JP5621236B2 - Urethane resin composition, cured body, and optical semiconductor device using cured body - Google Patents

Description

  The present invention relates to a urethane resin composition containing a polyol component and a polyisocyanate component, a cured body, and an optical semiconductor device using the cured body.

  In the optical semiconductor device, a sealing member that cures the resin composition and protects the optical semiconductor element is used. The resin composition is usually cured by filling the resin composition into a cavity formed by a molding die in a molding apparatus and heating the molding die. At this time, in order to suppress excessive adhesion between the cured product of the resin composition and the molding die, a release agent may be contained in the resin composition. Thereby, the hardening body excellent in the mold release property with a shaping die can be obtained. Patent Document 1 discloses that a saturated fatty acid is used as a mold release agent, and Patent Document 2 discloses that a compound having a plurality of ether bonds is used as a release agent.

On the other hand, the cured body is required to have close contact with peripheral components as a sealing member of the optical semiconductor device. Lead frames, which are parts in semiconductor devices, are generally silver-plated on the surface, and the interface between the sealing member and the silver-plated surface during molding, reflow mounting, or temperature cycle testing Delamination at is often a problem.
In addition, epoxy resin, silicone resin, urethane resin, and the like are used for the sealing member in terms of light transmittance and mechanical strength, but these resins are generally excellent in adhesion to materials. Although it is considered that, adhesion to silver and gold tends to be inferior compared to other metals.

JP 2001-234033 A International Publication No. 96/15191 Pamphlet

  In the manufacture of a semiconductor device, when a release agent is contained in the resin composition, it is possible to improve the releasability with a molding die, but there is a concern that the adhesion with a lead frame or the like may be reduced. . According to the study by the present inventors, some of the optical semiconductor devices mass-produced by including a release agent in the resin composition have peeling between the lead frame and the sealing member. I understood that. Thus, regarding the sealing member or the cured body, both the releasability from the molding die and the adhesion to the peripheral member of the optical semiconductor device are not necessarily maintained at a high level.

  This invention is made | formed in view of the said situation, and provides the hardened | cured material which is excellent in adhesiveness with silver plating, the optical semiconductor device using the same, and the urethane resin composition which can obtain them. With the goal.

In the present invention, a two-component urethane resin composition comprising a liquid A containing a polyol component and a liquid B containing a polyisocyanate component, the silane coupling agent having a thiol group in the liquid A or liquid B. A two-component urethane resin composition is provided.
A cured product obtained from such a two-component urethane resin composition has high adhesion to silver plating.

The reason why high adhesion between the cured product and the silver plating can be obtained by the urethane resin composition of the present invention is not necessarily clear, but the present inventors consider as follows.
In general, thiol groups are believed to form coordination or covalent bonds with Group 1B metals such as gold, silver and copper. In addition, in the urethane resin composition of the present invention, the present inventors react with the isocyanate group in the polyisocyanate component, and the thiol group or hydrolyzed silanol group of the silane coupling agent having a thiol group reacts with the thiol group. It is thought to form a urethane bond. Thus, it is considered that the effect of improving the adhesion can be obtained by forming a bond between the cured body and silver.

The polyisocyanate component contains a total of 30% by weight or more of a polyisocyanate having at least one isocyanate group bonded to secondary carbon and having a bifunctional or trifunctional alicyclic structure and an isocyanate group residual prepolymer. preferable.
By containing a predetermined amount of the polyisocyanate having such a structure and the isocyanate group residual prepolymer, the glass transition temperature of the obtained cured product can be improved.

  The thiol group-containing silane coupling agent is preferably γ-mercaptopropyltrimethoxysilane or γ-mercaptopropylmethyldimethoxysilane.

Moreover, it is preferable that 0.1-2.0 weight% of the said silane coupling agent which has a thiol group is contained with respect to the whole quantity of a polyol component and a polyisocyanate component.
By including the silane coupling agent having a thiol group in the above range, both the adhesiveness to the silver plating and the heat resistance of the obtained cured product can be improved in a balanced manner.

（式中、Ｒ^１は炭素数７〜２８の直鎖状又は分岐状の炭化水素基を表す。）

（式中、ｍ及びｎは、ｍ／ｎの比が０．５〜１．０を満たす正の整数である。Ｒ^２，Ｒ^３は、それぞれ独立に、２価の炭化水素基、又はポリエーテル鎖を示す。）
上記脂肪酸及びシリコーン−カプロラクトンブロック共重合体は、いずれも離型剤として機能する。上記Ｂ液が、これらの化合物をさらに含むことにより、ウレタン樹脂組成物を成型して硬化体を得る際に、銀メッキとの密着性を損なわずに、成型用の金型との離型性を向上させることができる。 The liquid B further contains a fatty acid represented by the following general formula (1) and a silicone-caprolactone block copolymer represented by the following general formula (2) having a weight average molecular weight of 16,000 or less. It is preferable.

(In the formula, R ¹ represents a linear or branched hydrocarbon group having 7 to 28 carbon atoms.)

(In the formula, m and n are positive integers satisfying an m / n ratio of 0.5 to 1.0. R ² and R ³ are each independently a divalent hydrocarbon group or a polyvalent group. Indicates an ether chain.)
Both the fatty acid and the silicone-caprolactone block copolymer function as a release agent. When the liquid B further contains these compounds, when the urethane resin composition is molded to obtain a cured product, releasability from the mold for molding is maintained without impairing adhesion to the silver plating. Can be improved.

The present invention also provides a cured product obtained by curing a urethane resin composition containing a silane coupling agent having a polyol component, a polyisocyanate component, and a thiol group.
The cured body thus obtained has high adhesion to silver plating.

  The urethane resin composition comprises a fatty acid represented by the general formula (1) and a silicone-caprolactone block copolymer represented by the general formula (2) having a weight average molecular weight of 16,000 or less. Furthermore, it is preferable to include.

Moreover, it is preferable that the said urethane resin composition further contains an inorganic filler.
By further including an inorganic filler, the thermal expansion coefficient of the cured body can be brought close to the thermal expansion coefficient of the lead frame, and separation from the lead frame can be made difficult to occur in a heat resistance test and a temperature cycle test.

The present invention further provides an optical semiconductor device including a sealing member made of the above cured body.
Such an optical semiconductor device has high optical transparency of the cured body, and is excellent in optical characteristics such as light-resistant coloring and mechanical characteristics.

  ADVANTAGE OF THE INVENTION According to this invention, the hardened | cured material excellent in adhesiveness with silver plating, palladium plating, etc., an optical semiconductor device, and the urethane resin composition which can obtain them can be provided.

It is sectional drawing which shows embodiment of the optical semiconductor device of this invention. It is the figure which represented typically the measurement of the shear bond strength of a hardening body.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
The urethane resin composition of the present invention comprises a two-component urethane resin composition comprising a liquid A containing a polyol component and a liquid B containing a polyisocyanate component, and containing a silane coupling agent having a thiol group in the liquid A or liquid B. It is a thing.

(Silane coupling agent having a thiol group)
The silane coupling agent having a thiol group is preferably a silane coupling agent having one thiol group. Specific examples thereof include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane.
The content of the silane coupling agent having a thiol group in the urethane resin composition is preferably 0.1 to 2.0% by weight with respect to the total amount of the polyol component and the polyisocyanate component. It is more preferably 0.0% by weight, and even more preferably 0.1 to 0.5% by weight. 1. When the content of the silane coupling agent having a thiol group is 0.1% by weight or more, the adhesiveness between the cured product obtained by curing the urethane resin composition and silver tends to be improved. When the content is 0% by weight or less, a decrease in heat resistance such as a glass transition temperature of the cured product can be suppressed. Moreover, even if the urethane resin composition contains a mold release agent described later, the adhesion between the cured body and silver can be improved without impairing the mold release property with the molding die.

(Polyol component)
The polyol component is a component composed of a compound (polyol) having two or more alcoholic hydroxyl groups. The polyol is preferably a polyol having an aliphatic hydrocarbon group structure (aliphatic polyol), more preferably an aliphatic polyol having three or more hydroxyl groups (polyfunctional aliphatic polyol). In particular, a polyol having a large number of functional groups is preferred because the crosslink density of the resulting cured product is improved.
Examples of the aliphatic polyol include 1,4-butanediol and 1,3-propanediol. Examples of the polyfunctional aliphatic polyol include trimethylolpropane, propane-1,2,3-triol, glycerin, and pentaerythritol. Etc. Other polyols include polycaprolactone diol, polycaprolactone triol, polycarbonate diol, polycarbonate triol, polyester diol, polyether diol and the like. These can be used individually by 1 type or in combination of 2 or more types.

  The polyol component may contain a hydroxyl group residual prepolymer. The hydroxyl group-remaining prepolymer is obtained by reacting the above-mentioned polyol monomer with the polyisocyanate monomer described later so that the hydroxyl group in the polyol becomes excessive with respect to the isocyanate group in the polyisocyanate. can get. When the hydroxyl group equivalent in the polyol is X and the ratio when the isocyanate group equivalent in the polyisocyanate is Y is X / Y, the hydroxyl group-retaining prepolymer has a polyol and a poly It is preferably obtained by mixing and reacting isocyanate. By setting X / Y to a value greater than 3, it is possible to suppress an increase in the molecular weight of the hydroxyl group-retaining prepolymer and maintain a viscosity that is easy to handle. When X / Y is a value smaller than 20, the effect of the prepolymer tends to be obtained effectively. The synthesis of the hydroxyl group-retaining prepolymer can be shortened by adding a catalyst, but it is preferable to carry out a reaction at room temperature or without heating in order to avoid coloring the polymer. By including the hydroxyl group residual prepolymer in the polyol component, the compatibility between the polyol component and the polyisocyanate component can be improved.

(Polyisocyanate component)
The polyisocyanate component is a component composed of a compound (polyisocyanate) having two or more isocyanate groups. The polyisocyanate preferably has a bifunctional or trifunctional alicyclic structure having an isocyanate group bonded to a secondary carbon atom. The polyisocyanate has two or three isocyanate groups in one molecule. Specific examples thereof include isophorone diisocyanate, 4,4′-methylenebis- (cyclohexyl isocyanate), 1,3-bis- (isocyanatomethyl) cyclohexane, norbornene diisocyanate (2,5- (2,6) bis- (isocyanate). Netomethyl) [2,2,1] heptane), isopropylidenebis- (4-cyclohexyl isocyanate), cyclohexyl diisocyanate, or a mixture thereof.
Further, an isocyanurate type or biuret type polyisocyanate using the alicyclic polyisocyanate as a raw material may be used, and an isocyanurate type polyisocyanate using isophorone diisocyanate as a raw material is particularly preferable. By using such polyisocyanate, the glass transition temperature of the obtained cured product can be improved.

  The polyisocyanate component preferably contains an isocyanate group residual prepolymer. The isocyanate group-remaining prepolymer is obtained by reacting the monomer of the polyisocyanate and the monomer of the polyol so that the isocyanate group in the polyisocyanate is excessive with respect to the hydroxyl group in the polyol. can get. The isocyanate group residual prepolymer is preferably obtained by mixing and reacting a polyol and a polyisocyanate so that the aforementioned ratio X / Y is 0.05 to 0.3. By setting X / Y to a value smaller than 0.3, an increase in the molecular weight of the isocyanate group residual prepolymer can be suppressed, and the viscosity can be maintained easily. When X / Y is greater than 0.05, the effect of the prepolymer tends to be obtained effectively. The synthesis of the isocyanate group-remaining prepolymer can be shortened by adding a catalyst. However, in order to avoid coloration of the polymer, it is preferable to carry out the reaction at room temperature or without heating. By including the isocyanate group residual prepolymer in the polyisocyanate component, the compatibility between the polyol component and the polyisocyanate component can be improved.

  The ratio of the alicyclic polyisocyanate and the isocyanate group residual prepolymer to the whole polyisocyanate component is more preferably 30% by weight or more in total. Thereby, the high temperature high humidity resistance of a hardening body can be improved more.

（式中、Ｒ^１は炭素数７〜２８の直鎖状又は分岐状の炭化水素基を示す。）

（式中、ｍ及びｎは、ｍ／ｎの比が０．５〜１．０を満たす正の整数である。Ｒ^２，Ｒ^３は、それぞれ独立に、２価の炭化水素基、又はポリエーテル鎖を示す。） (Release agent)
The urethane resin composition may further contain a fatty acid represented by the following general formula (1) and a silicone-caprolactone block copolymer represented by the following general formula (2) as a release agent.

(In the formula, R ¹ represents a linear or branched hydrocarbon group having 7 to 28 carbon atoms.)

(In the formula, m and n are positive integers satisfying an m / n ratio of 0.5 to 1.0. R ² and R ³ are each independently a divalent hydrocarbon group or a polyvalent group. Indicates an ether chain.)

Examples of the fatty acid represented by the general formula (1) include caprylic acid, pelargonic acid, lauric acid, mytilic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid, behenic acid, lignoceric acid, Saturated fatty acids such as serotic acid and montanic acid; unsaturated fatty acids such as palmitoyl acid, oleic acid, vaccenic acid, linoleic acid, eleostearic acid, and nervonic acid. In general formula (1), the carbon number of R ¹ is usually 7 to 28, preferably 10 to 22, and more preferably 14 to 18. Among them, isostearic acid having 17 carbon atoms is preferable because it is a liquid and does not increase the viscosity of the urethane resin composition.

In the silicone-caprolactone block copolymer represented by the general formula (2), the m / n ratio in the formula satisfies 0.5 to 1.0. When the ratio of m / n is larger than 0.5, the compatibility with other materials is high, and problems such as white turbidity in the cured product can be suppressed. Moreover, when the ratio of m / n is smaller than 1.0, excellent releasability from the molding die can be obtained. The silicone-caprolactone block copolymer has a weight average molecular weight of 16,000 or less in terms of excellent solubility.
By including the compounds represented by the general formulas (1) and (2) in the urethane resin composition, when the urethane resin composition is molded to obtain a cured product, the adhesiveness with the silver plating is not impaired. In addition, releasability from the molding die can be improved.

  The content of the release agent is preferably 0.01 to 5.0% by weight based on the total amount of the polyol component and the polyisocyanate component, and the fatty acid represented by the general formula (1) and the general formula The silicone-caprolactone block copolymer represented by (2) is used in combination. When the content of the release agent is greater than 0.01% by weight, the mold release property tends to be excellent, and when it is less than 5.0% by weight, the cured product has a heat resistance such as a glass transition temperature. There is a tendency to suppress the decrease.

(Inorganic filler)
The urethane resin composition may further include an inorganic filler. The inorganic filler is preferably silica in order to maintain the light transmittance of the cured product, and it is preferable to use a mixture of silica powders having different particle diameters in order to densely fill the urethane resin composition. By including an inorganic filler in the urethane resin composition, the thermal expansion coefficient of the cured body can be brought close to the thermal expansion coefficient of the lead frame of the optical semiconductor device. It becomes difficult to occur. Moreover, when a urethane resin composition contains a fluorescent substance as an inorganic filler, white can be obtained in combination with a blue light emitting diode (LED).

(Other materials)
A catalyst can be added to the urethane resin composition. Catalysts include organometallic catalysts such as zinc, zirconium or aluminum; tin-based catalysts such as dibutyltin laurate; phenol salts of DBU (1,8-diazabicyclo [5,4,0] undecan-7-ene), octyl Catalysts such as acid salts, amines, and imidazoles can be used. Among these, zinc stearate is preferable because it is excellent in heat resistant colorability and viscosity stability at room temperature of the urethane resin composition. The content of zinc stearate is preferably 0.002 to 0.1% by weight. When the content is larger than 0.002% by weight, the effect of promoting the curing tends to be seen, and when the content is smaller than 0.1% by weight, there is no problem that the cured product becomes cloudy, which is preferable.

  The urethane resin composition may further contain a hindered amine-based light stabilizer, a phosphorus-based or hindered phenol-based antioxidant, an ultraviolet absorber, an organic filler, a coupling agent, a polymerization inhibitor, and the like. Further, from the viewpoint of moldability, a plasticizer, an antistatic agent, a flame retardant, and the like may be added. These are preferably liquid from the viewpoint of ensuring the light transmittance of the cured product, but in the case of a solid, it is preferable to have a particle diameter equal to or smaller than the wavelength used.

(Hardened body)
A hardened | cured material can be manufactured by mixing A liquid containing a polyol component, and B liquid containing a polyisocyanate component, heating this and making it react.
Each component other than the above-described polyol component and polyisocyanate component constituting the urethane resin composition may be contained in either the A liquid or the B liquid, but the silane coupling agent having a thiol group is composed of the A liquid and the B liquid. It is preferable that it is contained in A liquid before mixing with a liquid. In addition, when the mold release agent is used by being melt mixed with the liquid B before mixing the liquid A and the liquid B, an excellent effect on the compatibility at the time of mixing, and further about the mold release property and light transmittance. An excellent effect can be obtained. An inorganic filler may be added to a urethane resin composition, after mixing A liquid and B liquid.

(Optical semiconductor device)
An optical semiconductor device can be manufactured by sealing an optical semiconductor element by liquid transfer molding or compression molding the urethane resin composition obtained as described above. At this time, the urethane resin composition preferably has a gelation time at 165 ° C. of 25 seconds to 200 seconds. By setting the gelation time within this range, it is possible to manufacture under almost the same molding conditions as in the conventional solid transfer molding. When the gelation time is shorter than 25 seconds, the molten urethane resin composition is cured before sufficiently filling the flow path in the molding die (hereinafter simply referred to as “mold”), and becomes a molded product of the cured body. Unfilled sites and voids tend to occur. On the other hand, when the gelation time is longer than 200 seconds, the molded product tends to be insufficiently cured.

  FIG. 1 is a cross-sectional view schematically showing one embodiment of an optical semiconductor device. An optical semiconductor device 200 shown in FIG. 1 includes a pair of lead frames 102 (102a and 102b), an adhesive member 103 provided on one lead frame 102a, and an optical semiconductor element 104 provided on the adhesive member 103. A wire 105 that electrically connects the optical semiconductor element 104 and the other lead frame 102b, and a part of the pair of lead frames 102, an adhesive member 103, an optical semiconductor element 104, and a sealing member 106 that seals the wire 105 And have. The optical semiconductor device 200 is called a surface mount type or a chip type.

  The lead frame 102 includes one lead frame 102a and the other lead frame 102b. The lead frame 102 is a member made of a conductive material such as metal, and the surface thereof is usually coated with silver plating. Also, one lead frame 102a and the other lead frame 102b are separated from each other. The bonding member 103 is a member for bonding and fixing one lead frame 102a and the optical semiconductor element 104 to each other and electrically connecting them. The adhesive member 103 is formed from, for example, a silver paste.

  Examples of the optical semiconductor element 104 include a light emitting diode element that emits light when a voltage is applied in the forward direction. The wire 105 is a conductive wire such as a thin metal wire that can electrically connect the optical semiconductor element 104 and the other lead frame 102b.

  The sealing member 106 is formed of a cured body of the urethane resin composition. Since the sealing member 106 protects the optical semiconductor element 104 from the outside air and plays a role of taking out light emitted from the optical semiconductor element 104 to the outside, it has high light transmittance. In this embodiment, the sealing member 106 is formed of a flat plate-like portion 106a on the lead frame 102 side and a lens portion 106b on the opposite side of the lead frame 102, and the optical portion is formed by the lens portion 106b having a convex lens shape. Light emitted from the element 104 is collected.

  The optical semiconductor device 200 of the present embodiment described above can employ liquid transfer molding or compression molding as part of its manufacturing process, thereby shortening the molding time and improving productivity. . Further, by adopting liquid transfer molding or compression molding, an effect of providing a lens shape that improves the light extraction efficiency as shown in FIG. 1 can be obtained.

  The optical semiconductor device 200 only needs to include an optical semiconductor element and a sealing member that seals the optical semiconductor element, and may be a shell type instead of the surface mount type as described above.

  Next, a preferred embodiment of a method for manufacturing an optical semiconductor device will be described taking as an example the case of manufacturing the optical semiconductor device 200 of FIG. The manufacturing method of the optical semiconductor device 200 according to the present embodiment includes a step of forming the sealing member 106 of the optical semiconductor device 200 by curing the urethane resin composition by liquid transfer molding or compression molding.

  First, a structure including a plurality of assembly parts is prepared. The assembly component includes a pair of lead frames 102 (102a and 102b), an adhesive member 103 provided on one of the lead frames 102a, an optical semiconductor element 104 and an optical semiconductor element 104 formed on the adhesive member 103. And a wire 105 that electrically connects the other lead frame 102b. This structure is placed at a predetermined position in a cavity formed by a mold provided in the molding apparatus. The molding apparatus is not particularly limited as long as it is used for liquid transfer molding or compression molding, and the cavity formed by the mold has the shape of the target cured body.

  Next, the urethane resin composition is prepared and filled in a pot of a molding apparatus. Specifically, the plunger is activated, and the urethane resin composition is press-fitted from the pot into a cavity of a mold heated to a predetermined temperature via a flow path such as a runner and a gate. The mold is usually composed of a separable upper mold and a lower mold, and a cavity is formed by connecting them. Then, the urethane resin composition filled in the cavity is cured on the structure by holding the urethane resin composition in the cavity for a certain period of time. Thereby, the hardening body of a urethane resin composition is shape | molded by the target shape, and while closely sealing a some assembly component, it closely_contact | adheres to a structure.

  The mold temperature is preferably set to such a temperature that the urethane resin composition has high fluidity in the flow path and can be cured in a short time in the cavity. Although this temperature is dependent also on the composition of a urethane resin composition, it is suitable that it is 120-200 degreeC, for example. Moreover, it is preferable to set the pressure at which the urethane resin composition is press-fitted into the cavity so that the urethane resin composition can be filled in the entire cavity without any gap, and specifically, 2 MPa or more. Is preferred. When the spray pressure is 2 MPa or more, unfilled portions in the cavity and voids in the sealing member 106 tend not to be generated.

  In order to make it easy to take out the cured body (sealing member 106) of the urethane resin composition from the mold, a release agent may be applied or sprayed onto the inner wall surface of the mold that forms the cavity. Furthermore, in order to suppress generation | occurrence | production of the void in a hardening body, you may use the well-known decompression device which can decompress the inside of a cavity.

  Subsequently, after the structure and the cured body of the urethane resin composition adhered thereto are taken out from the cavity, the lead frame is cut so as to separate the plurality of assembly parts individually. Thus, an optical semiconductor device provided with the cured body of the urethane resin composition as a sealing member for sealing the assembly component is obtained.

  According to the manufacturing method of the optical semiconductor device of this embodiment described above, since the liquid transfer molding method or the compression molding method is adopted, the curing time can be set short, and the productivity of the optical semiconductor device is improved. Moreover, it becomes possible to give arbitrary shapes to a hardening body by using the said shaping | molding method.

  When an optical semiconductor device is produced by the casting method or potting method using the urethane resin composition of the present invention, depending on the type, combination, and amount of each component, it is 1 to 10 hours at 60 to 150 ° C. It is preferable to heat cure to a certain extent, and it is particularly preferable that the temperature is about 80 to 150 ° C. for about 1 to 10 hours. Moreover, in order to reduce the internal stress generated by the rapid curing reaction, it is desirable to raise the curing temperature stepwise.

  As described above, the cured body of the present invention has high optical transparency, excellent optical characteristics such as heat resistance and light-resistant coloring, and mechanical characteristics. It is suitable as a sealing member for device use. Further, by using the urethane resin composition of the present invention, the optical semiconductor element can be efficiently sealed by liquid transfer molding, and an optical semiconductor device such as an LED package can be manufactured with high productivity. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these at all. The blending ratio is parts by weight unless otherwise specified.

Example 1
As the polyol component, 19.7 parts by weight of polycaprolactone triol having a molecular weight of 300 and a hydroxyl value of 540 (mg / g KOH) (A1: Placel 303 manufactured by Daicel Chemical Industries) and trimethylolpropane (A2: manufactured by Perstorp) 10.6 parts by weight were mixed and heated and stirred to obtain a uniform polyol component. Thereafter, 0.5 part by weight of γ-mercaptopropyltrimethoxysilane (F1: KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred as a silane coupling agent having a thiol group, and this was used as liquid A. .
On the other hand, 1.0 part by weight of trimethylolpropane (A2) and 14.4 parts by weight of 4,4′-methylenebis (cyclohexyl isocyanate) (B1: Desmodur W manufactured by Sumika Bayer Urethane Co., Ltd.) are mixed and a nitrogen atmosphere is mixed. Under the conditions, the mixture was reacted at 100 ° C. for 1 hour to prepare a residual isocyanate group prepolymer.
Further, as the polyisocyanate component, 15.4 parts by weight of the above prepolymer, 15.1 parts by weight of norbornene diisocyanate (B2: Cosmonate NBDI manufactured by Mitsui Takeda Chemical Co., Ltd.), isocyanurate type isocyanate 70 which is a trimer of isophorone diisocyanate 39.2 parts by weight of a butyl acetate solution (B3: VESTATAR® T1890, manufactured by Degussa) as a hindered phenolic antioxidant, 3,9-bis [2- {3- (3-tert-butyl -4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (C: Sumilyzer GA-80 manufactured by Sumitomo Chemical) After mixing 10 parts by weight, butyl acetate was distilled off under reduced pressure. It was P _B liquid.
As the P _B solution and the release agent, isostearic acid (D1: isostearic acid EX (a compound in which R ¹ is a branched alkyl group having 18 carbon atoms in General Formula (1)) manufactured by Higher Alcohol Industry Co., Ltd.) 2. 0 parts by weight, and polyether-modified silicone (E1: SLJ02 manufactured by Asahi Kasei Wacker Co., Ltd. (compound with general formula (2), m / n = 0.7, weight average molecular weight Mw = 9,000)) 2.0 The parts by weight were mixed, heated and melted at 150 ° C. for 10 minutes, and stirred at room temperature until it became transparent and uniform. Thereafter, 0.05 part by weight of zinc stearate (Nissan Electol MZ-2, manufactured by NOF Corporation) was added as a curing accelerator and stirred, and this was designated as B solution. 14.3 parts by weight of the liquid A and 37.8 parts by weight of the liquid B were mixed (ratio of hydroxyl group equivalent / isocyanate group equivalent of 1.0) and degassed under reduced pressure to obtain a urethane resin composition.

(Example 2)
As the polyol component, 19.7 parts by weight of polycaprolactone triol (A1) and 10.6 parts by weight of trimethylolpropane (A2) were mixed and stirred under heating to obtain a uniform polyol component. Thereafter, 0.5 part by weight of γ-mercaptopropylmethyldimethoxysilane (F2: KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a silane coupling agent having a thiol group and stirred, and this was used as solution A. .
On the other hand, 1.0 part by weight of trimethylolpropane (A2) and 14.4 parts by weight of 4,4′-methylenebis (cyclohexyl isocyanate) (B1) were mixed and reacted at 100 ° C. for 1 hour in a nitrogen atmosphere. An isocyanate group residual prepolymer was prepared.
As the polyisocyanate component, 15.4 parts by weight of the above prepolymer, 15.1 parts by weight of norbornene diisocyanate (B2), and a 70% by weight isocyanurate type isocyanate which is a trimer of isophorone diisocyanate (B3) 39 2 parts by weight, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl as a hindered phenolic antioxidant ] -2,4,8,10-tetraoxaspiro [5,5] undecane (C) were mixed 0.10 parts by weight, butyl acetate was distilled off under reduced pressure, which was used as a _{P B} liquid.
1. Lauric acid (D2: Lunac L-98 manufactured by Kao Corporation (in the general formula (1), R ¹ is a linear alkyl group having 11 carbon atoms)) as the P _B liquid and the release agent. 0 parts by weight and 2.0 parts by weight of polyether-modified silicone (E2: Asahi Kasei Wacker Co., Ltd. SLJ01 (compound with general formula (2), m / n = 0.8, Mw = 6,000))) The mixture was melt-mixed, heated and melted at 150 ° C. for 10 minutes, and stirred at room temperature until it became transparent and uniform. Thereafter, 0.05 part by weight of zinc stearate was added as a hardening accelerator and stirred, and this was designated as B solution. 30.3 parts by weight of the above A liquid and 74.3 parts by weight of B liquid were mixed (ratio of hydroxyl group equivalent / isocyanate group equivalent of 1.0) and degassed under reduced pressure to obtain a urethane resin composition.

Example 3
As the polyol component, 19.7 parts by weight of polycaprolactone triol (A1) and 10.6 parts by weight of trimethylolpropane (A2) were mixed and stirred under heating to obtain a uniform polyol component. Thereafter, 0.5 part by weight of γ-mercaptopropyltrimethoxysilane (F1) was added as a silane coupling agent having a thiol group and stirred, and this was designated as solution A.
On the other hand, 1.0 part by weight of trimethylolpropane (A2) and 14.4 parts by weight of 4,4′-methylenebis (cyclohexyl isocyanate) (B1) were mixed and reacted at 100 ° C. for 1 hour in a nitrogen atmosphere. An isocyanate group residual prepolymer was prepared.
As the polyisocyanate component, 15.4 parts by weight of the above prepolymer, 15.1 parts by weight of norbornene diisocyanate (B2), and a 70% by weight isocyanurate type isocyanate which is a trimer of isophorone diisocyanate (B3) 39 2 parts by weight, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl as a hindered phenolic antioxidant ] -2,4,8,10-spiro [5,5] undecane (C) were mixed 0.10 parts by weight, butyl acetate was distilled off under reduced pressure, which was used as a _{P B} liquid.
The P _B solution, as a curing accelerator, and stirred with 0.05 part by weight of zinc stearate, which was used as B solution. 30.3 parts by weight of the above A liquid and 74.3 parts by weight of B liquid were mixed (ratio of hydroxyl group equivalent / isocyanate group equivalent of 1.0) and degassed under reduced pressure to obtain a urethane resin composition.

Example 4
As a polyol component, 0.5 parts by weight of γ-mercaptopropyltrimethoxysilane (F1) is added as a silane coupling agent having a thiol group to 50.2 parts by weight of polycaprolactone triol (A1), and this is stirred. It was set as A liquid.
49.8 parts by weight of norbornene diisocyanate (B2), 2.0 parts by weight of isostearic acid (D1) and 2.0 parts by weight of polyether-modified silicone (E1) as a release agent are melt mixed and mixed at 150 ° C. for 10 minutes. The mixture was heated and melted and stirred at room temperature until it became transparent and uniform. Thereafter, 0.05 parts by weight of zinc stearate as a curing accelerator and 0.5 parts by weight of γ-mercaptopropyltrimethoxysilane (F1) as a silane coupling agent having a thiol group were added and stirred. This was designated as solution B. 50.2 parts by weight of the above-mentioned A liquid and 53.8 parts by weight of B liquid were mixed (ratio of hydroxyl group equivalent / isocyanate group equivalent of 1.0) and degassed under reduced pressure to obtain a urethane resin composition.

(Example 5)
51.7 parts by weight of polycaprolactone triol (A1) was used as the polyol component. Thereafter, 0.5 part by weight of γ-mercaptopropyltrimethoxysilane (F1) was added as a silane coupling agent having a thiol group and stirred, and this was designated as solution A.
48.2 parts by weight of aliphatic primary diisocyanate (B4: Takenate 600 manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), 2.0 parts by weight of isostearic acid (D1) and 2.0 parts by weight of polyether-modified silicone (E1) as a release agent The part was melted and mixed, heated and melted at 150 ° C. for 10 minutes, and stirred at room temperature until it became transparent and uniform. Thereafter, 0.05 part by weight of zinc stearate was added as a hardening accelerator and stirred, and this was designated as B solution. 51.7 parts by weight of the above A liquid and 52.2 parts by weight of B liquid were mixed (ratio of hydroxyl group equivalent / isocyanate group equivalent of 1.0) and degassed under reduced pressure to obtain a urethane resin composition.

(Comparative Example 1)
As the polyol component, 19.7 parts by weight of polycaprolactone triol (A1) and 10.6 parts by weight of trimethylolpropane (A2) were mixed and stirred under heating to obtain a uniform polyol component.
On the other hand, 1.0 part by weight of trimethylolpropane (A2) and 14.4 parts by weight of 4,4′-methylenebis (cyclohexyl isocyanate) (B1) were mixed and reacted at 100 ° C. for 1 hour in a nitrogen atmosphere. An isocyanate group residual prepolymer was prepared.
As the polyisocyanate component, 15.4 parts by weight of the above prepolymer, 15.1 parts by weight of norbornene diisocyanate (B2), and a 70% by weight isocyanurate type isocyanate which is a trimer of isophorone diisocyanate (B3) 39 2 parts by weight, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl as a hindered phenolic antioxidant ] -2,4,8,10-spiro [5,5] undecane (C) were mixed 0.10 parts by weight, butyl acetate was distilled off under reduced pressure, which was used as a _{P B} liquid.
The _{P B} liquid, as a release agent, isostearic acid (D1) 2.0 parts by weight, and polyether-modified silicone (E1) 2.0 parts by weight were mixed at room temperature by heating and melting for 10 minutes at 0.99 ° C. Stir until clear and uniform. Thereafter, 0.05 part by weight of zinc stearate was added as a hardening accelerator and stirred, and this was designated as B solution. 30.3 parts by weight of the above A liquid and 74.3 parts by weight of B liquid were mixed (ratio of hydroxyl group equivalent / isocyanate group equivalent of 1.0) and degassed under reduced pressure to obtain a urethane resin composition.

(Comparative Example 2)
As the polyol component, 19.7 parts by weight of polycaprolactone triol (A1) and 10.6 parts by weight of trimethylolpropane (A2) were mixed and stirred under heating to obtain a uniform polyol component. Thereafter, 0.5 part by weight of 3-isocyanatopropyltriethoxysilane (F3: KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a thiol group-containing silane coupling agent, followed by stirring. .
On the other hand, 1.0 part by weight of trimethylolpropane (A2) and 14.4 parts by weight of 4,4′-methylenebis (cyclohexyl isocyanate) (B1) were mixed and reacted at 100 ° C. for 1 hour in a nitrogen atmosphere. An isocyanate group residual prepolymer was prepared.
As the polyisocyanate component, 15.4 parts by weight of the above prepolymer, 15.1 parts by weight of norbornene diisocyanate (B2), and a 70% by weight isocyanurate type isocyanate which is a trimer of isophorone diisocyanate (B3) 39 2 parts by weight, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl as a hindered phenolic antioxidant ] -2,4,8,10-spiro [5,5] undecane (C) were mixed 0.10 parts by weight, butyl acetate was distilled off under reduced pressure, which was used as a _{P B} liquid.
The _{P B} liquid, as a release agent, isostearic acid (D1) 2.0 parts by weight, and polyether-modified silicone (E1) 2.0 parts by weight were mixed at room temperature by heating and melting for 10 minutes at 0.99 ° C. Stir until clear and uniform. Thereafter, 0.05 part by weight of zinc stearate was added as a hardening accelerator and stirred, and this was designated as B solution. 30.3 parts by weight of the above A liquid and 74.3 parts by weight of B liquid were mixed (ratio of hydroxyl group equivalent / isocyanate group equivalent of 1.0) and degassed under reduced pressure to obtain a urethane resin composition.

(Comparative Example 3)
As the polyol component, 19.7 parts by weight of polycaprolactone triol (A1) and 10.6 parts by weight of trimethylolpropane (A2) were mixed and stirred under heating to obtain a uniform polyol component. Thereafter, 0.5 part by weight of 3-glycidoxypropyltrimethoxysilane (F4: KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred, and this was designated as solution A.
On the other hand, 1.0 part by weight of trimethylolpropane (A2) and 14.4 parts by weight of 4,4′-methylenebis (cyclohexyl isocyanate) (B1) were mixed and reacted at 100 ° C. for 1 hour in a nitrogen atmosphere. An isocyanate group residual prepolymer was prepared.
As the polyisocyanate component, 15.4 parts by weight of the above prepolymer, 15.1 parts by weight of norbornene diisocyanate (B2), and a 70% by weight isocyanurate type isocyanate which is a trimer of isophorone diisocyanate (B3) 39 2 parts by weight, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl as a hindered phenolic antioxidant ] -2,4,8,10-spiro [5,5] undecane (C) were mixed 0.10 parts by weight, butyl acetate was distilled off under reduced pressure, which was used as a _{P B} liquid.
The _{P B} liquid, as a release agent, isostearic acid (D1) 2.0 parts by weight, and polyether-modified silicone (E1) 2.0 parts by weight were mixed at room temperature by heating and melting for 10 minutes at 0.99 ° C. Stir until clear and uniform. Thereafter, 0.05 part by weight of zinc stearate was added as a hardening accelerator and stirred, and this was designated as B solution. 30.3 parts by weight of the above A liquid and 74.3 parts by weight of B liquid were mixed (ratio of hydroxyl group equivalent / isocyanate group equivalent of 1.0) and degassed under reduced pressure to obtain a urethane resin composition.

The urethane resin composition obtained as described above was evaluated according to the following method.
<Gelification time>
The gelation time was measured using a gelation tester (manufactured by SYSTEM SEIKO). The urethane resin composition was placed on a hot plate at 165 ° C., the time (seconds) for the urethane resin composition to gel was measured, and the results are shown in Tables 1 and 2.

<Compatibility>
Using a liquid transfer molding machine, a test piece having a mold temperature of 165 ° C., a time of 20 seconds, 40 × 40 mm, and a thickness of 1 mm was molded, and then heated and cured at 150 ° C. for 3 hours. The obtained test piece was measured for light transmittance at a wavelength of 460 nm using a spectrophotometer (U-3310: manufactured by Hitachi, Ltd.). Evaluations were made as (◯) when the light was transmitted at 70% or more, and (X) when the light was transmitted at less than 70%.

<Adhesive strength>
A urethane resin composition droplet was dropped on a silver-plated copper plate and heated at 165 ° C. for 3 hours to form a cylindrical cured body having a radius of 1.5 mm. The shear bond strength (MPa) of the cured product was measured using a bond tester (dage series 4000: manufactured by Arctec Co., Ltd.). The measurement temperature was 165 ° C., the tool moving speed was 100 μm / s, the shear tool 3 was moved in the X direction shown in FIG. 2, and the results are shown in Tables 1 and 2.

<Peeling after molding / Peeling after reflow>
Liquid transfer molding machine LED package with a mold temperature of 165 ° C, injection pressure of 9.8MPa, injection time of 30 seconds, curing time of 120 seconds, and outer dimensions of 5.1mm x 3.9mm Was made. The manufactured LED package was moisture-absorbed for 9 hours under the conditions of 85 ° C. and 85% RH, and then subjected to a reflow treatment of a profile of 120 seconds at a holding temperature of 150 ° C. and 5 seconds at a maximum temperature of 260 ° C.
The peeling between the cured body and the lead frame in the LED package after molding and after reflow was observed with a microscope, and the results are shown in Tables 1 and 2. The numerator in the table represents the number of peeled packages, and the denominator represents the total number of packages evaluated under the same conditions.

  The cured body of the present invention is excellent in transparency, releasability from a molding die, and adhesion to a lead frame, and can exhibit excellent performance as a cured body used for sealing an optical semiconductor.

DESCRIPTION OF SYMBOLS 1 ... Hardened body, 2 ... Silver plated copper plate, 3 ... Share tool, 102, 102a, 102b ... Lead frame, 103 ... Adhesive member, 104 ... Optical semiconductor element, 105 ... Wire, 106 ... Sealing member, 200 ... Optical semiconductor device.

Claims (8)

And A solution containing a polyol component, a two-liquid type urethane resin composition comprising a liquid B containing a polyisocyanate component, seen containing a silane coupling agent having a thiol group in the A solution or B solution,
The content of the silane coupling agent having the thiol group is 0.1 to 2.0% by weight based on the total amount of the polyol component and the polyisocyanate component, and is a two-component type used for sealing an optical semiconductor. Urethane resin composition.   The polyisocyanate component contains a total of 30% by weight or more of a polyisocyanate having at least one isocyanate group bonded to secondary carbon and having a bifunctional or trifunctional alicyclic structure and an isocyanate group residual prepolymer. Item 2. A two-component urethane resin composition used for sealing an optical semiconductor according to Item 1.   The two-component urethane resin composition used for sealing an optical semiconductor according to claim 1 or 2, wherein the silane coupling agent having a thiol group is γ-mercaptopropyltrimethoxysilane or γ-mercaptopropylmethyldimethoxysilane. . The B liquid further includes a fatty acid represented by the following general formula (1) and a silicone-caprolactone block copolymer having a weight average molecular weight represented by the following general formula (2) of 16,000 or less. A two-component urethane resin composition used for sealing an optical semiconductor according to any one of 1 to 3 .

(In the formula, R ¹ represents a linear or branched hydrocarbon group having 7 to 28 carbon atoms.)

(In the formula, m and n are positive integers satisfying an m / n ratio of 0.5 to 1.0. R ² and R ³ are each independently a divalent hydrocarbon group or a polyvalent group. Indicates an ether chain.) Obtained by curing a urethane resin composition containing a polyol component, a polyisocyanate component, and a silane coupling agent having a thiol group ,
The content of the silane coupling agent having the thiol group in the urethane resin composition is 0.1 to 2.0% by weight with respect to the total amount of the polyol component and the polyisocyanate component. Cured body used for stopping. The urethane resin composition further includes a fatty acid represented by the following general formula (1) and a silicone-caprolactone block copolymer represented by the following general formula (2) having a weight average molecular weight of 16,000 or less. The hardening body used for sealing of the optical semiconductor of Claim 5 .

(In the formula, R ¹ represents a linear or branched hydrocarbon group having 7 to 28 carbon atoms.)

(In the formula, m and n are positive integers satisfying an m / n ratio of 0.5 to 1.0. R ² and R ³ are each independently a divalent hydrocarbon group or a polyvalent group. Indicates an ether chain.) The hardening body used for sealing of the optical semiconductor of Claim 5 or 6 in which the said urethane resin composition further contains an inorganic filler. An optical semiconductor device provided with a sealing member made of a cured product used for sealing an optical semiconductor according to any one of claims 5-7.

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