JP5680928B2 - Epoxy silicone resin-containing curable resin composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an epoxy silicone resin having a linear siloxane bond, and a thermosetting resin composition having the optical component, hardness, heat-resistant coloring property, and light-resistant coloring property, which is an essential component thereof, and more particularly to the field of electronic materials and optical semiconductors. The present invention relates to a thermosetting resin composition suitable for sealing.

  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 a lower strength and deflection than ordinary epoxy resins, so There is also a problem that the sealing material is easily cracked in an environment where various temperature changes can 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 high intensity | strength and toughness simultaneously with the further improvement of heat-resistant coloring property and light resistance.

  LED encapsulants based on silicone resins with excellent weather resistance have been developed, and resin compositions based on the addition reaction of hydrosilyl groups and alkenyl groups and silicone resins having epoxy groups are cured using a curing agent. The resin composition obtained by making it 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, the resin having a high hardness silicone skeleton containing a phenyl group has improved handling properties, but there is a problem in strength and deflection, and cracking is likely to occur due to a sudden temperature change at the time of turning on and off. Has disadvantages. The resin having a low epoxy equivalent containing an epoxy cyclohexyl group is also improved in handling properties, but the heat-resistant coloring property which is an advantage of silicone is impaired, and it cannot withstand the demand as an LED sealing material. There is a need for improvement.

  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 includes a liquid alicyclic epoxy resin having a viscosity at 25 ° C. of 1000 mPa · s or less and a solid alicyclic epoxy resin at 25 ° C. at a specific ratio, and a viscosity at 45 ° C. Discloses an epoxy resin composition containing an alicyclic epoxy resin mixture exhibiting 60000 mPa · s or less, an acid anhydride, and a dicarboxylic acid. Patent Document 2 discloses an epoxy resin composition using a carboxylic acid-modified triglycidyl isocyanurate and a cured epoxy resin. Patent Document 3 discloses a thermosetting silicone composition using a branched / or three-dimensional network-structured alkenyl group-containing phenyl group-rich organosiloxane. Patent Document 4 discloses a heat-curable silicone composition using an alkenyl group-containing high methyl group-containing organosiloxane. Patent Document 5 discloses a thermosetting resin composition using a silicone compound having at least two epoxycyclohexyl groups in one molecule, a weight average molecular weight Mw of 500 to 2100, and an epoxycyclohexyl equivalent of 180 to 230. Things are disclosed. However, it is difficult to say that the thermosetting resin compositions described in these patent documents also have the above characteristics sufficiently.

  Patent Document 6 discloses a thermosetting resin composition using an epoxy silicone resin in which an organopolysiloxane having an alcoholic hydroxyl group is half-esterified with an acid anhydride and the resulting carboxyl group is reacted with an epoxy group of an epoxy resin. It is disclosed. As for this disclosure, there is a report about luminance degradation due to continuous energization by sealing a light emitting diode by casting, but there is no description about the emission wavelength of the diode used, and it has a heat resistance that can withstand the demands of recent LEDs. No mention is made of colorability and light-coloration resistance. In addition, the content of reducing damage by reducing internal stress in the process of cooling from the curing temperature to room temperature is disclosed, but regarding reflow mounting damage and adhesion that are exposed to temperatures much higher than the curing temperature There is no description.

JP 2009-114390 A JP 2009-109779 A JP 2009-185226 A Japanese Patent No. 4071639 Japanese Patent No. 4371111 JP-A-6-1000076

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

（式中、Ｒ₁はメチル基あるいはフェニル基を表し、各々同一でも異なっていても良い。Ｒ₂は内部にエーテル結合性酸素原子を有していても良い炭素数２〜２０の２価の炭化水素基を表わす。ｎは０〜１００の整数を表す。）

（式中、Ｒ₃は単結合あるいは内部にエステル結合性酸素原子を有していても良い炭素数１〜２０の２価の炭化水素基を表す。） That is, the present invention relates to a hemiester (A2) having a carboxyl group at a terminal obtained by the reaction of a linear polysiloxane having an alcoholic hydroxyl group at both terminals represented by the general formula (1) and an acid anhydride, and a general formula The alicyclic epoxy resin (A3) which is liquid at room temperature represented by (2), the molar ratio of the carboxyl group of (A2) to the epoxy group of (A3), carboxyl group / epoxy group = 1 / 2-1 An epoxy silicone resin characterized by being obtained by reacting as / 10.

(In the formula, R ₁ represents a methyl group or a phenyl group, and may be the same or different. R ₂ is a divalent divalent hydrocarbon having 2 to 20 carbon atoms that may have an etheric oxygen atom therein. Represents a hydrocarbon group, and n represents an integer of 0 to 100.)

(In the formula, R ₃ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester bondable oxygen atom therein.)

（式中、Ｒ₃は単結合あるいは内部にエステル結合性酸素原子を有していても良い炭素数１〜２０の２価の炭化水素基を表す。） The present invention also relates to a linear polysiloxane (A1) having an alcoholic hydroxyl group at both ends represented by the general formula (1) and a hemiester (A2) having a carboxyl group at the end by reacting an acid anhydride. The hemiester (A2) or the reaction mixture containing this hemiester (A2) and the alicyclic epoxy resin (A3) that is liquid at room temperature represented by the general formula (2) are converted to the carboxyl of (A2). This is a method for producing an epoxy silicone resin, wherein the molar ratio of the group and the epoxy group of (A3) is reacted as carboxyl group / epoxy group = 1/2 to 1/10. Moreover, this invention is an epoxy silicone resin obtained with the manufacturing method of the said epoxy silicone resin.

(In the formula, R ₃ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester bondable oxygen atom therein.)

  Furthermore, the present invention is a thermosetting resin composition containing (A) an epoxy silicone resin, (B) a curing agent, and (C) a curing accelerator as essential components, Item 4. A thermosetting resin composition using the epoxy silicone resin according to item 1 or 3. Here, as the (B) curing agent, an acid anhydride is preferable. As a hardening accelerator, at least 1 sort (s) chosen from a quaternary ammonium salt and a quaternary phosphonium salt is mentioned as a preferable thing. Further, the present invention is a curable resin composition containing (A) an epoxy silicone resin and (D) a cationic curing catalyst as essential components, and the epoxy resin according to claim 1 or 3 as the (A) epoxy silicone resin. It is a curable resin composition characterized by using a silicone resin.

Furthermore, the present invention provides the above-mentioned thermosetting resin composition, 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 . It is.

  Further, the present invention is a cured product obtained by curing the above-mentioned thermosetting resin composition, and is obtained by film-forming and heat-treating the above-mentioned thermosetting resin composition. It is the film body characterized by this.

Another embodiment will be described below.
a) A reaction mixture containing an epoxy silicone resin obtained by the method for producing an epoxy silicone resin or an epoxy silicone resin obtained by the method for producing an epoxy silicone resin. The reaction mixture containing the epoxy silicone resin has a viscosity at room temperature of 0.1 to 200 Pa · s and an epoxy equivalent of 250 to 500 g / eq. It is desirable that
b) A thermosetting resin composition comprising (A) an epoxy silicone resin, (B) a curing agent, and (C) a curing accelerator as essential components, and (A) the epoxy silicone resin or It is a thermosetting resin composition using the reaction mixture containing the epoxy silicone resin obtained by the manufacturing method of the said epoxy silicone resin. In the thermosetting resin composition, any one of 1) the curing agent is an acid anhydride, and 2) the curing accelerator is selected from at least one of a quaternary ammonium salt and a quaternary phosphonium salt. It is desirable to satisfy the above. Also, (A) an epoxy silicone resin, (D) a thermosetting resin composition containing a cationic curing catalyst as an essential component, and (A) the epoxy silicone resin or the method for producing the epoxy silicone resin as an epoxy silicone resin It is a thermosetting resin composition using the reaction mixture containing the epoxy silicone resin obtained in (1).
c) In the above thermosetting resin composition, the thermosetting resin composition is 1) a resin composition for optical parts or a resin composition for electronic parts, and 2) a resin composition for optical semiconductor parts. It is desirable that Moreover, this invention is sealed using said thermosetting resin composition, It is an LED apparatus characterized by the above-mentioned. Moreover, this invention is a film body obtained by light irradiation or heat processing said thermosetting resin composition.

  The thermosetting resin composition of the present invention is excellent in surface hardness, strength, and deflection when it is made into a curable resin obtained by heat or light treatment, has transparency, and has excellent heat resistance and light resistance. An excellent cured product or film 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 and optical sheets, and in particular, coloring by heat and light, reflow mounting, Improvement of problems such as cracks, disconnection, and peeling from the substrate in a heat cycle environment can be expected.

  The epoxy silicone resin of the present invention is obtained by reacting a hemiester (A2) having a carboxyl group at the terminal with an alicyclic epoxy resin (A3). The hemiester (A2) is obtained by reacting a linear polysiloxane (A1) having an alcoholic hydroxyl group represented by the general formula (1) at both ends with an acid anhydride. The thermosetting resin composition of the present invention comprises (A) an epoxy silicone resin, (B) a curing agent, and (C) a curing accelerator, or (A) an epoxy silicone resin, and (D) a cationic curing catalyst as essential components. Is included.

  Hereinafter, the epoxy silicone resin (A) or (A) component, the curing agent (B) or (B) component, the curing accelerator (C) or (C) component, and the cationic curing catalyst (D ) Or (D) component. The linear polysiloxane (A1), hemiester (A2), and alicyclic epoxy resin (A3) may also be abbreviated in the same manner. In addition, it is understood that the epoxy resin and epoxy compound as used in this specification may have the same meaning.

  The epoxy silicone resin of the present invention is a hemiester having a carboxyl group at the terminal obtained by the reaction of a linear polysiloxane (A1) having an alcoholic hydroxyl group represented by the general formula (1) at both terminals and an acid anhydride. (A2) and the alicyclic epoxy resin that is liquid at room temperature represented by the general formula (2), the carboxyl group of (A2) / the epoxy group (molar ratio) of (A3) is 1/2 to 1 / 10 was obtained by reaction.

In the general formula (1), R ₁ represents a methyl group or a phenyl group, and may be the same or different, but is preferably a methyl group from the standpoint of availability and physical properties when cured. .

（式中、ｌは０〜３の数である。） R ₂ represents a divalent hydrocarbon group having 2 to 20 carbon atoms which may have an etheric oxygen atom inside, and may be the same or different. Examples of such hydrocarbon groups include, but are not limited to, an ethylene group, a propylene group, a butylene group, a hexylene group, a decylene group, a dodecylene group, or a group represented by the general formula (3). These may be the same or different. A preferable hydrocarbon group is a C2-12 alkylene group, preferably a propylene group, or a group represented by the general formula (3) in view of physical properties of the cured product and availability.

(In the formula, l is a number from 0 to 3.)

  N in General formula (1) represents the integer of 0-100, Preferably it is 0-50, More preferably, it is 0-30. By being an integer within this range, a resin satisfying the effects of the present invention when obtained as a cured product can be obtained. When n exceeds 100, the Tg of the cured product is reduced and the heat resistant colorability is lowered, so that a desired effect cannot be obtained. The linear polysiloxane (A1) having alcoholic hydroxyl groups at both ends represented by the general formula (1) can also be a resin having a molecular weight distribution. In this case, n is an average (number average) The number of repetitions is preferably in the above range.

ここで、Ｒ₄は環状構造を有していても良い炭素数２〜２０の有機残基を表す。 The acid anhydride to be reacted with the linear polysiloxane (A1) represented by the general formula (1) is represented by the general formula (4).

Here, R ₄ represents an organic residue having 2 to 20 carbon atoms which may have a cyclic structure.

Preferred examples of R ₄ include an ethylene group, vinylene group, cyclohexylene group, methylcyclohexylene group, norbornylene group, methylnorbornylene group, and phenylene group, but are not limited thereto, and any known compound can be used. Various compounds can be selected, and two or more may be used as necessary. More preferable structures are a cyclohexylene group and a methylcyclohexylene group from the viewpoint of easy availability and various physical properties when cured. Suitable acid anhydrides include, for example, succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride, nadic anhydride, hydrogenated nadic anhydride, trimellitic anhydride It is.

  The amount of the linear polysiloxane (A1) represented by the general formula (1) and the acid anhydride is stoichiometrically determined based on 1 mol of the component (A1) having an alcoholic hydroxyl group. Although a mole is used, the component having an alcoholic hydroxyl group may be excessively used from the viewpoint of controlling the curing rate when the thermosetting resin is used and controlling the crosslinking density. When used in an excessive amount, from the viewpoint of not impairing the effects of the present invention, up to 2 mol of the component (A1) is preferable with respect to 2 mol of the acid anhydride. On the other hand, if an excess amount of the acid anhydride is used, it is not preferable because gelation is likely to occur during the synthesis of the epoxy silicone resin (A).

  A hemiester (A2) having carboxyl groups at both ends is obtained by the reaction of the alcohol mixture and the acid anhydride. In this hemiester (A2), an acid anhydride and an alcoholic hydroxyl group react to form an ester, and the other carboxyl group generated from the acid anhydride remains as a free carboxyl group. When the theoretical amount of the linear polysiloxane (A1) and the acid anhydride are used, the hemiester (A2) is selectively formed. However, when the linear polysiloxane (A1) is used in excess, the hemiester (A2) ) And one end of which is a hemiester, or a reaction mixture containing these and (A1). The one end of which is a hemiester does not have a carboxyl group, but has a hydroxyl group at the end, so the reactivity is different, but the reaction with an epoxy resin is possible, so that the hemiester (A2) has one end The reaction mixture containing the hemiester and (A1) can be used for the next reaction without separation.

  Moreover, you may use together the bivalent organic alcohol compound which does not have a siloxane structure, unless the range of this invention is impaired. Examples of such organic alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonane. Linear functional bifunctional alcohols such as diol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, 4,4′-bicyclohexanol, 4,4′-bi Bifunctional alcohols at both ends including cycloaliphatic such as cyclohexanedimethanol, dihydroxydecalin, dihydroxymethyldecalin, spiroglycol, etc., ester-containing bifunctional alcohols such as polycaprolactone diol, N-methyl Bifunctional alcohols containing both ends of amide groups such as N ′, N ″ dihydroxyethyl isocyanurate, and bifunctional alcohols containing aromatic groups obtained by adding ethylene oxide to bisphenols such as bisphenol A, bisphenol F, and bisphenol S Although it is raised, it is not limited to these, You may use 2 or more types as needed.

The hemiester (A2) and the alicyclic epoxy resin (A3) that is liquid at room temperature represented by the general formula (2), the carboxyl group that the hemiester (A2) has, and the epoxy group that the alicyclic epoxy resin (A3) has Are reacted at a ratio of carboxyl group: epoxy group = 1: 2 to 1:10 to obtain an epoxy silicone resin (A). In this reaction, the carboxyl group of the hemiester (A2) reacts with the epoxy group of the alicyclic epoxy resin (A3) having two epoxy groups in one molecule to produce an ester bond, and the hemiester (A2 ) End of the alicyclic epoxy group. Here, as the hemiester, when using a hemiester (A2), one having a hemiester at one end, or a reaction mixture containing these and a linear polysiloxane (A1), a part of the epoxy group is an alcoholic OH group. May be combined. Since an epoxy group is used excessively as described above, an epoxy silicone resin having an alicyclic epoxy group bonded to the terminal is a main component. Moreover, although the epoxy silicone resin (A) to produce | generate is a mixture normally, these may be isolate | separated and may be used as an epoxy silicone resin (A) with a reaction mixture.

（式中、Ｒ₃は単結合あるいは内部にエステル結合性酸素原子を有していても良い炭素数１〜２０の２価の炭化水素基を表す。） The alicyclic epoxy resin used in the present invention is liquid at room temperature and is represented by the general formula (2).

(In the formula, R ₃ represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms which may have an ester bondable oxygen atom therein.)

Preferred R ₃ includes a single bond, an alkylene or alkylidene represented by CnH2n, an ester-containing group represented by CnH2nOCO or COCnH2nOCO. Here, n is 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

  As such an alicyclic epoxy resin, if it is a well-known thing, it will be selected from various structures and may use 2 or more types together. For example, epoxy resins represented by the following formulas (5) to (9) are used.

（式中、ｌ及びｍは独立に１〜２０の整数を表す）

(Wherein l and m independently represent an integer of 1 to 20)

  In particular, an epoxy resin represented by the general formula (8) where l is 1 is preferable from the viewpoints of availability and effects of the invention.

  The epoxy silicone resin (A) can be advantageously obtained by the method for producing an epoxy silicone resin of the present invention. In the production method of the present invention, the linear polysiloxane (A1) is reacted with an acid anhydride to form a hemiester (A2) having a carboxyl group at the terminal, and this hemiester (A2) or this hemiester (A2) A alicyclic epoxy resin (A3) that is liquid at room temperature, and the ratio of the carboxyl group of (A2) to the epoxy group of (A3) is carboxyl group / epoxy group = 1/2 to 1/10 It is the method of making it react by the molar ratio.

  In order to obtain the hemiester (A2) from the acid anhydride and the linear polysiloxane (A1), the above (A1) and the acid anhydride can be mixed and reacted. It does not specifically limit as reaction temperature at this time, Usually, 70 to 200 degreeC, Preferably it is 90 to 160 degreeC. If it is 80 ° C. or lower, the reaction time becomes longer, which is not preferable. Moreover, since there exists a concern of superposition | polymerization and decomposition | disassembly at 200 degreeC or more, it is unpreferable. This reaction is preferably performed until the acid anhydride disappears from the viewpoint of reaction control and storage stability of the epoxy silicone resin (A).

  In addition, this reaction can be performed without a solvent, but a solvent that does not participate in the reaction may be used for reasons such as increasing the stirring efficiency. Examples thereof include aromatic hydrocarbon compounds such as toluene, xylene and cumene, linear hydrocarbon compounds such as undecane and dodecane, and ketone compounds such as methylisobutylkenton, cyclopentanone and cyclohexanone.

  In the reaction for obtaining the epoxy silicone resin (A) from the hemiester (A2), the reaction mixture containing the hemiester (A2) or hemiester (A2) obtained above is reacted with the liquid alicyclic epoxy (A3). Here, the number of moles of the carboxyl group of the hemiester (A2) and the epoxy group of the alicyclic epoxy resin (A3) which is liquid at room temperature is carboxyl group: epoxy group = 1: 2 to 1:10, preferably 1: 3. The range is ˜1: 9.5. When the molar ratio of the epoxy groups is less than 2, the molecular weight and the siloxane concentration in the resin are increased, and the effects of the present invention may not be obtained in terms of epoxy equivalent and viscosity at room temperature. Moreover, when the molar ratio of the epoxy group is 10 or more, the concentration of the linear siloxane structure present in the component (A) is low, and the brittleness of the cured product and coloring in a long-term heat test are not preferable. .

  The reaction conditions of the hemiester (A2) and the alicyclic epoxy resin (A3) that is liquid at room temperature are not particularly limited because they are general reactions of carboxyl groups and epoxy groups, and are preferable for those skilled in the art. It can be implemented in the form.

  For example, about reaction temperature, it is 50 to 230 degreeC normally, Preferably it is 70 to 170 degreeC. If it is less than 50 ° C., the reaction time becomes longer, which is not preferable. On the other hand, if the temperature exceeds 230 ° C., the resin decomposes or causes side reactions during the reaction, which is not preferable.

  Although this reaction can be performed without a catalyst, it is preferable to use a catalyst from the viewpoint of shortening the reaction time. As such a catalyst, if it has an effect which accelerates | stimulates the reaction of a carboxyl group and an epoxy group, various compounds can be selected from known ones. For example, imidazole compounds and their salt compounds. Although a tertiary amine compound, a tertiary phosphine compound, a quaternary ammonium salt compound, a quaternary phosphonium salt compound, etc. are raised, it is not limited to these, You may use 2 or more types together as needed. Preferred compounds are quaternary ammonium salt compounds and quaternary phosphonium salt compounds from the viewpoint of suppressing coloring during the reaction.

  When the catalyst is used, the amount to be used is not particularly limited, but when the obtained epoxy silicone resin (A) is 100 parts by weight, it is usually 0.001 to 5 parts by weight, preferably 0.005 to parts by weight. 3 parts by weight. Moreover, when using, the method of preparing a solution beforehand using the solvent which dissolves a catalyst, and throwing this catalyst solution into a reaction system may be used.

  Moreover, you may react by adding antioxidant from a viewpoint of preventing coloring of an epoxy silicone resin (A). As this 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.

  The reaction for obtaining the epoxy silicone resin (A) can be carried out without solvent, but a solvent that does not contribute to the reaction may be used for reasons such as increasing the stirring efficiency. Examples thereof include aromatic hydrocarbon compounds such as toluene, xylene and cumene, linear hydrocarbon compounds such as undecane and dodecane, and ketone compounds such as methylisobutylkenton, cyclopentanone and cyclohexanone.

  The above reaction is preferably performed until the carboxy group disappears. The epoxy silicone resin (A) obtained by this reaction is advantageously used as it is in the reaction mixture obtained by separating the solvent from the reaction mixture, but if necessary, the epoxy silicone resin (A) can be further concentrated or It may be separated.

  The epoxy silicone resin (A) of the present invention or the reaction mixture containing the epoxy resin has a viscosity at room temperature of 0.1 Pa · s to 200 Pa · s and an epoxy equivalent of 250 to 500 g / eq. It is desirable that 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 viscosity at room temperature and the epoxy equivalent are out of this range, it is not preferable because the cured product becomes brittle and the heat-resistant colorability deteriorates.

  The thermosetting resin composition of the present invention includes (A) an epoxy silicone resin, (B) a curing agent and (C) a curing accelerator as essential components, (A) an epoxy silicone resin, and (D) a cationic curing. Some have a catalyst as an essential component. The former may be distinguished from thermosetting resin composition-1 and the latter as thermosetting resin composition-2.

  In thermosetting resin composition-1, any one of 1) the curing agent is an acid anhydride, and 2) the curing accelerator is selected from at least one of a quaternary ammonium salt and a quaternary phosphonium salt. It is desirable to satisfy one or more.

  The epoxy silicone resin (A) contained in the thermosetting resin composition of the present invention includes (i) the epoxy silicone resin (A) of the present invention, and (ii) the epoxy silicone resin (A) obtained by the production method of the present invention. ), And (iii) a reaction mixture containing the epoxy silicone resin (A) obtained by the production method of the present invention, the epoxy equivalent is 250 to 500 g / eq. The reaction mixture containing (iii) epoxy silicone resin (A) having a viscosity at room temperature of 0.1 to 200 Pa · s is preferable.

  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 curing agents for epoxy resins. 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 slit acid, can be applied hydrazide compounds such as adipic acid hydrazide, it may be used two or more, if necessary. In particular, a preferable curing agent for obtaining the effects of the present invention is an acid anhydride, more preferably hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride, or 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, quaternary phosphonium salts, and more preferred catalysts are quaternary phosphonium salts.
It is.

  The thermosetting resin composition of the present invention comprises the above components (A), (B) and (C) as essential components, but for the purpose of adjusting the viscosity, the curing rate, etc., to a preferred form for those skilled in the art As the component (E), an epoxy resin or an epoxy compound having two or more epoxy groups in one molecule other than the component (A) may be used.

  As the component (E), various compounds can be selected as long as they are known materials. For example, epoxy resins derived from monocyclic dihydric phenols such as resorcinol, hydroquinone, 2,5-ditertiarybutylhydroquinone, and those obtained by nuclear hydrogenation of the aromatic ring, 1,3-naphthalenediol, 1, Epoxy resins derived from naphthalene diols such as 4-naphthalene diol, 1,5-naphthalene diol, 1,6-naphthalene diol, 2,7-naphthalene diol, and those obtained by nuclear hydrogenation of the aromatic ring, 4, 4'-isopropylidenediphenol, 4,4'-isopropylidenebis (2-methylphenol), 4,4'-isopropylidenebis (2,6-dimethylphenol), 4,4'-dihydroxydiphenylmethane, 4, 4'-dihydroxy-3,3'-dimethyldiphenylmethane, 4,4 ' Dihydroxy-3,3 ′, 5,5′-tetramethyldiphenylmethane, 4,4′-secondary butylidenebisphenol, 4,4′-isopropylidenebis (2-tertiarybutylphenol), 4,4′-cyclohexylidene Phenol, 4,4′-butylidenebis (6-tertiarybutyl-2-methyl) phenol, 4,4 ′-(1-α-methylbenzylidene) bisphenol, 4,4′-dihydroxytetraphenylmethane, α, α ′ -Bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, α, α'-bis (4-hydroxy-3-methylphenyl) -1,4-diisopropylbenzene, α, α'-bis (4-hydroxy) −3,5-dimethylphenyl) -1,3-dimethylbenzene, α, α′-bis (4-hydroxy) −3,5-dimethylphenyl) -1,4-dimethylbenzene, 4,4′-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, 4,4 ′ Derived from bisphenols such as thiobis (2-tertiarybutyl-5-methylphenol), 4,4′-biphenol, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethyldiphenyl Epoxy resins, and epoxy resins obtained by nuclear hydrogenation of aromatic rings thereof, alicyclic epoxy resins listed in general formulas (5) to (9), triglycidyl isocyanurate, N-methyl-N ′, N ″ -di Isocyanuric skeleton represented by glycidyl isocyanurate, N-allyl-N ′, N ″ -diglycidyl isocyanurate An epoxy compound having

General formula (10)
(R ₆ SiO _3/2 ) _k (R ₇ R ₈ SiO) _j (Me ₃ SiO _1/2 ) _i (10)
(In the formula, R _{6 to} R ₈ 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 _{6 to} R ₈ always contains an epoxy group, and R ₇ and R ₈ do not have an epoxy group at the same time, i to k are i + j + k = 1. , 0 ≦ k <1, 0 <j <1, 0 <i0.75)) or an epoxy silicone resin represented by the general formula (11)

（式中、Ｒ₁は一般式（１）における定義と同義であり、Ｒ₉は炭素数１〜２０の２価の有機残基を表し、Ｅ₁は式（１２）で表される基であり、ｈは０〜１００の整数である）で表されるエポキシシリコーン樹脂などが挙げられるがこれらに限定されず、必要に応じて２種以上を用いてもよい。

(In the formula, R ₁ has the same definition as in general formula (1), R ₉ represents a divalent organic residue having 1 to 20 carbon atoms, and E ₁ is a group represented by formula (12). Yes, h is an integer of 0 to 100), but is not limited thereto, and two or more kinds may be used as necessary.

  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 epoxy / oxetane composite resin, and the like, but are not limited thereto.

  The curable resin composition of the present invention comprises the above components (A) to (C) as essential components, but the resin component (in addition to the resin, a component that is cured to become part of the resin, for example, a monomer, a curing agent) 60 wt% or more, preferably 80 wt% or more, more preferably 90 wt% or more of the (A) component to the (B) component. Moreover, the blending ratio of the component (A), the component (B) and the component (C) may be determined as follows.

  It is preferable that the epoxy group of (A) component and the functional group in the hardening | curing agent of (B) component are the range of 0.8-1.5 by an equivalent ratio. 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 the thermosetting resin of the present invention is thermosetting resin composition-2, the components (B) to (C) are not essential, and the components (A) and (D) a cationic curing catalyst are essential. . And (A) component and other arbitrary components are the same as that of the thermosetting resin composition-1.

  As the component (D) which is the cationic curing catalyst, various compounds can be applied as long as they are known. For example, an onium salt compound composed of an organic cation molecule having a sulfonium cation, an iodonium cation, and an anionic species having Lewis acidity such as a tetrafluoroboron anion, a hexafluorophosphorus anion, a hexafluoroarsenic anion, and a hexafluoroantimony anion. Etc. Among these, it is desirable to use an onium salt composed of an organic cation molecule having a sulfonium cation and a hexafluoroantimony anion.

  (D) As a mixture ratio of a component, the range of 0.1 wt%-5 wt% with respect to (A) component is preferable. If it is less than 0.1, 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%, it is not preferable because the cured product is colored.

  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. A transfer mold method in which heat transfer is performed and a dispensing method in which a resin is injected into a predetermined position after mixing with a liquid epoxy resin to obtain a desired viscosity can be employed.

  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.

  Examples of optical component applications include optical lenses, optical semiconductor encapsulants, optical semiconductor housings, optical semiconductor adhesives, etc., but the applications are not limited to these, and known applications and manufacturing processes. If so, it 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.

  As a housing for an optical semiconductor device, the thermosetting resin composition of the present invention is mixed with a filler such as silica, titanium oxide, and alumina, kneaded with a kneader or a heat three roll, and then tableted and sealed. For example, a transfer mold method in which the resin is sent to the cavity of the mold and thermally cured can be applied.

  As an adhesive for an optical semiconductor device, a material obtained by pasting the thermosetting resin composition of the present invention into a known material such as an epoxy resin and a phenol resin and a filler by kneading with a roll or the like by a method such as dispensing. For example, a method in which a film formed using a known film material is bonded to a substrate, and the optical semiconductor element is mounted and thermally cured can be applied.

  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. At this time, if the (D) cation curing catalyst is a material that generates cation species by light irradiation, a film body can be obtained by performing heat treatment after light irradiation treatment.

  The film obtained by the above method can be applied to various uses as long as it is a known electronic component use and optical component use, such as a flexible printed wiring board, an anisotropic conductive film, and a cover lay film. The present invention is applicable to optical parts such as films, films for optical waveguides, and optical semiconductor films.

  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.

Example 1
As component (A1), XF42-C3294 (made by Momentive Performance Materials Japan GK; in general formula (1), R ₁ is a methyl group, n is 8, R ₂ is represented by general formula (3) , 887 parts by weight of a linear polydimethylsiloxane compound having an alcoholic hydroxyl group at both ends having an average l of 1.5: alcoholic hydroxyl group equivalent of 480 g / mol), and 285 parts by weight of hexahydrophthalic anhydride as an acid anhydride component It was used. (A1) An acid anhydride is 2 mol with respect to 1 mol.
The raw material was charged into a 3 L separable flask equipped with a stirring motor, a reflux condenser, and a nitrogen line, and the temperature was raised to 160 ° C. while stirring. After reaching 160 ° C., stirring was continued for 4 hours to synthesize a hemiester compound (A2) having carboxyl groups at both ends. The obtained (A2) was sampled and the acid value was measured with a 0.1N KOH / methanol solution. As a result, it was 90 mgKOH / g, and it was confirmed that the reaction had progressed quantitatively.
Next, 1118 parts by weight of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (epoxy equivalent 130 g / eq.) As component (A3) was added to the hemiester compound (A2). At this time, the molar ratio of the carboxyl group to the epoxy group is 1: 4.7. Next, 0.9 parts by weight of a 4% acetic acid solution of tetraethylammonium chloride was dropped as a reaction catalyst, and the reaction was performed at a reaction temperature of 170 ° C. for 5 hours. After sampling and confirming that the carboxyl group disappeared by measuring the acid value, the resin in the reaction mixture was filtered using a 150 mesh wire net. In this way, 2130 parts by weight of the epoxy silicone resin (A) was obtained. The epoxy equivalent of the obtained resin was 381 g / eq. The viscosity at room temperature was 11.1 Pa · s. This epoxy silicone resin (A) is referred to as ES1.

Example 2
(A3) The epoxy silicone resin (A) was prepared in the same manner as in Example 1 except that 1,491 parts by weight of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate was used as the component. Of 2450 parts by weight was obtained. The epoxy equivalent of this epoxy silicone resin (A) is 302 g / eq. The viscosity at room temperature was 5.1 Pa · s. This epoxy silicone resin (A) is referred to as ES2.

Example 3
As component (A1), XF42-B0970 (made by Momentive Performance Materials Japan GK); in the general formula (1), R ₁ is a methyl group, n is 18, R ₂ is represented by the general formula (3) , 820 parts by weight of a linear polydimethylsiloxane compound having an alcoholic hydroxyl group at both ends with an average l of 1.5: an alcoholic hydroxyl group equivalent of 820 g / mol), and 154 parts by weight of hexahydrophthalic anhydride as an acid anhydride component In the same manner as in Example 1 except that 806 parts by weight of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate was used as the component (A3), an epoxy silicone resin (A 1650 parts by weight of The epoxy equivalent of this epoxy silicone resin (A) is 372 g / eq. The viscosity at room temperature was 6.5 Pa · s. This epoxy silicone resin (A) is referred to as ES3.

Example 4
As component (A1), OFOH702-E (made by Momentive Performance Materials Japan GK); in the general formula (1), R ₁ is a methyl group, n is 26, and R ₂ is represented by the general formula (3). , 532 parts by weight of a linear polydimethylsiloxane compound having alcoholic hydroxyl groups at both ends with an average l of 1.5: alcoholic hydroxyl group equivalent of 1063 g / mol), 77 parts by weight of hexahydrophthalic anhydride as an acid anhydride component In the same manner as in Example 1 except that 605 parts by weight of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate was used as the component (A3), an epoxy silicone resin (A 1132 parts by weight of The epoxy equivalent of this epoxy silicone resin (A) is 299 g / eq. The viscosity at room temperature was 2.1 Pa · s. This epoxy silicone resin (A) is referred to as ES4.

Synthesis example 1
As component (A1), 50 parts by weight of XF-42-C3294 and 17 parts by weight of methylhexahydrophthalic anhydride were used and heated and stirred at 100 ° C. for 4 hours to synthesize a hemiester compound (A2) having carboxyl groups at both ends. did. The obtained (A2) was sampled and the acid value was measured with a 0.1N KOH / methanol solution. As a result, it was 85 mgKOH / g, and it was confirmed that the reaction was progressing quantitatively. To this, 134 parts by weight of a bisphenol F type epoxy resin (epoxy equivalent 167 g / eq.) And 100 ml of methyl isobutyl ketone were added and dissolved by stirring and heating. Under reflux of the solvent at 120 ° C., a solution of 1.4 parts by weight of tri-n-hexylphosphine in 10 parts by weight of methyl isobutyl ketone was added dropwise over about 3 hours, followed by reaction for 15 hours. The solvent was distilled off from the resulting reaction solution to obtain 178 parts by weight of an epoxy silicone resin (ES5). The epoxy equivalent of ES5 is 288 g / eq. The viscosity at room temperature was 86 Pa · s.

Examples 6-9
The epoxy silicone resin (A) (ES1-4) obtained in Examples 1 to 4 as component (A) and methylated hexahydrophthalic anhydride (MH: acid anhydride equivalent 168 g / eq.) As component (B) Is added so that the molar ratio of the epoxy group of the epoxy component to the acid anhydride group of the acid anhydride is 1: 1, and mixed well. Further, tetra-n-butyl is used as a curing accelerator for the component (C). Phosphonium o, o′-diethyl phosphorodithionate is added at 0.5% by weight, vacuum degassed and cured in a mold at 120 ° C. for 4 hours and further at 160 ° C. for 12 hours, and 5 cm in length. A resin plate having a width of 5 cm, a thickness of 1 mm, a length of 5 cm, a width of 3 cm, and a length of 4 mm was prepared, and various physical properties were measured. Moreover, 80 mm x 10 mm x 4 mm was used for the bending test.

Example 10
As the component (A), the epoxy silicone resin (ES1) obtained in Example 1 is used. Further, as the component (E), in general formula (11), h is 8, R ₁ is a methyl group, and R ₉ is propylene. Resin plates having a thickness of 1 mm and 4 mm by performing the same operation as in Example 6 except that an epoxy silicone resin (EST) in which E ₁ is represented by the formula (12) was used at a weight ratio of 1: 1. It was created.

Comparative Example 1
Except that the epoxy silicone resin (ES5) obtained in Synthesis Example 1 was used, the same operation as in Example 6 was performed to prepare resin plates having a thickness of 1 mm and 4 mm.

Comparative Example 2
Other than using (A) component, using 26 parts by weight of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (EpC) and 34 parts by weight of MH as component (E) Performed the same operation as Example 6, and produced the resin plate of thickness 1mm and 4mm.

Comparative Example 3
The same as Example 6 except that (A) component was not used and 20 parts by weight of triglycidyl isocyanurate (EpT, epoxy equivalent 100 g / eq.) As component (E) and 34 parts by weight of MH were used. The operation was performed to prepare resin plates having a thickness of 1 mm and 4 mm.

Comparative Example 4
66 parts by weight of the epoxy silicone resin (ES5) obtained in Synthesis Example 1, bisphenol F type epoxy resin (EpF, epoxy equivalent of 167 g / eq.), 27 parts of EpC and 100 parts of MH are mixed well, and a curing accelerator. As in Example 6, except that 0.4 parts by weight of 2-ethyl-4-methylimidazole was added and mixed, resin plates having a thickness of 1 mm and 4 mm were prepared.

Comparative Example 5
(A) A component is not used, EpC is 55 weight part, and an epoxy equivalent is 1,200 g / eq. 40 parts by weight of 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (EpHx, epoxy) Example 6 except that 8 parts by weight of an equivalent 180 g / eq.), 8 parts by weight of a stoichiometric reaction product (HxH) of 1,6-hexanediol and methylated hexahydrophthalic anhydride, and 82 parts by weight of MH were used. The same operation was performed to prepare resin plates having a thickness of 1 mm and 4 mm.

Comparative Example 6
(A) An epoxy resin in which triglycidyl isocyanurate was partially subjected to addition reaction using propionic acid without using the component (EpTP epoxy equivalent: 140 g / eq. 28 parts by weight, MH was used by 34 parts by weight) Except for the above, the same operations as in Example 6 were performed to prepare 1 mm and 4 mm resin plates.

Comparative Example 7
In the above general formula (10) without using the component (A), k = 0, j = 0.8, i = 0.2, R ₇ is a methyl group, and R ₈ is 2- (3,4 -Epoxycyclohexyl) Ethyl group epoxy silicone resin (ESC, epoxy equivalent 207 g / eq.) Was used in the same manner as in Example 6 except that 42 parts by weight and MH was 27 parts by weight. A resin plate was created.

Comparative Example 8
(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 4 mm.

Comparative Example 9
((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. A resin plate having thicknesses of 1 mm and 4 mm was prepared by curing in the same manner as in Comparative Example 8 using 48 parts by weight of methyl hydrogen silicone oil.

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 A straight line measured at a temperature of 30 ° C. to 270 ° C. using a thermal stress strain measuring device TMA / SS120U manufactured by Seiko Denshi Kogyo Co., Ltd. The linear expansion coefficient was calculated from the slope of. The heating rate was 5 ° C./min.

(3) Initial transmittance of cured product Using a self-recording spectrophotometer U-3410 manufactured by Hitachi, Ltd., a transmittance 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 of the cured product at room temperature was measured using a TECKLOCK Co., Ltd. hardness meter TYPE-D.

(8) Shape of cured product after removing the mold 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.

(9) Bending and Deflection Characteristic Test Based on JIS-7171, using a test piece of 80 mm × 10 mm × 4 mm, the bending elastic modulus, bending strength, and bending deflection were measured by an autograph (manufactured by Shimadzu Corporation). .

  Tables 1 and 2 show the composition of Examples 6 to 10 and Comparative Examples 1 to 4 and the measurement results of the tests of the obtained cured products. In the blending composition, the description of component (C) is omitted because the type is constant, and the blending ratio is as described in the text.

  Table 3 shows the measurement results of each test of the cured products obtained in Comparative Examples 5 to 9.

Examples 11-15, Comparative Examples 10-18
The blends obtained by blending Examples 6 to 10 and Comparative Examples 1 to 9 were filled into a blue LED pre-molded package having a silver-plated bottom portion by casting, 100 ° C. for 2 hours, 150 ° C. 5 It was time cured 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 4.
(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 the presence or absence of cracks and peeling of the sealing material was confirmed with a microscope. The results are shown in Tables 4-5.

Examples 16-19
3-methyl-2-butyl as the thermal cationic curing catalyst of component (D) with respect to 100 parts by weight of epoxy silicone resin (A) (ES1-4) obtained in Examples 1-4 of component (A) Tetramethylenesulfonium hexafluoroantimonate (trade name: Adeka Opton CP-77, manufactured by ADEKA) was added in 0.4 parts by weight, mixed well, and vacuum degassed. This compounded solution was applied onto a PET film using a bar coater and cured at 65 ° C. for 4 hours and further at 150 ° C. for 3 hours.

Example 20
As the component (A), the epoxy silicone resin (ES1) obtained in Example 1 is used. Further, as the component (E), in general formula (11), h is 8, R ₁ is a methyl group, and R ₉ is propylene. A cured product was obtained in the same manner as in Example 16 except that an epoxy silicone resin (EST) in which E ₁ was represented by the formula (12) was used at a weight ratio of 1: 1.

Comparative Examples 19-22, 24, 25
Using 100 parts by weight of the resin or resin composition shown in Table 6 and 0.4 parts by weight of CP-77, the same operation as in Example 16 was performed to obtain a cured product.

Comparative Example 23
Epoxy formulation shown in Comparative Example 5 (without using component (A), EpC 55 parts by weight, epoxy equivalent of 1,200 g / eq. Hydrogenated bisphenol A type epoxy resin (EpHA) 40 parts by weight, 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (EpHx, epoxy equivalent 180 g / eq.) 8 parts by weight, 1,6-hexane The same operation as in Example 16 was carried out except that 100 parts by weight of a diol and methylated hexahydrophthalic anhydride (8 parts by weight of a stoichiometric reaction product (HxH)) and 0.4 parts by weight of CP-77 were used. A cured product was obtained.

Comparative Example 26
A PET film was coated according to the formulation of Comparative Example 8, and cured at 100 ° C. for 2 hours and 150 ° C. for 5 hours to prepare a cured product.

Comparative Example 27
The composition of Comparative Example 9 was applied to a PET film and cured at 100 ° C. for 2 hours and 150 ° C. for 5 hours to prepare a cured product.

Evaluation of film properties The cured products obtained in Examples 16 to 20 and Comparative Examples 19 to 27 were peeled off from the PET film and folded in half. Those that were broken when peeled from the PET film were evaluated as x, those that were broken when folded in half were evaluated as Δ, and those that were not broken even when folded in half were evaluated as ○.

Claims (11)

A hemiester (A2) having a carboxyl group at the terminal obtained by the reaction of a linear polysiloxane having an alcoholic hydroxyl group represented by the general formula (1) at both ends and an acid anhydride, and the general formula (2). The liquid cycloaliphatic epoxy resin (A3) at room temperature is reacted with the molar ratio of the carboxyl group of (A2) to the epoxy group of (A3) as carboxyl group / epoxy group = 1/2 to 1/10. An epoxy silicone resin characterized by being obtained.

(In the formula, R ₁ represents a methyl group or a phenyl group, and may be the same or different. R ₂ represents a divalent group represented by the general formula (3). N is an integer of 0 to 100. Represents.)

(Wherein, R ₃ is represented alkylene or alkylidene group, or a C _n H _2n OCO or COC _n H _2n 2 divalent ester-containing groups (where represented by OCO a single bond or C _n H _2n, n is 1 to 6)) .)

(In the formula, l is a number exceeding 0 and 3 or less.)
A linear polysiloxane (A1) having an alcoholic hydroxyl group at both ends represented by the general formula (1) is reacted with an acid anhydride to produce a hemiester (A2) having a carboxyl group at the end, and this hemiester ( A2) or a reaction mixture containing this hemiester (A2) and a alicyclic epoxy resin (A3) which is liquid at room temperature represented by the general formula (2), a carboxyl group of (A2) and an epoxy of (A3) A method for producing an epoxy silicone resin, wherein a molar ratio of groups is reacted as carboxyl group / epoxy group = 1/2 to 1/10.

(In the formula, R ₁ represents a methyl group or a phenyl group, and may be the same or different. R ₂ represents a divalent group represented by the general formula (3) and may be the same or different. n represents an integer of 0 to 100.)

(Wherein, R ₃ is represented alkylene or alkylidene group, or a C _n H _2n OCO or COC _n H _2n 2 divalent ester-containing groups (where represented by OCO a single bond or C _n H _2n, n is 1 to 6)) .)

(In the formula, l is a number exceeding 0 and 3 or less .)   An epoxy silicone resin obtained by the method for producing an epoxy silicone resin according to claim 2. It is a thermosetting resin composition having (A) an epoxy silicone resin, (B) a curing agent, and (C) a curing accelerator as essential components, and the epoxy according to claim 1 as the (A) epoxy silicone resin. A thermosetting resin composition comprising a silicone resin.   (B) The thermosetting resin composition according to claim 4, wherein the curing agent is an acid anhydride.   The thermosetting resin composition according to claim 4 or 5, wherein the curing accelerator (C) is selected from at least one of a quaternary ammonium salt and a quaternary phosphonium salt. (A) An epoxy silicone resin, (D) a curable resin composition comprising a cationic curing catalyst as an essential component, wherein the epoxy silicone resin according to claim 1 is used as the (A) epoxy silicone resin. A curable resin composition. Thermosetting resin composition, the thermosetting resin composition according to any one of claims 4-7, characterized in that an optical component resin composition or electronic components for the resin composition.   The thermosetting resin composition according to claim 4, wherein the thermosetting resin composition is a resin composition for optical semiconductor components.   A cured product obtained by curing using the thermosetting resin composition according to claim 8.   A film body obtained by forming the thermosetting resin composition according to any one of claims 4 to 7 and heat-treating it.