowed to stand at 200 ° C. for 24 hours is 75 or more.   The white coating agent of Claim 1 or 2 used between conductor members.   The white coating agent as described in any one of Claims 1-3 whose said thermosetting resin is an epoxy resin.   The said elastomer is at least 1 sort (s) selected from the group which consists of an acrylic resin, a urethane resin, a polybutadiene resin, a polyester resin, a silicone resin, and these modified resins, It is any one of Claims 1-4. White coating agent.   The white coating agent according to any one of claims 1 to 5, wherein the elastomer is a dendritic polyester resin.   The white pigment is at least one selected from the group consisting of titanium oxide, silica, alumina, magnesium oxide, antimony oxide, aluminum hydroxide, barium sulfate, magnesium carbonate, barium carbonate, and magnesium hydroxide. Item 7. The white coating agent according to any one of Items 1 to 6.   The white coating agent as described in any one of Claims 1-7 whose average particle diameters of the said white pigment are 0.1-50 micrometers.   The white coating agent according to any one of claims 1 to 8, wherein the content of the white pigment is 10 to 85% by volume based on the total solid content of the white coating agent.   The white resin layer which consists of a base material, the some conductor member formed in the surface of this base material, and the white coating agent as described in any one of Claims 1-9 formed between the said some conductor members And a substrate for mounting an optical semiconductor element. An optical semiconductor device comprising an optical semiconductor element mounted on the optical semiconductor element mounting substrate according to claim 10.

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