JP5914110B2 - Curable resin composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an epoxy resin composition using a terminal isocyanuric skeleton-containing epoxy resin and a cured product thereof from which a cured product excellent in coloring resistance and the like is obtained, and in particular, curability suitable for the electronic material field and optical semiconductor encapsulation. The present invention relates to a resin composition.

  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 that exhibits a high glass transition temperature is used, but such an epoxy resin is highly elastic and has lower strength and deflection than a normal epoxy resin and is lit off. There is also a problem that the sealing material is likely to be cracked due to a rapid temperature change due to. 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-resistant coloring property.

  In order to improve heat resistance and light resistance, LED encapsulants based on epoxy resins containing an isocyanuric acid skeleton have been developed. LED sealing material using an epoxy resin containing an isocyanuric acid skeleton is an aromatic epoxy resin, an epoxy resin obtained by nuclear hydrogenation of this, and a heat-resistant coloring property and a light-resistant coloring property as compared with an epoxy resin having a cyclohexene oxide group However, it has not been improved enough to satisfy the recent demand for higher output of LEDs.

  On the other hand, an isocyanuric skeleton-containing epoxy resin typified by triglycidyl isocyanurate has a high melting point of around 100 ° C., an aromatic epoxy resin usually used as an LED sealing material, and an epoxy resin obtained by nuclear hydrogenation thereof, cyclohexene The compatibility with the epoxy resin having an oxide group and the acid anhydride compound is very poor, and when mixing, it is necessary to raise the temperature to near the melting point of the isocyanuric skeleton-containing epoxy resin. In addition, since the isocyanuric skeleton-containing epoxy resin is very strong in crystallinity, when the resin composition after mixing is cooled, the isocyanuric skeleton-containing epoxy resin easily precipitates and becomes a non-uniform composition. It has the disadvantage of being very bad.

  In addition, the isocyanuric skeleton-containing epoxy resin has the advantage that a very high glass transition temperature can be obtained when it is made into a cured product due to its rigidity, but its high polarity, rigidity, and high crosslink density. Therefore, it has the disadvantages that it has higher hygroscopicity than conventional aromatic epoxy resins, has poor mechanical strength, and is very brittle. This is because when a LED package using an LED encapsulant based on an isocyanuric skeleton-containing epoxy resin is turned off and on, a rapid temperature change that occurs when the LED package is turned off, a rapid thermal cycle of the surrounding environment, and when reflow mounting the LED Moisture due to moisture absorption of the cured product evaporates explosively, leading to a defect that causes cracks in the sealing material.

  In order to improve the compatibility and mechanical strength of the isocyanuric skeleton-containing epoxy resin, the isocyanuric skeleton-containing epoxy resin is partially reacted with a monofunctional carboxylic acid or acid anhydride to make the composition compatible. At the same time, attempts have been made to improve mechanical strength by reducing the crosslink density when the epoxy groups in the resin are thinned out to obtain cured products. However, although the isocyanuric skeleton-containing epoxy resin modified with a monofunctional carboxylic acid can improve the compatibility, it cannot be said that the heat-resistant coloring property and the hygroscopicity are sufficiently improved. In addition, the resin partially reacted with the acid anhydride further increases the melting point of the isocyanuric skeleton-containing epoxy resin that originally has a high melting point, causing workability deterioration and difficult to control the reaction, Often an amorphous gel is formed. Even if the reaction is stopped halfway before the acid anhydride is completely reacted, the unreacted acid anhydride remains in the resin, so the reaction proceeds during storage and the LED is sealed. There is a need for further improvements in terms of work, such as when the resin does not melt and a molding defect occurs.

  In order to improve the mechanical strength of the isocyanuric skeleton-containing epoxy resin, attempts have been made to introduce a siloxane structure therein. Although a certain effect is observed with this method, the linear expansion coefficient of the cured product is increased due to the flexible siloxane, and stress tends to concentrate on specific parts such as the wire bonding part of the package during the thermal cycle, and the wire bonding part Further improvements are required because of problems such as detachment.

  Thus, even if the isocyanuric skeleton is excellent in heat-resistant coloring property and light-resistant coloring property, a material that completely satisfies the physical properties required for the LED sealing material has not been obtained, and storage stability, workability, low There is a demand for materials that are excellent in hygroscopicity, mechanical strength, heat-resistant coloring, and light-coloring resistance.

  On the other hand, an epoxy resin composition of a polyester having a carboxyl group at a terminal and triglycidyl isocyanurate has been studied for a long time as a powder coating, but this composition further includes an epoxy resin curing agent or other alicyclic epoxy, etc. It has not been studied for blending and making the material excellent in transparency.

  Patent Document 1 discloses a mixture of a hydrogenated epoxy resin having a hydrogenation rate of 90 to 100% of an aromatic ring obtained by directly hydrogenating a triazine ring-containing epoxy resin and an aromatic epoxy resin, an acid anhydride curing agent, and curing. An epoxy resin composition for a light-emitting device sealing material containing an accelerator is disclosed. Patent Document 2 is selected from the group consisting of optionally substituted triglycidyl isocyanurates modified with carboxylic acids, hydrogenated aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Disclosed is a composition comprising at least one epoxy resin mixed with an epoxy resin that is liquid at 25 ° C. Patent Document 3 contains, as a resin component, a solid pulverized product obtained by reacting a triazine derivative epoxy resin and an acid anhydride at an epoxy equivalent / acid anhydride group equivalent ratio of 0.6 to 2.0. A thermosetting epoxy resin composition is disclosed. Patent Document 4 discloses an epoxy resin composition for an optical semiconductor device containing an epoxy resin having two or more epoxy groups in one molecule, an acid anhydride curing agent, a curing accelerator, a polylactone polyol, and a polyorganosiloxane. It is disclosed. Patent Document 5 includes a linear polysiloxane having an alcoholic hydroxyl group at both ends and a dihydric alcohol having an alcoholic hydroxyl group at both ends of a hydrocarbon group, and a carboxyl group at the end obtained by the reaction of an acid anhydride. Epoxy resin obtained by reacting a hemiester having triglycidyl isocyanurate with a molar ratio of carboxyl groups in the hemiester to epoxy groups of triglycidyl isocyanurate as carboxyl groups / epoxy groups = 1/3 to 1/10 A resin is disclosed. Patent Document 6 discloses a powder coating material containing an epoxy resin obtained by reacting a polyester having a carboxyl group with triglycidyl isocyanurate. However, it is difficult to say that the curable resin compositions described in these patent documents have sufficient characteristics.

JP 2005-306952 A JP 2008-45014 A WO2007 / 15427 JP 2011-153165 A JP 2012-1570 A JP-A-4-63872

  The present invention is excellent in storage stability, workability, low moisture absorption, mechanical strength, heat-resistant coloring, light-coloring resistance, low coefficient of linear expansion and crack resistance, and is suitable for the electronic material field and optical semiconductor encapsulation. It is an object of the present invention to provide an epoxy resin composition.

That is, the present invention includes the following components (A) to (C):
(A) It is represented by the general formula (1), has a molecular weight distribution, a saturated cycloaliphatic dicarboxylic acid compound (A1) at both ends, triglycidyl isocyanurate (A2), a carboxyl group of (A1), ( A terminal isocyanuric group-containing epoxy resin obtained by reacting the molar ratio of the epoxy group of A2) as carboxyl group / epoxy group = 1/3 to 1/10;
A curable resin composition for optical parts or electronic parts , comprising (B) a curing agent and (C) a curing accelerator as essential components.

式（２）中、Ｒ₂、Ｒ₃は炭素数２〜２０の2価の炭化水素基を表し、内部にエステル構造を有していても良く、各々同一でも異なっていても良い。Estはエステル基を表し、ｎは１〜１００の数を表す平均の繰り返し単位数であるが、式（２）中に含まれる平均の炭素数は２０以上である。 In formula, Z represents the C4-C12 bivalent saturated cycloaliphatic group which may have a substituent, and may have a condensed ring structure. R ₁ is a divalent hydrocarbon group having 20 or more carbon atoms having an ester bond inside represented by the formula (2).

In the formula (2), R ₂ and R ₃ represent a divalent hydrocarbon group having 2 to 20 carbon atoms, and may have an ester structure inside, and may be the same or different. Est represents an ester group, and n is the average number of repeating units representing a number of 1 to 100, but the average number of carbons contained in the formula (2) is 20 or more.

It is desirable that the terminal isocyanuric group-containing epoxy resin (A) satisfies any one or more of the following.
1) Does not contain an acid anhydride compound as an impurity and has a carboxylic acid value of less than 1.0 mgKOH / g.
2) Epoxy equivalent is 150-800 g / eq. Be.
3) Z in the general formula (1) has a cyclohexylene group structure.
4) R ₁ in the general formula (1) is in the range of an average molecular weight of 500 to 3000, and is composed of a divalent hydrocarbon group having two or more ester bonds inside.
5) R ₁ in the general formula (1) is represented by either the formula (3) or the formula (4).

（式中、Ｒ₄は炭素数２〜２０の２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。Ｒ₅は炭素数４〜１１の２価の炭化水素基を表す。ｍは１〜２０の数を表す平均の繰り返し単位数であるが、式（３）中に含まれる平均の炭素数は２０以上である。）

（式中、Ｒ₆は炭素数２〜２０の２価の炭化水素基を表す。ｌ、ｋはそれぞれ１〜２０の数を表す平均の繰り返し単位数であるが、式（４）中に含まれる平均の炭素数は２０以上である。）

(In the formula, R ₄ represents a divalent hydrocarbon group having 2 to 20 carbon atoms and may be the same or different. R ₅ represents a divalent hydrocarbon group having 4 to 11 carbon atoms. M Is the average number of repeating units representing a number of 1 to 20, but the average number of carbons contained in formula (3) is 20 or more.)

(In the formula, R ₆ represents a divalent hydrocarbon group having 2 to 20 carbon atoms. L and k are the average number of repeating units each representing a number of 1 to 20, but are included in formula (4). The average number of carbon atoms is 20 or more.)

  Moreover, this invention is said curable resin composition whose hardening agent of (B) component is an acid anhydride. Furthermore, this invention is said curable resin composition whose hardening accelerator of (C) component is at least 1 sort (s) chosen from a quaternary ammonium salt and a quaternary phosphonium salt.

It is desirable that the curable resin composition of the present invention further includes at least one component selected from the following components (D) and (E).
(D) A liquid epoxy resin having two or more cyclohexene oxide structures in one molecule. In this case, the epoxy equivalent of (A) component which is an epoxy resin component, and (D) component is 160-300 g / eq. The component (D) is preferably used so that the viscosity at 25 ° C. is 0.1 to 500 Pa · s.
(E) A phenolic compound represented by the formula (5).

（式中、Ｒ_yは水素原子又は炭素数１〜６の１価の炭化水素基を表し、Ｙは炭素数１〜６０の２価の炭化水素基を表し、内部にエステル結合性酸素原子を２〜８個有していても良い。）

(In the formula, R _y represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; Y represents a divalent hydrocarbon group having 1 to 60 carbon atoms; (You may have 2-8)

  Moreover, this invention is said resin composition for optical components, the resin composition for electronic components, or the resin composition for optical semiconductor components, Said curable resin composition characterized by the above-mentioned. Furthermore, the present invention is an LED device that is sealed using the above resin composition for optical semiconductor components.

  The curable resin composition of the present invention includes a terminal isocyanuric skeleton-containing epoxy resin, a curing agent, and a curing accelerator, and is excellent in storage stability and compatibility with a liquid epoxy resin at room temperature, and a curable resin using the same. The composition is excellent in strength, deflection and low linear expansion when used as a cured resin obtained by performing a curing treatment, has a transparency, and can obtain a cured product excellent in heat resistance and light resistance. . Therefore, it is useful for electronic component materials such as semiconductors and circuit boards, and optical component materials such as optical lenses, and in particular, improvement of coloring due to heat and light, cracks due to temperature changes, etc., which are currently a problem in LED sealing materials. Can be expected.

IR spectrum of terminal isocyanuric group-containing epoxy resin (E2) IR spectrum of terminal isocyanuric group-containing epoxy resin (E3) IR spectrum of terminal isocyanuric group-containing epoxy resin (E4)

Hereinafter, embodiments of the present invention will be described in detail.
The curable resin composition of the present invention contains components (A) to (C) as essential components. That is, (A) a terminal isocyanuric group-containing epoxy resin, (B) a curing agent, and (C) a curing accelerator are included as essential components. Hereinafter, the terminal isocyanuric group-containing epoxy resin may be referred to as the component (A), the curing agent as the component (B), and the curing accelerator as the component (C). In addition, it is understood that the epoxy resin and epoxy compound as used in this specification may have the same meaning. Therefore, an epoxy resin or an epoxy compound may be used in a meaning that represents both.

The terminal isocyanuric group-containing epoxy resin (A) of the component (A) is represented by the general formula (1), has a molecular weight distribution, has an average carbon number of 20 or more in R ₁ , and has a terminal saturated cyclic fat. The dicarboxylic acid compound (A1) composed of a group dicarboxylic acid group, triglycidyl isocyanurate (A2), the molar ratio of the carboxyl group of (A1) and the epoxy group of (A2), carboxyl group / epoxy group = It can be obtained by reacting as 1/3 to 1/10.

  Z in the general formula (1) represents a divalent saturated cycloaliphatic group having 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and may have a condensed ring structure inside. Z may have a substituent, and when it has a substituent, an alkyl group having 1 to 6 carbon atoms is preferable. Examples of such saturated cycloaliphatic groups include cyclobutanylene group, cyclopentylene group, cyclohexylene group, methylcyclohexylene group, cycloheptylene group, norbornylene group, methylnorbornylene group, decahydronaphthylene group, bicyclohexene group. Although a silene group etc. are mentioned, it is not limited to these. Preferred Z is a cyclohexylene group from the viewpoint of economy and ease of reaction.

R ₁ in the general formula (1) is a divalent hydrocarbon group having 20 or more carbon atoms having an ester bond inside represented by the above formula (2), and represents a structure having a molecular weight distribution.

  In formula (2), Est represents an ester group. There are two types of ester groups, -C (O) -O- and -O-C (O)-, but either form may be used.

In formula (2), R ₂ and R ₃ represent a divalent hydrocarbon group having 2 to 20 carbon atoms, and may be the same or different. Examples of such a group include, but are not limited to, ethylene group, propylene group, butylene group, pentylene group, 3-methylpentylene group, hexylene group, octylene group, decylene group, dodecylene group, stearylene group, and the like. Not. Preferably, it is a C2-C12 alkylene group.

  In formula (2), n represents the average number of repeating units of 1 to 100, but represents the number of carbon atoms constituting formula (2) being 20 or more. Preferred n is a number in which the average molecular weight of the group represented by the formula (2) falls within the range of 500 to 3,000. By having such a structure, it becomes possible to improve the poor solubility, high hygroscopicity, and low mechanical strength, which were the drawbacks of the isocyanuric skeleton-containing epoxy resin.

  Among the structures represented by the formula (2), a preferable form for obtaining the effects of the present invention is a divalent polyester structure represented by the above formula (3) or the formula (4).

In Formula (2) and Formula (3), it is understood that R ₄ corresponds to R ₂ and R ₅ corresponds to R ₃ . In Formula (2) and Formula (4), it can be said that R ₆ corresponds to R ₃ and the pentylene group corresponds to R ₂ .

In formula (3), R ₄ represents a divalent hydrocarbon group having 2 to 20 carbon atoms. Examples of such a group include an ethylene group, a propylene group, a butylene group, a pentylene group, a 3-methylpentylene group, a hexylene group, an octylene group, a decylene group, a dodecylene group, and a stearylene group. Preferred R ₄ is the same as described for R ₂ .
R ₅ represents a divalent hydrocarbon group having 4 to 11 carbon atoms. Examples of such a group include a butylene group, a pentylene group, a hexylene group, an octylene group, and a decylene group. Preferably, it is a C2-C10 alkylene group.
More preferably, in the formula (3), R ₄ is a 3-methylpentylene group and R ₅ is a butylene group or an octylene group.

  M in Formula (3) represents the average number of repeating units of 1 to 20 and represents the number of carbon atoms constituting Formula (3) being 20 or more. Preferred m is the same as that described for n in the formula (2).

In the formula (4), R ₆ represents a divalent hydrocarbon group having 2 to 20 carbon atoms. Examples of such a group include an ethylene group, a propylene group, a butylene group, a pentylene group, a 3-methylpentylene group, a hexylene group, an octylene group, a decylene group, a dodecylene group, and a stearylene group. Preferred groups are the same as described for R ₃ .

  In the formula (4), l and k each represent an average number of repeating units of 1 to 20 and the number of carbon atoms constituting the formula (4) is 20 or more. Preferred l + k is a number in which the average molecular weight of the group represented by the formula (4) falls within the range of 500 to 3000.

  The terminal isocyanuric group-containing epoxy resin (A) used in the present invention comprises a compound (A1) in which the terminal group represented by the general formula (1) is a saturated cycloaliphatic dicarboxylic acid group, and triglycidyl isocyanurate (A2). ) Can be obtained by reacting the molar ratio of the carboxyl group of (A1) and the epoxy group of (A2) as carboxyl group / epoxy group = 1/3 to 1/10, preferably 1/3. The range is 5 to 1/6. When the molar ratio of the epoxy group is less than 3, there is a possibility of causing gelation during the reaction, and the curable resin composition of the present invention cannot be obtained. Further, when the molar ratio of the epoxy group exceeds 10, the concentration derived from the (A1) structure existing in the component (A) is low, the brittleness of the cured product, which is a defect specific to the isocyanuric skeleton, high hygroscopicity, In addition, since coloration occurs in a long-term heat test, it is not preferable.

  It is desirable that the terminal isocyanuric group-containing epoxy resin (A) does not contain an acid anhydride compound in the resin and has an acid value of less than 1 mgKOH / g. The acid anhydride compound will be described in the item of the production method described later, but when the acid anhydride is used as a raw material when the compound represented by the general formula (1) is synthesized, the acid anhydride is completely reacted. It can be confirmed by using a known method such as gas chromatography that it does not remain. This acid anhydride compound is an impurity because it is contained as an unreacted component when the dicarboxylic compound (A1) as the component (A) or intermediate is produced. By preventing the acid anhydride compound from being present in the component (A), the storage stability of the component (A) is significantly improved.

On the other hand, the acid value is also related to the content of the acid anhydride compound, but since the acid anhydride compound is not substantially contained, it can be said that the acid value is substantially related to the residual amount of the carboxy group of the dicarboxylic compound (A1). The acid value is less than 1 mgKOH / g, preferably less than 0.5 mgKOH / g.
The acid value will be described in the item of the production method described later, but it is excellent in storage stability by reacting the dicarboxylic acid compound (A1) and triglycidyl isocyanurate (A2) until the predetermined acid value is reached. The terminal isocyanuric group-containing epoxy resin can be obtained.

  When synthesizing the dicarboxylic compound (A1), if an acid anhydride remains, gelation occurs when synthesizing a terminal isocyanuric group-containing epoxy resin, and viscosity increase or epoxy equivalent increase during storage, Since gelation occurs, it is not preferable. Even when the acid value in the terminal isocyanuric group-containing epoxy resin is 1 mg KOH / g or more, an increase in viscosity or an increase in epoxy equivalent occurs during storage of the component (A), which causes a problem in quality. Absent.

Next, the manufacturing method of the terminal isocyanuric group containing epoxy resin of (A) component is demonstrated.
The terminal isocyanuric group-containing epoxy resin used in the present invention comprises a dicarboxylic acid compound (A1) represented by the general formula (1), triglycidyl isocyanurate (A2), a carboxyl group of (A1), and (A2) It is manufactured by making the molar ratio of the epoxy group react as carboxyl group / epoxy group = 1/3 to 1/10.

  The dicarboxylic acid compound (A1) can be prepared by subjecting a polyester diol having an alcoholic hydroxyl group at both ends represented by the formula (8) to an addition reaction with an acid anhydride compound represented by the formula (9), or a formula (10 However, it is not limited to these, although it can obtain by the method of carrying out a condensation reaction with the bifunctional carboxylic acid, ester compound, or acid halide represented by this. At this time, when impurities such as multimers are generated, purification such as recrystallization is necessary.

（式中、Ｒ₂、Ｒ₃、Ｅｓｔ、ｎは、式（２）と同義である。）

(In the formula, R ₂ , R ₃ , Est and n have the same meanings as in formula (2).)

（式中、Ｚ₁、Ｚ₂は、一般式（１）におけるZと同義である。また、Ｘは水酸基、Ｃ１〜Ｃ３のアルキルオキシ基、又はハロゲン原子を表す。）

(In the formula, Z ₁ and Z ₂ are synonymous with Z in the general formula (1). X represents a hydroxyl group, a C1-C3 alkyloxy group, or a halogen atom.)

  A particularly preferred method for obtaining the dicarboxylic acid compound (A1) is represented by the polyester diol having both terminal alcoholic hydroxyl groups represented by the formula (8) and the formula (9) in view of ease of reaction operation and economy. This is an addition reaction using an acid anhydride compound.

  As the polyester diol having a both-end alcoholic hydroxyl group represented by the formula (8), various known ones can be selected as long as n does not exceed the above range. (11) It is a compound represented by (14).

（式中、ｍは平均繰り返し単位数であり、１．５＜ｍ＜１３を満たす数である。）

(In the formula, m is the average number of repeating units and is a number satisfying 1.5 <m <13.)

If the average number of repeating units exceeds 1.5, the average carbon number in R ₁ in the general formula (1) is 20 or more, and the average molecular weight can be interpreted as 500 or more. If m is a number less than 13, the average molecular weight can be interpreted as less than 3000. Such compounds may be commercially available, for example, Kuraray Polyols P-510 (average molecular weight 500), P-1010 (average molecular weight 1000), P-2010 (average molecular weight 2000) manufactured by Kuraray Co., Ltd. ), P-3010 (average molecular weight 3000), and the like.
In addition, the average molecular weight and the average number of repetitions in this specification mean number average.

（式中、ｍは１．３＜ｍ＜１０を満たす数である。）
なお、平均繰り返し単位数ｍが１．３を超える数であれば、一般式（１）におけるＲ₁中の平均炭素数が２０以上となり、平均分子量が５００以上と解釈できる。また、ｍが１０未満の数であれば、平均分子量が３０００未満と解釈できる。このような化合物は、市販されているものを用いてもよく、例えば（株）クラレ製Ｋｕｒａｒａｙ Ｐｏｌｙｏｌｓ Ｐ−２０５０（平均分子量２０００）等の形で入手が可能である。

(In the formula, m is a number satisfying 1.3 <m <10.)
If the average repeating unit number m exceeds 1.3, the average carbon number in R ₁ in the general formula (1) is 20 or more, and the average molecular weight can be interpreted as 500 or more. If m is a number less than 10, the average molecular weight can be interpreted as less than 3000. Such a compound may be commercially available, and is available in the form of, for example, Kuraray Polyols P-2050 (average molecular weight 2000) manufactured by Kuraray Co., Ltd.

（式中、Ｒ_2bはエチレン基又はブチレン基のいずれかを表し、各々同一でも異なっていても良い。ｍは２．３＜ｍ＜１７を満たす数である。）
なお、平均繰り返し単位数ｍが２．３を超える数であれば、一般式（１）におけるＲ₁中の平均炭素数が２０以上となり、平均分子量が５００以上と解釈できる。また、ｍが１７未満の数であれば、平均分子量が３０００未満と解釈できる。このような化合物は、市販されているものを用いてもよく、例えばＤＩＣ（株）製ＯＤ−Ｘ−３５５（平均分子量１０００），ＯＤ−Ｘ−２３３０（平均分子量２０００）等の形で入手が可能である。

(In the formula, R _2b represents either an ethylene group or a butylene group, and may be the same or different. M is a number satisfying 2.3 <m <17.)
If the average repeating unit number m exceeds 2.3, the average carbon number in R ₁ in the general formula (1) is 20 or more, and the average molecular weight can be interpreted as 500 or more. If m is a number less than 17, the average molecular weight can be interpreted as less than 3000. Such a compound may be commercially available, and is available in the form of, for example, OD-X-355 (average molecular weight 1000), OD-X-2330 (average molecular weight 2000) manufactured by DIC Corporation. Is possible.

（式中、Ｒ₆は一般式（４）における説明と同義であり、ｌ、ｋは１より大きい数であり、３＜（ｌ＋ｋ）＜２６を満たす数である。）
なお、平均繰り返し単位数の合計である（ｌ＋ｋ）が３を超える数であれば、一般式（１）におけるＲ₁中の平均炭素数が２０以上となり、平均分子量が５００以上と解釈できる。また、（ｌ＋ｋ）が２６未満の数であれば、平均分子量が３０００未満と解釈できる。このような化合物は、市販されているものを用いてもよく、例えば（株）ダイセル製プラクセル２０５（平均分子量５００）、プラクセル２１０（平均分子量１０００）、プラクセル２２０（平均分子量２０００）等の形で入手が可能である。

(In the formula, R ₆ has the same meaning as in the general formula (4), l and k are numbers larger than 1, and 3 <(l + k) <26).
In addition, if (l + k) which is the sum of the average number of repeating units is a number exceeding 3, the average carbon number in R ₁ in the general formula (1) is 20 or more, and the average molecular weight can be interpreted as 500 or more. If (l + k) is a number less than 26, the average molecular weight can be interpreted as less than 3000. Such compounds may be commercially available, for example, in the form of Plascel 205 (average molecular weight 500), Plaxel 210 (average molecular weight 1000), Plaxel 220 (average molecular weight 2000) manufactured by Daicel Corporation. Available.

  Two or more polyester diols having both terminal alcoholic hydroxyl groups as represented by formulas (11) to (14) may be used as necessary.

  As the acid anhydride compound represented by the formula (9), various compounds can be selected as long as they are known. For example, cyclobutane-1,2-dicarboxylic acid anhydride, cyclopentane-1,2-dicarboxylic acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, 3-methylcyclohexane-1,2-dicarboxylic acid anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid Although saturated cyclic aliphatic acid anhydride compounds, such as an anhydride, are mentioned, it is not limited to these, You may use 2 or more types together. A preferred acid anhydride compound is cyclohexane-1,2-dicarboxylic acid anhydride from the viewpoints of economy and ease of reaction operation.

  In order to obtain the dicarboxylic acid compound (A1), the amount of the polyester diol having an alcoholic hydroxyl group at both ends and an acid anhydride used in a particularly preferred manner is stoichiometrically 1 mol of a component having an alcoholic hydroxyl group. On the other hand, although 2 mol of acid anhydride is used, it is preferable to use an excessive component having an alcoholic hydroxyl group from the viewpoint of controlling the curing rate when the curable 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 a polyester diol having an alcoholic hydroxyl group at both ends is preferred with respect to 2 mol of the acid anhydride. On the contrary, when an acid anhydride compound is used in an excessive amount, gelation tends to occur during the synthesis of the terminal isocyanuric group-containing epoxy resin (A).

  The end point of the reaction using a particularly preferred method for obtaining the dicarboxylic acid compound (A1) is achieved by confirming that the acid anhydride has completely disappeared and does not remain. The presence or absence of residual acid anhydrides can be confirmed using known methods such as acid value measurement and gas chromatography. When the following epoxy modification reaction is carried out with the acid anhydride remaining, gelation is likely to occur, and the quality such as epoxy equivalent and viscosity is greatly affected without gelation. Absent.

  Regarding the reaction conditions using this particularly preferred technique, the polyester diol having an alcoholic hydroxyl group at both ends and an acid anhydride are usually reacted at 80 ° C to 200 ° C, preferably 100 ° C to 150 ° C. 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 not preferable.

  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.

  The terminal isocyanuric group-containing epoxy resin used in the present invention has (A1) and (A2), the number of moles of the carboxyl group (A1) and the epoxy group (A2) is carboxyl group / epoxy group = 1 / It is obtained by reacting at a ratio of 3 to 1/10. In this reaction, the carboxyl group of (A1) and the epoxy group of (A2) react to produce an ester bond, and the terminal of (A1) It has a structure in which an epoxy-substituted isocyanuric group is bonded to. Here, since (A2) has three epoxy groups, some of the unreacted epoxy groups may be bonded to other (A1) to form a crosslinked structure.

In addition, when the dicarboxylic acid compound (A1) contains, as impurities, a polyester diol having both alcoholic hydroxyl groups at both ends or a monool with one side reacted as impurities, the alcoholic OH groups of these impurities are (A2). In some cases, a compound in which the epoxy group is reacted is produced, but such a compound may be contained in a small amount in the component (A).
Since an epoxy group is used excessively as described above, an epoxy resin having an epoxy-substituted isocyanuric group bonded to the terminal is the main component. Moreover, although the terminal isocyanuric group-containing epoxy resin (A) to be produced is usually a mixture having a molecular weight distribution, these may be separated and used as the terminal isocyanuric group-containing epoxy resin (A) as it is. Also good.

  In this reaction, the molar ratio is more preferably in the range of 1 / 3.5 to 1/6. When the molar ratio of the epoxy group is less than 3, there is a possibility that gelation may occur during the reaction, and the resin of the present invention may not be obtained. Further, when the molar ratio of the epoxy group exceeds 10, the concentration derived from the (A1) structure existing in the component (A) is low, the brittleness of the cured product, which is a defect specific to the isocyanuric skeleton, high hygroscopicity, In addition, since coloration occurs in a long-term heat test, it is not preferable.

  About reaction conditions, since it is general reaction of a carboxyl and an epoxy group, it does not specifically limit.

  For example, about reaction temperature, it is 50 to 230 degreeC normally, Preferably it is 70 to 170 degreeC. When it is less than 50 ° C., the reaction time becomes longer. Moreover, when it exceeds 230 degreeC, it will become easy to raise | generate decomposition | disassembly or side reaction of resin during reaction.

  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 reaction of carboxyl and an epoxy group, various compounds can be selected with a well-known thing. Examples include imidazole compounds and salts thereof, tertiary amine compounds, tertiary phosphine compounds, quaternary ammonium salt compounds, quaternary phosphonium salt compounds, etc., but are not limited thereto, and two or more kinds are used in combination as necessary. You may do it. A preferred catalyst is a quaternary ammonium salt compound or a quaternary phosphonium salt compound from the viewpoint of suppressing coloring during the reaction.

  When the above catalyst is used, the amount to be used is not particularly limited. When the obtained terminal isocyanuric group-containing epoxy resin (A) is 100 parts by weight, it is usually 0.001 to 5 parts by weight, preferably 0.005. Parts by weight to 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 which prevents coloring of a terminal isocyanuric group containing epoxy 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 terminal isocyanuric group-containing epoxy resin (A) can be performed without a 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 terminal isocyanuric group-containing epoxy resin (A) obtained by this reaction is advantageously used as a reaction mixture obtained by separating a solvent and the like from the reaction mixture.

  As the reaction proceeds, the carboxyl group in the dicarboxylic acid (A1) disappears as the reaction proceeds. The reaction is preferably performed until the carboxyl group disappears until the acid value becomes less than 1.0 mgKOH / g. By eliminating the carboxyl group until the acid value is 1.0 mgKOH / g, the storage stability of the terminal isocyanuric group-containing epoxy resin (A) becomes good, and the cured product using the component (A) is transparent and heat resistant. Colorability and low hygroscopicity are good. When the reaction is stopped at an acid value of 1.0 mgKOH / g or more, moisture absorption increases during storage, and the quality such as epoxy equivalent and viscosity is greatly affected.

  The reaction mixture containing the terminal isocyanuric group-containing epoxy resin (A) has an epoxy equivalent of 150 to 800 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. If the epoxy equivalent is out of this range, the cured product may become brittle, the heat-resistant coloring property may deteriorate, and the transparency of the cured product may be impaired.

  As the curing agent (B) contained in the curable 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′- Dihydric phenol compounds such as biphenol, novolak resin or aralkyl phenol resin obtained by condensation reaction of phenol or naphthols with formaldehyde or xylylene glycols, succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride Acid anhydrides such as methylated hexahydrophthalic anhydride, nadic anhydride, hydrogenated nadic anhydride, trimellitic anhydride, pyromellitic anhydride, and hydrazide compounds such as adipic hydrazide You can use, may be used two or more, if necessary. In particular, a preferable curing agent for obtaining the effect of the present invention is an acid anhydride, more preferably an aliphatic cyclic acid anhydride such as hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride, hydrogenated nadic anhydride, or the like. It is.

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 cured resin composition of the present invention comprises the above components (A), (B) and (C) as essential components, but 2 molecules in one molecule other than the component (A) for the purpose of adjusting viscosity and curing rate. An epoxy resin or an epoxy compound having at least one epoxy group may be used. In particular, it is preferable to use a liquid epoxy resin having two or more cyclohexene oxide groups in one molecule as the component (D).

  The component (D) is not particularly limited as long as it is a liquid epoxy resin having two or more cyclohexene oxide groups in one molecule, but an epoxy resin having a cyclohexene oxide group represented by the following formulas (15) to (17) can be used. preferable.

（式中、Ｒ₇、Ｒ₈は炭素数１〜２０の２価の有機残基を表す。）

(In the formula, R ₇ and R ₈ represent a divalent organic residue having 1 to 20 carbon atoms.)

（式中、Ｒ₉は炭素数１〜２０の２価の炭化水素基または単結合を表す。）

(In the formula, R ₉ represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a single bond.)

Generally, the curable resin composition using only the component (D) has the disadvantage that it is brittle and inferior in heat resistant colorability. The terminal isocyanuric group-containing epoxy resin (A) used in the present invention overcomes the poor solubility that is a defect of the epoxy resin containing an isocyanuric acid skeleton, and is further used in combination with the component (D). It is also possible to improve both the brittleness and the heat resistant colorability which are the defects of the components. That is, by using the component (D) in combination, it is possible to achieve further improved workability and mechanical strength while maintaining the good heat resistant colorability, hardness, strength, deflection, and low linear expansion characteristic of the present invention. It becomes possible. As a preferable structure of the component (D), R ₇ among the epoxy resins represented by the formula (15) from the viewpoint of low viscosity, the effect of combined use with the terminal isocyanuric group-containing epoxy resin (A), and the economical efficiency of acquisition. Is an epoxy resin represented by a methylene group, and the amount of the component (D) used in combination is that after mixing the component (A), the epoxy equivalent after mixing is 160 to 300 g / eq, at 25 ° C. More preferably, the viscosity is 0.1 to 500 Pa / s. It is preferable to use the component (D) at a maximum of 80%, preferably within 50% with respect to the total epoxy component. When the component (D) is used in excess of 80%, the remarkable effect due to the component (A) is reduced.

  (A) The usage-amount of a component is 20-100 wt% with respect to all the epoxy components, Preferably it is 50-100 wt%, More preferably, it is 70-100 wt%. Here, the total epoxy component refers to the total of these when an epoxy resin is blended in addition to the component (A) and the component D.

  Furthermore, other known epoxy resins other than the component D can be used in combination. Other epoxy resins include, for example, epoxy resins derived from monocyclic dihydric phenols such as resorcinol, hydroquinone, 2,5-ditertiarybutyl hydroquinone, and those obtained by nuclear hydrogenation of the aromatic ring, 1, Epoxy resins derived from naphthalenediols such as 3-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,7-naphthalenediol, and aromatic rings Hydrogenated, 4,4′-isopropylidenediphenol, 4,4′-isopropylidenebis (2-methylphenol), 4,4′-isopropylidenebis (2,6-dimethylphenol), 4,4 '-Dihydroxydiphenylmethane, 4,4'-dihydroxy-3,3'-dimethyl Phenylmethane, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethyldiphenylmethane, 4,4′-secondary butylidenebisphenol, 4,4′-isopropylidenebis (2-tertiarybutylphenol), 4,4′-cyclohexylidenediphenol, 4,4′-butylidenebis (6-tertiarybutyl-2-methyl) phenol, 4,4 ′-(1-α-methylbenzylidene) bisphenol, 4,4′-dihydroxy Tetraphenylmethane, 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-methyl) Phenyl) sulfide, 4,4′-thiobis (2-tertiarybutyl-5-methylphenol), 4,4′-biphenol, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethyldiphenyl And epoxy resins derived from bisphenols, and epoxy resins obtained by nuclear hydrogenation of the aromatic ring.

  Further, as an epoxy resin having an isocyanuric skeleton, an epoxy having an isocyanuric skeleton represented by N-methyl-N ′, N ″ -diglycidyl isocyanurate or N-allyl-N ′, N ″ -diglycidyl isocyanurate There are compounds.

  Furthermore, although the epoxy silicone resin etc. which are represented by following formula (18), Formula (19), etc. are mentioned, it is not limited to these, You may use 2 or more types as needed.

(R ₁₀ SiO _3/2 ) _j (R ₁₁ R ₁₂ SiO) _i (Me ₃ SiO _1/2 ) _h (18)
(In the formula, R _{10 to} R ₁₂ 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 _{10 to} R ₁₂ always contains an epoxy group, and R ₁₁ and R ₁₂ 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.)

（式中、Ｒ₁₃は環状構造を有していても良い、炭素数２〜２０の１価の炭化水素基を表す。Ｒ₁₄は炭素数１〜２０の２価の有機残基を表す。ｇは０〜１００の整数である）

(In the formula, R ₁₃ represents a monovalent hydrocarbon group having 2 to 20 carbon atoms which may have a cyclic structure. R ₁₄ represents a divalent organic residue having 1 to 20 carbon atoms. g is an integer of 0 to 100)

  The blending amount of these other epoxy resins other than the components (A) and (D) is desirably 30 wt% or less of the total epoxy resin components.

  When the curable 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, a phenol compound represented by the above formula (5) is particularly preferably used. Interestingly, the antioxidant represented by the formula (5) uses triglycidyl isocyanurate alone as an epoxy resin, and in a cured product obtained by heat treatment with an acid anhydride compound, the improvement in heat-resistant colorability is not at all. Although not seen, when the terminal isocyanuric group-containing epoxy resin (A) used in the present invention is used, a drastic improvement in heat resistant colorability is achieved. Although the detailed mechanism is unknown, it is speculated that the compatibility with antioxidants has been improved by introducing a polyester structure inside that is different from triglycidyl isocyanurate, which is originally a poorly soluble compound. .

In formula (5), _Ry represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y represents a divalent hydrocarbon group having 1 to 60 carbon atoms, and has ester bondable oxygen therein. You may have 2-8 atoms.

  Although it will not specifically limit if it is a well-known thing as a phenolic compound represented by Formula (5), For example, the compound represented by following formula (20)-(22) is mentioned, As needed, 2 More than one species may be used.

（式（20）、（21）、（22）中、Ｒ_yは式（５）における説明と同義である。）

(In formulas (20), (21), and (22), R _y has the same meaning as described in formula (5).)

Among the phenolic compounds, in order to obtain the effects of the present invention, a particularly preferable structure is 3,9-bis (2- (3- (3-tetrabutyl-4-hydroxy-) represented by the following formula (23). 5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane.

  In addition to the phenolic compound represented by the formula (5), other antioxidants can be blended together with or in place of the phenolic compound represented by the formula (5). It is advantageous to blend with a phenolic compound represented by

  As the other 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, penta Polymeric phenols such as lithitol tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 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- Oxaphosphaphenanthrene oxides such as dihydro-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, Examples thereof include ester skeleton-containing thioether compound-based antioxidants such as 3'-thiodipropionate and pentaerythrityltetrakis (3-laurylthiopropionate). Two or more of these antioxidants may be used as necessary.

  Moreover, other curable resin can also be mix | blended with the curable resin composition of this invention. Examples of such curable resins include unsaturated polyester resins, thermosetting acrylic resins, thermosetting amino resins, thermosetting melamine resins, thermosetting urea resins, thermosetting cyanate resins, thermosetting urethane resins, Examples include, but are not limited to, thermosetting oxetane resins and thermosetting epoxy / oxetane composite resins.

  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. If it exceeds 5.0 wt%, curing proceeds during the molding and unfilling tends to occur.

  When the curable 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 curable resin composition of the present invention, kneaded with a kneader or three heat rolls, and then tableted and fed into a cavity of a sealing mold. A transfer molding method in which heat curing is performed or 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, a method of bonding a copper foil by press molding after impregnating the curable resin composition of the present invention to a base material such as glass cloth, or the curable resin composition of the present invention to a copper foil An object 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, a transfer mold method, or a liquid injection molding method.

  As a sealing material for an optical semiconductor device (LED device), a method in which an optical semiconductor element is connected to an external electrode with a gold wire or the like and then filled using a known technique such as a transfer molding method, a potting method, or a dispensing method is applied. it can. At this time, various known fluorescent powders may be used in the curable 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, a filler such as silica, titanium oxide, or alumina is mixed with the curable resin composition of the present invention, kneaded with a kneader or a heat three roll, and then tableted for sealing. It is possible to apply a transfer mold method in which a mold is sent into a mold cavity and thermally cured.

  As an adhesive for an optical semiconductor device, a paste obtained by kneading a curable resin composition of the present invention with a known material such as an epoxy resin and a phenol resin and a filler by a roll or the like is applied to a substrate by a method such as dispensing. For example, a method of applying or applying a film-like film using a known film material to a substrate and mounting the optical semiconductor element and thermosetting it can be applied.

  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 example 1
In formula (11), polyester diol having an average number of repeating units m of 1.56 (Kuraray Polyols P-510, Kuraray Co., Ltd., alcoholic hydroxyl group equivalent 250 g / mol, average molecular weight 500, average carbon number about 25) 37 weight And 23 parts by weight of hexahydrophthalic anhydride were charged into a 300 ml separable flask equipped with a stirring motor, a reflux condenser, and a nitrogen line. About the number-of-moles of each raw material used, the acid anhydride compound is 2 mol with respect to 1 mol of polyester diol. The compound (A1-1) was synthesized by continuing stirring for 4 hours after reaching 160 ° C. In the compound (A1-1), R ₁ in the general formula (1) is represented by the formula (3), R ₄ in the formula (3) is a 3-methylpentylene group, R ₅ is a butylene group, and m is A dicarboxylic acid compound in which Z is 1.56 and Z is a cyclohexylene group. The obtained compound (A1-1) was sampled and its acid value was measured with a 0.1N KOH / methanol solution. As a result, it was 144 mgKOH / g, and it was confirmed that the reaction had progressed quantitatively. Further, when analyzed by gas chromatography, unreacted acid anhydride was not detected.

  Subsequently, 69 parts by weight of triglycidyl isocyanurate (epoxy equivalent 100 g / eq.) As the component (A2) was added to 60 parts by weight of the obtained compound (A1-1). At this time, the molar ratio of the carboxyl group to the epoxy group is 1: 4.7. Next, 0.6 parts by weight of a 4% methanol 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. Sampling was performed and the acid value was measured to be 0.21 mg KOH / g, and it was confirmed that the carboxyl group had substantially disappeared. The reaction resin solution was filtered using a 150 mesh wire net. In this way, 118 parts by weight of the terminal isocyanuric group-containing epoxy resin as component (A) was obtained. The epoxy equivalent of the obtained resin was 235 g / eq. The softening point was a solid resin having a temperature of 50 ° C., and the viscosity at 150 ° C. was 0.22 Pa · s. This terminal isocyanuric group-containing epoxy resin is designated as E1.

Synthesis example 2
In the formula (11), 74 polyester diols having an average number of repeating units m of 3.61 (Kuraray Polyols P-1010 manufactured by Kuraray Co., Ltd., alcoholic hydroxyl group equivalent 500 g / mol, average molecular weight 1000, average carbon number about 43) are 74. After reaching 160 ° C. in the same manner as in Example 1 by using parts by weight and 23 parts by weight of hexahydrophthalic anhydride, stirring was continued for 4 hours. In this way, R ₁ of the general formula (1), R ₄ in the formula (3) is 3-methyl pentylene group, R ₅ is a butylene group, m is 3.61, Z is a cyclohexylene group A dicarboxylic acid compound (A1-2) was synthesized. This was sampled, and the acid value was measured with a 0.1N KOH / methanol solution. As a result, it was 85.6 mgKOH / g, and it was confirmed that the reaction had progressed quantitatively. Further, when analyzed by gas chromatography, unreacted acid anhydride was not detected.

  Subsequently, 69 parts by weight of triglycidyl isocyanurate was added to 97 parts by weight of the obtained compound (A1-2), and the same operation as in Synthesis Example 1 was performed. Sampling was performed and the acid value was measured to be 0.18 mg KOH / g, and it was confirmed that the carboxyl group substantially disappeared. The reaction resin solution was filtered using a 150 mesh wire net. In this way, 151 parts by weight of a terminal isocyanuric group-containing epoxy resin was obtained. The epoxy equivalent of this resin is 306 g / eq. The resin was a semisolid resin at room temperature, and the viscosity at 150 ° C. was 0.25 Pa · s. This terminal isocyanuric group-containing epoxy resin is designated as E2. The IR spectrum of this resin is shown in FIG.

Synthesis example 3
In the formula (11), a polyester diol having an average number of repeating units m of 7.7 (Kuraray Polyols P-2010, Kuraray Co., Ltd., alcoholic hydroxyl group equivalent 1000 g / mol, average molecular weight 2000, average carbon number of about 100) 148 Stirring was continued for 4 hours after reaching 160 ° C. in the same manner as in Synthesis Example 1 using parts by weight and 23 parts by weight of hexahydrophthalic anhydride. Thus, R ₁ in the general formula (1) is R ₄ in the formula (3) is a 3-methylpentylene group, R ₅ is a butylene group, m is 7.7, and Z is a cyclohexylene group. A dicarboxylic acid compound (A1-3) was synthesized. This was sampled, and the acid value was measured with a 0.1N KOH / methanol solution. As a result, it was 48.6 mgKOH / g, and it was confirmed that the reaction had progressed quantitatively. Further, when analyzed by gas chromatography, unreacted acid anhydride was not detected.

  Subsequently, 69 parts by weight of triglycidyl isocyanurate was added to 171 parts by weight of the obtained compound (A1-3), and the same operation as in Synthesis Example 1 was performed. Sampling was performed and the acid value was measured to be 0.15 mg KOH / g, and it was confirmed that the carboxyl group had substantially disappeared. The reaction resin solution was filtered using a 150 mesh wire net. In this way, 231 parts by weight of a terminal isocyanuric group-containing epoxy resin was obtained. The epoxy equivalent of this resin is 442 g / eq. The resin was semisolid at room temperature, and the viscosity at 150 ° C. was 0.43 Pa · s. This terminal isocyanuric group-containing epoxy resin is designated as E3. The IR spectrum of this resin is shown in FIG.

Synthesis example 4
In the formula (12), a polyester diol having an average repeating unit number m of 6.27 (Kuraray Polyols P-2050 manufactured by Kuraray Co., Ltd., alcoholic hydroxyl group equivalent of 1000 g / mol, average molecular weight of 2000, average carbon number of about 107) is 148. Stirring was continued for 4 hours after reaching 160 ° C. in the same manner as in Synthesis Example 1 using parts by weight and 23 parts by weight of hexahydrophthalic anhydride. In this way, R ₁ of the general formula (1), R ₄ in the formula (3) is 3-methyl pentylene group, R ₅ is octylene group, m is 6.27, Z is a cyclohexylene group A dicarboxylic acid compound (A1-4) was synthesized. When this was sampled and the acid value was measured with a 0.1N KOH / methanol solution, it was 48.4 mgKOH / g, and it was confirmed that the reaction had progressed quantitatively. Further, when analyzed by gas chromatography, unreacted acid anhydride was not detected.

  Subsequently, 69 parts by weight of triglycidyl isocyanurate was added to 171 parts by weight of the obtained compound (A1-4), and the same operation as in Synthesis Example 1 was performed. Sampling was performed and the acid value was measured to be 0.17 mg KOH / g, and it was confirmed that the carboxyl group substantially disappeared. The reaction resin solution was filtered using a 150 mesh wire net. In this way, 228 parts by weight of a terminal isocyanuric group-containing epoxy resin was obtained. The epoxy equivalent of this resin is 448 g / eq. The resin was semisolid at room temperature, and the viscosity at 150 ° C. was 0.48 Pa · s. This terminal isocyanuric group-containing epoxy resin is designated as E4. The IR spectrum of this resin is shown in FIG.

Synthesis example 5
In the formula (13), R _2b is a hybrid structure of an ethylene group and a butylene group, a polyester diol having an average repeating unit number m of about 10.5 (OD-X-2330 manufactured by DIC Corporation, alcoholic hydroxyl group equivalent 1000 g / mol) And 148 parts by weight of an average molecular weight of 2000 and an average carbon number of about 95) and 23 parts by weight of hexahydrophthalic anhydride. After reaching 160 ° C. as in Synthesis Example 1, stirring was continued for 4 hours. In this way, R ₁ in the general formula (1) is a hybrid structure of R ₄ in the formula (3), an ethylene group and a butylene group, R ₅ is a butylene group, m is 10.5, and Z is a cyclohexyl. A dicarboxylic acid compound (A1-5) which is a silene group was synthesized. When this was sampled and the acid value was measured with a 0.1N KOH / methanol solution, it was 48.3 mgKOH / g, and it was confirmed that the reaction had progressed quantitatively. Further, when analyzed by gas chromatography, unreacted acid anhydride was not detected.

  Subsequently, 69 parts by weight of triglycidyl isocyanurate was added to 171 parts by weight of the obtained compound (A1-5), and the same operation as in Synthesis Example 1 was performed. Sampling was performed and the acid value was measured to be 0.17 mg KOH / g, and it was confirmed that the carboxyl group substantially disappeared. The reaction resin solution was filtered using a 150 mesh wire net. In this way, 226 parts by weight of a terminal isocyanuric group-containing epoxy resin was obtained. The epoxy equivalent of this resin is 432 g / eq. The resin was semisolid at room temperature, and the viscosity at 150 ° C. was 0.40 Pa · s. This terminal isocyanuric group-containing epoxy resin is designated as E5.

Synthesis Example 6
Using 148 parts by weight of polyester diol represented by formula (14) (polycaprolactone diol, Placel 220 manufactured by Daicel Corporation, alcoholic hydroxyl group equivalent 1000 g / mol, average molecular weight 2000) using 23 parts by weight of hexahydrophthalic anhydride As in Synthesis Example 1, after reaching 160 ° C., stirring was continued for 4 hours. In this way, R ₁ in the general formula (1) is represented by the formula (4), R ₆ in the formula (4) is a divalent hydrocarbon group having 2 to 20 carbon atoms, and Z is A dicarboxylic acid compound (A1-6) having a cyclohexylene group was synthesized. When this was sampled and the acid value was measured with a 0.1N KOH / methanol solution, it was 48.6 mgKOH / g, and it was confirmed that the reaction had progressed quantitatively. Further, when analyzed by gas chromatography, unreacted acid anhydride was not detected.

  Subsequently, 69 parts by weight of triglycidyl isocyanurate was added to 171 parts by weight of the obtained compound (A1-6), and the same operation as in Synthesis Example 1 was performed. Sampling was performed and the acid value was measured to be 0.12 mg KOH / g, and it was confirmed that the carboxyl group had substantially disappeared. The reaction resin solution was filtered using a 150 mesh wire net. In this way, 226 parts by weight of a terminal isocyanuric group-containing epoxy resin was obtained. The epoxy equivalent of this resin is 438 g / eq. The resin was semisolid at room temperature, and the viscosity at 150 ° C. was 0.52 Pa · s. This terminal isocyanuric group-containing epoxy resin is designated as E6.

（式中、ｐは平均繰り返し単位数を表し、約１８である。） Synthesis example 7
126 parts by weight of hexahydroanhydride containing a hydroxyl group-containing silicone oil represented by the following formula (24) (XF42-B0940, Momentive Performance Materials Japan GK, average molecular weight 1700, alcoholic hydroxyl group equivalent 850 g / mol) Stirring was continued for 4 hours after reaching 160 ° C. using 23 parts by weight of phthalic acid as in Synthesis Example 1. In this way, a polysiloxane compound having a terminal group composed of a saturated cycloaliphatic dicarboxylic acid group was synthesized. When this was sampled and the acid value was measured with a 0.1N KOH / methanol solution, it was 55.8 mgKOH / g, and it was confirmed that the reaction had progressed quantitatively. When the obtained (A1) similar terminal carboxyl group-containing silicone resin was analyzed by gas chromatography, no unreacted acid anhydride was detected.

(In the formula, p represents the average number of repeating units and is about 18.)

  Subsequently, 69 parts by weight of triglycidyl isocyanurate was added to 171 parts by weight of the obtained silicone resin, and the same operation as in Synthesis Example 1 was performed. Sampling was performed and the acid value was measured to be 0.17 mg KOH / g, and it was confirmed that the carboxyl group substantially disappeared. The reaction resin solution was filtered using a 150 mesh wire net. In this way, 226 parts by weight of epoxy silicone resin was obtained. The epoxy equivalent of this epoxy silicone resin is 432 g / eq. The resin was semisolid at room temperature, and the viscosity at 150 ° C. was 0.40 Pa · s. This epoxy silicone resin is designated E7.

Synthesis Example 8
Using the polyester diol (P-2010) used in Synthesis Example 3 with 148 parts by weight and hexahydrophthalic anhydride 23 parts by weight, the temperature reached 160 ° C. as in Synthesis Example 3 and stirring was continued for 4 hours. Thus, R ₁ in the general formula (1) is R ₄ in the formula (3) is a 3-methylpentylene group, R ₅ is a butylene group, m is 7.7, and Z is a cyclohexylene group. A dicarboxylic acid compound (A1-8) was synthesized. When this was sampled and the acid value was measured with a 0.1N KOH / methanol solution, it was 48.6 mgKOH / g, and it was confirmed that the reaction had progressed quantitatively. Further, when analyzed by gas chromatography, unreacted acid anhydride was not detected.

  Then, 129 parts by weight of bisphenol A type liquid epoxy resin (Epototo YD-128 manufactured by Nippon Kayaku Epoxy Co., Ltd., epoxy equivalent 187 g / eq.) Is added to 171 parts by weight of the obtained compound (A1-8). The same operation as in Synthesis Example 1 was performed. Sampling was performed and the acid value was measured to be 0.25 mg KOH / g, and it was confirmed that the carboxyl group was substantially lost. The reaction resin solution was filtered using a 150 mesh wire net. In this way, 283 parts by weight of ester-modified epoxy resin was obtained. The ester equivalent epoxy resin has an epoxy equivalent of 559 g / eq. The resin was semisolid at room temperature, and the viscosity at 150 ° C. was 0.88 Pa · s. This ester-modified epoxy resin is designated as E8.

Examples 1-6
By using methylated hexahydrophthalic anhydride (MH: acid anhydride equivalent 168 g / eq.), The terminal isocyanuric group-containing epoxy resin (E1-6) which is the component (A) obtained in Synthesis Examples 1-6 was used. Add the epoxy equivalent to the anhydride equivalent so that the ratio is 1: 1, mix well, and add tetra-n-butylphosphonium o, o'-diethyl phosphorodithionate as a curing accelerator to a total of 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 to prepare resin plates having a thickness of 1 mm and 4 mm.

Example 7
70 parts by weight of the terminal isocyanuric group-containing epoxy resin (E2) obtained in Synthesis Example 2 is used as the component (A), and 3,4-epoxycyclohexenylmethyl-3 ′, 4′- is used as the component (D). A resin liquid containing 30 parts by weight of epoxycyclohexenecarboxylate (EpC: epoxy equivalent 130 g / eq.) Was prepared. The epoxy equivalent of the resin liquid containing the component (A) and the component (D) is 218 g / eq. Met. 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.

Example 8
As component (A), 50 parts by weight of the terminal isocyanuric group-containing epoxy resin (E3) obtained in Synthesis Example 3 is used, and as component (D), 3,4-epoxycyclohexenylmethyl-3 ′, 4′- A resin liquid containing 50 parts by weight of epoxycyclohexene carboxylate (EpC: epoxy equivalent 130 g / eq.) Was prepared. The epoxy equivalent of the resin liquid containing the component (A) and the component (D) is 199 g / eq. Met. Using this resin solution, the same operation as in Example 7 was performed to prepare resin plates having a thickness of 1 mm and 4 mm.

Example 9
As component (A), 50 parts by weight of the terminal isocyanuric group-containing epoxy resin (E4) obtained in Synthesis Example 4 is used, and as component (D), 3,4-epoxycyclohexenylmethyl-3 ′, 4′- A resin liquid containing 50 parts by weight of epoxycyclohexene carboxylate (EpC: epoxy equivalent 130 g / eq.) Was prepared. The epoxy equivalent of the resin liquid containing the component (A) and the component (D) is 199 g / eq. Met. Using this resin solution, the same operation as in Example 7 was performed to prepare resin plates having a thickness of 1 mm and 4 mm.

Example 10
As component (A), 50 parts by weight of the terminal isocyanuric group-containing epoxy resin (E5) obtained in Synthesis Example 5 is used, and as component (D), 3,4-epoxycyclohexenylmethyl-3 ′, 4′- A resin liquid containing 50 parts by weight of epoxycyclohexene carboxylate (EpC: epoxy equivalent 130 g / eq.) Was prepared. The epoxy equivalent of the resin liquid containing the component (A) and the component (D) is 200 g / eq. Met. Using this resin solution, the same operation as in Example 7 was performed to prepare resin plates having a thickness of 1 mm and 4 mm.

Example 11
As the component (A), the terminal isocyanuric group-containing epoxy resin (E3) obtained in Synthesis Example 3 and MH are added so that the ratio of epoxy equivalent to acid anhydride equivalent is 1: 1, for a total of 100. A part by weight of a resin solution was prepared. Subsequently, 3,9-bis (2- (3- (3-tetrabutyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10 is used as a phenol compound. -Tetraoxaspiro [5.5] undecane (hereinafter referred to as PH1) was added in an amount of 0.3 parts by weight and mixed. Further, tetra-n-butylphosphonium o, o′-diethyl phosphorodithionate was added as a curing accelerator in an amount of 0.5% by weight, vacuum degassed, and in a mold at 120 ° C. for 4 hours, and further 160 It hardened | cured at 20 degreeC for 12 hours, and produced the resin board of thickness 1mm and 4mm.

Example 12
As the component (A), the terminal isocyanuric group-containing epoxy resin (E4) obtained in Synthesis Example 4 and MH are added so that the ratio of epoxy equivalent to acid anhydride equivalent is 1: 1, for a total of 100. A part by weight of a resin solution was prepared. Subsequently, 0.3 parts by weight of PH1 was added as a phenolic compound and mixed. Further, tetra-n-butylphosphonium o, o′-diethyl phosphorodithionate was added as a curing accelerator in an amount of 0.5% by weight, vacuum degassed, and in a mold at 120 ° C. for 4 hours, and further 160 It hardened | cured at 20 degreeC for 12 hours, and produced the resin board of thickness 1mm and 4mm.

Example 13
As the component (A), the terminal isocyanuric group-containing epoxy resin (E5) obtained in Synthesis Example 5 and MH are added so that the ratio of epoxy equivalent to acid anhydride equivalent is 1: 1, for a total of 100. A part by weight of a resin solution was prepared. Subsequently, 0.3 parts by weight of PH1 was added as a phenolic compound and mixed. Further, tetra-n-butylphosphonium o, o′-diethyl phosphorodithionate was added as a curing accelerator in an amount of 0.5% by weight, vacuum degassed, and in a mold at 120 ° C. for 4 hours, and further 160 It hardened | cured at 20 degreeC for 12 hours, and produced the resin board of thickness 1mm and 4mm.

Comparative Example 1
Except that the epoxy silicone resin (E7) obtained in Synthesis Example 7 was used, the same operation as in Example 1 was performed to prepare resin plates having a thickness of 1 mm and 4 mm.

Comparative Example 2
Except that the ester-modified epoxy resin (E8) obtained in Synthesis Example 8 was used, the same operation as in Example 1 was performed to prepare resin plates having a thickness of 1 mm and 4 mm.

Comparative Example 3
The same procedure as in Comparative Example 1 was carried out except that 20 parts by weight of triglycidyl isocyanurate (EpT, epoxy equivalent 100 g / eq.) And 34 parts by weight of MH were used without using the component (A). And the resin board of 4 mm was created.

Comparative Example 4
Example 8 was used except that (A) component was not used and 26 parts by weight of 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (EpC) and 34 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 5
An epoxy resin mixture (C1) was prepared using 50 parts by weight of EpT and 50 parts by weight of EpC. A resin plate having a thickness of 1 mm and 4 mm was prepared in the same manner as in Example 8 except that MH was used so that the ratio of epoxy equivalent to acid anhydride equivalent was 1: 1.

Comparative Example 6
EpT and MH were added so that the ratio of epoxy equivalent to acid anhydride equivalent was 1: 1 to prepare a total of 100 parts by weight of a resin solution. Subsequently, 0.3 parts by weight of PH1 was added as a phenolic compound and mixed. Further, tetra-n-butylphosphonium o, o′-diethyl phosphorodithionate was added as a curing accelerator in an amount of 0.5% by weight, vacuum degassed, and in a mold at 120 ° C. for 4 hours, and further 160 It hardened | cured at 20 degreeC for 12 hours, and produced the resin board of thickness 1mm and 4mm.

Comparative Example 7
EpC and MH were added so that the ratio of epoxy equivalent to acid anhydride equivalent was 1: 1 to prepare a total of 100 parts by weight of a resin solution. Subsequently, 0.3 parts by weight of PH1 was added as a phenolic compound and mixed. Further, tetra-n-butylphosphonium o, o′-diethyl phosphorodithionate was added as a curing accelerator in an amount of 0.5% by weight, vacuum degassed, and in a mold at 120 ° C. for 4 hours, and further 160 It hardened | cured at 20 degreeC for 12 hours, and produced the resin board of thickness 1mm and 4mm.

Comparative Example 8
233 parts by weight of an epoxy resin obtained by reacting triglycidyl isocyanurate and acetic acid at a molar ratio of 1: 0.3 and partially modifying the epoxy group on triglycidyl isocyanurate with a carboxyl group (hereinafter referred to as EpTA). And 100 parts by weight of hydrogenated bisphenol A type liquid epoxy resin (YX-8000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 202 g / eq., Hereinafter referred to as EpH), and the epoxy resin mixture (C2). Created. The epoxy equivalent of this mixture is 136 g / eq. Met. To this mixture, MH was added so that the ratio of epoxy equivalent to acid anhydride equivalent was 1: 1, and tetra-n-butylphosphonium o, o′-diethyl phosphorodithionate was added as a accelerating accelerator to a total of 0. The resin plate having a thickness of 1 mm and 4 mm was prepared by charging 5% by weight, vacuum degassing, and curing in a mold at 120 ° C. for 4 hours and further at 160 ° C. for 12 hours.

Synthesis Example 9
In a reaction kettle, 39 parts by weight of triglycidyl isocyanurate, 61 parts by weight of MH, 0.5 parts by weight of a 4% methanol solution of tetraethylammonium chloride as a reaction catalyst were added and melt mixed at 100 ° C. for 1 hour. The reaction product gelled.

Comparative Example 9
In a reaction kettle, 39 parts by weight of triglycidyl isocyanurate, 61 parts by weight of MH, pentaerythritol tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (hereinafter referred to as antioxidant) , PH2)) was added in an amount of 0.5 part by weight, and melted and mixed at 100 ° C. for 3 hours to cause partial reaction. Next, the mixture was cooled and solidified to obtain a reaction intermediate (H9) having a softening point of 60 ° C. The acid value of this reaction intermediate was 205 mgKOH / g. This solid is pulverized, and further, 0.5% by weight of tetra-n-butylphosphonium o, o′-diethyl phosphorodithionate is added, and uniformly melted and mixed in a two-roll hot mill, cooled and pulverized. A composition was obtained. This composition was cured in a mold at 120 ° C. 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 10
10 parts by weight of triglycidyl isocyanurate, 17 parts by weight of MH, and 1.7 parts by weight of Plaxel 305 (manufactured by Daicel Corporation; alcoholic hydroxyl group equivalent: 166 g / mol, hereinafter referred to as P305) 0.1 parts by weight of benzylamine was mixed, vacuum degassed, and cured in a mold at 150 ° C. for 3 hours to prepare resin plates having a thickness of 1 mm and 4 mm.

(Storage stability)
The epoxy resins E1 to E8 obtained in Synthesis Examples 1 to 8 and the reaction intermediate (H9) described in Comparative Example 9 were allowed to stand at room temperature for 3 months, and the viscosity at 150 ° C. was measured. The viscosity of the resin left after 3 months at room temperature is shown in Table 1 as a multiple of the initial viscosity.

(Presence or absence of crystal precipitation)
A mixture with a weight ratio of 50:50 was made using the resins E1 to E8 obtained in Synthesis Examples 1 to 8 and EpC (EB1 to EB8). Here, the mixture of the resin E1 and EpC is EB1, and so on. Further, the epoxy resin mixture (C1) prepared in Comparative Example 5 and the epoxy resin mixture (C2) prepared in Comparative Example 8 were allowed to stand at room temperature for 3 months, and the presence or absence of crystal precipitation was visually confirmed. ○: no crystal precipitation, x crystal precipitation.

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.
Measured in the range of 30 ° C to 270 ° C using a thermal stress strain measuring device TMA / SS120U manufactured by Seiko Electronics Industry Co., Ltd., and the linear expansion coefficient was calculated from the slope of a straight line connected at two points of 40 ° C and 60 ° C. did. 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) Hardened | cured material shape The cured | curing material shape after metal mold | die removal determined visually the crack of the hardened | cured material by the uniformity of cured | curing material, or hardening shrinkage | contraction, when the mold was removed. ○: 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). . In the bending deflection test, ○ means no breakage.

(10) Measurement of moisture absorption rate A cured product having a thickness of 4 mm was treated under a vacuum of 110 ° C. for 3 hours and then left in an environment of 85 ° C. and 85% for 100 hours. The increase in weight before and after the test was weighed with an electronic balance, and the increment was expressed as a percentage.

  Table 3 shows the measurement results of the tests of the cured products obtained in Examples 1 to 6.

  Table 4 shows the measurement results of each test of the cured products obtained in Examples 7 to 13.

  Table 5 shows the measurement results of each test of the cured products obtained in Comparative Examples 1 to 5. In Tables 5-6, (A) component is used by the meaning containing the component similar to (A) component.

  Table 6 shows the measurement results of each test of the cured products obtained in Comparative Examples 6 to 10.

Examples 14-26, Comparative Examples 11-20
The composition obtained by blending Examples 1 to 13 and Comparative Examples 1 to 10 was filled into a blue LED pre-molded package with a base plated with silver at 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.
(11) Measurement of thermal shock test.
The sealed LED package was subjected to a test of −40 ° C. to 100 ° 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 4. For cracks and peeling of the sealing material, or for wire breakage, “O” indicates no, and “X” indicates presence.

Claims (12)

The following components (A) to (C);
(A) Both-end saturated cycloaliphatic dicarboxylic acid compound (A1) represented by general formula (1), having a molecular weight distribution and having an average carbon number of 20 or more in R ₁ , and triglycidyl isocyanurate (A2) Terminal isocyanuric group-containing epoxy resin obtained by reacting the carboxyl group of (A1) and the epoxy group of (A2) with a molar ratio of carboxyl group / epoxy group = 1/3 to 1/10,
A curable resin composition for optical components or electronic components, comprising (B) a curing agent and (C) a curing accelerator as essential components.

(In the formula, Z represents a divalent saturated cycloaliphatic group which may have a substituent having 4 to 12 carbon atoms, and may have a condensed ring structure. R ₁ represents formula (2). And a divalent hydrocarbon group having 20 or more carbon atoms and having an ester bond therein, wherein R ₂ and R ₃ represent a divalent hydrocarbon group having 2 to 20 carbon atoms. And may have the same or different ester structure, and Est represents an ester group, and n represents an average number of repeating units of 1 to 100. ) The average number of carbons contained in it is 20 or more.)   2. The curable resin according to claim 1, wherein the terminal isocyanuric group-containing epoxy resin as component (A) does not contain an acid anhydride compound as an impurity and has a carboxylic acid value of less than 1.0 mgKOH / g. Composition.   The epoxy equivalent of the terminal isocyanur group-containing epoxy resin as the component (A) is 150 to 800 g / eq. The curable resin composition according to claim 1, wherein the curable resin composition is a curable resin composition.   The curable resin composition according to claim 1, wherein Z in the general formula (1) has a cyclohexylene group structure. R ₁ in the general formula (1) has an average molecular weight in the range of 500 to 3000 and is composed of a divalent hydrocarbon group having two or more ester bonds therein. The curable resin composition according to any one of the above. R < ₁ > in General formula (1) is represented by either Formula (3) or Formula (4), The curable resin composition in any one of Claims 1-5 characterized by the above-mentioned.

(In the formula, R ₄ represents a divalent hydrocarbon group having 2 to 20 carbon atoms and may be the same or different. R ₅ represents a divalent hydrocarbon group having 4 to 11 carbon atoms. M Is the average number of repeating units representing a number of 1 to 20, but the average number of carbons contained in formula (3) is 20 or more.)

(In the formula, R ₆ represents a divalent hydrocarbon group having 2 to 20 carbon atoms. L and k are the average number of repeating units each representing a number of 1 to 20, but are included in formula (4). The average number of carbon atoms is 20 or more.)   The curable resin composition according to any one of claims 1 to 6, wherein the curing agent (B) is an acid anhydride.   (C) The hardening accelerator of a component is at least 1 sort (s) chosen from a quaternary ammonium salt and a quaternary phosphonium salt, The curable resin composition in any one of Claims 1-7 characterized by the above-mentioned. Furthermore, component (D),
(D) A liquid epoxy resin having two or more cyclohexene oxide structures in one molecule is used, and the epoxy equivalents of the (A) component and the (D) component which are epoxy resin components are 160 to 300 g / eq. The curable resin composition according to claim 1, wherein the component (D) is used so that the viscosity at 25 ° C. is 0.1 to 500 Pa · s. Furthermore, (E) component,
(E) The phenolic compound represented by Formula (5) is used, The curable resin composition in any one of Claims 1-9 characterized by the above-mentioned.

(In the formula, R _y represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; Y represents a divalent hydrocarbon group having 1 to 60 carbon atoms; (You may have 2-8) It is a curable resin composition for optical semiconductor components, The curable resin composition in any one of Claims 1-10 characterized by the above-mentioned. It seals using the curable resin composition of Claim 11 , The LED device characterized by the above-mentioned.

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