JP5738142B2 - Epoxy silicone resin and curable resin composition using the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an epoxy silicone resin having a cyclic siloxane bond, and a thermosetting resin composition excellent in optical properties, hardness, bending properties, heat-resistant coloring properties, and light-resistant coloring properties, which are essential components thereof. The present invention relates to a thermosetting resin composition suitable for the field of optical semiconductor materials.

  Epoxy resins are mainly used in many applications in the paint, civil engineering, and electrical fields because of their excellent electrical properties, adhesiveness, heat resistance, and the like. In particular, aromatic epoxy resins such as bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, phenol novolac type epoxy resin, and cresol novolac type epoxy resin are water resistant, adhesive, mechanical properties, heat resistant, and electrical insulating properties. It is widely used in combination with various curing agents because of its excellent economic efficiency. However, since these resins contain an aromatic ring, they are easily deteriorated by ultraviolet rays or the like, and there are restrictions in use in fields where weather resistance and light resistance are required.

  As for the epoxy resin composition, since the hardness of the cured product is high, it is excellent in handling properties. In low-power white LED sealing applications, the required durability is obtained, so it is often used in low-power applications. Yes. However, high-power LEDs tend to cause discoloration due to an increase in light emission and heat generation, and thus have a disadvantage that it is difficult to obtain a sufficient lifetime. In order to prevent discoloration due to an increase in calorific value, an epoxy resin exhibiting a high glass transition temperature is used, but such an epoxy resin is highly elastic and has bending properties such as strength and deflection as compared with a normal epoxy resin. Since it is low, there is a problem that the sealing material is easily cracked in an environment where cutting such as dicing or a rapid temperature change may occur. In addition, due to the recent shortening of the light emission wavelength of LEDs, there are also problems such as the occurrence of discoloration and continuous reduction in light emission output when used continuously. For this reason, it is calculated | required that a sealing material has mechanical strength simultaneously with the further improvement of heat-resistant coloring property and light resistance.

  In recent years, LED encapsulants based on silicone resins that are excellent in heat resistance and light yellowing resistance have been developed. Resin compositions by addition reaction of hydrosilyl groups and alkenyl groups and rigid isocyanuric rings are included in the structure. However, a silicone resin having an epoxy group as a reactive substituent and a resin composition obtained by curing using a curing agent have been reported.

  However, many silicone resins and epoxy resins having a silicone skeleton in the main chain have high flexibility derived from the silicone skeleton, but the hardness of the cured product is low and the surface tends to be sticky, and the strength is high. Has low disadvantages. For this reason, transparency is easily deteriorated due to adhesion of dust and the like, and handling at the time of manufacturing the LED is difficult, and the manufacturing method, configuration, design, and use are limited. In addition, a resin containing a phenyl group and having a silicone skeleton having high hardness is improved in handling properties, but it is difficult to say that the stickiness is lost due to the low glass transition temperature. In addition, there are problems in strength and deflection, and there are disadvantages such as a tendency to crack due to a sudden temperature change at the time of turning on and off. In addition, a silicone resin that has a rigid isocyanuric ring in the structure and has an epoxy group as a reactive substituent can provide a hard and non-sticky cured product. Although colorability improves, there is still room for improvement. In addition, when the LED sealing material is used, the high linear expansion coefficient derived from the flexible silicone chain leads to peeling from the base material, and the wire bonded to the chip is turned on or during a heat cycle test. There is a high concern that the stress due to the expansion or contraction due to the temperature of the sealing material cannot be withstood, and disconnection from the chip causes poor conduction. In addition, in terms of mechanical strength, the introduction of silicone chains reduces the elastic modulus and increases the deflection, but the yield point occurs at a relatively early stage, the absolute strength is insufficient, and stress is concentrated. Since there is a concern that cracks are likely to occur at the site, improvement is demanded from the aspects of linear expansion coefficient and strength.

  Moreover, since there are many LEDs mounted on the backlight of a mobile phone or a monitor, it is necessary to go through a reflow process in which the circuit board is mounted by batch soldering. The entire LED package is exposed to a reflow oven at about 260 ° C in order to mount it with lead-free solder that is suitable for the environment. Coloring and cracking of the sealing material due to a rapid temperature change, adhesion of the sealing material to the bonding site Damages such as peeling due to insufficient force and wire breakage due to expansion of the sealing material occur, and improvement in yield and productivity is demanded.

  As described above, even if a silicone resin having excellent weather resistance is used as a base, a material that completely satisfies the physical properties required for the LED sealing material has not been obtained, and has sufficient hardness, strength, and deflection, There is a demand for materials that are excellent in heat-resistant coloring and UV-coloring resistance and have mass productivity and handling properties similar to those of epoxy resins.

  Patent Document 1 discloses a resin composition obtained by addition reaction of a polyorganosiloxane resin having a hydrosilyl group and a polyorganosiloxane resin having an alkenyl group. Patent Document 2 discloses a curable polyorganosiloxane composition containing a phenyl group, an optical semiconductor element sealing agent and an optical semiconductor device using the same. Patent Document 3 discloses an organopolysiloxane having diglycidyl isocyanuryl alkyl groups at least at both ends of the main chain and a composition containing the same. Patent Documents 4 and 5 disclose an epoxy silicone resin having an isocyanuric ring in the resin chain and having an epoxy group at the terminal, and a composition containing the same. However, it is difficult to say that the thermosetting resin compositions described in these patent documents also have the above characteristics sufficiently.

JP 2010-248413 A JP 2010-084118 A JP 2010-285563 A JP 2008-274004 A International Publication WO2007-074813

  The present invention has a high hardness of the cured product, excellent heat resistance coloring property, UV resistance property, strength and deflection, and has a low coefficient of linear expansion while having a siloxane skeleton inside, and damage to the package even under reflow and heat cycles. An object of the present invention is to provide a thermosetting resin composition suitable for the electronic material field and optical semiconductor encapsulation. Another object is to provide an epoxy silicone resin suitable as a material for the thermosetting resin composition.

（式中、Ｒ₁は炭素数１〜１０の１価の炭化水素基を表し、各々同一でも異なっていても良い。Ｒ₂は炭素数１から２０の２価の炭化水素基を表し、内部にエーテル結合性酸素原子を１〜３個有していても良い。Ｅ₁はエポキシ基を少なくとも１つ以上有する１価の有機残基であり、Ｚは一般式（２）で表されるイソシアヌル環を有する2価の有機残基である。ｌ及びｍは独立に０〜３の整数であり、１≦ｌ＋ｍ≦４を満たす。ｎは０＜ｎ≦１００の数である。）

（式中、Ｒ₃は炭素数１〜１０の炭化水素基を表し、Ｒ₄は水素原子または炭素数１〜１０の、芳香族環を含んでいても良い炭化水素基を表す。） That is, this invention is represented by General formula (1), and epoxy equivalent is 200-2000 g / eq. It is an epoxy silicone resin characterized by

(In the formula, R ₁ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. R ₂ represents a divalent hydrocarbon group having 1 to 20 carbon atoms; May have 1 to 3 ether-bonded oxygen atoms, E ₁ is a monovalent organic residue having at least one epoxy group, and Z is an isocyanurate represented by the general formula (2) A divalent organic residue having a ring. L and m are each independently an integer of 0 to 3, satisfying 1 ≦ l + m ≦ 4, and n is a number of 0 <n ≦ 100.

(In the formula, R ₃ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may contain an aromatic ring.)

E ₁ in the general formula (1) includes an organic residue represented by the formula (3).

  In the present invention, the both-end SiH-containing cyclic organosiloxane represented by the general formula (4) is reacted with the both-end vinyl group-containing isocyanuric acid derivative represented by the general formula (5) in less than the theoretical amount, End-capping reaction using an epoxy resin reactive with a SiH group having a residual SiH group having at least one epoxy group in one molecule and one carbon-carbon double bond in one molecule It is the manufacturing method of the epoxy silicone resin characterized by performing.

（一般式（４）中、Ｒ₁、ｌ、ｍは一般式（１）と同意である。一般式（５）中、Ｒ₄は一般式（２）と同意である。Ｒ₅は炭素数１〜８の炭化水素基を表し、Ｒ₆は水素原子またはメチル基を表す。）

(In general formula (4), R ₁ , l and m are the same as in general formula (1). In general formula (5), R ₄ is the same as in general formula (2). R ₅ is the number of carbon atoms. 1 to 8 hydrocarbon groups are represented, and R ₆ represents a hydrogen atom or a methyl group.)

  Examples of the epoxy resin reactive with the SiH group include monoallyl diglycidyl isocyanurate.

  Furthermore, the present invention relates to a thermosetting resin composition containing the epoxy resin (A), the curing agent (B), and the curing accelerator (C) as essential components, the epoxy silicone resin (A1) as an epoxy resin component. It is a thermosetting resin composition characterized by including. Hereinafter, the epoxy silicone resin represented by the general formula (1) blended in the thermosetting resin composition is referred to as an epoxy silicone resin (A1).

  Examples of the curing agent (B) include acid anhydride compounds. Moreover, as a hardening accelerator (C), a quaternary ammonium salt or a quaternary phosphonium salt is mentioned.

  The epoxy resin (A) includes an epoxy silicone resin (A1) and an epoxy resin (D) which is liquid at room temperature, and 5 to 5 epoxy resins (D) which are liquid at room temperature with respect to 100 parts by weight of the epoxy silicone resin (A1). The epoxy equivalent of the epoxy resin (A) which mix | blends 150 weight part and means the whole epoxy resin component is 180-1000 g / eq. It is good that it is.

  Furthermore, the present invention is a thermosetting resin composition suitable for light reflection, characterized by containing (E) a white pigment, and examples of the white pigment include silica, titanium oxide, alumina, magnesium oxide, zirconium oxide, and It can be selected from at least one of inorganic hollow particles.

  The thermosetting resin composition is suitable as a resin composition for optical parts, a resin composition for electronic parts, or a resin composition for optical semiconductor parts. Furthermore, it is also suitable as a liquid sealing resin composition for semiconductors.

  Moreover, this invention is the LED device sealed using said thermosetting resin composition.

  The epoxy silicone resin of the present invention is a curable resin composition, which is excellent in surface hardness, strength, deflection, low linear expansion when used as a cured resin obtained by applying heat, has transparency, and has heat-resistant coloring properties. Further, a cured product or film having excellent light resistance can be obtained. Therefore, it is useful for electronic component materials such as semiconductors and circuit boards, and optical component materials such as optical lenses, optical sheets, and light-reflecting white molding materials. Improvement of problems such as coloring due to rust, reflow mounting, cracks in the heat cycle environment, disconnection, and peeling from the substrate can be expected.

IR spectrum of the epoxy silicone resin (ES1) of the present invention. IR spectrum of the epoxy silicone resin (ES2) of the present invention. IR spectrum of the epoxy silicone resin (ES4) of the present invention. IR spectrum of the epoxy silicone resin (ES5) of the present invention.

Hereinafter, embodiments of the present invention will be described in detail.
The epoxy silicone resin of this invention is represented by the said General formula (1), and an epoxy equivalent (g / eq.) Is 200-2000.

In the general formula (1), R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a hexyl group, a phenyl group, and a naphthyl group. Also good. Preferable R ₁ is a methyl group from the viewpoints of physical properties such as heat-resistant coloring property and light-coloring resistance when it is easily obtained and a cured product obtained by subjecting to a thermosetting resin composition and heat treatment.

  In general formula (1), l and m are an integer of 0-3 independently, and l + m is an integer of 1-4. Preferred values of l and m are l = 1 and m = 1 because of easy availability. n is an average value (number average), n represents a number greater than 0 and 100 or less. A preferable number of n is 0.05 ≦ n ≦ 30, more preferably 0.05 ≦ n ≦ 20, and more preferably 0 from the viewpoint of heat resistance coloring property, light coloring resistance, and mechanical properties when cured. .1-10. Since the epoxy silicone resin of the present invention is a mixture of molecules having different n, a component with n = 0 may exist, but a component with n = 0 is not 100%, and a component with n = 0 Is preferably 0 to 90 wt%, more preferably 0 to 70%.

（式中、ｈは１〜３の数を表す。） In the general formula (1), R ₂ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and may have 1 to 3 ether-bonded oxygen atoms therein. Examples of such a structure include a methylene group, an ethylene group, a propylene group, an isopropylene group, an isopropylidene group, a butylene group, an isobutylene group, a hexylene group, a xylylene group, a dodecylene group, represented by the following general formula (6). Group, but not limited thereto. Preferred R ₂ is preferably a C1-6 hydrocarbon group, more preferably a propylene group, from the physical properties when cured.

(In the formula, h represents a number of 1 to 3.)

  In the general formula (1), Z is a divalent organic residue containing an isocyanuric ring represented by the general formula (2).

In the general formula (2), R ₃ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. Examples of such a hydrocarbon group include, but are not limited to, a methylene group, an ethylene group, a propylene group, an isopropylene group, an isopropylidene group, a butylene group, an isobutylene group, a hexylene group, and a decylene group. Preferable R ₃ is a C1-6 hydrocarbon group, more preferably a propylene group, from the physical properties of a cured product.

In general formula (2), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Specific examples of the hydrocarbon group include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, an isoamyl group, a phenyl group, a benzyl group, a toluyl group, and a naphthyl group. A hydrocarbon group having an aromatic ring such as a phenyl group or a benzyl group is also preferred. Preferred R ₄ is preferably a hydrogen atom, a methyl group, or a phenyl group, more preferably a hydrogen atom or a methyl group, from the viewpoint of easy availability of raw materials and physical properties when cured.

  In the general formula (1), E1 is a monovalent organic residue having at least one epoxy group, and preferably an epoxy isocyanuric group represented by the general formula (3).

The epoxy silicone resin of the present invention can be advantageously produced by the production method of the present invention. The method for producing an epoxy silicone resin of the present invention comprises a theoretical amount of a vinyl group-containing isocyanuric acid derivative represented by the general formula (5) in the SiH-containing cyclic organosiloxane represented by the general formula (4). Reactive epoxy resin, and then the remaining SiH group having at least one epoxy group in one molecule and an epoxy resin reactive with SiH group having one carbon-carbon double bond in one molecule Is used to perform end-capping reaction. In the general formula (4), the same symbols as those in the general formula (1) have the same meaning. In the general formula (5), R ₄ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ₅ is a hydrocarbon group having 1 to 8 carbon atoms, and R ₆ is a hydrogen atom or a methyl group. . l

  The both-end vinyl group-containing isocyanuric acid derivative compound represented by the general formula (5) is not particularly limited as long as it is a known compound, and various compounds can be selected. For example, diallyl isocyanuric acid, dimethallyl isocyanuric acid, monomethyl diallyl isocyanurate, monomethyl dimethallyl isocyanurate, monoethyl diallyl isocyanurate, monoethyl dimethallyl isocyanurate, monopropyl diallyl isocyanurate, monopropyl dimethallyl isocyanurate, monoisoamyl Diallyl isocyanurate, monoisoamyl dimethallyl isocyanurate, monophenyl diallyl isocyanurate, monophenyl dimethallyl isocyanurate, mononaphthyl diallyl isocyanurate, mononaphthyl dimethallyl isocyanurate, etc. Two or more types may be used in combination. Among these, preferred isocyanuric acid derivative compounds are diallyl isocyanuric acid, monomethyl diallyl isocyanurate, and monophenyl diallyl isocyanurate, and particularly preferred are diallyl isocyanuric acid and monomethyl diallyl isocyanurate.

  In addition, as described in US Pat. No. 2830051, the both-end vinyl group-containing isocyanuric acid derivative compound is prepared by, for example, triallyl cyanurate in the presence of a Lewis acid such as aluminum chloride, iron chloride or activated clay. It is also possible to obtain a diallyl isocyanuric acid by adding a receptor such as phenol and reacting with a reaction solvent such as xylene as necessary, and if necessary, Further, N-alkylation may be performed by reacting with an alkyl halide. In addition, Journal of Organic chemistry vol. 35, no. 7, p. A method for obtaining diallyl isocyanuric acid by reacting allyl isocyanate and potassium cyanate with an aprotic polar solvent such as dimethylformamide and then neutralizing with an acid as described in 2253-2257 (1970) It is also possible to obtain N-alkylation by reacting with an alkyl halide as necessary. In addition, Journal of American Chemical Society vol. 51, p. 2221 (1929), it is also possible to obtain monophenyl diallyl isocyanurate by reacting with phenyl halide and methyl carbamate to obtain monophenyl isocyanuric acid and then reacting with allyl halide. However, the present invention is not limited to these, and it can be carried out in a form preferable to those skilled in the art to obtain a vinyl terminal-containing isocyanuric acid derivative compound.

As a method for producing the epoxy silicone resin of the present invention, both ends SiH group-containing organosiloxane is first charged into the reaction system, and then the amount of unreacted SiH groups remaining is always used to contain both ends vinyl groups. It is particularly preferred to add a compound sequentially and confirm that the reaction is complete before conducting a terminal termination reaction using an SiH group and reactive epoxy resin. When using only the epoxy silicone resin represented by the general formula (1), the amount of the both-end vinyl group-containing isocyanuric acid derivative compound is such that two unreacted SiH groups remain in one molecule. However, when trying to obtain a resin containing the epoxy silicone resin represented by the general formula (1), the epoxy silicone resin obtained by end-capping with an epoxy resin having a double bond satisfies the epoxy equivalent. If it is a thing, it will not specifically limit. Preferably, when the reaction with the both-end vinyl group-containing isocyanuric acid derivative compound is completed, 20 to 80% of SiH groups of both-end SiH group-containing organosiloxane may remain. For the reasons described above, in the general formula (1), E ₁ is an epoxy isocyanuric group represented by the general formula (3), R ₂ is a propylene group, R ₁ is a methyl group, m = 1, and l = 1. It is preferable to use the raw material which becomes. Z is preferably a group represented by the general formula (2) in which R ₃ is a propylene group and R ₄ is a hydrogen atom or a methyl group. Moreover, the both terminal vinyl group containing isocyanuric acid derivative compound represented by General formula (5) may use 2 or more types together.

  The epoxy resin reactive with the SiH group has at least one epoxy group in one molecule and one carbon-carbon double bond reactive with the SiH group in one molecule. . For example, monocyclic epoxy resins such as o-allylphenyl glycidyl ether, 2-allyl-4-methylphenyl glycidyl ether, 2-allyl-5-methylphenyl glycidyl ether, 2-allyl-6-methylphenyl glycidyl ether and their nuclear hydrogen Epoxy resin, 1-methyl-4-isopropenylcyclohexene oxide, 1,4-dimethyl-4-vinylcyclohexene oxide, 4-vinyl-1-cyclohexene-1,2-oxide, vinylnorbornene monooxide, dicyclopentadiene Examples include epoxy resins derived from olefin compounds containing a cyclic structure such as monooxide, and epoxy resins containing a heteroatom in the ring structure such as monoallyl diglycidyl isocyanurate, but are not limited thereto. There. Moreover, you may use these epoxy resins for reaction, using 2 or more types together. Among these, a particularly preferred epoxy resin reactive with SiH groups is monoallyl diglycidyl isocyanurate which gives an organic residue represented by the general formula (3).

  Methods other than the above, for example, carrying out a hydrosilylation reaction by simultaneously adding SiH group-containing cyclic organosiloxane, both-end vinyl group-containing isocyanuric acid derivative compound, and monoallyl diglycidyl isocyanurate into the reaction system during the reaction. Or mixed with both end vinyl group-containing isocyanuric acid derivative compound, monoallyl diglycidyl isocyanurate, which is a component having a carbon-carbon double bond that is reactive with SiH group, and put it into the reaction system. When hydrosilylation is carried out by introducing a SiH group-containing polyorganosiloxane, the reaction rate of the hydrosilylation reaction differs from that of a monoallyl diglycidyl isocyanurate from both end vinyl group-containing isocyanuric acid derivative compounds. Siloxane resin without epoxy group is generated in the systemFor this reason, the resulting epoxy silicone resin causes phase separation and becomes cloudy, and the transparency is lost. Moreover, even if the cloudiness does not occur, the effect of the present invention cannot be obtained in terms of physical properties of the cured product.

  It is well known that the hydrosilyl addition reaction proceeds in the presence of a noble metal catalyst. As the catalyst, various precious metals or complex compounds thereof can be used as long as they are known. Examples of the noble metal catalyst include platinum, rhodium, palladium, ruthenium, and iridium, but are not limited thereto, and two or more kinds may be used as necessary. Further, a material in which these metals are immobilized on a particulate carrier material such as carbon, activated carbon, aluminum oxide, silica, or the like may be used.

Noble metal complex compounds include platinum halogen compounds (PtCl ₄ , H ₂ PtCl ₆ .6H ₂ O, Na ₂ PtCl ₆ .4H ₂ O, etc.), platinum-olefin complexes, platinum-alcohol complexes, platinum-alcolate complexes, platinum -Ether complexes, platinum-carbonyl complexes, platinum-ketone complexes, platinum-vinylsiloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, bis (γ-picoline) -platinum dichloride , Trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride, bis (alkynyl) bis (triphenylphosphine) platinum complex, bis (alkynyl) (cyclooctadiene) ) Platinum complex, rhodium chloride, tri (Triphenylphosphine) rhodium chloride, although such tetrakis ammonium over rhodium chloride complex are mentioned not particularly limited, may be used two or more.

  The noble metal catalysts may be used alone or in advance in a solvent to be dissolved, and then charged into the reaction system. The use ratio of the noble metal catalyst is not particularly limited, but is usually in the range of 0.1 ppm to 100,000 ppm, preferably 1 ppm to 10,000 ppm, based on the total weight of the raw materials used in the reaction.

  The hydrosilylation reaction can be carried out without a solvent, but the reaction system may be diluted with an organic solvent as necessary, and is not particularly limited as long as it is a compound that does not adversely influence the reaction. For example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, benzene, toluene, orthoxylene, Examples include aromatics such as meta-xylene, para-xylene, chlorobenzene, and dichlorobenzene, ethers such as diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, and esters such as ethyl acetate and n-butyl acetate. Two or more of these organic solvents may be selected and used as a mixed solvent.

  Although it does not specifically limit about the temperature conditions in hydrosilyl addition reaction, Usually, 0 to 200 degreeC, Preferably it is 30 to 180 degreeC. Below 0 ° C, the reaction takes time and is not economical. When the reaction is carried out at 200 ° C. or higher, the addition reaction between the epoxy group and the hydrosilyl moiety proceeds, making it difficult to control the reaction.

  The epoxy silicone resin of the present invention preferably has an epoxy equivalent of 200 to 2000. By being in this range, a cured product excellent in transparency, heat resistant colorability, glass transition temperature, and bending deflection can be obtained. When the epoxy equivalent is out of this range, it is not preferable because the cured product becomes brittle, the surface hardness is lowered to cause stickiness, and the heat resistant colorability is deteriorated.

  Next, the thermosetting resin composition of the present invention will be described. The thermosetting resin composition contains the epoxy resin (A), the curing agent (B), and the curing accelerator (C) as essential components, and includes the epoxy silicone resin (A1) of the present invention as an epoxy resin component.

  As the curing agent (B) contained in the thermosetting resin composition of the present invention, various compounds can be applied as long as they are known as epoxy resin curing agents. For example, organic amine compounds, dicyandiamide and derivatives thereof, imidazoles and derivatives thereof such as 2-methylimidazole and 2-ethyl-4-methylimidazole, bisphenol A, bisphenol F, brominated bisphenol A, naphthalenediol, 4,4′- Bivalent phenolic compounds such as biphenol, novolak resin or aralkylphenol resin obtained by condensation reaction of phenol or naphthol with formaldehyde or xylylene glycols, polyvalent carboxylic acid obtained by reaction of acid anhydride compound with polyhydric organic alcohol Acid, succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride, anhydrous nadic acid, hydrogenated nadic anhydride, trimellitic anhydride, pyrone anhydride Acid anhydrides such as lit acid, hydrazide compounds such as adipic acid hydrazide, organic cation molecules having sulfonium cation and iodonium cation, tetrafluoroboron anion, hexafluorophosphorus anion, hexafluoroarsenic anion, hexafluoroantimony anion, etc. A cationic curing agent comprising an onium salt compound composed of an anionic species can be applied, and two or more types may be used as necessary. In particular, the preferred curing agent for obtaining transparency, heat resistance coloration, and light resistance resistance in the present invention is an acid anhydride or an amine compound which is liquid at room temperature, more preferably hexahydrophthalic anhydride, methylated hexahydro anhydride. Phthalic acid, hydrogenated nadic anhydride.

As the curing accelerator (C), various compounds can be applied as long as they are known as epoxy resin curing accelerators. Examples include tertiary amines and salts thereof, imidazoles and salts thereof, organic phosphine compounds and salts thereof, and organic metal salts such as zinc octylate and tin octylate. Two or more kinds may be used as necessary. . Particularly preferred curing accelerators for obtaining the effects of the present invention are quaternary ammonium salts, organic phosphine compounds, and quaternary phosphonium salts, more preferably quaternary ammonium salts or quaternary phosphonium salts, still more preferably. Quaternary phosphonium salts.
It is.

  The thermosetting resin composition of the present invention comprises the above components (A1), (B) and (C) as essential components, but for the purpose of adjusting the viscosity, the curing rate, etc., to those skilled in the art, As the component (D), an epoxy resin or epoxy compound which is liquid at room temperature having two or more epoxy groups in one molecule other than (A1) may be used. At this time, the effect of this invention is acquired because the epoxy equivalent is the range of 180-1000 with the mixture of (A1) and (D).

  The component (D) is an epoxy resin different from the component (A1), and various compounds can be selected as long as they are singly or mixed and have a liquid state at room temperature. For example, an aromatic ring of an epoxy resin derived from monocyclic dihydric phenols such as resorcinol, hydroquinone, 2,5-ditertiarybutylhydroquinone, nuclear hydrogenated 1,3-naphthalenediol, 1,4- Epoxy resins derived from naphthalene diols such as naphthalene diol, 1,5-naphthalene diol, 1,6-naphthalene diol, 2,7-naphthalene diol, and the like, and nuclear hydrogenated aromatic rings thereof, 4,4 ′ -Isopropylidene diphenol, 4,4'-isopropylidenebis (2-methylphenol), 4,4'-isopropylidenebis (2,6-dimethylphenol), 4,4'-dihydroxydiphenylmethane, 4,4 ' -Dihydroxy-3,3'-dimethyldiphenylmethane, 4,4'-dihydro Cis-3,3 ′, 5,5′-tetramethyldiphenylmethane, 4,4′-secondary butylidenebisphenol, 4,4′-isopropylidenebis (2-tertiarybutylphenol), 4,4′-cyclohexylidene Examples thereof include epoxy resins derived from bisphenols such as phenol and 4,4′-butylidenebis (6-tertiarybutyl-2-methyl) phenol, and epoxy resins obtained by nuclear hydrogenation of the aromatic ring.

  Examples of the component (D) include alicyclic epoxy resins represented by the following general formulas (7) to (11) and epoxy silicone resins represented by the general formula (12), but are not limited thereto. Instead, two or more kinds may be used as necessary.

（式中、ｇ、ｆは１〜２０の整数を表す。）

(In formula, g and f represent the integer of 1-20.)

(R ₇ SiO _3/2 ) _w (R ₈ R ₉ SiO) _x (Me ₃ SiO _1/2 ) _y (12)
(In the formula, R _{7 to} R ₉ are each a hydrocarbon group having 1 to 20 carbon atoms and an aromatic group each optionally containing an epoxy group, and having 1 to 3 etheric oxygen atoms inside. However, at least one of R _{7 to} R ₉ always contains an epoxy group, and R ₈ and R ₉ do not have an epoxy group at the same time, and w to y is w + x + y = (1,0 0 ≦ w <1, 0 <x <1, 0 <y0.75))

  The epoxy resin (A) means the whole epoxy resin component containing the epoxy silicone resin (A1) as an essential component. In addition to the epoxy silicone resin (A1), the liquid epoxy resin (D) and other components blended as necessary. Of epoxy resin. The compounding amount of the epoxy resin (D) may be in the range of 5 to 150 parts by weight with respect to 100 parts by weight of the epoxy silicone resin (A1), and the epoxy equivalent of the epoxy resin (A) may be in the range of 180 to 1000. Good. The content of the epoxy silicone resin (A1) in the epoxy resin (A) is 40 wt% or more, preferably 60 wt% or more.

  When the thermosetting resin composition in the present invention is used as an LED sealing application, it is preferable to add an antioxidant to prevent oxidative deterioration during heating and to obtain a cured product with little coloring.

  As the antioxidant, various compounds can be applied as long as they are known. For example, 2,6-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-tert-butyl-p-ethylphenol, stearyl-β- (3,5-di-tert-butyl-4-4 Monophenols such as -hydroxyphenyl) propionate, 2,2-methylenebis (4-methyl-6-tert-butylphenol), 2,2-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'- Bisphenols such as thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl- 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetra [Methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] polymeric phenols such as methane, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, 10- (3,5-di-tert-butyl 4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro Oxaphosphaphenanthrene oxides such as -9-oxa-10-phosphaphenanthrene-10-oxide, dilauryl 3,3′-dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-dilauryl 3,3 '-Thiodipropionate, distearyl 3,3'-dilauryl 3,3'-thiodip Examples thereof include ester skeleton-containing thioether compound-based antioxidants such as lopionate and pentaerythrityltetrakis (3-laurylthiopropionate). Two or more of these antioxidants may be used as necessary.

  Moreover, another thermosetting resin can also be mix | blended with the thermosetting resin composition of this invention. Examples of such thermosetting resins include unsaturated polyester resins, thermosetting acrylic resins, thermosetting amino resins, thermosetting melamine resins, thermosetting urea resins, thermosetting urethane resins, and thermosetting oxetane resins. , Thermosetting cyanate resin, thermosetting epoxy / oxetane composite resin, and the like.

  The curable resin composition of the present invention comprises the (A) component, the (B) component, and the (C) component including the above (A1) as essential components. 60 wt% or more, preferably 80 wt% or more, more preferably 90 wt% or more of a component to be a part, for example, a monomer, a curing agent, and a curing accelerator are included but a solvent and a filler are not included) It is preferable that it is (B) component. Moreover, the blending ratio of the component (A), the component (B) and the component (C) may be determined as follows.

  When the component (B) is not a cationic curing agent, the epoxy group of the component (A) and the functional group in the curing agent of the component (B) are preferably in the range of 0.8 to 1.5. Outside this range, an unreacted epoxy group or a functional group in the curing agent remains after curing, and functions such as hardness and heat resistance when cured are reduced, which is not preferable. Moreover, as a mixture ratio of (C) component which is a hardening accelerator, the range of 0.1 wt%-5 wt% is preferable with respect to the sum total of (A) component and (B) component. If it is less than 0.1 wt%, the gelation time is delayed, resulting in a decrease in workability due to a decrease in rigidity at the time of curing. Conversely, if it exceeds 5.0 wt%, curing proceeds during the molding and unfilling is likely to occur. Become.

  When (B) component is a cationic hardening | curing agent, it is 0.01-10 weight part with respect to 100 weight part of (A) component, Preferably it is 0.1 weight part-5 weight part. When the amount is less than 0.01 parts by weight, poor curing tends to occur. Conversely, when the amount exceeds 5 parts by weight, it is not preferable in terms of transparency and heat resistant colorability.

  The thermosetting resin composition of this invention can be made into the thermosetting resin composition suitable for light reflection by containing (E) white pigment.

  As the white pigment (E), various materials can be selected as long as they are known materials. Examples include metal oxides such as silica, alumina, magnesium oxide, antimony oxide, titanium oxide, and zirconium oxide, inorganic hollow particles such as sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, and shirasu. It is not limited and may use 2 or more types together as needed. Preferred white pigments include at least one selected from silica, titanium oxide, alumina, magnesium oxide, zirconium oxide and inorganic hollow particles, and alumina and titanium oxide from the viewpoint of thermal conductivity and light reflection characteristics.

  The content of the white pigment (E) is preferably in the range of 10 to 85 vol% based on the total amount of the resin composition. When the content of the white pigment (E) is 10 vol% or less, the whiteness is insufficient and the light reflectivity of the cured product cannot be obtained sufficiently. Moreover, when it exceeds 85 vol%, the kneadability and moldability of the resin composition may be deteriorated.

  The thermosetting resin composition suitable for light reflection may use an additive such as a coupling agent for the purpose of improving interfacial adhesion with the white pigment (E). Examples of the coupling agent include alkoxysilanes or alkoxytitanates having any one of an epoxy group, amino group, thiol group, acrylic group, vinyl group, and isocyanate group. You can choose one. The amount of such an additive used is not particularly limited, and a preferable amount can be used by those skilled in the art, but usually 5 wt.% Based on the total amount of the resin composition. % Or less.

  If necessary, the thermosetting resin composition of the present invention may contain other additives. Thereby, it becomes advantageous as a resin composition for optical parts, a resin composition for electronic parts, or a resin composition for optical semiconductor parts. An example of the resin composition for optical parts is a thermosetting resin composition for light reflection, which is obtained by blending the white pigment (E) as described above.

  The method for uniformly dispersing and mixing the thermosetting resin composition of the present invention is not particularly limited, and can be carried out by a method preferable for those skilled in the art. Examples thereof include a method in which various components are kneaded using an apparatus such as a mixing roll, an extruder, a kneader, a roll, an extruder, a rotation / revolution stirring mixer, and the obtained kneaded product is cooled and pulverized. Moreover, when kneading | mixing, it is preferable to carry out at the temperature which can handle a resin composition in a molten state from a dispersible viewpoint.

  The thermosetting resin composition of the present invention can be obtained as a molded body by dispersing and mixing, cooling and pulverizing, tableting into a tablet, and using a technique such as transfer molding. At this time, it can be applied as a housing for mounting an optical semiconductor by forming a concave shape on a lead frame previously provided with metal wiring. Moreover, a white copper clad laminated board is obtained by apply | coating and press-molding to copper foil. This white copper-clad laminate can be applied as a circuit board for mounting an optical semiconductor.

  When the thermosetting resin of the present invention is applied as an electronic component, its use and manufacturing process are not particularly limited as long as they are known. For example, in the case of a semiconductor sealing material, a filler such as silica is mixed with the thermosetting resin composition of the present invention, kneaded with a kneader or a hot three roll, and then tableted into a cavity of a sealing mold. It is possible to adopt a transfer mold method in which heat-curing is performed. In addition, after mixing with a curing agent that is liquid at room temperature, and using a filler such as silica, alumina, titanium oxide, etc. as necessary, a dispensing method is adopted in which a resin is injected into a predetermined position. I can do it.

  In addition, as a circuit board, for example, after impregnating a base material such as glass cloth with the thermosetting resin composition of the present invention, a method of laminating copper foil by press molding, or thermosetting of the present invention to copper foil The resin composition can be applied by a casting method or the like and bonded to a desired substrate.

  Also, when used as an underfill material that seals and protects the junction between the substrate and the semiconductor, it is mixed with a curing agent that is liquid at room temperature, and if necessary, such as silica, alumina, titanium oxide, rubber particles, etc. A dispensing method in which a resin is injected into a predetermined position after a desired viscosity using a filler or the like can be employed.

  Examples of optical component applications include optical lenses, sealing materials for optical semiconductors, white molding materials for optical semiconductors, and optical semiconductor adhesives. Any process can be applied.

  For example, the optical lens material can be manufactured by a known process such as a dispense method or a transfer mold method.

  As a sealing material for an optical semiconductor device (LED device), a method of filling an optical semiconductor element with a known technique such as a transfer molding method or a potting method after connecting an optical semiconductor element to an external electrode with a gold wire or the like can be applied. At this time, various known fluorescent powders may be used in the thermosetting resin composition of the present invention for the purpose of converting light emitted from the optical semiconductor element. Moreover, in order to express moderate thixotropy, you may add well-known fillers, such as a silica and an aerosil, silane coupling materials, and surfactants. The optical semiconductor device of the present invention is sealed and cured using the thermosetting resin composition of the present invention.

  As the adhesive for optical semiconductor devices, the thermosetting resin composition of the present invention, which is paste-formed by kneading with a roll or the like using a filler such as silica, titanium oxide, alumina, silver powder, if necessary, is dispensed. It is possible to apply a method of applying the film to a base material by the above method, or further bonding a film shape using a known film material onto the base material, mounting the optical semiconductor element, and thermosetting.

  The thermosetting resin composition of the present invention is applied to a thin film using a spin coater, bar coater, etc. on a substrate such as a fluororesin plate, PET film, polyimide, etc. A film body can be obtained by peeling.

  The thermosetting resin and the thermosetting film obtained by the above method can be applied to various uses as long as they are known electronic component uses and optical component uses, such as flexible printed wiring boards, anisotropic conductive films, cover lay films, It can be applied to electronic parts such as die attach film and interlayer insulating material, optical parts such as transparent protective film, optical waveguide film and optical semiconductor film.

  Next, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Synthesis of Raw Material Diallyl isocyanuric acid was synthesized using activated clay, dissolving triallyl cyanurate in xylene based on US Pat. No. 2830051.
Monomethyl diallyl isocyanurate was prepared by dissolving trimethyl cyanurate in xylene, adding phenol, and then synthesizing monomethyl isocyanuric acid using activated clay, based on US Pat. No. 2830051. The obtained monomethyl isocyanuric acid was synthesized in DMF solvent using allyl bromide and sodium hydroxide and tetraethylammonium as a phase transfer catalyst.

Example 1
In the general formula (4), R ₁ is a methyl group, 1 = 1, m = 1, 180 parts by weight of a cyclic organosiloxane having SiH groups at both ends (1.36 equivalents as SiH groups), 220 parts by weight of dioxane, Carbon-supported platinum (platinum support amount 3%) 0.83 part by weight was charged into a 2 L separable flask equipped with a stirring motor, a reflux condenser, and a nitrogen line, and the temperature was raised to 100 ° C. while stirring. Subsequently, 37 parts by weight of diallyl isocyanuric acid (0.35 equivalent as a vinyl group) was charged into the reaction system over 1 hour. After confirming that the increase in molecular weight was stopped by gel permeation chromatography (GPC), 281 parts by weight of monoallyl diglycidyl isocyanurate (1.00 equivalent as a vinyl group) was dissolved in 280 parts by weight of dioxane. The solution was charged over 1 hour. After completion of the addition, the internal temperature was raised to 110 ° C., and the reaction was carried out while refluxing dioxane. The reaction was traced by GPC, and it was confirmed that the monoallyl diglycidyl isocyanurate peak disappeared and the reaction solution was dropped into a 0.1 N potassium hydroxide / methanol solution, and generation of hydrogen gas was stopped. The remaining platinum catalyst was filtered using Celite. By evaporating the filtrate of the filtrate using an evaporator, in the general formula (1), l = 1, m = 1, n has an average value of 0.3, R ₁ is a methyl group, and R ₂ is propylene. Group, E ₁ is an organic residue represented by the general formula (3), Z is an organic residue represented by the general formula (2), R ₃ is a propylene group, and R ₄ is a hydrogen atom. 470 parts by weight of an epoxy silicone resin (ES1) provided with a group-containing isocyanuric ring was obtained. The epoxy equivalent of this resin was 250, the property at room temperature was solid, and the viscosity at 150 ° C. was 0.12 Pa · s. The IR spectrum of this resin is shown in FIG.

Example 2
In the general formula (4), R ₁ is a methyl group, 1 = 1, m = 1, a cyclic organosiloxane having SiH groups on both ends (1.94 equivalents as SiH groups), 360 parts by weight of dioxane, 1.07 parts by weight of carbon-supported platinum (platinum support amount 3%) was put into a 2 L separable flask equipped with a stirring motor, a reflux condenser, and a nitrogen line, and the temperature was raised to 100 ° C. while stirring. Subsequently, 99 parts by weight of diallyl isocyanuric acid (0.94 equivalent as a vinyl group) was charged into the reaction system over 1 hour. A solution in which 281 parts by weight of monoallyl diglycidyl isocyanurate (1.00 equivalent as a vinyl group) is dissolved in 281 parts by weight of dioxane after confirming that the increase in molecular weight has been stopped by gel permeation chromatography (GPC). Was added over 1 hour. After completion of the addition, the internal temperature was raised to 110 ° C., and the reaction was carried out while refluxing dioxane. The reaction was traced by GPC, and it was confirmed that the monoallyl diglycidyl isocyanurate peak disappeared and the reaction solution was dropped into a 0.1 N potassium hydroxide / methanol solution, and generation of hydrogen gas was stopped. The remaining platinum catalyst was filtered using Celite. By evaporating the solvent of the filtrate using an evaporator, in the general formula (1), l = 1, m = 1, n has an average value of 0.9, R ₁ is a methyl group, and R ₂ is propylene. Group, E ₁ is an organic residue represented by the general formula (3), Z is an organic residue represented by the general formula (2), R ₃ is a propylene group, and R ₄ is a hydrogen atom. 619 parts by weight of an epoxy silicone resin (ES2) provided with a group-containing isocyanuric ring was obtained. The epoxy equivalent of this resin was 325, the property at room temperature was solid, and the viscosity at 150 ° C. was 0.56 Pa · s. The IR spectrum of this resin is shown in FIG.

Example 3
In the general formula (4), R ₁ is a methyl group, l = 1, m = 1, cyclic organosiloxane having SiH groups at both ends thereof (203 parts by weight (1.52 equivalents as SiH groups)), dioxane (310 parts by weight), 0.75 parts by weight of carbon-supported platinum (platinum support amount 3%) was charged into a 2 L separable flask equipped with a stirring motor, a reflux condenser, and a nitrogen line, and the temperature was raised to 100 ° C. while stirring. Subsequently, 106 parts by weight (1.01 equivalent as a vinyl group) of diallyl isocyanuric acid was charged into the reaction system over 1 hour. A solution in which 141 parts by weight of monoallyl diglycidyl isocyanurate (0.51 equivalent as a vinyl group) is dissolved in 141 parts by weight of dioxane after confirming that the increase in molecular weight has been stopped by gel permeation chromatography (GPC). Was added over 1 hour. After completion of the addition, the internal temperature was raised to 110 ° C., and the reaction was carried out while refluxing dioxane. The reaction was traced by GPC, and it was confirmed that the monoallyl diglycidyl isocyanurate peak disappeared and the reaction solution was dropped into a 0.1 N potassium hydroxide / methanol solution, and generation of hydrogen gas was stopped. The remaining platinum catalyst was filtered using Celite. By evaporating the solvent of the filtrate using an evaporator, in the general formula (1), l = 1, m = 1, n has an average value of 2.0, R ₁ is a methyl group, and R ₂ is propylene. A group, E ₁ is an organic residue represented by the general formula (3), Z is an organic residue represented by the general formula (2), R ₃ is a propylene group, and R ₄ is a hydrogen atom. 398 parts by weight of an epoxy silicone resin (ES3) provided with an epoxy group-containing isocyanuric ring was obtained. The epoxy equivalent of this resin was 455, the property at room temperature was a solid, and the viscosity at 150 ° C. was 1.61 Pa · s.

Example 4
In the general formula (4), R ₁ is a methyl group, 1 = 1, m = 1, 175 parts by weight of a cyclic organosiloxane having SiH groups at both ends (1.31 equivalents as SiH groups), 210 parts by weight of dioxane, Carbon-supported platinum (platinum support amount 3%) 0.82 part by weight was charged into a 2 L separable flask equipped with a stirring motor, a reflux condenser, and a nitrogen line, and the temperature was raised to 100 ° C. while stirring. Subsequently, 34 parts by weight of monomethyldiallyl isocyanurate (0.31 equivalent as a vinyl group) was charged into the reaction system over 1 hour. A solution in which 281 parts by weight of monoallyl diglycidyl isocyanurate (1.0 equivalent as a vinyl group) is dissolved in 281 parts by weight of dioxane after confirming that the increase in molecular weight has been stopped by gel permeation chromatography (GPC). Was added over 1 hour. After completion of the addition, the internal temperature was raised to 110 ° C., and the reaction was carried out while refluxing dioxane. The reaction was traced by GPC, and it was confirmed that the monoallyl diglycidyl isocyanurate peak disappeared and the reaction solution was dropped into a 0.1 N potassium hydroxide / methanol solution, and generation of hydrogen gas was stopped. The remaining platinum catalyst was filtered using Celite. By evaporating the filtrate of the filtrate using an evaporator, in the general formula (1), l = 1, m = 1, n has an average value of 0.3, R ₁ is a methyl group, and R ₂ is propylene. Group, E ₁ is an organic residue represented by the general formula (3), Z is an organic residue represented by the general formula (2), R ₃ is a propylene group, and R ₄ is a methyl group. 438 parts by weight of an epoxy silicone resin (ES4) provided with a group-containing isocyanuric ring was obtained. The epoxy equivalent of this resin is 250 g / eq. The property at room temperature was solid, and the viscosity at 150 ° C. was 0.08 Pa · s. The IR spectrum of this resin is shown in FIG.

Example 5
In the general formula (4), R ₁ is a methyl group, 1 = 1, m = 1, 257 parts by weight of a cyclic organosiloxane having SiH groups at both ends (1.91 equivalents as SiH groups), 360 parts by weight of dioxane, 1.07 parts by weight of carbon-supported platinum (platinum support amount 3%) was put into a 2 L separable flask equipped with a stirring motor, a reflux condenser, and a nitrogen line, and the temperature was raised to 100 ° C. while stirring. Subsequently, 102 parts by weight of monomethyldiallyl isocyanurate (0.91 equivalent as a vinyl group) was charged into the reaction system over 1 hour. A solution in which 281 parts by weight of monoallyl diglycidyl isocyanurate (1.0 equivalent as a vinyl group) is dissolved in 281 parts by weight of dioxane after confirming that the increase in molecular weight has been stopped by gel permeation chromatography (GPC). Was added over 1 hour. After completion of the addition, the internal temperature was raised to 110 ° C., and the reaction was carried out while refluxing dioxane. The reaction was traced by GPC, and it was confirmed that the monoallyl diglycidyl isocyanurate peak disappeared and the reaction solution was dropped into a 0.1 N potassium hydroxide / methanol solution, and generation of hydrogen gas was stopped. The remaining platinum catalyst was filtered using Celite. By evaporating the solvent of the filtrate using an evaporator, in the general formula (1), l = 1, m = 1, n has an average value of 0.9, R ₁ is a methyl group, and R ₂ is propylene. Group, E ₁ is an organic residue represented by the general formula (3), Z is an organic residue represented by the general formula (2), R ₃ is a propylene group, and R ₄ is a methyl group. 565 parts by weight of an epoxy silicone resin (ES5) provided with an epoxy group-containing isocyanuric ring was obtained. The epoxy equivalent of this resin was 327, the property at room temperature was solid, and the viscosity at 150 ° C. was 0.11 Pa · s. The IR spectrum of this resin is shown in FIG.

Example 6
In the general formula (4), R ₁ is a methyl group, 1 = 1, m = 1, 224 parts by weight of a cyclic organosiloxane having SiH groups at both ends (1.67 equivalents as SiH groups), 360 parts by weight of dioxane, 0.75 parts by weight of carbon-supported platinum (platinum support amount 3%) was charged into a 2 L separable flask equipped with a stirring motor, a reflux condenser, and a nitrogen line, and the temperature was raised to 100 ° C. while stirring. Subsequently, 130 parts by weight of monomethyldiallyl isocyanurate (1.17 equivalent as a vinyl group) was charged into the reaction system over 1 hour. A solution in which 141 parts by weight of monoallyl diglycidyl isocyanurate (0.50 equivalent as a vinyl group) is dissolved in 141 parts by weight of dioxane after confirming that the increase in molecular weight has been stopped by gel permeation chromatography (GPC). Was added over 1 hour. After completion of the addition, the internal temperature was raised to 110 ° C., and the reaction was carried out while refluxing dioxane. The reaction was traced by GPC, and it was confirmed that the monoallyl diglycidyl isocyanurate peak disappeared and the reaction solution was dropped into a 0.1 N potassium hydroxide / methanol solution, and generation of hydrogen gas was stopped. The remaining platinum catalyst was filtered using Celite. By evaporating the solvent of the filtrate using an evaporator, in the general formula (1), l = 1, m = 1, n has an average value of 2.0, R ₁ is a methyl group, and R ₂ is propylene. Group, E ₁ is an organic residue represented by the general formula (3), Z is an organic residue represented by the general formula (2), R ₃ is a propylene group, and R ₄ is a methyl group. 397 parts by weight of an epoxy silicone resin (ES6) having a group-containing isocyanuric ring arranged thereon was obtained. The epoxy equivalent of this resin was 460, the property at room temperature was solid, and the viscosity at 150 ° C. was 0.19 Pa · s.

Example 7
In the general formula (4), R ₁ is a methyl group, 1 = 1, m = 1, 254 parts by weight of a cyclic organosiloxane having SiH groups at both ends (1.89 equivalents as SiH groups), 410 parts by weight of dioxane, 0.92 parts by weight of carbon-supported platinum (platinum support amount 3%) was put into a 2 L separable flask equipped with a stirring motor, a reflux condenser, and a nitrogen line, and the temperature was raised to 100 ° C. while stirring. Subsequently, 156 parts by weight of monomethyldiallyl isocyanurate (1.39 equivalent as a vinyl group) was charged into the reaction system over 1 hour. A solution in which 141 parts by weight of monoallyl diglycidyl isocyanurate (0.50 equivalent as a vinyl group) is dissolved in 141 parts by weight of dioxane after confirming that the increase in molecular weight has been stopped by gel permeation chromatography (GPC). Was added over 1 hour. After completion of the addition, the internal temperature was raised to 110 ° C., and the reaction was carried out while refluxing dioxane. The reaction was traced by GPC, and it was confirmed that the monoallyl diglycidyl isocyanurate peak disappeared and the reaction solution was dropped into a 0.1 N potassium hydroxide / methanol solution, and generation of hydrogen gas was stopped. The remaining platinum catalyst was filtered using Celite. By evaporating the solvent of the filtrate using an evaporator, in the general formula (1), l = 1, m = 1, n has an average value of 2.8, R ₁ is a methyl group, and R ₂ is propylene. Group, E ₁ is an organic residue represented by the general formula (3), Z is an organic residue represented by the general formula (2), R ₃ is a propylene group, and R ₄ is a methyl group. 486 parts by weight of an epoxy silicone resin (ES7) provided with an epoxy group-containing isocyanuric ring was obtained. The epoxy equivalent of this resin was 575, the property at room temperature was solid, and the viscosity at 150 ° C. was 0.26 Pa · s.

Synthesis example 1
73 parts by weight of organohydrogensiloxane represented by the following formula (13) (0.2 equivalent as SiH group), 128 parts by weight of dioxane, 0.21 part by weight of carbon-supported platinum (platinum support amount 3%), The mixture was put into a 500 mL separable flask equipped with a reflux condenser and a nitrogen line, and heated to 100 ° C. with stirring. Subsequently, a solution in which 56.2 parts by weight of monoallyl diglycidyl isocyanurate (0.2 equivalent as a vinyl group) was dissolved in 56 parts by weight of dioxane was added over 1 hour. After completion of the addition, the internal temperature was raised to 110 ° C., and the reaction was carried out while refluxing dioxane. The reaction solution was dropped into a 0.1 N potassium hydroxide / methanol solution, and it was confirmed that hydrogen gas was not generated. The remaining platinum catalyst was filtered using celite. By evaporating the solvent of the filtrate using an evaporator, 74 parts by weight of an epoxy silicone resin (ES8) having a main chain composed only of dimethylsiloxane and having an epoxy group-containing isocyanuric ring arranged at both ends was obtained. The epoxy equivalent of this resin was 320, it was liquid at room temperature, and the viscosity at 25 ° C. was 5.9 Pa · s.

Synthesis example 2
72 parts by weight of 1,3,5,7-tetramethylcyclotetrasiloxane, 100 parts by weight of dioxane, 0.35 parts by weight of platinum carrying carbon (platinum carrying amount 3%), equipped with a stirring motor, reflux condenser, and nitrogen line The 1 L separable flask was charged and heated to 100 ° C. with stirring. Subsequently, a solution in which 25 parts by weight of triallyl isocyanurate was dissolved in 25 parts by weight of dioxane was added dropwise over 1 hour. After confirming that the increase in molecular weight was stopped by gel permeation chromatography (GPC), 112 parts by weight of 4-vinylcyclohexene oxide was added dropwise over 2 hours. After completion of the addition, the internal temperature was raised to 110 ° C., and the reaction was carried out while refluxing dioxane. Follow up the reaction with GPC and confirm that the 4-vinylcyclohexene oxide peak disappeared and that the reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution to stop the generation of hydrogen gas. The remaining platinum catalyst was filtered using Celite. After adding 0.1 part by weight of triphenylphosphine to this solution, the solvent is distilled off from the filtrate using an evaporator, so that the resin chain has an isocyanuric ring and a cyclic organosiloxane skeleton. An epoxy silicone resin (ES9) having an epoxy group was obtained. The epoxy equivalent of this resin was 241.

Examples 8-14
The epoxy silicone resins (ES1 to ES7) obtained in Examples 1 to 7 were mixed with methylated hexahydrophthalic anhydride (MH: acid anhydride equivalent 168 g / eq.), And the equivalent ratio of both was 1: 1. In addition, mix well, and add 0.5% by weight of tetra-n-butylphosphonium o, o'-diethyl phosphorodithionate as a curing accelerator, vacuum degassed, and in the mold The resin plates were cured at 120 ° C. for 4 hours and further at 160 ° C. for 12 hours to produce 1 mm and 4 mm thick resin plates.

Example 15
70 parts by weight of the epoxy silicone resin (ES5) obtained in Example 5 is used as the component (A1), and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxy is further used as the component (D). A resin liquid containing 30 parts by weight of a rate (EpC: epoxy equivalent 130) was prepared. Using this resin solution and MH, the ratio of epoxy equivalent to acid anhydride equivalent is added to 1: 1, and mixed well. Further, tetra-n-butylphosphonium o, o′-diethyl is used as a curing accelerator. Add 0.5% by weight of phosphorodithionate, vacuum degas, and cure in a mold at 120 ° C for 4 hours and further at 160 ° C for 12 hours to create 1mm and 4mm thick resin plates did.

Comparative Example 1
(A1) The epoxy silicone resin of component was not used, but 26 parts by weight of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (EpC) and 34 parts by weight of MH were used. The same operations as in Example 8 were performed to prepare 1 mm and 4 mm thick resin plates.

Comparative Example 2
In place of EpC, 20 parts by weight of triglycidyl isocyanurate (EpT, epoxy equivalent 100) and 34 parts by weight of MH were used, and the same operations as in Comparative Example 1 were performed to prepare 1 mm and 4 mm thick resin plates. did.

Comparative Example 3
((Me ₂ CH ₂ ═CH) SiO _1/2 ) _1.0 (MeSiO _3/2 ) _1.11 (Me ₂ SiO) 100 parts by weight of a silicone resin represented by _0.05 , and a vinyl equivalent of 1,400 g / eq. 20 parts by weight of a dimethylsiloxane oil containing vinyl groups at both ends and a hydrosilyl equivalent of 64 g / eq. Using 48 parts by weight of methyl hydrogen silicone oil, 20 ppm of a platinum-tetravinyldisiloxane complex xylene solution as a curing catalyst is added to the total weight, vacuum degassed, and 120 ° C. for 4 hours in a mold. Further, it was cured at 160 ° C. for 12 hours to prepare resin plates having thicknesses of 1 mm1 mm and 4 mm.

Comparative Example 4
(C ₆ H ₅ ) _0.62 (CH ₂ ═CH) _0.38 (CH ₃ ) _0.38 30 parts by weight of a phenyl silicone resin represented by SiO _1.31 and a hydrosilyl equivalent of 163 g / eq. 16 parts by weight of methyl hydrogen silicone oil represented by the formula, 20 ppm of a platinum-tetravinyldisiloxane complex xylene solution as a curing catalyst is added to the total weight, vacuum degassed at 120 ° C. in a mold. It was cured for 4 hours and further at 160 ° C. for 12 hours to prepare resin plates having a thickness of 1 mm and 1 mm.

Comparative Example 5
Instead of EpC, 32 parts by weight of the epoxy silicone resin (ES8) obtained in Synthesis Example 1 and 17 parts by weight of MH were used, and the same operation as in Comparative Example 1 was performed to obtain resin plates having thicknesses of 1 mm and 4 mm. Created.

Comparative Example 6
Instead of EpC, the same operation as in Comparative Example 1 was performed except that 24 parts by weight of the epoxy silicone resin (ES9) obtained in Synthesis Example 2 and 17 parts by weight of MH were used. Created.

The physical properties of the cured resin plate were measured by the following method.
(1) Measurement of glass transition temperature (Tg) of cured product Temperature measured in the range of 30 ° C. to 270 ° C. using a thermal stress strain measuring device TMA / SS120U manufactured by Seiko Denshi Kogyo Co., Ltd. Was the glass transition temperature. The heating rate was 5 ° C./min.

(2) Measurement of linear expansion coefficient (CTE) Measured in the range of 30 ° C to 270 ° C using a thermal stress strain measuring device TMA / SS120U manufactured by Seiko Denshi Kogyo Co., Ltd., and connected at two points of 40 ° C and 60 ° C. The linear expansion coefficient was calculated from the slope of the obtained straight line. The heating rate was 5 ° C./min.

(3) Initial transmittance of cured product Using a self-recording spectrophotometer U-3410 manufactured by Hitachi, Ltd., the transmittance at a wavelength of 400 nm of a cured product having a thickness of 1 mm was measured.

(4) Measurement of UV resistance Using a weather resistance tester QUV manufactured by Q Panel Co., Ltd., a 4 mm thick cured product, the transmittance at 400 nm after UV irradiation for 600 hours was measured in the same manner as the initial transmittance. . A UVA of 340 nm was used for the QUV lamp, and the black panel temperature was 55 ° C.

(5) Measurement of initial heat resistance A cured product having a thickness of 1 mm was exposed to an environment of 150 ° C., and the transmittance at 400 nm after 72 hours was measured in the same manner as the initial transmittance.

(6) Measurement of long-term heat resistance A cured product having a thickness of 1 mm was exposed to an environment of 150 ° C., and the transmittance at 400 nm after 480 hours was measured in the same manner as the initial transmittance.

(7) Measurement of hardness The surface hardness (Shore D) of the hardened | cured material at room temperature was measured using TECLOCK Co., Ltd. hardness meter TYPE-D.

(8) Evaluation of stickiness The cured product was put in a polyethylene bag, and the case where there was even stickiness was judged to be sticky. In Tables 1 and 2, ○ means no stickiness, and X means stickiness.

(9) Hardened product shape after mold removal (appearance)
When the mold was removed, the uniformity of the cured product and cracking of the cured product due to curing shrinkage were visually determined. ○: Uniform cured product. (Triangle | delta): Although the shape of a metal mold | die is maintained, the crack has arisen in hardened | cured material. X: The shape of the mold was not maintained and the resin was cracked.

(10) Bending and deflection characteristic test Based on JIS-7171, the bending elastic modulus, bending strength, and bending deflection were measured by an autograph (manufactured by Shimadzu Corporation) using a test piece of 80 mm x 10 mm x 4 mm. . In addition, (circle) means not fracture | ruptured.

  Table 1 shows the measurement results of each test of the cured products obtained in Examples 8 to 15. In Tables 1 and 3, the component (A) means the component (A1).

  Table 2 shows the measurement results of each test of the cured products obtained in Comparative Examples 1 to 6. Note that NM means that measurement is not possible.

Examples 16 to 23, Comparative Example 8
As the white pigment (E), fused silica and titanium oxide were added to the resin liquids blended in Examples 8 to 15 and Comparative Example 2, and the blended resin liquid: fused silica: titanium oxide = 15: 74: 11 (wt.%). ) And a kneaded product was obtained by melt-kneading at 50 ° C. for 10 minutes using two rolls. Next, the obtained kneaded material was cooled and pulverized to obtain a white solid light-reflective thermosetting resin composition. This composition was subjected to transfer molding using a brass spacer having a thickness of 2 mm under the conditions of a molding mold temperature of 175 ° C., a molding pressure of 5 MPa, and a curing time of 300 seconds, and then removed from the mold. A test piece having a thickness of 2 mm was prepared by curing at 12 ° C. for 12 hours.

Comparative Examples 7, 9-12
In the resin liquid blended in Comparative Examples 1 and 3-6, fused silica and titanium oxide as the white pigment (E) are blended resin liquid: fused silica: titanium oxide = 15: 74: 11 (wt.%). A white paste-like thermosetting resin composition for light reflection was obtained by blending at such a weight ratio and using a rotation / revolution stirrer for 5 minutes at a rotational speed of 2000 rpm. This paste-like composition was press-molded using a brass spacer having a thickness of 2 mm under the conditions of a mold temperature of 175 ° C., a molding pressure of 1 MPa, and a curing time of 300 seconds, and then removed from the mold. The test piece having a thickness of 2 mm was prepared by curing at 150 ° C. for 12 hours.

(11) Presence or absence of deformation at the time of demolding After demolding after transfer molding or press molding, the presence or absence of deformation of the test piece due to stress at the time of demolding is visually confirmed to determine the shape retention at the time of molding. Went. In Tables 4 and 5, ◯ means no deformation, and X means deformation.

(12) Measurement of initial reflectance The light reflectance at a wavelength of 460 nm was measured using a self-recording spectrophotometer U-3410 manufactured by Hitachi, Ltd.

(13) Measurement of initial heat resistance A cured product having a thickness of 2 mm was exposed to an environment of 150 ° C., and the reflectance at 460 nm after 72 hours was measured in the same manner as the initial reflectance.

(14) Measurement of long-term heat resistance A cured product having a thickness of 2 mm was exposed to an environment of 150 ° C., and the reflectance at 460 nm after 480 hours was measured in the same manner as the initial reflectance.

  Table 3 shows the measurement results of the white cured products obtained in Examples 16 to 23.

  Table 4 shows the measurement results of each test of the cured products obtained in Comparative Examples 7-12.

Examples 24-31, Comparative Examples 13-18
The compounds obtained by the blending of Examples 8 to 15 and Comparative Examples 1 to 6 were filled by casting into a blue LED package in which the bottom part was silver-plated and the light emitting element was wire-bonded. It was cured for 5 hours at 150 ° C. and sealed to produce an LED device.

The physical properties of the sealed LED device were measured by the following method.
(10) Reflow test When the sealed LED package is continuously passed through a reflow oven set to hold 260 ° C. for 15 seconds, the presence or absence of coloring, cracking, or peeling of the sealing material is confirmed. did. The results are shown in Table 5. In Table 5, “◯” means that there is no coloring, cracking, and peeling, and “x” means that coloring, cracking, and peeling are present.

(11) Measurement of thermal shock test.
The sealed LED package was subjected to a test of −40 ° C. to 120 ° C. and 500 cycles, and cracks and the sealing material were peeled off with a microscope, and the presence or absence of wire breakage was confirmed. The results are shown in Table 6. In Table 6, ○ means no, and x means yes.

Claims (11)

It is represented by the general formula (1) and has an epoxy equivalent of 200 to 2000 g / eq. An epoxy silicone resin characterized by

(In the formula, R ₁ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms and may be the same or different. R ₂ represents a divalent hydrocarbon group having 1 to 20 carbon atoms; E ₁ may be a monovalent organic residue represented by the formula (3) having an epoxy group, and Z may be represented by the general formula (2). A divalent organic residue having an isocyanuric ring, wherein l and m are each independently an integer of 0 to 3, satisfying 1 ≦ l + m ≦ 4, and n is a number satisfying 0 <n ≦ 100. )

(In the formula, R ₃ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

In the manufacturing method of the epoxy silicone resin of Claim 1, the both-ends vinyl group containing isocyanuric acid derivative represented by General formula (5) is added to the both-ends SiH containing cyclic organosiloxane represented by General formula (4). A method for producing an epoxy silicone resin, comprising reacting at less than a theoretical amount, and then subjecting the remaining SiH groups to end-capping reaction using monoallyldiglycidyl isocyanurate.

(Wherein R ₁ Represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. m and l are each independently an integer of 0 to 3, and satisfy 1 ≦ l + m ≦ 4. )

(Wherein R _Four Represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R _Five Represents a hydrocarbon group having 1 to 8 carbon atoms. R ₆ Represents a hydrogen atom or a methyl group. ) In the thermosetting resin composition which contains an epoxy resin (A), a hardening | curing agent (B), and a hardening accelerator (C) as an essential component, the epoxy silicone resin (A1) of Claim 1 is included as an epoxy resin component. The thermosetting resin composition characterized by the above-mentioned. The thermosetting resin composition according to claim 3, wherein the curing agent (B) is an acid anhydride. The thermosetting resin composition according to claim 3 or 4, wherein the curing accelerator (C) is a quaternary ammonium salt or a quaternary phosphonium salt . The epoxy resin (A) contains an epoxy silicone resin (A1) and an epoxy resin (D) which is liquid at room temperature, and 5 to 150 parts by weight of the epoxy resin (D) with respect to 100 parts by weight of the epoxy silicone resin (A1). And the epoxy equivalent of the entire epoxy resin component is 180 to 1000 g / eq. The thermosetting resin composition according to claim 3, wherein the composition is a thermosetting resin composition. The thermosetting resin composition according to any one of claims 3 to 6, further comprising a white pigment (E) . 8. The thermosetting resin composition according to claim 7, wherein the white pigment is at least one selected from silica, titanium oxide, alumina, magnesium oxide, zirconium oxide and inorganic hollow particles . The thermosetting resin composition according to any one of claims 3 to 8, wherein the thermosetting resin composition is a resin composition for optical parts, a resin composition for electronic parts, or a resin composition for optical semiconductor parts . Resin composition. The thermosetting resin composition according to claim 9, wherein the optical component resin composition is a light-reflecting thermosetting resin composition. The thermosetting resin composition of Claim 9 is a liquid sealing resin composition for optical semiconductors, It seals using this resin composition, The LED device characterized by the above-mentioned.

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