Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
  • H01L23/293—Organic, e.g. plastic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
  • H01L2924/0001—Technical content checked by a classifier
  • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

• the present invention relates to an epoxy resin curing agent, an epoxy resin composition, a cured product thereof, and an optical semiconductor device. More specifically, the present invention relates to an epoxy resin curing agent, an epoxy resin composition, a cured product thereof, and an optical semiconductor device that give a cured product with little coloring and excellent crack resistance and transparency.
• epoxy resin cured products obtained from acid anhydrides and epoxy resins are inexpensive and have excellent transparency, electrical insulation, chemical resistance, moisture resistance, adhesiveness, etc., electrical insulation materials, semiconductor materials, adhesives It is used in various applications such as materials and paint materials.
• a sealing material for protecting a light emitting element of a light emitting diode (hereinafter abbreviated as LED) can be given.
• LED light emitting diode
• the epoxy resin composition using such an alicyclic epoxy resin has a drawback that the obtained cured product has poor toughness and easily cracks due to changes in conditions such as temperature.
• a method for toughening a cured product obtained from an epoxy resin composition a method using a modifier composed of various polymers is known.
• a method for improving toughness without impairing the transparency of a cured product by adding a polyester resin to an epoxy resin composition has been proposed (see, for example, Patent Document 4).
• the method of adding the dendritic polymer has a problem that it is difficult to handle because the viscosity after mixing tends to be high and the strength of the cured product tends to be poor. Thereby, it was not suitable especially when fine processing and surface smoothness were required for sealing of LED.
• the present invention has been made in view of the above problems, and can cure both low viscosity after mixing and strength after curing, and is cured with an epoxy resin that provides a cured product with little coloration and excellent crack resistance and transparency.
• An agent is provided.
• the present invention also provides a low-viscosity epoxy resin composition, a cured product and an optical semiconductor device that are less colored and excellent in crack resistance and transparency.
• the inventors of the present invention have achieved low viscosity by using an epoxy resin curing agent in which a specific dendritic polymer is added and mixed as a modifier to the polycarboxylic anhydride.
• the present inventors have found that an epoxy resin composition that is easy to handle and a cured product that is less colored and that is excellent in strength, crack resistance and transparency can be easily obtained.
• the present invention relates to the following [1] to [15].
• R 1 to R 4 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two selected from R 1 to R 4 are bonded to form a ring. It may be formed.
• An epoxy resin composition comprising an epoxy resin, a polyvalent carboxylic acid anhydride, and a dendritic polymer having a hydroxyl value of 550 mgKOH / g or less.
• R 1 to R 4 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two selected from R 1 to R 4 are bonded to form a ring. It may be formed.
• an epoxy resin curing agent that provides an epoxy resin composition that has low viscosity after mixing and is easy to handle and that has a cured product with good strength.
• a cured product having excellent transparency can be obtained.
• the polycarboxylic acid anhydride used in the present invention is not particularly limited.
• succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, itaconic anhydride examples include acid, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and the like. Two or more of these may be used in combination.
• the polyvalent carboxylic acid anhydride is represented by the general formula (1).
• a compound is preferred.
• Examples of such compounds include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenehexahydrophthalic anhydride, and the like. Two or more of these may be used in combination.
• the amount of polycarboxylic anhydride used is preferably such that the acid anhydride group is 0.8 to 1 equivalent, and 0.9 to 1 equivalent, relative to 1 equivalent of epoxy group in the epoxy resin. It is more preferable to blend so that.
• the acid anhydride group is 0.8 equivalent or more, curing is sufficient, and there is no possibility that the mechanical properties of the cured product are significantly deteriorated.
• the acid anhydride group is 1 equivalent or less, a decrease in mechanical properties of the cured product can be similarly avoided.
• the dendritic polymer used in the present invention has a hydroxyl value of 550 mgKOH / g or less, preferably a hydroxyl value of 400 to 500 mgKOH / g. If it is 550 mgKOH / g or less, it can prevent becoming high viscosity.
• the weight average molecular weight is preferably 2000 or less, more preferably 1000 to 2000.
• a dendritic polymer having a viscosity of 10 Pa ⁇ s (25 ° C.), more preferably 1 to 10 Pa ⁇ s (25 ° C.).
• the dendritic polymer is preferably a polyester. Further, it is more preferable that the polyester has 1 to 50 generations, preferably 1 to 10 generations of at least one dihydroxymonocarboxylic acid added to a nucleus having at least one reactive epoxy group or hydroxyl group.
• 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.
• dihydroxy monocarboxylic acid examples include 2,2-bis (hydroxymethyl) propionic acid and 2,2-bis (hydroxymethyl) butanoic acid.
• the dendritic polymer is preferably contained in an amount of 1 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the polyvalent carboxylic acid anhydride.
• the content of the dendritic polymer is 1 part by weight or more, the toughness of the obtained cured product is sufficient, and there is no possibility that the crack resistance is lowered.
• the content of the dendritic polymer is 60 parts by weight or less, it is easy to handle without high viscosity, and there is no fear that the glass transition temperature of the obtained cured product is remarkably lowered, which is preferable in practical use.
• the epoxy resin used in the present invention is not particularly limited, but an alicyclic epoxy resin is preferable from the viewpoint of light resistance and heat resistance.
• the alicyclic epoxy resin has an alicyclic skeleton and two or more epoxy groups in one molecule.
• an epoxy resin other than the alicyclic epoxy resin can be used depending on the purpose.
• examples of such epoxy resins include bisphenol type epoxy resins obtained by reaction of bisphenols such as bisphenol A and bisphenol S with epichlorohydrin, and phenol novolak types obtained by reaction of phenol novolac and epichlorohydrin.
• examples thereof include an epoxy resin, a glycidyl ester type epoxy resin obtained by a reaction between a polyvalent carboxylic acid and epichlorohydrin. Two or more of these may be used in combination.
• the amount of the epoxy resin other than these alicyclic epoxy resins used is preferably 0 to 80 parts by weight, more preferably 0 to 20 parts by weight with respect to 100 parts by weight of the alicyclic epoxy resin. If the usage-amount of epoxy resins other than an alicyclic epoxy resin is 80 weight part or less, it can prevent that the light resistance and heat resistance of hardened
• a target epoxy resin curing agent can be obtained by mixing a polyvalent carboxylic acid anhydride and a dendritic polymer, but the production method is not particularly limited, and a known method is applied. can do.
• the epoxy resin composition can be obtained by mixing the epoxy resin curing agent and the epoxy resin, but the production method is not particularly limited, and known methods can be applied.
• an epoxy resin composition can be obtained by separately mixing a dendritic polymer and a polyvalent carboxylic acid anhydride with an epoxy resin.
• a curing accelerator can be appropriately added depending on the purpose.
• the curing accelerator include imidazoles such as 2-ethyl-4-methylimidazole and 1-methylimidazole, tertiary amines such as benzyldimethylamine and N, N-dimethylaniline, tetramethylammonium chloride, and benzyltriethylammonium chloride.
• Quaternary ammonium salts such as tetra-n-butylphosphonium o, o-diethyl phosphorodithionate, phosphonium salts such as tetrabutylphosphonium benzotriazolate, metal salts such as zinc octylate and zinc stearate, zinc acetylacetone, Examples thereof include metal complexes such as benzoylacetone zinc.
• the blending amount in the epoxy resin composition is preferably 0.01 to 8% by weight, and more preferably 0.1 to 5% by weight. A sufficient effect is obtained when the blending amount of the curing accelerator is 0.01% by weight or more. Moreover, when the compounding quantity of a hardening accelerator is 8 weight% or less, it can reduce that the hardened
• various additives can be further added according to the purpose within a range that does not impair the properties of the obtained cured product.
• the additive include a flexibilizer, a heat stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent, an antifoaming agent, a thixotropic agent, and a release agent.
• an antioxidant for further improving the light resistance and heat resistance of the cured product, a chain transfer agent for controlling the polymerization reaction during curing, and improving the mechanical properties, adhesiveness, and handleability of the cured product.
• the epoxy resin composition in the present invention By curing the epoxy resin composition in the present invention with heat, a cured product with little coloration and excellent crack resistance and transparency can be obtained.
• cured material A well-known method is applicable.
• the temperature and time for heat curing are not particularly limited, but are preferably 90 to 180 ° C. and 1 to 12 hours.
• the LED light-emitting element or the like can be sealed by providing the epoxy resin composition on the surface of the LED light-emitting element or the like by a method such as coating, potting, or impregnation, followed by heat curing.
• the optical semiconductor device of the present invention is an optical semiconductor element such as an LED light emitting element or a photodiode element sealed with the above cured product, has little coloring, is excellent in crack resistance and transparency, and further has light resistance and It also has excellent heat resistance.
• Example 1 Polyester dendritic polymer (hydroxyl value 470 mg KOH / g, weight average molecular weight 1800, viscosity 7.6 Pa ⁇ s (25 ° C.), BOLTORN P-1000: trade name manufactured by Perstorp) 20 parts by weight polyhydric carboxylic anhydride 116 parts by weight of 4-methylhexahydrophthalic anhydride (HN-7000: manufactured by Hitachi Chemical Co., Ltd./acid anhydride equivalent 168 (g / eq)) was added as a product, and the mixture was heated to 70 ° C. and stirred uniformly. It was made to melt
• Example 2 An epoxy resin curing agent (II) was obtained in the same manner as in Example 1 except that 40 parts by weight of the polyester dendritic polymer was used instead of 20 parts by weight.
• An epoxy resin composition (II) was obtained in the same manner as in Example 1 except that 156 parts by weight of the epoxy resin curing agent (II) was used instead of the epoxy resin curing agent (I). Further, a cured product (II) was obtained in the same manner as in Example 1.
• Example 3 As a polyvalent carboxylic anhydride, a mixture of 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride (hereinafter referred to as 3 & 4-methylhexahydrophthalic anhydride. HN-5500E: Hitachi Chemical Co., Ltd.) Product / acid anhydride equivalent 168 (g / eq)) Except for using 116 parts by weight, an epoxy resin curing agent (III) was obtained in the same manner as in Example 1.
• Example 4 An epoxy resin curing agent (IV) was obtained in the same manner as in Example 3 except that 40 parts by weight of the polyester dendritic polymer was used instead of 20 parts by weight.
• An epoxy resin composition (IV) was obtained in the same manner as in Example 1 except that 156 parts by weight of the epoxy resin curing agent (IV) was used instead of the epoxy resin curing agent (I). Further, a cured product (IV) was obtained in the same manner as in Example 1.
• Comparative Example 2 An epoxy resin curing agent (VI) was obtained in the same manner as in Comparative Example 1 except that 40 parts by weight of the polyester dendritic polymer was used instead of 20 parts by weight.
• An epoxy resin composition (VI) was obtained in the same manner as in Example 1 except that 156 parts by weight of the epoxy resin curing agent (VI) was used instead of the epoxy resin curing agent (I). Further, a cured product (VI) was obtained in the same manner as in Example 1.
• a cured product (VII) was obtained from the epoxy resin composition (VII) in the same manner as in Example 1.
• Viscosity Measured with an E-type viscometer at 25 ° C.
• Measuring device SSC-5200 (manufactured by Seiko Electronics Co., Ltd.) Measurement conditions: Load 20 g / minute 10 ° C. Heating / bending strength: Measured according to JIS (Japanese Industrial Standard) standard number K7171.
• Comparative Example 1 has a relatively low viscosity due to a small amount of the dendritic polymer, but has a poor bending strength.
• Comparative Example 2 the bending strength increased with an increase in the amount of the dendritic polymer added, but the viscosity became very high, and the cured product was colored yellow.
• the cured product of Comparative Example 3 cracks occurred and the bending strength was low, and the cured product was colored yellow.
• an epoxy resin composition having a low viscosity and easy handling, and a cured product excellent in crack resistance and transparency, having high strength and little coloring.
• an epoxy resin curing agent that provides an epoxy resin composition that has low viscosity after mixing and is easy to handle and that has a cured product with good strength.
• a cured product having excellent transparency can be obtained.

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• 2009
  • 2009-07-23 WO PCT/JP2009/063188 patent/WO2010013638A1/ja active Application Filing
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