TWI440647B - Modified resin composition, method for producing same and curable resin composition containing same - Google Patents

Description

Modified resin composition, method for producing the same, and curable resin composition containing the same

The present invention relates to a modified resin composition obtained by reacting an epoxy resin with an alkoxydecane compound, a method for producing the same, and a curable resin composition containing the composition and use thereof.

Conventionally, an epoxy resin composition using an acid anhydride-based hardener has provided a transparent cured product, and since it has high heat resistance and adhesion, it is suitably used as a light emitting diode (LED) or A sealing resin for optical semiconductors such as photodiodes. However, in recent years, as the performance of optical semiconductors is being developed, it is expected to have excellent heat resistance and light resistance as well as excellent heat resistance and high heat resistance and adhesion as required for LED sealing resins. A cured product that is crack-resistant and has no tackiness during thermal cycling, and is conventionally composed of an epoxy resin such as bisphenol A epoxy resin or bisphenol F epoxy resin. The composition does not actually have sufficient characteristics.

As a resin for a light-emitting element sealing material, a research review on a silicone resin having a helium oxide as a repeating unit for heat or light is being carried out. However, the above-mentioned polyoxyxene resin is excellent in light resistance and heat resistance, but has low adhesion, and thus peeling from the substrate occurs, and the hardness of the cured product may be low, and surface adhesion may be unsatisfactory. Therefore, in fact, more improvements are still needed.

On the other hand, a number of research studies on modified resin compositions containing a siloxane backbone as a repeating unit and an epoxy group in an organic group are being conducted. The modified resin composition not only provides a cured product having excellent transparency, heat resistance and surface non-adhesive properties possessed by the epoxy resin, but also requires the cured product to have both light resistance and oxidation resistance possessed by polyfluorene. It is further flexible.

For example, Patent Document 1 proposes a modified resin composition containing a T structure as a necessary repeating unit, and the content of the organic group containing an epoxy group is 0.1 with respect to all the organic groups bonded to the ruthenium atom in one molecule. Up to 40% of the range.

Patent Document 2 describes a composition comprising a polyfluorene oxide having a molecular weight of a specific range and having at least two epoxy groups in one molecule, and the use of the composition in an optical semiconductor sealing material.

Patent Documents 3 to 5 disclose a resin composition obtained by mixing an epoxy resin with a previously condensed polyoxymethylene resin.

Patent Documents 6 to 11 disclose resin compositions obtained by mixing an epoxy resin with an alkoxysilane or a partial condensate thereof, and secondarily by a dealcoholization reaction.

Patent Document 12 discloses a resin composition comprising a modified phenoxy resin and an epoxy resin having a number of alkoxy groups contained in a molecule twice the number of Si atoms.

[Patent Literature]

(Patent Document 1) Japanese Patent No. 3263177

(Patent Document 2) Japanese Patent Laid-Open Publication No. 2005-171021

(Patent Document 3) Japanese Patent Laid-Open Publication No. 2006-225515

(Patent Document 4) Japanese Patent Laid-Open Publication No. 2006-241230

(Patent Document 5) Japanese Patent Laid-Open Publication No. 2008-120843

(Patent Document 6) Japanese Patent Laid-Open Publication No. 2001-059011

(Patent Document 7) Japanese Patent Laid-Open Publication No. 2001-059013

(Patent Document 8) Japanese Patent Laid-Open Publication No. 2002-179762

(Patent Document 9) Japanese Patent Laid-Open Publication No. 2002-249539

(Patent Document 10) Japanese Patent Laid-Open Publication No. 2003-246838

(Patent Document 11) Japanese Patent Laid-Open Publication No. 2005-179401

(Patent Document 12) Japanese Patent Laid-Open Publication No. 2007-321130

However, the resin compositions described in Patent Documents 1 and 2 have insufficient light resistance, and the crack resistance and adhesion have not yet reached a satisfactory level. Further, the modified resin composition tends to have low storage stability, and the viscosity of the resin tends to increase remarkably during storage, and it cannot be said that it has sufficient practicality.

Further, the compositions obtained by mixing the pre-condensed polyoxyxylene resin and the epoxy resin in the absence of the epoxy resin described in Patent Documents 3 to 5 have low storage stability and are in storage during storage. There is a tendency for the viscosity to increase significantly. Further, there is a case where the epoxy resin and the polyoxymethylene resin may not be uniformly mixed, and it is not sufficient to have sufficient practicality.

Further, when polyfluorene oxide is produced by the dealcoholization reaction, the alkoxy group tends to remain in the polyfluorene oxide, and the resin composition containing the alkoxysilane residue described in Patent Documents 6 to 12 is hardened. The cured product obtained is vaporized by the hydrolysis of the alcohol by the time-lapse hydrolysis, so that the crack resistance or the adhesion property during the thermal cycle tends to decrease.

In view of the above facts, an object of the present invention is to provide a modified resin composition having good storage stability, which can be formed to have good transparency, and has excellent heat resistance, heat discoloration resistance, light resistance, and heat cycle. A hardened material that is resistant to cracking.

Further, an object of the present invention is to provide an excellent LED or the like which is excellent in adhesion to an element or a packaging material, which does not cause cracking, and which has a small decrease in brightness over a long period of time, or can be formed after injection molding and hardening. An optical lens which is hard, has excellent dimensional stability, and has light resistance, and a semiconductor device using the above-described light-emitting component and/or optical lens.

Further, an object of the present invention is to provide a photosensitive composition which is excellent in adhesiveness which can suppress polymerization inhibition by oxygen, a coating agent containing the composition, and a coating film obtained by curing the coating agent. .

Further, an object of the present invention is to provide a fluorescent resin composition excellent in dispersion stability of a phosphor and a light storing material using the fluorescent resin composition.

Further, an object of the present invention is to provide a conductive resin composition which is excellent in fluidity, electrical conductivity, and adhesion and which does not cause voids.

Further, an object of the present invention is to provide an insulating resin composition which is excellent in fluidity, insulation, and adhesion and which does not cause voids.

In order to solve the above problems, the inventors of the present invention have found that a modified resin composition obtained by reacting an epoxy resin with a specific alkoxydecane compound at a specific ratio is obtained by the resin composition. The amount of the residual alkoxy group is adjusted to a specific range, and the above problems can be solved, and the present invention has been completed.

That is, the present invention is as follows:

[1] A modified resin composition obtained by reacting an epoxy resin (A) with an alkoxydecane compound represented by the following general formula (1),

(R ¹ ) _n -Si-(OR ² ) _4-n (1)

(here, n represents an integer of 0 or more and 3 or less;

Further, R ¹ each independently represents a hydrogen atom and at least one organic group selected from the group consisting of a) to c) below:

a) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 4 or more and 24 or less And an organic group of a cyclic ether group having an oxygen atom number of 1 or more and 5 or less:

b) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 1 or more and 24 or less and oxygen a monovalent aliphatic organic group having an atomic number of 0 or more and 5 or less;

c) having an unsubstituted or substituted aromatic hydrocarbon unit and, if necessary, having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups a monovalent aromatic organic group having a carbon number of 6 or more and 24 or less and an oxygen atom number of 0 or more and 5 or less;

On the other hand, each of R ² independently represents a hydrogen atom or one or more organic groups selected from the group consisting of d):

d) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chains, branches, and rings, and having a carbon number of 1 or more and 8 or less Price organic basis);

The alkoxydecane compound described above contains the following (B) and (C):

(B) at least one alkoxydecane compound having n = 1 or 2 and having at least one cyclic ether group as R ¹

(C) at least one alkoxydecane compound having n = 1 or 2 and having at least one aromatic organic group as R ¹ ;

The mixing index α of the alkoxydecane compound represented by the following general formula (2) is 0.001 or more and 19 or less:

Mixed index α=(αc)/(αb) ...(2)

(In the formula (2), αb represents the content (mol%) of the component (B) in the alkoxydecane compound represented by the general formula (1), and αc represents an alkoxy group represented by the general formula (1). The content (mol%) of the aforementioned component (C) in the decane compound;

Further, the amount of residual alkoxy groups in the modified resin composition is 5% or less.

[2] The modified resin composition according to the above [1], wherein the modified resin composition has a viscosity at 25 ° C of 1000 Pa ‧ or less.

[3] The modified resin composition according to the above [1] or [2] wherein the modified resin composition has an epoxy equivalent of from 100 g/eq to 700 g/eq.

[4] The modified resin composition according to any one of [1] to [3] wherein the alkoxydecane compound has a condensation ratio of 80% or more.

[5] The modified resin composition according to any one of [1] to [4] wherein the epoxy resin (A) has a viscosity at 25 ° C of 500 Pa ‧ or less.

[6] The modified resin composition according to any one of [1] to [5] wherein the epoxy resin (A) has an epoxy equivalent of from 100 g/eq to 300 g/eq.

[7] The modified resin composition according to any one of [1] to [6] wherein the epoxy resin (A) is a polyfunctional epoxy composed of a glycidyl etherate of a polyphenol compound. Resin.

[8] The modified resin composition according to any one of [1] to [7] wherein the epoxy resin (A) is a bisphenol A type epoxy resin.

[9] The modified resin composition according to any one of the above [1] to [8] wherein the alkoxydecane compound represented by the following general formula (3) has a mixing index β of 0.01 or more and 1.4 or less. :

Mixed index β={(βn2)/(βn0+βn1)} (3)

(In the formula (3), βn2 represents the content (mol%) of the alkoxydecane compound of n=2 in the alkoxydecane compound represented by the general formula (1), and βn0 represents a general formula (1). The content (mol%) of the alkoxydecane compound of n=0 in the alkoxydecane compound, and βn1 represents the content of the alkoxydecane compound of n=1 in the alkoxydecane compound represented by the general formula (1) (mol) %), and these systems satisfy the values of the following formula:

0≦{(βn0)/(βn0+βn1+βn2)}≦0.1).

[10] The modified resin composition according to any one of the above [1] to [9] wherein the epoxy resin (A) represented by the following general formula (4) and the alkoxydecane compound are The mixing index γ is 0.02 to 15:

Mixed index γ=(γa)/(γs) (4)

(In the formula (4), γa represents the mass (g) of the epoxy resin (A), and γs represents an alkoxydecane of n=0 to 2 in the alkoxydecane compound represented by the general formula (1). The mass of the compound (g)).

[11] A method for producing a modified resin composition, which comprises at least an alkoxy group of (B) and (C) represented by the following general formula (1) in the presence of an epoxy resin (A) A method of producing a modified resin composition according to any one of the above [1] to [10], wherein the method comprises the following steps (a) and (b):

(a) a step of subjecting an alkoxydecane compound containing at least (B) and (C) represented by the general formula (1) in the presence of an epoxy resin (A) by a reflux step without dehydration a step of cohydrolysis to produce an intermediate;

(b) a step of subjecting the intermediate produced in the step (a) to a dehydration condensation reaction;

(R ¹ ) _n -Si-(OR ² ) _4-n (1)

(here, n represents an integer of 0 or more and 3 or less;

Further, R ¹ each independently represents a hydrogen atom and at least one organic group selected from the group consisting of a) to c) below:

a) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 4 or more and 24 or less And an organic group of a cyclic ether group having an oxygen atom number of 1 or more and 5 or less;

b) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups, and having a carbon number of 1 or more and 24 or less a monovalent aliphatic organic group having an oxygen atom number of 0 or more and 5 or less;

c) having an unsubstituted or substituted aromatic hydrocarbon unit and, if necessary, having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups a monovalent aromatic organic group having an aliphatic hydrocarbon unit of 6 or more and 24 or less and an oxygen atom of 0 or more and 5 or less;

On the other hand, each of R ² independently represents a hydrogen atom or one or more organic groups selected from the group consisting of d):

d) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chains, branches, and rings, and having a carbon number of 1 or more and 8 or less Price organic basis),

(B) at least one alkoxydecane compound having n = 1 or 2 and having at least one cyclic ether group as R ¹ ;

(C) at least one alkoxydecane compound having n = 1 or 2 and having at least one aromatic organic group as R ¹ ;

Further, the mixing index α of the alkoxydecane compound represented by the following general formula (2) is 0.001 or more and 19 or less:

Mixed index α=(αc)/(αb) ...(2)

(In the formula (2), αb represents the content (mol%) of the component (B), and αc represents the content (mol%) of the component (C).

[12] A method for producing a modified resin composition, which comprises at least an alkoxy group of (B) and (C) represented by the following general formula (1) in the presence of an epoxy resin (A). The method for producing a modified resin composition according to any one of the above [1] to [10], wherein the method comprises the following steps (c) and (d):

(c) a step of producing an intermediate by at least alkoxydecane compound of (B) and (C) represented by the general formula (1) by co-hydrolysis without a reflux step with dehydration;

(d) a step of subjecting the epoxy resin (A) to coexistence in the intermediate produced by the step (c), and performing a dehydration condensation reaction;

(R ¹ ) _n -Si-(0R ² ) _4-n (1)

(here, n represents an integer of 0 or more and 3 or less;

Further, R ¹ each independently represents a hydrogen atom and at least one organic group selected from the group consisting of a) to c) below:

a) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 4 or more and 24 or less And an organic group of a cyclic ether group having an oxygen atom number of 1 or more and 5 or less;

b) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups, and having a carbon number of 1 or more and 24 or less a monovalent aliphatic organic group having an oxygen atom number of 0 or more and 5 or less;

c) having an unsubstituted or substituted aromatic hydrocarbon unit and, if necessary, having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups a monovalent aromatic organic group having an aliphatic hydrocarbon unit of 6 or more and 24 or less and an oxygen atom of 0 or more and 5 or less;

On the other hand, each of R ² independently represents a hydrogen atom or one or more organic groups selected from the group consisting of d):

d) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chains, branches, and rings, and having a carbon number of 1 or more and 8 or less Price organic basis),

(B) at least one alkoxydecane compound having n = 1 or 2 and having at least one cyclic ether group as R ¹ ;

(C) at least one alkoxydecane compound having n = 1 or 2 and having at least one aromatic organic group as R ¹ ;

Further, the mixing index α of the alkoxydecane compound represented by the following general formula (2) is 0.001 or more and 19 or less:

Mixed index α=(αc)/(αb) ...(2)

(In the formula (2), αb represents the content (mol%) of the component (B), and αc represents the content (mol%) of the component (C).

[13] The method for producing a modified resin composition according to the above [11] or [12], wherein the alkoxydecane compound represented by the following general formula (3) has a mixing index β of 0.01 to 1.4.

Mixed index β={(βn2)/(βn0+βn1)} (3)

(In the formula (3), βn2 represents the content (mol%) of the alkoxydecane compound of n=2 in the alkoxydecane compound represented by the general formula (1), and βn0 represents a general formula (1). The content (mol%) of the alkoxydecane compound of n=0 in the alkoxydecane compound, and βn1 represents the content of the alkoxydecane compound of n=1 in the alkoxydecane compound represented by the general formula (1) (mol) %), and these systems satisfy the values of the following formula:

0≦{(βn0)/(βn0+βn1+βn2)}≦0.1).

[14] The method for producing a modified resin composition according to any one of the above [11] to [13] wherein the epoxy resin (A) represented by the following general formula (4) and the alkoxydecane are as described above. The compounding index γ of the compound is 0.02 to 15:

Mixed index γ=(γa)/(γs) (4)

(In the formula (4), γa represents the mass (g) of the epoxy resin (A), and γs represents an alkoxydecane compound of n=0 to 2 in the alkoxydecane compound represented by the general formula (1). Quality (g)).

[15] The method for producing a modified resin composition according to any one of the above [11] to [14] wherein the temperature in the reflux step without dehydration is 50 to 100 °C.

[16] The method for producing a modified resin composition according to any one of [11] to [15] wherein the condensation ratio of the intermediate obtained by co-hydrolysis without a reflux step with dehydration is 78%. the above.

[17] The method for producing a modified resin composition according to any one of [11] to [16] wherein, in the co-hydrolysis, an alkoxide-based organotin is used as a catalyst.

[18] A resin composition obtained by adding an oxetane compound (D) to the modified resin composition of the above [1].

[19] A fluorescent resin composition obtained by adding a phosphor (E) to the modified resin composition of the above [1].

[20] A conductive resin composition obtained by adding a conductive metal powder (F) to the modified resin composition of the above [1].

[21] An insulating resin composition obtained by adding an insulating powder (G) to the modified resin composition of the above [1].

[22] A resin composition obtained by adding an epoxy resin (A') to the modified resin composition of the above [1].

[23] A curable resin composition obtained by adding a curing agent (H) to the resin composition according to any one of the above [1], [18], or [19].

[24] A curable resin composition obtained by adding a curing accelerator (I) to the resin composition of the above [23].

[25] A photosensitive resin composition obtained by adding a photo-acid generator (J) to the resin composition according to any one of the above [1], [18], or [19] Made.

[26] A light-emitting component obtained by using the resin composition of the above [24] or [25].

[27] An optical lens obtained by using the resin compositions of the above [24] and [25].

[28] A light-storing material obtained by using the resin composition of the above [24] or [25].

[29] A semiconductor device comprising the light-emitting component of the above [26] and/or the optical lens of the above [27].

[30] A curable resin composition obtained by adding the curing accelerator (I) to the resin composition according to any one of the above [20] to [22].

[31] A photosensitive resin composition obtained by adding a photoacid generator (J) to the resin composition according to any one of the above [20] to [22].

[32] A coating agent comprising the resin composition according to any one of the above [24], [25], [30], or [31].

[33] A coating film obtained by using the coating agent of the above [32].

According to the present invention, it is possible to provide a modified resin composition having good storage stability which can form a cured product having excellent light resistance and thermal shock resistance (thermal cycle crack resistance).

Hereinafter, the form for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to the form shown below.

The modified resin composition in the present embodiment is a modified resin composition obtained by reacting an epoxy resin (A) with an alkoxydecane compound represented by the following general formula (1).

(R ¹ ) _n -Si-(OR ² ) _4-n (1)

(here, n represents an integer of 0 or more and 3 or less;

Further, R ¹ each independently represents a hydrogen atom and at least one organic group selected from the group consisting of a) to c) below:

a) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 4 or more and 24 or less And an organic group of a cyclic ether group having an oxygen atom number of 1 or more and 5 or less;

b) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 1 or more and 24 or less and oxygen a monovalent aliphatic organic group having an atomic number of 0 or more and 5 or less;

c) having an unsubstituted or substituted aromatic hydrocarbon unit and, if necessary, having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups a monovalent aromatic organic group having an aliphatic hydrocarbon unit of 6 or more and 24 or less and an oxygen atom of 0 or more and 5 or less;

On the other hand, each of R ² independently represents a hydrogen atom or one or more organic groups selected from the group consisting of d):

d) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chains, branches, and rings, and having a carbon number of 1 or more and 8 or less Price organic basis),

Wherein the alkoxydecane compound contains the following (B) and (C):

(B) at least one alkoxydecane compound having n = 1 or 2 and having at least one cyclic ether group as R ¹ ;

(C) at least one alkoxydecane compound having n = 1 or 2 and having at least one aromatic organic group as R ¹ ;

The mixing index α of the alkoxydecane compound represented by the following general formula (2) is 0.001 or more and 19 or less:

Mixed index α=(αc)/(αb) ...(2)

(In the formula (2), αb represents the content (mol%) of the component (B) in the alkoxydecane compound represented by the general formula (1), and αc represents an alkoxy group represented by the general formula (1). The content (mol%) of the aforementioned component (C) in the decane compound;

Further, the amount of residual alkoxy groups in the modified resin composition is 5% or less.

The epoxy resin (A) used in the present embodiment is not particularly limited, and examples thereof include an alicyclic epoxy resin, an aliphatic epoxy resin, and a polyglycidyl ether compound of a polyphenol compound. a functional epoxy resin, a polyfunctional epoxy resin belonging to a glycidyl etherate of a novolac resin, a nuclear hydride of an aromatic epoxy resin, a heterocyclic epoxy resin, a glycidyl ester epoxy resin, A glycidylamine-based epoxy resin, an epoxy resin obtained by glycidylating a halogenated phenol, etc. These epoxy resins may be used singly or in combination of plural kinds.

The alicyclic epoxy resin which can be used in the present embodiment is not particularly limited as long as it is an epoxy resin having an alicyclic epoxy group, and examples thereof include cyclohexene oxide. An epoxy resin such as a tricyclodecene oxide group or a cyclopentene oxide group. Specific examples of the alicyclic epoxy resin include, as the monofunctional alicyclic epoxy compound, 4-vinyl epoxy cyclohexane, epoxy hexahydrophthalic acid dioctyl ester, and epoxy hexahydro epoxide. Di-2-ethylhexyl phthalate. As the bifunctional alicyclic epoxy compound, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl- 3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-two Alkane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)hexane Acid ester, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane Alkane, dicyclopentadiene diepoxide, ethylene glycol bis(3,4-epoxycyclohexylmethyl) ether, ethyl bis(3,4-epoxycyclohexanecarboxylate), 1,2,8,9-diepoxylimene (1,2,8,9-diepoxylimonene) and the like. As the polyfunctional alicyclic epoxy compound, for example, 1,2-epoxy-4-(2-oxiranyl) of 2,2-bis(hydroxymethyl)-1-butanol Cyclohexene adducts and the like. In addition, as a commercial item of a polyfunctional alicyclic epoxy compound, EPOLEAD GT401, EHPE 3150 (made by Daicel Chemical Industry Co., Ltd.), etc. are mentioned.

The following is a representative example of the alicyclic epoxy resin.

The aliphatic epoxy resin which can be used in the present embodiment is not particularly limited, and specific examples thereof include 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and poly A glycidyl ether of a polyhydric alcohol such as propylene glycol, pentaerythritol or xylylene glycol derivative.

The following is a representative example of an aliphatic epoxy resin.

The polyfunctional epoxy resin composed of the glycidyl ether compound of the polyphenol compound which can be used in the present embodiment is not particularly limited, and specific examples thereof include bisphenol A, bisphenol F, and bisphenol S. 4,4'-biphenol (4,4'-biphenol), tetramethylbisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1-(4-hydroxybenzene 2-[4-(1,1-bis-(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-methylene-bis-(4-methyl-6- Tributylphenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), trihydroxyphenylmethane, resorcinol, hydroquinone, 2,6 - bis(t-butyl)hydroquinone, pyrogallol, phenols having diisopropylidene backbone, 1,1-bis(4-hydroxyphenyl)anthracene, etc. A polyfunctional epoxy resin or the like which is a glycidyl ether compound of a polyphenol compound of a polybutadiene.

The following are representative examples of polyfunctional epoxy resins which are glycidyl etherates of phenols having bisphenol backbone.

When a polyfunctional epoxy resin which is a glycidyl ether compound of a polyphenol compound is used, the repeating unit (n in the chemical formula of the above representative example) is not particularly limited, and is preferably in the range of 0 or more and less than 50. When the repeating unit is 50 or more, the fluidity is lowered, and there is a problem in practical use. From the viewpoint of improving the reactivity with the alkoxystane compound, from the viewpoint of improving the fluidity of the obtained modified resin composition, the range of the repeating unit is preferably in the range of 0.001 or more and 10 or less. It is preferably in the range of 0.01 or more and 2 or less.

The polyfunctional epoxy resin which is a glycidyl ether compound of a phenol resin is not particularly limited, and examples thereof include phenol, cresol, ethyl phenol, butyl phenol, octyl phenol, and bisphenol. A phenolic resin containing various phenols such as bisphenol F, bisphenol S and naphthol as raw materials; phenol novolac resin containing dimethylbenzene (xylylene) backbone, and phenolic phenolic aldehyde containing dicyclopentadiene backbone A resin, a phenolic phenolic resin containing a biphenyl backbone, a glycidyl etherified product of various phenol resins such as a phenolic phenol resin, and the like.

The following is a representative example of a polyfunctional epoxy resin which is a glycidyl etherate of a phenol resin.

The nuclear hydride of the aromatic epoxy resin which can be used in the present embodiment is not particularly limited, and examples thereof include a phenol compound (bisphenol A, bisphenol F, bisphenol S, 4, 4'-linked). Glycidyl etherate of phenol, etc.; various phenols (phenol, cresol, ethyl phenol, butyl phenol, octyl phenol, bisphenol A, bisphenol F, bisphenol S, naphthol, etc.) a nuclear hydride of an aromatic ring; or a nuclear hydride of a glycidyl etherate of a phenolic resin.

The heterocyclic epoxy resin is not particularly limited, and examples thereof include a heterocyclic epoxy resin having a hetero ring such as an isocyanuric ring or a hydantoin ring.

The glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include an epoxy resin composed of a carboxylic acid such as hexahydrophthalic acid diglycidyl ester or tetrahydrofurfuric acid diglycidyl ester. .

The glycidylamine-based epoxy resin is not particularly limited, and examples thereof include aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivatives, and diamine-based groups. An epoxy resin obtained by glycidylating an amine such as a benzene derivative.

The epoxy resin obtained by glycidylating a halogenated phenol is not particularly limited, and examples thereof include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, and brominated phenol novolac. An epoxy resin obtained by glycidyl etherification of a halogenated phenol such as cresol novolac, chlorinated bisphenol S or chlorinated bisphenol A.

In the above, the cured product obtained by curing the modified resin composition of the present embodiment is excellent in transparency, heat resistance, heat discoloration resistance, light resistance, and heat cycle. Because of the tendency of crack resistance, it is preferable to use an alicyclic epoxy resin, an aliphatic epoxy resin, a polyfunctional epoxy resin composed of a glycidyl ether compound of a polyphenol compound, and an alicyclic epoxy resin. A polyfunctional epoxy resin composed of a resin and a glycidyl ether compound of a polyphenol compound is preferred, and a polyfunctional epoxy resin composed of a glycidyl ether compound of a polyphenol compound is more preferable, and bisphenol is preferably used. Type A epoxy resin is especially good.

The viscosity of the epoxy resin (A) used in the present embodiment at 25 ° C is not particularly limited. However, in order to ensure the fluidity of the liquid, the compatibility with the alkoxydecane compound tends to be improved. A liquid of 1000 Pa ‧ or less is preferred, preferably 500 Pa ‧ or less, more preferably 300 Pa ‧ or less, and 100 Pa ‧ s or less.

The epoxy equivalent (WPE) of the epoxy resin (A) used in the present embodiment is not particularly limited, and is 100 g/eq or more from the viewpoint of improving the storage stability of the modified resin composition of the present embodiment. In view of improving the crack resistance of the cured product obtained by curing the modified resin composition of the present embodiment, it is preferably 700 g/eq or less, and more preferably 100 g/eq or more and 500 g/eq or less. It is more preferably in the range of 100 g/eq or more and 300 g/eq or less.

The alkoxydecane compound which can be used in the present embodiment means an anthracene compound having 1 to 4 alkoxy groups, and is represented by the following general formula (1).

(R ¹ ) _n -Si-(OR ² ) _4-n (1)

(here, n represents an integer of 0 or more and 3 or less;

Further, R ¹ each independently represents a hydrogen atom and at least one organic group selected from the group consisting of a) to c) below:

a) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 4 or more and 24 or less And an organic group of a cyclic ether group having an oxygen atom number of 1 or more and 5 or less;

b) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 1 or more and 24 or less and oxygen a monovalent aliphatic organic group having an atomic number of 0 or more and 5 or less;

c) having an unsubstituted or substituted aromatic hydrocarbon unit and, if necessary, having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups a monovalent aromatic organic group having an aliphatic hydrocarbon unit of 6 or more and 24 or less and an oxygen atom of 0 or more and 5 or less;

On the other hand, each of R ² independently represents a hydrogen atom or one or more organic groups selected from the group consisting of d):

d) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chains, branches, and rings, and having a carbon number of 1 or more and 8 or less Price organic basis).

Here, the cyclic ether group in the present embodiment will be described. The cyclic ether group in the present embodiment means an organic group having an ether obtained by substituting a carbon atom of a cyclic hydrocarbon with an oxygen atom, and generally means a cyclic ether group having a ring structure of 3 to 6 members. Among them, a cyclic ether group of a 3-membered ring or a 4-membered ring having a large ring strain energy and high reactivity is preferred, and a cyclic ether group having a 3-membered ring is particularly preferable.

Next, R ¹ in the present embodiment will be described. In the present embodiment, R ¹ each independently represents a hydrogen atom and at least one organic group selected from the group consisting of a) to c) below:

a) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 4 or more and 24 or less And an organic group of a cyclic ether group having an oxygen atom number of 1 or more and 5 or less;

b) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 1 or more and 24 or less and oxygen a monovalent aliphatic organic group having an atomic number of 0 or more and 5 or less;

c) having an unsubstituted or substituted aromatic hydrocarbon unit and, if necessary, having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups The aliphatic hydrocarbon unit is a monovalent aromatic organic group having a carbon number of 6 or more and 24 or less and an oxygen atom number of 0 or more and 5 or less.

The above a) has an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic structures, and contains a carbon number of 4 or more and 24 Examples of the organic group of the cyclic ether group in which the number of oxygen atoms is 1 or more and 5 or less are, for example, β-glycidoxyethyl or γ-glycidoxypropyl. a glycidyloxyalkyl group such as γ-glycidyloxybutyl group or the like which is bonded by an oxyglycidyl group having 4 or less carbon atoms; glycidyl group, β-(3,4-epoxycyclohexyl)B , γ-(3,4-epoxycyclohexyl)propyl, β-(3,4-epoxycycloheptyl)ethyl, β-(3,4-epoxycyclohexyl)propyl, β- a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as (3,4-epoxycyclohexyl)butyl or β.-(3,4-epoxycyclohexyl)pentyl Substituted alkyl and the like.

The above b) has an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and has a carbon number of 1 or more and 24 or less and oxygen. The monovalent aliphatic organic group having an atomic number of 0 or more and 5 or less may, for example, be exemplified by:

(b-1) methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, hexyl Base, n-heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl a chain-like organic group composed of an aliphatic hydrocarbon such as a heptadecyl group or an octadecyl group;

(b-2) an organic group consisting of a hydrocarbon having a cyclic unit such as a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, or a norbornyl group;

(b-3) an organic group containing an ether bond such as a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a methoxypropyl group, an ethoxypropyl group or a propoxypropyl group;

(b-4) Vinyl, allyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl and the like.

The above c) has an unsubstituted or substituted aromatic hydrocarbon unit, and if necessary, has one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups. Examples of the aliphatic hydrocarbon unit and the monovalent aromatic organic group having 6 or more and 24 or less carbon atoms and 0 to 5 or less oxygen atoms include phenyl, tolyl, xylyl, benzyl and α-. Methylstyryl, 3-methylstyryl, 4-methylstyryl, and the like.

The alkoxydecane compound may be a mixture of two or more kinds of the above-mentioned a) to c) organic groups.

Further, the organic group may contain a hydroxyl group, an alkoxy unit, a mercapto unit, a carboxyl group, an alkenyl unit, a decyl unit, or a halogen such as fluorine or chlorine in the range of the number of carbon atoms and the number of oxygen atoms. The atom or the ester bond may further contain a hetero atom such as nitrogen, phosphorus or sulfur in addition to an oxygen atom or a halogen atom. Further, the above a) to c) may be one type or two or more types of organic groups may be mixed.

The organic base R ¹ has a tendency to obtain good light resistance or to improve stability during storage in order to obtain a cured product obtained by modifying the modified resin composition of the present embodiment, and to increase the total Si unit. a molar number containing a hydroxyl unit, an alkoxy unit, a mercapto unit, a carboxyl unit, an alkenyl unit, a decyl unit, a halogen atom such as fluorine or chlorine, or an ester bond, and further containing an oxygen atom or a halogen atom. The total number of mole atoms of the ruthenium atom to which the organic group of the hetero atom other than nitrogen, phosphorus, sulfur or the like is bonded is preferably 10% or less, preferably 1% or less, and more preferably not contained at all.

On the other hand, when a cured product is produced using the modified resin composition of the present embodiment, in order to have a tendency to be cured stably and reproducibly, the total number of moles of the total Si unit is (b- 4) The total number of moles of monovalent aliphatic organic groups such as vinyl, allyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, etc. is preferably 10% or less, and 5% or less. The following is preferred, and 1% or less is more preferable, and it is particularly preferable to be completely excluded.

In order to improve the heat resistance and the discoloration resistance of the modified resin composition of the present embodiment, the organic group R ¹ of the general formula (1) in the present embodiment is selected from the above a). The groups b-1), b-2), and c) are preferably selected from the group consisting of a) β-glycidyloxyethyl, γ-glycidoxypropyl, γ-glycidyl. An oxybutyl group or the like which is a glycidyloxyalkyl group bonded by an oxyglycidyl group having 4 or less carbon atoms, a glycidyl group, a β-(3,4-epoxycyclohexyl)ethyl group, or a γ-( 3,4-epoxycyclohexyl)propyl, β-(3,4-epoxycycloheptyl)ethyl, β-(3,4-epoxycyclohexyl)propyl, β-(3,4- Epoxycyclohexyl)butyl, β-(3,4-epoxycyclohexyl)pentyl, and b-1) and b-2) have a carbon number of 1 or more and 8 or less and an oxygen atom of 0. The organic group of the group, and the group selected from the group consisting of phenyl and benzyl are more preferred; and are selected from the group consisting of a) β-glycidyloxyethyl, γ-glycidoxypropyl, γ a glycidyloxyalkyl group such as glycidyloxybutyl group or the like which is bonded by an oxyglycidyl group having 4 or less carbon atoms, glycidol , β-(3,4-epoxycyclohexyl)ethyl, and b-1) and b-2) an organic group having a carbon number of 1 or more and 3 or less and having an oxygen atom of 0, and benzene The selection of the group is particularly good.

Next, R ² in the present embodiment will be described. In the present embodiment, R ² each independently represents a hydrogen atom, and d) an aliphatic group having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups. a hydrocarbon unit having a monovalent organic group having a carbon number of 1 or more and 8 or less, and the d) monovalent organic group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or an isobutyl group. Tributyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, octyl, decyl, decyl, undecyl, dodecyl, ten a chain-like organic group composed of an aliphatic hydrocarbon such as a trialkyl group, a tetradecyl group, a pentadecyl group, a hexadecenyl group, a heptadecyl group or an octadecyl group; a cyclopentyl group, An organic group composed of a hydrocarbon having a cyclic unit such as a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, or a norbornyl group.

The alkoxydecane compound may be a mixture of two or more kinds of the above-mentioned d) organic groups. Further, one type or two or more types of organic groups may be present in combination.

Among these organic groups, a methyl group, an ethyl group, a n-propyl group and an isopropyl group are preferred, and a methyl group or an ethyl group is more preferred because of the tendency to increase the reactivity of the alkoxydecane compound.

In the present embodiment, the alkoxydecane compound of the above formula (1) contains at least (B) n = 1 or 2 and at least one cyclic ether group as the alkoxydecane compound. At least one alkoxydecane compound of R ¹ and at least one alkoxydecane compound having (C) n = 1 or 2 and having at least one aromatic organic group as R ¹ . When the (A) = 1 or 2 and at least one cyclic ether group is used as at least one alkoxydecane compound of R ¹ , the cured product obtained by curing the modified resin composition of the present embodiment is cured. Crack resistance and adhesion are not sufficient. On the other hand, does not contain (C) n = 1 or 2 and having at least one aromatic organic radical R ¹ is an alkoxy compound of at least one kind of silicon-alkoxy, modified resin composition will phase separation, and could not be It is resistant to thermal shock resistance and adhesion to reproducibility.

Specific examples of the component (B) used in the present embodiment include 3-glycidyloxypropyl (meth)dimethoxydecane and 3-glycidyloxypropyl (methyl). Diethoxydecane, 3-glycidoxypropyl (methyl) dibutoxydecane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxydecane, 2 -(3,4-epoxycyclohexyl)ethyl(phenyl)diethoxydecane, 2,3-epoxypropyl(methyl)dimethoxydecane, 2,3-epoxypropyl ( Phenyl)dimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropyltributoxide Baseline, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 2,3-epoxypropyl Trimethoxy decane, 2,3-epoxypropyltriethoxy decane, and the like. These may be used alone or in combination of two or more.

Specific examples of the component (C) used in the present embodiment include dimethoxymethylphenyl decane, diethoxymethyl phenyl decane, phenyl triethoxy decane, and trimethoxy [ 3-(phenylamino)propyl]decane, dimethoxydiphenylnonane, diphenyldiethoxydecane, phenyltrimethoxydecane, and the like. These may be used alone or in combination of two or more.

Further, in the modified resin composition of the present embodiment, in addition to the components (A) to (C), the following may be used as the other component: the general formula (1) indicates the number of R ¹ Wherein n = 0, specifically, an alkoxydecane compound obtained by combining four (OR ² ). Examples of such alkoxydecane compounds include tetramethoxynonane, tetraethoxymethoxynonane, tetrapropoxydecane, and the like. These may be used alone or in combination of two or more.

Here, the mixing index α used in the present embodiment will be described.

In the alkoxydecane used in the present embodiment, "(B) in the general formula (1), n = 1 or 2 and at least one cyclic ether group as at least one alkoxydecane of R ¹ The compounding ratio of the compound "(c), in the general formula (1), n = 1 or 2 and at least one aromatic organic group as at least one alkoxydecane compound of R ¹ " is defined as The mixing index α calculated by the formula (2).

Mixed index α=(αc)/(αb) (2)

(In the formula (2), αb represents the content (mol%) of the component (B) in the alkoxydecane represented by the general formula (1), and αc represents the alkoxydecane represented by the general formula (1). Content (mol%) of the component (C).

In the present embodiment, in order to ensure the fluidity and storage stability of the modified resin composition, the mixing index α must be 0.001 or more, and on the other hand, in order to ensure the fluidity of the modified resin composition or the crack resistance of the cured product. The above mixing index α must be in the range of 19 or less. The value of α is preferably in the range of 0.2 or more and 5 or less, more preferably 0.3 or more and 2 or less.

In the modified resin composition of the present embodiment, the amount of residual alkoxy groups in the composition is 5% or less. When the residual alkoxy group exceeds 5%, the crack resistance or adhesion at the time of thermal cycling of the cured product obtained by curing the composition is not good. The amount of the residual alkoxy group in the modified resin composition is preferably 3% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably not contained at all.

Further, the quantitative value of the amount of the residual alkoxy group is an internal standard peak measured by H-NMR measurement using 1,1,2,2-tetrabromoethane as an internal standard substance, and the residue derived from the residue The area ratio of the peak of the alkoxy group is thus obtained.

Specifically, it can be obtained by the method described below and the analysis method.

<H-NMR measurement>

(1) 10 mg of the modified resin composition, 20 mg of an internal standard material (1,1,2,2-tetrabromoethane; Tokyo Chemical Industry Co., Ltd.) and 970 mg of a hydrogenated chloroform were uniformly mixed as a solution for H-NMR measurement.

(2) The solution of the above (1) was measured for H-NMR spectrum under the following conditions.

Device: "A-400 type" manufactured by Japan Electronics Co., Ltd.

Nuclear species: H

Cumulative number: 200 times

<Analysis of measurement results>

(3) The area value of the peak derived from the residual alkoxy group in the H-NMR spectrum was calculated.

(4) Calculate the area value of the peak derived from the internal standard substance in the H-NMR spectrum.

(5) The respective area values obtained in the above (3) and (4) are substituted into the following formula, and the obtained result is defined as the residual alkoxy group amount (%).

The amount of residual alkoxy group (%) = (area value derived from the peak of the residual alkoxy group) / (area value derived from the peak of the internal standard substance) × 100

The viscosity of the modified resin composition of the present embodiment at 25 ° C is not particularly limited. However, in order to ensure the fluidity of the liquid, the handling property is improved, and the additive added as necessary is required. The mixing tends to be easy, and the liquid is preferably 1,000 Pa ‧ or less, preferably 500 Pa ‧ or less, more preferably 300 Pa s or less, and particularly preferably 100 Pa s or less.

The epoxy equivalent (WPE) of the modified resin composition of the present embodiment is not particularly limited, but from the viewpoint of improving the storage stability of the modified resin composition, the epoxy equivalent is selected to be 100 g/eq or more. The functional group is preferably a functional group having an epoxy equivalent of 700 g/eq or less, preferably from the viewpoint of improving the crack resistance of the cured product obtained by curing the composition of the hardened modified resin. A range of 100 g/eq or more and 500 g/eq or less, more preferably in the range of 100 g/eq or more and 300 g/eq or less.

Next, the mixing index β used in the present embodiment will be described.

In the alkoxydecane compound used in the present embodiment, "n=2 alkoxydecane compound", "n=1 alkoxydecane compound", and "n=0 alkoxydecane compound" The mixing ratio is defined as the mixing index β calculated according to the following formula (3).

Mixed index β={(βn2)/(βn0+βn1)} (3)

(In the formula (3), βn2 represents the content (mol%) of the alkoxydecane compound of n=2 in the alkoxydecane compound represented by the general formula (1), and βn0 represents a general formula (1). The content (mol%) of the alkoxydecane compound of n=0 in the alkoxydecane compound, and βn1 represents the content of the alkoxydecane compound of n=1 in the alkoxydecane compound represented by the general formula (1) (mol) %), and these are values satisfying 0 ≦ {(βn0) / (βn0 + βn1 + βn2)} ≦ 0.1).

In the present embodiment, in order to improve the fluidity of the modified resin composition and to improve the handleability, the mixing index β is 0.01 or more, and the hardened modified resin composition is hardened. The material tends to have improved crack resistance, and the mixed index β is preferably 1.4 or less, more preferably 0.03 or more and 1.2 or less, and more preferably 0.05 or more and 1.0 or less.

Next, the mixing index γ used in the present embodiment will be described.

The mixing ratio of the epoxy resin (A) and the alkoxydecane compound of "n = 0 to 2" in the alkoxydecane compound used in the present embodiment is defined as the following formula (4). The mixed indicator γ.

Mixed index γ=(γa)/(γs) (4)

(In the formula (4), γa represents the mass (g) of the epoxy resin (A), and γs represents an alkoxydecane compound of n=0 to 2 in the alkoxydecane represented by the general formula (1). Quality (g)).

In the present embodiment, the crack resistance in the thermal cycle of the cured product obtained by curing the modified resin composition tends to be improved, and the mixing index γ is 0.02 or more. On the other hand, in order to harden the modified resin composition Further, the light resistance of the cured product tends to be improved, and the mixing index γ is preferably in the range of 15 or less, more preferably in the range of 0.04 or more and 7 or less, and still more preferably in the range of 0.08 or more and 5 or less.

In the modified resin composition of the present embodiment, the storage stability of the modified resin composition, that is, the condensation ratio of the alkoxydecane compound from the viewpoint of suppressing the viscosity of the resin during storage and improving the handleability Preferably, it is 80% or more, more preferably 82% or more, more preferably 85% or more, and more preferably 88% or more.

In addition, the condensation ratio of the alkoxydecane compound of the present embodiment is changed with respect to the number of moles (U) of the (OR ² ) group contained in the alkoxydecane compound represented by the general formula (1). The number of moles (V) of the (OR ² ) group in the polyoxonium component present in the resin composition is expressed by the molar fraction represented by the following formula (5):

The condensation rate (%) of the alkoxydecane compound = [(U-V) / U] × 100 (5) Next, an example of a specific production method of the modified resin composition of the present embodiment will be described.

The modified resin composition of the present embodiment may contain at least the following general formula (1) (B) and (C) in the presence of the epoxy resin (A) and the following general formula (2) The alkoxydecane compound in which the mixing index α of the alkoxydecane compound is 0.001 or more and 19 or less is produced by the following method of [Production Method 1] or [Production Method 2]:

(R ¹ ) _n -Si-(OR ² ) _4-n (1)

(wherein, n represents an integer of 0 or more and 3 or less. Further, R ¹ each independently represents a hydrogen atom, at least one or more organic groups selected from the group consisting of a) to c):

a) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 4 or more and 24 or less An organic group having a cyclic ether group composed of 1 or more and 5 or less oxygen atoms;

b) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 1 or more and 24 or less and an oxygen atom a monovalent aliphatic organic group having a number of 0 or more and 5 or less;

c) having an unsubstituted or substituted aromatic hydrocarbon unit and, if necessary, having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched or cyclic groups a monovalent aromatic organic group having an aliphatic hydrocarbon unit and having a carbon number of 6 or more and 24 or less and an oxygen atom number of 0 or more and 5 or less;

On the other hand, each of R ² independently represents a hydrogen atom or one or more organic groups selected from the group consisting of d):

d) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 1 or more and 8 or less Organic base),

(B) at least one alkoxydecane compound having n = 1 or 2 and having at least one cyclic ether group as R ¹ .

(C) at least one alkoxydecane compound having n = 1 or 2 and having at least one aromatic organic group as R ¹ ;

Mixed index α=(αc)/(αb) ...(2)

(In the formula (2), αb represents the content (mol%) of the component (B), and αc represents the content (mol%) of the component (C).

[Production Method 1] The method for producing a modified resin composition comprising the following two steps: (a) step and (b) step.

(a) a step of subjecting an alkoxydecane compound containing at least (B) and (C) represented by the general formula (1) in the presence of an epoxy resin (A) by a reflux step without dehydration The step of co-hydrolysis to produce an intermediate.

Step (b): a step of subjecting the intermediate produced in the step (a) to a dehydration condensation reaction.

[Production Method 2] The method for producing a modified resin composition comprising the following two steps: (c) step and (d) step.

(c) Step: a step of producing an intermediate by at least alkoxydecane compound of the above (B) and (C) represented by the general formula (1) by co-hydrolysis without a reflux step with dehydration.

(d) Step: In the intermediate produced by the step (c), the epoxy resin (A) is allowed to coexist and the step of dehydration condensation reaction is carried out.

Here, the "step of producing an intermediate by co-hydrolysis without a reflux step with dehydration" and "the step of performing a dehydration condensation reaction" will be described.

The "step of producing an intermediate by co-hydrolysis without a reflux step with dehydration" means water or a solvent to be blended for co-hydrolysis, and water or a solvent derived from an alkoxydecane compound produced in the reaction. The step of carrying out the reaction while flowing back to the reaction solution. The reaction pattern is not particularly limited, and it can be carried out by one or a combination of two or more kinds of reaction modes such as a batch type, a semi-batch type, or a continuous type. Specific examples include a method in which a cooling tube is attached to the upper portion of the reaction vessel, and the generated water or solvent is refluxed while being reacted, or a reaction is carried out while stirring and/or circulating the reaction solution in a closed vessel.

On the other hand, the "step of performing the dehydration condensation reaction" means a step of performing a condensation reaction by removing the added water or solvent and the water or solvent produced in the above-mentioned "reflow step without dehydration". For example, it can be carried out by using one or a combination of two or more of the following devices: a rotary evaporator, a vertical stirring tank equipped with a distillation tube, a surface renewal type stirring tank, a thin film evaporation apparatus, and a surface renewal type double shaft. A kneader, a biaxial transverse agitator, a wet-wall reactor, a free-falling type porous plate type reactor, and a reactor in which a volatile component is distilled off while the compound is dropped along the support.

The modified resin composition of the present embodiment can be produced by any of the above [Production Method 1] and [Production Method 2]. When the modified resin composition of the present embodiment is produced, the reaction method of the alkoxydecane compound is not particularly limited, and the reaction may be carried out by adding all of them at the initial stage, or may be added to the reaction system one by one or continuously for reaction.

Further, in any of [Production Method 1] and [Production Method 2], the epoxy resin (A) may be added all at once or may be added separately.

Further, in the case of [Production Method 1], the steps (a) and (b) may be continuously carried out, or the reaction mixture obtained in the step (a) may be separated or recovered, and then the step (b) may be carried out.

On the other hand, in the case of [Production Method 2], the steps (c) and (d) may be continuously carried out, or the reaction mixture obtained in the step (c) may be recovered, and then the step (d) may be carried out.

Therefore, the epoxy resin (A) and the alkoxydecane compound used in [Production Method 1] and [Production Method 2] are the same as the above-exemplified epoxy resin (A) and alkoxydecane compound. Substance.

Further, in [Production Method 1] and [Production Method 2], the suitable range of the mixing index α to γ of the alkoxydecane compound is the same as the above.

In the [Production Method 1] or the [Production Method 2] of the present embodiment, when the step of producing an intermediate by co-hydrolysis without a reflux step with dehydration is completed, the condensation ratio of the intermediate is preferably 78% or more. More preferably, 80% or more, and more preferably 83% or more. When the condensation ratio of the intermediate is less than 78%, even after the subsequent dehydration condensation step, many OH groups derived from polyoxymethylene remain in the resin composition to be produced, and the residual OH group may be in storage. The condensation causes a significant increase in the viscosity or saponification of the resin composition, which tends to deteriorate the preservation stability.

Further, in the present embodiment, the condensation ratio of the intermediate at the end of the step of producing the intermediate by co-hydrolysis is based on the (OR ² ) group contained in the alkoxydecane compound represented by the general formula (1). The number of ears (R), using the number of moles (S) of the (OR ² ) group in the polyoxonium component present in the modified resin composition, is expressed by the molar fraction shown by the following formula (6):

Condensation rate (%) of alkoxydecane compound = [(R-S) / R] × 100 (6)

In the method for producing a modified resin composition of the present embodiment, the alkoxydecane compound is used from the viewpoint of improving the storage stability of the modified resin composition, that is, from the viewpoint of suppressing the viscosity of the resin during storage and improving the handleability. The condensation ratio is preferably 80% or more, more preferably 82% or more, still more preferably 85% or more, and particularly preferably 88% or more.

In addition, the condensation ratio of the alkoxydecane compound of the present embodiment is based on the number of moles (U) of the (OR ² ) group contained in the alkoxydecane compound represented by the general formula (1). The number of moles (U) of the (OR ² ) group of the polyoxonium component present in the resin composition is expressed by the molar fraction shown by the following formula (5):

Condensation rate (%) of alkoxydecane compound = [(U-V) / U] × 100 (5)

In the method for producing a modified resin composition of the present embodiment, the amount of residual alkoxy groups in the obtained modified resin composition is set to 5% or less. When the amount of the residual alkoxy group exceeds 5%, the crack resistance or adhesion at the time of thermal cycling of the cured product obtained by hardening the composition becomes insufficient. The amount of the residual alkoxy group in the obtained modified resin composition is preferably 3% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably not contained at all.

In the step (a) or (c) of the present embodiment, in order to hydrolyze the alkoxydecane compound, it is allowed to coexist with water in the reaction system. The addition of water is mainly for the hydrolysis of alkoxydecane compounds. The time point at which water is added is not particularly limited as long as it is added until the step of producing the intermediate until co-hydrolysis, and a method of adding all at once in the initial stage of the reaction and adding it in the reaction may be used. Or any method of the method of continuously adding in the reaction. Among them, a method of using all of the addition at the initial stage of the reaction is preferred.

Here, the amount of added water will be described. The ratio of the amount of added water (molar number) to the amount of (OR ² ) in the general formula (1) (mole number) is defined as a mixing index ε represented by the following formula (7).

Mixed index ε = (εw) / (εs) ... (7)

(In the formula (7), εw represents the amount of addition of water (number of moles), and εs represents the amount of (OR ² ) in the general formula (1) (number of moles)).

The mixing index ε of the present embodiment is preferably in the range of 0.1 or more and 5 or less, more preferably 0.2 or more and 3 or less, and more preferably 0.3 or more and 1.5 or less. When the mixing index ε is less than 0.1, the hydrolysis reaction may not be carried out, and when it exceeds 5, the storage stability of the modified resin composition may be lowered.

The above step (a) or (c) may be carried out without a solvent or may be carried out in a solvent. When a solvent is used, a known solvent can be used as long as it is an organic solvent which can dissolve an epoxy resin and an alkoxysilane compound and is inactive.

The solvent to be used may be exemplified by dimethyl ether, diethyl ether, diisopropyl ether, and 1,4-two. Alkane, 1,3-two An ether solvent such as alkane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, anisole; acetone, methyl ethyl ketone, methyl Ketone solvent such as butyl ketone; aliphatic hydrocarbon solvent such as hexane, cyclohexane, heptane, octane or isooctane; aromatics such as toluene, o-xylene, m-xylene, p-xylene or ethylbenzene A hydrocarbon solvent; an ester solvent such as ethyl acetate or butyl acetate: an alcohol solvent such as methanol, ethanol, butanol, isopropanol, n-butanol, butyl cellosolve or butyl carbitol. These solvents may be used alone or in combination of two or more. In particular, an ether solvent, a ketone solvent, an aliphatic hydrocarbon solvent, or an aromatic hydrocarbon solvent is preferred from the viewpoint of suppressing ring opening of the epoxy group in the reaction, and the solvent is contained in an amount of 50% by mass or more. The solvent is preferably selected from the group consisting of 1,4-two More preferably, at least one or a mixture of two or more of a group of alkane, tetrahydrofuran, ethylene glycol dimethyl ether, and propylene glycol dimethyl ether is 1,4-two Alkane and tetrahydrofuran are particularly preferred.

With respect to the amount of the solvent to be added, in the step (a), the epoxy resin (A) and the alkoxydecane compound are added at the end of the step of producing the intermediate by co-hydrolysis without a reflux step with dehydration. The total mass of the alkoxydecane compound added at the end of the step of producing the intermediate by the co-hydrolysis by the reflow step without dehydration in the step (c), The amount is preferably 0.01 to 20 times, more preferably 0.02 to 15 times, more preferably 0.03 to 10 times. Since the molecular weight of the modified resin composition of the present embodiment can be controlled depending on the amount of the solvent to be added, the amount of the solvent to be added is in the above range, and a resin composition having an appropriate molecular weight and an appropriate viscosity can be obtained.

The reaction temperature in the step (a) or (c) is usually in the range of from 0 ° C to 200 ° C. When it is less than 0 ° C, water sometimes solidifies. On the other hand, when it exceeds 200 ° C, the resin composition may be colored. From the viewpoint of improving the reaction rate and suppressing the modification of the resin such as ring opening of the epoxy group, the reaction temperature is preferably in the range of from 20 ° C to 150 ° C, more preferably from 40 ° C to 120 ° C, and preferably 50 ° C. The above range of 100 ° C or less is more preferable. The reaction temperature is not particularly limited as long as it is within the above range, and may be changed in the middle of the reaction.

The reaction time in the step (a) or (c) is not particularly limited, but from the viewpoint of increasing the reaction rate of (OR ² ) in the above general formula (1) while suppressing the modification of the resin, it is 0.1 hour or longer. The range of less than 100 hours is preferably, and the range of 1 hour or more and less than 80 hours is preferable, and the range of 3 hours or more and less than 60 hours is more preferable, and the range of 5 hours or more and less than 50 hours is preferable. It is especially good.

On the other hand, the reaction temperature of the step (b) or the step (d) is usually in the range of from 0 ° C to 200 ° C. When the temperature is less than 0 ° C, the reaction rate is lowered, and the reaction time is prolonged. When the temperature exceeds 200 ° C, the resin composition may be colored. From the viewpoint of improving the reaction rate and suppressing the modification of the resin such as ring opening of the epoxy group, the reaction temperature is preferably in the range of from 20 ° C to 150 ° C, and preferably in the range of from 40 ° C to 120 ° C. A range of 50 ° C or more and 100 ° C or less is more preferable. The reaction temperature is not particularly limited as long as it is within the above range, and may be changed at the initial stage of the reaction or during the course of the reaction.

The reaction time in the step (b) or the step (d) is not particularly limited, but from the viewpoint of improving the reaction rate and suppressing the modification of the resin, it is preferably in the range of 0.1 hour or more and less than 100 hours, and is 0.5. The range of hours or more and less than 80 hours is preferable, and the range of 1 hour or more and less than 50 hours is more preferable, and the range of 3 hours or more and less than 50 hours is particularly preferable.

The modified resin composition of the present embodiment can be produced in an inert gas such as nitrogen, helium, neon, argon, helium, neon, carbon dioxide or a lower saturated hydrocarbon or air. Among these gases, from the viewpoint of suppressing the modification of the resin, an inert gas such as nitrogen, helium, neon, argon, helium, neon, carbon dioxide or lower saturated hydrocarbon is preferred, and nitrogen, helium, Helium, argon, helium, neon, and carbon dioxide are preferred, and nitrogen and helium are preferred, and nitrogen is preferred.

The steps (a) to (d) of producing the modified resin composition of the present embodiment can be carried out under the above-described gas atmosphere, under the above-mentioned gas flow, under reduced pressure, under pressure, or a combination thereof. Further, the pressure does not have to be a constant value, and may vary during the course of the reaction.

Wherein the step (a) or the step (c) is because the water or solvent blended for the co-hydrolysis, and the water or solvent derived from the alkoxydecane compound produced in the reaction must be industrially easily flowed It is preferred to carry out the reaction while returning to the reaction solution, so that it is preferably carried out under the atmospheric pressure of the above gas and/or under pressure.

On the other hand, in the steps (b) and (d), it is necessary to remove the water or solvent added in the step (a) or (c) and the water or solvent produced in the above-mentioned "reflow step without dehydration". It is preferred to carry out the condensation reaction while flowing under an inert gas and/or under reduced pressure.

In the present embodiment, when the (A) epoxy resin and the alkoxydecane compound are co-hydrolyzed, a hydrolysis condensation catalyst may be added.

The hydrolysis-condensation catalyst is not particularly limited as long as it is a conventionally known hydrolysis-promoting reaction, and examples thereof include metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, and the like). Titanium, cobalt, antimony, tin, lead, antimony, arsenic, antimony, boron, cadmium, manganese, antimony, etc.), organic metals (lithium, sodium, potassium, strontium, barium, magnesium, calcium, strontium, barium, zinc, aluminum , titanium, cobalt, antimony, tin, lead, antimony, arsenic, antimony, boron, cadmium, manganese, antimony, etc., organic oxides, organic acid salts, organic halides, alkoxides, etc.), inorganic bases (magnesium hydroxide , calcium hydroxide, barium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, etc.), organic alkali (ammonia, Tetramethylammonium hydroxide, etc.).

Among the above organometallics, organic tin is also preferred. The organotin refers to a compound in which at least one organic group is bonded to a tin atom, and examples of the structure include monoorganotin, diorganotin, triorganotin, tetraorganotin and the like. The organotin may, for example, be tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra-n-octyltin, tetra-n-butyltin oxide, dibutyltin oxide, dibutyltin diacetate or dioctanoic acid. Dibutyltin, dibuty tin diversatate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin ‧ ethylate reactant, a compound of dibutyltin salt and bismuth salt, a compound of dioctyltin salt and bismuth citrate, dibutyltin of bis(acetonitrile), dibutyltin bis(ethylmalate), dibutyltin of bis(butylmalate) , bis(2-ethylhexylmalic acid) dibutyltin, bis(benzylmalic acid)dibutyltin, bis(stearyl malate)dibutyltin, bis(oleyl malate)dibutyltin, dibutyltin malate, Dibutyltin bis(0-phenylphenoxide), bis(2-ethylhexyl thioacetate) dibutyltin, bis(2-ethylhexylhydrothiopropionic acid) dibutyltin, bis(isodecyl)- 3-hydrothiopropionic acid) dibutyltin, bis(isooctylhydrothioacetate) dibutyltin Bis(3-hydrothiopropionic acid) dibutyltin, dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dioctoate, di(dodecyl)hydrogen Thioyldioctyltin, dioctyltin velsumate, dioctyltin distearate, bis(ethylmalate)dioctyltin, bis(octylmalate)dioctyltin,malic acid Dioctyltin, bis(isooctylhydrothioacetic acid) dioctyltin, bis(2-ethylhexylhydrothioacetic acid) dioctyltin, dibutyltin dimethoxide, dibutyltin diethoxylate Dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxylate, dioctyltin dibutoxide, tin octylate, tin stearate, and the like.

Further, among the above organometallics, an alkali organometallic which exhibits a basicity when the ligand is free is suitable. By using an alkali organometallic as a hydrolysis condensation catalyst, the storage stability of the modified resin composition of the present embodiment tends to be improved. In addition, since the alkali metal is used, the progress of the condensation reaction tends to be rapid, so that it is very useful when a resin composition having a condensation ratio of the intermediate of 78% or more is obtained.

Among the alkali organometallics, alkali organotin is also preferred, and alkoxide-based organometallics are preferred. Examples of the alkoxide-based organotin include dibutyltin dimethoxide, dibutyltin diethoxylate, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxylate, and Octyltin dibutyl oxide and the like.

On the other hand, when an acid-based organic metal which exhibits acidity when a ligand is used is used as a hydrolysis condensation catalyst, the hydrolysis reaction proceeds rapidly, but the condensation reaction tends to be difficult to proceed, which is not preferable in practical use.

These hydrolysis-condensation catalysts may be used singly or in combination of two or more. For example, an organic acid tin may be used in combination with an alkali organotin to react an organic acid salt such as tin, or may be treated with an inorganic base. The inorganic base at this time is preferably a hydroxide of a polyvalent cation such as magnesium hydroxide, calcium hydroxide, barium hydroxide or barium hydroxide.

The amount of the hydrolysis-condensation catalyst to be added is not particularly limited, and a suitable addition amount is determined by the following mixing index δ as a ratio of (OR ² ) in the above formula (1).

The mixing index δ is expressed by the following formula (8):

Mixed index δ = (δe) / (δs) ... (8)

(In the formula (8), δe represents the amount of addition (mol number) of the hydrolysis condensation catalyst, and δs represents the amount (mol number) of (OR ² ) in the above formula (1).

The mixing index δ is preferably in the range of 0.0005 or more and 5 or less, more preferably in the range of 0.001 or more and 1 or less, and still more preferably in the range of 0.005 or more and 0.5 or less.

According to the composition of the modified resin composition, when the mixing index δ is less than 0.0005, the promoting effect of hydrolysis condensation may be difficult to obtain, and when it exceeds 5, the ring opening of the cyclic ether group may be promoted, which may result in preservation stability. Sexual deterioration.

The modified resin composition of the present embodiment is a modified resin composition capable of forming a cured product having excellent transparency, heat resistance, heat discoloration resistance, light resistance, and crack resistance during thermal cycling while having good storage stability. Since the cured product is formed by heat or energy rays, it can be suitably used as a raw material resin composition such as a light-emitting element sealing material, an optical lens, a photosensitive resin, a fluorescent resin, a conductive resin, or an insulating resin.

Further, in the modified resin composition of the present embodiment, oxetane (D), phosphor (E), conductive metal powder (F), and insulating powder (G) may be blended. ), epoxy resin (A'), hardener (H), hardening accelerator (I), photoacid generator (J), cationic polymerization catalyst, modifier, vinyl ether compound, An organic resin other than the epoxy resin (A') or a decane coupling agent.

A resin composition obtained by adding an oxetane compound (D) to the modified resin composition of the present embodiment will be described.

The oxetane compound (D) is not particularly limited as long as it is a compound containing an oxetane ring, and is, for example, 3-ethyl-3-hydroxymethyloxetane or 3-ethyl- 3-(2-ethylhexyloxymethyl)oxetane, bis(3-ethyl-3-oxetanylmethyl)ether, 3-ethyl-3-(phenoxymethyl) Oxetane, 3-ethyl-3-(2,3-epoxypropoxymethyl)oxetane, and the like. When the oxetane compound is blended, the polymerization rate tends to increase, and the viscosity of the composition tends to decrease.

Representative examples of the oxetane compound are shown below.

The blending amount of the above oxetane compound is not particularly limited. It is preferably blended in a mass ratio of a resin composition: oxetane compound = 20:80 to 95:5 (total 100), preferably 40:60 to 80:20. When the blending ratio of the resin composition is less than 20, the hardening reaction may not proceed normally, and when it exceeds 95, the adhesion of the cured product may be deteriorated.

In order to improve the compatibility of the resin composition with the oxetane compound, for example, with respect to the resin composition using the epoxy resin having a bisphenol backbone as a raw material, an oxetane compound having an aromatic ring is usually used. Combine and so on and select the appropriate combination.

A fluorescent resin composition obtained by adding a phosphor (E) to the modified resin composition of the present embodiment will be described.

In the present embodiment, the phosphor (E) is a substance that emits fluorescence. In short, as long as it absorbs energy such as electron beams, X-rays, ultraviolet rays, and electric fields, the absorbed energy is more efficiently used as visible light. The substance to be emitted (light-emitting) is not particularly limited, and any type of inorganic or organic type can be used. Among them, an inorganic phosphor which exhibits excellent luminosity is usually preferred.

The size of the inorganic fluorescent material which can be used in the present embodiment is not particularly limited, and a powder having a particle diameter of from 1 to several tens of μm is usually used. Further, in order to express the performance of the inorganic phosphor, an element B called an activator (light-emitting center) is introduced into the compound A called a parent, and is usually a "parent A: activator B". .

In particular, when the fluorescent resin composition is used as a sealing material for an LED, it is preferable to use a strontium aluminate phosphor (YAG: Ce phosphor) which is activated by an endowment for the reason described later. When it is used as a light-receiving material, it is preferable to use a fluorescent light-emitting body, and these may be used alone or in combination of two or more.

Regarding the blending amount of the phosphor, the resin composition is preferably a resin composition: a phosphor = 30:70 to 95:5, more preferably 50:50 to 80:20 (total 100). When the amount of the phosphor is more than that of the resin composition: phosphor = 30:70, the fluidity of the fluorescent resin composition is deteriorated, and when it is less than 95:5, the function of the phosphor There are insufficient situations.

The precursor A and the activator B are not particularly limited. For example, the precursor A may be, for example, an oxide phosphor or a nitride phosphor. Further, examples of the activator B include rare earth elements such as lanthanum (Eu) and cerium (Ce).

As the above-mentioned oxide phosphor, for example, a "YAG:Ce phosphor" in which the precursor A is yttrium aluminate (Y ₃ Al ₅ O ₁₂ : hereinafter referred to as YAG) and the activator B is cerium (Ce) is known. . When blue light is irradiated (near 460 nm), yellow light emission is effectively caused. This fluorescent system can change the structure of the mother A by replacing a part of Y of "Y ₃ Al ₅ O ₁₂ " with another Gd or Tb or the like, or by substituting a part of Al with Ga or the like. It is very useful to move to the long wavelength side or the short wavelength side.

In short, the "YAG:Ce phosphor" is a structure in which the parent A is YAG, or a part of Y is replaced by another Gd or Tb, or a part of Al is substituted by Ga or the like, and the structure of the parent A is changed, and The activator B is not particularly limited as long as it is a phosphor of Ce. Specific examples thereof include "Y ₃ Al ₅ O ₁₂ :Ce ³⁺ " or "(Y ₃ , Gd _0.9 )Al ₅ O ₁₂ : Ce ³⁺ ” and so on.

The other, on the oxide phosphor embodiment, A is a known precursor of barium silicate ‧ strontium (Sr, Ba) ₂ SiO ₄ and is introduced to europium (Eu) as an activator of B _{"(Sr, Ba) 2 SiO 4} : E _u phosphor." This material can adjust the luminescent color from green to orange by changing the composition ratio of Sr to Ba.

As the above-described nitride phosphor, for example, the following examples are given.

ial-Sialon phosphor: The precursor A is a crystal formed by solid-solving metal ions such as Ca and aluminum and oxygen in the α-type tantalum nitride crystal, with "[Mp(Si, Al) ₁₂ (O, N) ₁₆ ] Here, M represents a metal ion, and p represents a solid solution amount, and specific examples thereof include "Cap (Si, Al) ₁₂ (O, N) ₁₆ : Eu" and the like.

β-Sialon phosphor: The matrix A is represented by a composition of “Si _6-q Al _q O _g N _8-q ” which is obtained by solid-solving aluminum and oxygen in a β-type tantalum nitride crystal. q represents the amount of solid solution. Specifically, "Si _6-q Al _q O _q N _8-q :Eu" or the like can be mentioned.

CaAlSiN ₃ phosphor: The precursor A is a nitride crystal obtained by reacting calcium nitride, aluminum nitride and tantalum nitride at a high temperature of 1800 ° C, and specific examples thereof include "CaAlSiN ₃ :Eu".

Specific examples of the inorganic fluorescent material include, for example, "6MgO‧As ₂ O ₅ :Mn ⁴⁺ , Y(PV)O ₄ :Eu", "CaLa _0.1 Eu _0.9". Ga ₃ O ₇ ”, “BaY _0.9 Sm _0.1 Ga ₃ O ₇ ”, “Ca(Y _0.5 Eu _0.5 )(Ga _0.5 In _0.5 ) ₃ O ₇ ”, “Y ₃ O ₃ :Eu, YVO ₄ :Eu”, "Y ₂ O ₂ :Eu", "3.5MgO‧0.5Mg F ₂ GeO ₂ :Mn ⁴⁺ ", "(Y‧Cd)BO ₂ :Eu", etc.

For those having a blue luminescent color, "(Ba, Ca, Mg) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ ", "(Ba, Mg) ₂ Al ₁₆ O ₂₇ : Eu ²⁺ ",""Ba ₃ MgSi ₂ O ₈ :Eu ²⁺ ", "BaMg ₂ Al ₁₆ O ₂₇ :Eu ²⁺ ", "(Sr,Ca) ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ²⁺ "," (Sr, Ca) ₁₀ (PO ₄ ) ₆ Cl ₂ ‧nB ₂ O ₃ :Eu ²⁺ ”, “Sr ₁₀ (PO ₄ ) ₆ Cl ₂ :Eu ²⁺ ”, “(Sr,Ba,Ca) ₅ (PO ₄ ) ₃ Cl:Eu ²⁺ ","Sr ₂ P ₂ O ₇ :Eu", "Sr ₅ (PO ₄ ) ₃ Cl:Eu", "(Sr,Ba,Ca) ₃ (PO ₄ ) ₆ Cl:Eu""SrO‧P ₂ O ₅ ‧B ₂ O ₅ :Eu", "(BaCa) ₅ (PO ₄ ) ₃ Cl:Eu", "SrLa _0.95 Tm _0.05 Ga ₃ O ₇ ", "ZnS:Ag"," GaWO ₄ ”, “Y ₂ SiO ₆ :Ce”, “ZnS:Ag,Ga,Cl”, “Ca ₂ B ₄ OCl:Eu ²⁺ ”, “BaMgAl ₄ O ₃ :Eu ²⁺ ”, “(Ml, Eu) ₁₀ (PO ₄ ) ₆ Cl ₂ (Ml is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba) and the like.

Examples of the green color luminescent color include "Y ₃ Al ₅ O ₁₂ :Ce ³⁺ (YAG)", "Y ₂ SiO ₅ :Ce ³⁺ , Tb ³⁺ ", and "Sr ₂ Si ₃ O ₈ ‧ 2SrCl ₂ :Eu", "BaMg ₂ Al ₁₆ O ₂₇ :Eu ²⁺ ,Mn ²⁺ ", "ZnSiO ₄ :Mn", "Zn ₂ SiO ₄ :Mn", "LaPO ₄ :Tb", "SrAl ₂ O ₄ : Eu", "SrLa _0.2 Tb _0.8 Ga ₃ O ₇ ", "CaY _0.9 Pr _0.1 Ga ₃ O ₇ ", "ZnGd _0.8 Ho _0.2 Ga ₃ O ₇ ", "SrLa _0.6 Tb _0.4 Al ₃ O ₇ , ZnS: Cu, Al", "(Zn, Cd)S: Cu, Al", "ZnS: Cu, Au, Al", "Zn ₂ SiO ₄ : Mn", "ZnSiO ₄ : Mn", "ZnS: Ag, Cu""(Zn‧Cd)S:Cu","ZnS:Cu","GdOS:Tb","LaOS:Tb","YSiO ₄ :Ce‧Tb", "ZnGeO ₄ :Mn", "GeMgAlO: Tb", "SrGaS: Eu ²⁺ ", "ZnS: CU‧ Co", "MgO‧nB ₂ O ₃ : Ge, Tb", "LaOBr: Tb, Tm", "La ₂ O ₂ S: Tb", etc. .

Further, "YVO ₄ : Dy" having a white-based luminescent color or "CaLu _0.5 Dy _0.5 Ga ₃ O ₇ " having a yellow-based luminescent color may be mentioned.

Specific examples of the organic fluorescent material include, for example, 1,4-bis(2-methylstyryl)benzene (Bis-MSB) and trans-4,4'-two having a blue-based luminescent color. A stilbene-based dye such as phenyl stilbene (DPS) or a coumarin-based dye such as 7-hydroxy-4-methylcoumarin (coumarin 4).

Examples of the fluorescent color having a yellow color to a green color include, for example, Brilliant sulfoflavine FF, Basic yellow HG, and Sinloihi Color FZ-5005 (manufactured by SINLOIHI Co., Ltd.).

Examples of the fluorescent color having a yellow color to a red color include commercially available products such as Eosine, Rhodamine 6G, and Rhodamine B.

When a general phosphor is blocked by light or an electron beam as an excitation source, the light is immediately attenuated and destroyed. However, as an exception, there is a phosphor which exhibits residual light for several seconds to several tens of hours after blocking the excitation source, and this is called a light-storing phosphor. As long as the property is exhibited, the type is not particularly limited. Specific examples thereof include "CaS: Eu, Tm", "CaS: Bi", "CaAl ₂ O ₄ : Eu, Nd", and "CaSrS". : Bi", "Sr ₂ MgSi ₂ O ₇ :Eu, Dy", "Sr ₄ Al ₁₄ O ₂₅ :Eu, Dy", "SrAl ₂ O ₄ :Eu,Dy", "SrAl ₂ 0 ₄ :Eu", "ZnS:Cu", "ZnS:Cu,Co", "Y ₂ O ₂ S:Eu,Mg,Ti", "CaS:Eu,Tm", etc., among which "Sr ₂ MgSi" exhibits long residual light. ₂ O ₇ :Eu, Dy", "Sr ₄ Al ₁₄ O ₂₅ :Eu, Dy", "SrAl ₂ O ₄ :Eu, Dy", and "SrAl ₂ O ₄ :Eu" are preferred.

The method for producing the fluorescent resin composition of the present embodiment is not particularly limited. For example, the modified resin composition and the phosphor may be simultaneously or separately heated as needed, and the mixing device described later may be stirred. A method of mixing or dispersing; or a method of performing a defoaming treatment under reduced pressure after the above method. Further, a curing agent, a curing accelerator, a polymerization initiator, an additive, and the like which will be described later may be appropriately added in any of the above steps.

The mixing device is not particularly limited, and examples thereof include a kneader, a three-cylinder mill, a ball mill, a planetary mixer, a line mixer, and a homogenizer. , uniform dispersion machine, etc.

A conductive resin composition obtained by adding a conductive metal powder (F) to the modified resin composition of the present embodiment will be described.

The conductive metal powder (F) which can be used in the present embodiment is not particularly limited as long as it is a metal powder containing silver, and may be not only silver powder but also metal powder in which silver is adhered or coated on the surface. The metal powder referred to herein may, for example, be a metal element such as aluminum, lanthanum, boron, carbon, magnesium, nickel, copper, graphite, gold or palladium, or a metal oxide or a metal nitride powder thereof. Among the above, aluminum, nickel, gold, and palladium are preferred from the viewpoint of conductivity.

Specific examples of the metal oxide and the metal nitride include alumina, magnesia, aluminum nitride, boron nitride, tantalum nitride, molten cerium oxide, crystalline cerium oxide, magnesium citrate, aluminum, and aluminum. An oxide of a composite metal of bismuth, an oxide of a composite metal of aluminum and magnesium, and the like.

The conductive metal powder may also be polyethylenimine, polyvinylpyrrolidone, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, having a polyethylenimine moiety and polyethylene oxide ( Polyetbylene oxide) A part of a polymer such as a copolymer is surface coated. By such a polymer coating, the dispersibility of the resin composition tends to be improved.

Since silver is an element having a low volume resistivity, and the conductivity of the metal powder is more dependent on the surface state or the like depending on the support as the core, the entire particles of the conductive metal powder can be used even if it is not silver. A metal powder that adheres or coats silver on its surface.

The shape of the silver powder is not particularly limited, and examples thereof include a scaly shape, a spherical shape, and a tree shape.

The scaly silver powder-based silver powder has many joints and is excellent in electrical conductivity, and when it is made into a conductive resin composition from the orientation, it exhibits thixotropy and is excellent in workability. On the contrary, when used in a precision material, there is a problem that causes a problem due to poor electrical connection of the alignment. Further, the size thereof is not particularly limited, and the average particle diameter obtained by the laser diffraction type particle size distribution measuring apparatus is preferably 50 μm or less, and more preferably 1 to 20 μm. When the average particle diameter is used in a precision electronic component or the like, it is preferable because the possibility of causing electrical bonding failure is reduced.

Since the spherical silver powder has almost no alignment, it is less likely to cause problems in electrical bonding. However, since the particles are in point contact with each other, the conductivity tends to be deteriorated. Further, the size thereof is not particularly limited, and the average particle diameter is preferably 20 μm or less, preferably 5 μm or less. When the average particle diameter exceeds 20 μm, the conductivity tends to be low. In addition, when it is used together with the scaly silver powder for the purpose of burying the gap and achieving conductivity, it is preferable to select 5 μm or less.

The dendritic silver powder has a large specific surface area and excellent electrical conductivity, but its quality is unstable due to its specific shape. The size thereof is not particularly limited, and the average particle diameter is preferably 30 μm or less, preferably 5 μm or less. By setting the average particle diameter, the treatment tends to be excellent, which is preferable.

In the present embodiment, in view of the nature of the application, it is preferable to use silver powder of different shapes in view of its nature.

Further, a suitable blending amount of the conductive metal powder is from 60 to 85% by mass, preferably from 70 to 80% by mass, based on the resin composition. When the blending amount is 60% by mass or more, the conductivity is preferably changed, and when it is 85% by mass or less, the bleed phenomenon tends to be prevented.

An insulating resin composition obtained by adding an insulating powder (G) to the modified resin composition of the present embodiment will be described.

Specific examples of the insulating powder (G) which can be used in the present embodiment include non-oxide ceramic powders such as carbon, boron carbide, boron nitride, aluminum nitride, and titanium nitride; bismuth, magnesium, aluminum, and titanium. Oxide powder; cerium oxide, cerium nitride, molten cerium oxide, crystalline cerium oxide, other cerium-containing filling materials; magnesium silicate, aluminum and cerium composite metal oxide, aluminum and magnesium composite Metal oxides; powders of muscovite, phlogopite, mitanite, stataite, alumina, soda glass, borosilicate glass, quartz glass, wood, etc. Resin powder such as rubber) or Teflon (registered trademark). These may be used alone or in combination. Among the above, from the viewpoints of easy availability and insulation, it is preferable to use ruthenium oxide, tantalum nitride, molten ruthenium dioxide, crystalline ruthenium dioxide, and other fillers containing ruthenium.

The insulating powder may also be a decane compound, or a polyethylenimine, a polyvinylpyrrolidone, a polyacrylic acid, a carboxymethylcellulose, a polyvinyl alcohol, a polyethylenimine moiety and a polyethylene oxide. Some polymers such as copolymers are surface coated. By such a polymer coating, the dispersibility of the resin composition tends to be improved.

Further, the suitable blending amount of the insulating powder is from 5 to 50% by mass, preferably from 10 to 30% by mass, based on the resin composition. When the blending amount is 5% by mass or more, the insulating property is preferably changed. When the blending amount is 50% by mass or less, the reliability of the semiconductor device tends to be improved due to the stress relieving effect.

In the modified resin composition of the present embodiment, the epoxy resin (A') other than the epoxy resin (A) contained in the modified resin composition of the present embodiment may be further contained. Further, an organic resin other than the epoxy resin (A'), for example, an organic resin such as a polyoxyxylene resin, an acrylic resin, a urea resin or a quinone imide resin may be blended.

In the modified resin composition of the present embodiment, a curing agent (H) and/or a curing accelerator (I) may be added to form a curable resin composition.

The curing agent (H) is a material used to harden the resin composition, and is not particularly limited.

As the curing agent, for example, an acid anhydride compound, an amine compound, a guanamine compound, a phenol compound, or the like can be used. In particular, an acid anhydride compound such as an aromatic acid anhydride, a cyclic aliphatic acid anhydride or an aliphatic acid anhydride is preferred, and a carboxylic acid anhydride is preferred. good.

Further, the acid anhydride compound contains an alicyclic acid anhydride, and the carboxylic acid anhydride preferably contains an alicyclic carboxylic acid anhydride. These hardened materials may be used singly or in combination of two or more.

Specific examples of the curing agent include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methyl nadic anhydride (Methyl). Nadic anhydride), hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, diaminodiphenylmethane, Diethylenetriamine, triethylenetetramine, diaminodiphenylphosphonium, isophoronediamine, dicyandiamide, tetraethylenepentamine, dimethylbenzylamine, ketimine a compound, a polyamidamine resin synthesized from a 2-mer of linolenic acid and ethylenediamine, a bisphenol, a phenol (phenol, an alkyl-substituted phenol, a naphthol, an alkyl group) Polycondensation of naphthol, dihydroxybenzene, dihydroxynaphthalene, etc. with various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylols, or dimethoxy a condensate of a methylbiphenyl with a naphthol or a phenol, a bisphenol and a modified substance thereof, an imidazole, a boron trifluoride-amine complex, a guanidine derivative .

Specific examples of the alicyclic carboxylic anhydride include 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and "4-methylhexa". Hydrophthalic anhydride/hexahydrophthalic anhydride=70/30”, 4-methylhexahydrophthalic anhydride, “methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride/bicyclo[2.2.1]g Alkane-2,3-dicarboxylic anhydride" and the like.

In the curing agent (H), since the light resistance of the cured product obtained by curing the modified resin composition of the present embodiment tends to be improved, the alicyclic acid anhydride has two or more molecules in one molecule. Preferably, the functional group of the acid anhydride is a polyoxyl oxide as a substituent, and methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3- Dicarboxylic anhydride is more preferred. These hardeners may be used alone or in combination of two or more.

The amount of the curing agent (H) to be added can be determined by a mixing index as a ratio of the epoxy group and the cyclic ether group contained in the alkoxy siloxane compound. The mixed indicator is expressed by the following formula (9):

Mixed indicator ζ=(ζf)/(ζk) ...(9)

(In the formula (9), ζf represents the amount (mol number) of the hardener (H), and ζk represents the amount of the cyclic ether group contained in the epoxy resin and the alkoxy siloxane compound (mol number) )).

The mixing index 为 is preferably in the range of 0.1 or more and 1.5 or less, more preferably 0.2 or more and 1.3 or less, and more preferably 0.3 or more and 1.3 or less. When the mixing index is less than 0.1, the hardening speed is lowered. When it exceeds 1.5, the moisture resistance of the cured product is deteriorated.

The hardening accelerator (I) is a hardening catalyst used for the purpose of promoting a hardening reaction. As the hardening accelerator (I), a tertiary amine and a salt thereof are preferred. Specific examples of the hardening accelerator include the following:

Grade 3 amines: benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, triethanolamine, etc.; imidazoles: 2-methylimidazole, 2-n-heptyl imidazole, 2-n-undecylalkyl imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyano) Ethyl)-2-n-undecylalkylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methyl Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2- Phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylalkyl imidazolium salt 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium terephthalate Salt, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-S-three 2,4-Diamino-6-(2'-n-undecylalkylimidazolyl)ethyl-s-three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-three , an isomeric cyanuric acid addition product of 2-methylimidazole, an isomeric cyanuric acid addition product of 2-phenylimidazole, etc.; an organophosphorus compound: diphenylphosphine, triphenylphosphine, phosphorous acid Phenyl esters; 4 grades of phosphonium salts: benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, bromination N-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium 0,0-diethyldithiophosphate (tetra -n-butyl phosphonium 0,0-diethyl phosphorodithionate), tetra-n-butyl benzyl benzotriazole, tetra-n-butyl fluorene tetrafluoroborate, tetra-n-butyl sulfonium tetraphenylborate, tetraphenyl tetraphenylborate Hey.

Diazabicycloolefins: 1,8-diazabicyclo[5.4.0]undecene-7 (1,8-Diazabicyclo[5.4.0]undec-7-ene) and organic acid salts thereof; Organometallic compounds: zinc octoate, tin octoate, acetonitrile aluminum complex, etc.; grade 4 ammonium salts: tetraethylammonium bromide, tetra-n-butylammonium bromide, etc.; metal halide: boron trifluoride, A boron compound such as triphenyl borate; zinc chloride, stannic chloride, or the like.

The amount of the curing accelerator (I) to be added can be determined from the following mixing index η as a ratio of the mass of the epoxy resin and the alkoxy siloxane compound. The mixed index η is expressed by the following formula (10):

Mixed index η = (ηg) / (ηk) ... (10)

(In the formula (10), ηg represents the mass (g) of the hardening accelerator (I), and ηk represents the mass (g) of the epoxy resin and the alkoxy siloxane compound).

The mixing index η is preferably in the range of 0.01 or more and 5 or less, more preferably 0.05 or more and 3 or less, and more preferably 0.1 or more and 1 or less. When the mixing index η is less than 0.01, the hardening does not proceed well, and when it exceeds 5, the cured product is colored.

A photosensitive resin composition obtained by adding a photoacid generator (J) to the modified resin composition of the present embodiment will be described.

The photoacid generator (J) which can be used in the present embodiment is not particularly limited as long as it is a compound which emits acid upon irradiation with light and starts to polymerize, and a phosphonium salt is preferred. Specifically, for example, a diazonium salt, a sulfonium salt, a sulfonium salt or the like may be mentioned, and the cation portion is an aromatic diazonium, an aromatic hydrazine, an aromatic hydrazine, and the anion portion is BF. ₄ ^- , PF ₆ ^- , SbF ₆ ^- , [Bx ₄ ] ^- (here, X is a phenyl group substituted with at least two fluorine atoms or a trifluoromethyl group), and the like. Representative examples of the photoacid generator are shown below.

Here, R, R' and R'' represent an arbitrary substituent.

More specific examples include, for example, an aryldiazonium salt of boron tetrafluoride, a triarylsulfonium salt of phosphorus hexafluoride, a diarylsulfonium salt of phosphorus hexafluoride, and a triarylsulfonium salt of antimony hexafluoride. , a diarylsulfonium salt of ruthenium hexafluoride, a tris-methylphenyl phosphonium salt of arsenic hexafluoride, a tris-methylphenyl phosphonium salt of antimony tetrafluoride, a quinone (pentafluorophenyl) a triarylsulfonium borate salt, a diarylsulfonium salt of ruthenium (pentafluorophenyl)borate, a mixture of an aluminum acetoacetate and an o-nitrobenzyl decyl ether, a phenylthiopyridinium salt, a phosphorus hexafluoride Propadiene-iron complex and the like. Commercial products such as CD-1012 (manufactured by SARTOMER Co., Ltd.), PCI-019, PCI-021 (manufactured by Nippon Kayaku Co., Ltd.), OPTMER SP-150, and OPTMER SP-170 (made by ADEKA Co., Ltd.) ), UVI-6990, UVI-6974 (manufactured by The Dow Chemical Company), CPI-100P, CPI-100A, CPI-100L (manufactured by San-apro Co., Ltd.), TEPBI-S (Japan Catalyst) (Rhodorsil 2074 (manufactured by Rhodia Co., Ltd.), etc., may be used alone or in combination of two or more. Among the above, from the viewpoint of less coloration of the cured product, the onium salt and the onium salt are preferred, and when the hardenability is considered, the onium salt is particularly preferred.

Further, in the above-mentioned photosensitive resin composition, a vinyl ether compound may be blended in accordance with the demand. Examples of such a compound include vinyl ether compounds which do not contain a hydroxyl group. Specific examples thereof include ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether, Pentaerythritol tetravinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, and the like.

Further, the modified resin composition of the present embodiment may be blended with a conventional cationic polymerization catalyst. A series of cationic polymerization catalysts which can be used are, for example, a Lewis acid catalyst represented by BF ₃ ‧ amine complex, PF ₅ , BF ₃ , AsF ₅ , SbF ₅ or the like; a phosphonium salt or a 4-grade ammonium salt, Bismuth salt, benzyl ammonium salt, benzyl pyridinium salt, benzyl sulfonium salt, hydrazine a thermosetting cationic polymerization catalyst represented by a hydrazinium salt, a carboxylic acid ester, a sulfonate or an amine quinone; a diaryl sulfonium hexafluorophosphate or a bis(dodecylalkyl) hexafluoroantimonate An ultraviolet curable cationic polymerization catalyst represented by hydrazine or the like. Among the above, it is preferred to use a thermosetting cationic polymerization catalyst because a transparent cured product having a high glass transition temperature and excellent solder heat resistance or adhesion is obtained. The commercially available product of the thermosetting cationic polymerization catalyst is, for example, SI-100L or SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) of a phosphonium salt-based cationic polymerization catalyst; CP-66, CP-77; (above, Asahi Chemical Industrial Co., Ltd.).

The modified resin composition obtained in the present embodiment may contain a modifier as needed from the viewpoint of imparting flexibility to the cured product and improving peeling adhesion. The modifier to be used may be a polyol having two or more hydroxyl groups in one molecule, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, or the like. 1,3-propanediol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,2-butanediol, 1,4-butanediol, neopentyl glycol, glycerol, pentaerythritol, trimethylolpropane, 1, An aliphatic polyhydric alcohol such as 2,4-butanetriol or a polycarbonate diol or a polyoxyl group having a sterol group at the end is preferred. These modifiers may be used singly or in combination of two or more.

In the modified resin composition of the present embodiment, various decane coupling agents can be used for the purpose of improving physical properties such as adhesion. At this time, the residual alkoxy group in the modified resin composition must be 5% or less. When the residual alkoxy group exceeds 5%, the crack resistance or adhesion of the cured product obtained by hardening the composition during thermal cycling becomes insufficient.

Examples of the decane coupling agent suitable for the modified resin composition of the present embodiment include 3-glycidyloxypropyltrimethoxydecane, 3-glycidyloxypropyltriethoxydecane, and 3- Glycidyloxypropylmethyldimethoxydecane, 3-glycidyloxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3 - glycidyloxypropyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl three Ethoxy decane, 3-aminopropyl trimethoxy decane, 3-aminopropyl triethoxy decane, 3-aminopropyl methyl diethoxy decane, 3-aminopropyl dimethyl Ethoxy decane, N-(2-aminoethyl)aminomethyltrimethoxydecane, N-(2-aminoethyl)(3-aminopropyl)trimethoxynonane, N- (2-Aminoethyl)(3-aminopropyl)triethoxydecane, N-(2-aminoethyl)(3-aminopropyl)methyldimethoxydecane, N- [N'-(2-Aminoethyl)(2-aminoethyl)](3-aminopropyl)trimethoxynonane, 2-(2-aminoethyl)thioethyltriethoxy Base decane , 2-(2-Aminoethyl)thioethylmethyldiethoxydecane, 3-(N-phenylamino)propyltrimethoxydecane, 3-(N-cyclohexylamino)propane Trimethoxy decane, (N-phenylaminomethyl)trimethoxynonane, (N-phenylaminomethyl)methyldimethoxydecane, (N-cyclohexylaminomethyl) III Ethoxy decane, (N-cyclohexylaminomethyl)methyldiethoxy decane, piperazine Methyltrimethoxydecane, piperazine Methyl triethoxy decane, 3-piper Propyltrimethoxydecane, 3-piperidyl Propyl propyl dimethoxy decane, 3-ureidopropyl triethoxy decane, thiomethyl methyl trimethoxy decane, thiomethyl methyl triethoxy decane, thiomethyl methyl group Dimethoxy decane, thiomethylmethyldiethoxy decane, 3-hydrothiopropyltrimethoxydecane, 3-hydrothiopropyltriethoxydecane, 3-hydrogenthio Propylmethyldimethoxydecane, 3-hydrothiopropylmethyldiethoxydecane, 3-(trimethoxydecyl)propyl succinic anhydride, 3-(triethoxydecyl)propyl Succinic anhydride, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy Base decane, propyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, cyclohexyl trimethoxy decane, cyclohexyl triethoxy decane, cyclopentyl trimethoxy decane, ring Pentyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, methyl vinyl Oxydecane, methylvinyl diethoxy decane, methyl phenyl dimethoxy decane, methyl phenyl diethoxy decane, methyl cyclohexyl dimethoxy decane, methyl cyclohexyl di Oxydecane, methylcyclopentyldimethoxydecane, methylcyclopentyldiethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropene oxime Oxypropyltrimethoxydecane, 3-methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, and the like. Partial condensates of such decane coupling agents can also be used.

Further, in the modified resin composition of the present embodiment, an inorganic filler, a coloring agent, a leveling agent, a lubricant, or the like may be appropriately added in accordance with the purpose, without departing from the scope of the function. Surfactant, antioxidant, light stabilizer, and the like. In addition, it can be blended with other plasticizers, flame retardants, stabilizers, antistatic agents, impact enhancers, foaming agents, antibacterial, antifungal agents, conductive fillers, antifogging agents, etc., which are generally used as resin additives. Crosslinking agent, etc.

As the inorganic filler, for example, cerium oxide (melt-crushed cerium oxide, crystal-crushed cerium oxide, spherical cerium oxide, fumed silica, colloidal cerium oxide) Colloidal silica), tantalum dioxide, etc., tantalum carbide, tantalum nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesia, zirconia, Aluminum hydroxide, magnesium hydroxide, calcium citrate, aluminum citrate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, and the like. In particular, cerium oxide, calcium carbonate, aluminum oxide, aluminum hydroxide, calcium citrate or the like is preferred, and in addition, when the physical properties of the cured product are considered, cerium oxide is more preferable. These inorganic fillers may be used singly or in combination of two or more.

The coloring agent is not particularly limited as long as it is used for the purpose of coloring, and examples thereof include phthalocyanine, azo, disazo, quinacridone, anthraquinone, and scutellaria. Ketone (Flavanthrone), perinone (perinone), bismuth, two (dioxazine), condensed azo, azomethine are various organic pigments; titanium oxide, lead sulfate, chrome yellow, zinc yellow, chrome vermilion, red iron oxide (Bengala), cobalt violet, Prussia Inorganic pigments such as blue, ultramarine blue, carbon black, chrome green, chromium oxide, and cobalt green. These coloring agents may be used singly or in combination of two or more.

The coating agent is not particularly limited, and examples thereof include an oligomeric polymer having a molecular weight of 4,000 to 12,000 composed of an acrylate such as ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate; and an epoxidized soybean fatty acid; Epoxidized rosin alcohol, hydrogenated castor oil, titanium coupling agent, and the like. These leveling agents may be used singly or in combination of two or more.

The lubricant is not particularly limited, and examples thereof include hydrocarbon-based lubricants such as solid paraffin, microcrystalline wax, and polyethylene wax; and advanced lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Fatty acid-based lubricants; higher fatty acid amide-based lubricants such as stearylamine, palm amide, linoleamide, methylenebisstearylamine, ethyl bis-stearylamine; hardened castor oil, hard fat Higher fatty acid ester-based lubricants such as butyl acrylate, ethylene glycol monostearate, pentaerythritol (mono, di-, tri- or tetra) stearate; cetyl alcohol, stearyl alcohol, poly Alcohol-based lubricants such as ethylene glycol and polyglycerin; magnesium, calcium, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid, naphthenic acid, etc. Metal soaps of metal salts such as cadmium, bismuth, zinc, lead, etc.; natural waxes such as carnauba wax, candelilla wax, beeswax, montan wax, and the like. These lubricants may be used singly or in combination of two or more.

The surfactant is an amphiphilic substance having a hydrophilic group having no affinity for a solvent in its molecule and an affinity group (usually water-based) having affinity for a solvent. The type of the surfactant is not particularly limited, and examples thereof include a polyoxyn surfactant and a fluorine-based surfactant. The surfactant may be used singly or in combination of two or more.

The antioxidant is not particularly limited, and examples thereof include an organic phosphorus-based antioxidant such as triphenyl phosphate or phenyl isodecyl phosphate; and an organic sulfur-based antioxidant such as distearyl-3,3′-thiodipropionate. a phenolic antioxidant such as 2,6-di-t-butyl-p-cresol or the like.

The light stabilizer is not particularly limited, and examples thereof include a benzotriazole system, a benzophenone system, a salicylate system, a cyanoacrylate system, a nickel system, and a trisole. A UV absorber, or a hindered amine light stabilizer.

The modified resin composition of the present embodiment or the oxycene compound (D), the phosphor (E), the conductive metal powder (F), and the insulating material are blended with the modified resin composition of the present embodiment. Powder (G), epoxy resin (A'), hardener (H) and hardening accelerator (I), or photoacid generator (J), and furthermore, the necessary cationic polymerization catalyst, modifier, A curable resin composition obtained by using a vinyl ether compound, an organic resin other than the epoxy resin (A'), and a decane coupling agent can be obtained by a conventional method. Among them, a curing method by heating, a curing method by irradiation with light, or a curing method of an epoxy resin generally used can be exemplified as a method suitable for the present embodiment. The temperature at the time of curing by heating is not particularly limited as long as it varies depending on the epoxy resin or the curing agent to be used, but it is usually in the range of 20 to 200 °C.

On the other hand, the light used for curing by irradiation with light is preferably ultraviolet light or visible light, and ultraviolet light is more preferable. The source of light generation may, for example, be a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a UV lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a helium ion laser, a cadmium telluride. Laser, 氦氖 laser, 氪 ion laser, various semiconductor lasers, YAG laser, excimer laser, light-emitting diodes, CRT light source, plasma light source and other light sources.

The hardening reaction may be carried out in the air, or may be carried out in an inert gas atmosphere such as nitrogen, helium or argon as necessary.

In the modified resin composition of the present embodiment, for example, a) the modified resin composition of the present embodiment, and b) the oxetane compound (D) is added to the modified resin composition of the present embodiment. a resin composition, c) a fluorescent resin composition obtained by adding a phosphor (E) to the modified resin composition of the embodiment, or a hardener (H) added to the above a) to c) The resin composition is excellent in light-shielding material which is excellent in adhesion to an element or a package material, does not cause cracking, and has a small decrease in brightness over a long period of time; It is a raw material for a curable resin composition which is excellent in dimensional stability and which is excellent in dimensional stability after being cured, and is used for producing an optical lens having light resistance. Moreover, the curable resin composition obtained by further adding the curing accelerator (I) to the resin composition obtained by adding the curing agent (H) to the above a) to c), or in the above a) to c) A photosensitive resin composition obtained by adding a photo-acid generator (J) may be used as the above-mentioned light-emitting element sealing material, or a curable resin composition for producing an optical lens, or a photosensitive resin composition.

By using a curable resin composition containing the modified resin composition of the present embodiment, the light-emitting element is sealed, whereby a light-emitting component such as a light-emitting diode can be manufactured. In addition, as the light-emitting diode and/or the optical lens described above, for example, a backlight such as a liquid crystal display device, illumination, various light sources such as a sensor, a printer, a copy machine, or the like, and a vehicle light source can be suitably used. A semiconductor device such as a signal lamp, a display lamp, a display device, a light source of a planar illuminator ^{, a} display, a decoration, and various lamps.

The light-emitting wavelength of the light-emitting element sealed by the sealing material for a light-emitting element comprising the curable resin composition containing the modified resin composition of the present embodiment is from infrared to red, green, blue, purple, and ultraviolet. It can be used in a wide range of applications, and it is possible to use light having a wavelength of 250 nm to 550 nm which is deteriorated due to insufficient light resistance of the sealing material. Therefore, a white light-emitting diode having a long life, high energy efficiency, and high color reproducibility can be obtained. Here, the emission wavelength refers to the wavelength of the main emission peak.

Specific examples of the light-emitting element to be used include a light-emitting element formed by laminating a semiconductor material on a substrate. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, SiC, and the like.

Examples of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. A buffer layer may also be formed between the substrate and the semiconductor material as necessary. Examples of such a buffer layer include GaN, AlN, and the like.

The method of laminating the semiconductor material on the substrate is not particularly limited, and for example, an MOCVD method, an HDVPE method, a liquid phase growth method, or the like can be used.

The structure of the light-emitting element may, for example, be MIS bonding, PN bonding, homojunction of PIN bonding, heterojunction, double heterostructure, or the like. Single or multiple multi-quantum well structures can also be fabricated.

A light-emitting element can be produced by sealing a light-emitting element using a light-emitting element sealing material comprising a curable resin composition containing the modified resin composition of the present embodiment. In this case, the light-emitting element may be sealed only by the light-emitting element sealing material, but it may be sealed by another sealing material. In the case of using another sealing material, after sealing with a light-emitting element sealing material obtained by using the modified resin composition obtained in the present embodiment, the sealing material may be sealed with another sealing material, or may be performed with another sealing material. After the sealing, the periphery of the light-emitting element sealing material obtained by using the modified resin composition obtained in the present embodiment was sealed. Examples of the other sealing material include an epoxy resin, a polyoxymethylene resin, an acrylic resin, a urea resin, a quinone imine resin, and glass.

A method of sealing a light-emitting element by using a light-emitting element sealing material obtained by using the modified resin composition of the present embodiment, for example, a light-emitting element sealing material is preliminarily injected into a mold frame, and a light-emitting element is fixed in the mold. A method of hardening a lead frame or the like, a method of injecting a light-emitting element sealing material into a mold frame into which a light-emitting element has been inserted, and a method of hardening. In this case, a method of injecting the light-emitting element sealing material may be, for example, injection molding, transfer molding, or injection molding. Further, other sealing methods include a method in which a light-emitting element sealing material is dropped onto a light-emitting element, and is applied by stencil printing, screen printing, or a barrier mask to be hardened; In a cup or the like of a light-emitting element, a method of injecting a light-emitting element sealing material by a dispenser or the like and hardening it.

The curable resin composition containing the modified resin composition of the present embodiment can also be used as a passivation film for fixing a light-emitting element to a die bonding material or a die bonding material or a light-emitting element. , a package substrate. The shape of the sealing portion may, for example, be a lens shape of a projectile type, a plate shape, a film shape or the like.

The light-emitting diode obtained by using the modified resin composition of the present embodiment can be improved in performance according to a conventional method. The method for improving the performance includes, for example, a method of providing a light reflecting layer or a light collecting layer on the back surface of the light emitting element, a method of forming a complementary coloring portion on the bottom portion, and providing light having a shorter wavelength than the main light emitting peak on the light emitting element. a layer method, a method of molding a hard material after sealing a light-emitting element, a method of inserting a light-emitting diode into a through-hole, and fixing the light-emitting element by flip chip connection or the like A method of connecting a lead member or the like and extracting light from the substrate direction.

The light-emitting diode obtained by using the modified resin composition of the present embodiment is, for example, a backlight for a liquid crystal display or the like, a light source such as a sensor, a printer, a copying machine, a light source for a vehicle, a light source for a vehicle, and a signal lamp. Light-emitting parts such as display lamps, display devices, light sources for planar illuminators, displays, decorations, and various lights.

On the other hand, a curable resin composition obtained by adding a curing agent (H) to a fluorescent resin composition obtained by adding a phosphor (E) to the modified resin composition of the present embodiment, In addition, the photosensitive resin composition obtained by adding the photoacid generator (J) to the modified resin composition of the present embodiment is cured, whereby a light-storing material having excellent luminosity can be produced.

Next, the light storage material will be described. In general, a light-storing material is excited by light, such as sunlight, a fluorescent lamp, or ultraviolet light, and converts energy to emit light. Even if the excitation due to the light stimulation is stopped, the light is gradually released. A material that lasts for a long time.

The use of the light-storing material using the modified resin composition of the present embodiment is not particularly limited, and examples thereof include nighttime display, disaster prevention, safety signs, clocks, wallpapers, electric switches, billboards, and clothing. Reflectors such as shoes, bicycles, locomotives, adhesive tapes, fishing hooks, fishing gears, sports accessories, accessories, and toys.

In addition, for example, the conductive resin composition obtained by adding the conductive metal powder (F) to the modified resin composition of the present embodiment is excellent in fluidity, conductivity, and adhesion, and suppresses voids. In the present embodiment, the insulating resin composition obtained by adding the insulating powder (G) to the modified resin composition of the present embodiment, f) is used in the present embodiment. An insulating resin composition obtained by adding an epoxy resin (A') and an insulating powder (G) to the morphologically modified resin composition, or a curing agent (H) added to the above d) to f) The resin composition is used as a raw material of an insulating resin composition which is excellent in insulating properties and adhesion and which has curability in suppressing occurrence of voids. Further, in the resin composition obtained by adding the curing agent (H) to the above d) to f), a curing resin composition obtained by further adding a curing accelerator (I) or the above-mentioned d) to f) The photosensitive resin composition obtained by adding the photoacid generator (J) may be used as a curable conductive resin composition or a curable insulating resin composition.

The use of the conductive resin composition using the modified resin composition of the present embodiment is not particularly limited. For example, it may be replaced with a semiconductor element and a peripheral member, a conductor wiring, or a surface assembly. Welding; insulators, quartz crystal vibrators (quartz crystal units), AC transformers, switchgear, etc., injection molding and circuit units, packaging of various parts, ICs, LEDs, semiconductors, generators, motors, etc. Coil impregnation, printer wiring board, transparent substrate instead of glass, medium-sized insulators, coils, connectors, terminals, and other electronic components, and adhesives or die bonding agents used in wiring; conductivity Coatings, electrodes, printed circuits, conductive resins, etc.

The use of the insulating resin composition using the modified resin composition of the present embodiment is not particularly limited, and examples thereof include mounting of a semiconductor chip in a semiconductor device; A wafer (IC, LSI, or the like) is bonded to a die bond or an adhesive such as a ceramic case, a lead frame, or a substrate. Furthermore, it can be applied to an interposer of a semiconductor package, a printed circuit board, a display, a solar cell, a generator, a substrate for a motor, a substrate for an automobile, or the like, which is required to have a highly exothermic insulating material.

Further, for example, a) a resin composition of the present embodiment, b) a resin composition obtained by adding an oxetane compound (D) to the modified resin composition of the embodiment, and c) A fluorescent resin composition obtained by adding a phosphor (E) to a modified resin composition of the form, and adding a curing agent (H) and a curing accelerator (I) to the obtained a) to c) Further, the curable resin composition or the photosensitive resin composition obtained by further adding the photoacid generator (J) to the above a) to c), for example, d) the modified resin composition of the present embodiment A conductive resin composition obtained by adding a conductive metal powder (F) to the middle, and e) an insulating resin composition obtained by adding an insulating powder (G) to the modified resin composition of the embodiment, and f) An insulating resin composition obtained by adding an epoxy resin (A') and an insulating powder (G) to the modified resin composition of the present embodiment, and adding a hardener (H) to the obtained d) to f) a curable resin composition obtained by adding a curing agent (I) or a photosensitive resin composition obtained by further adding a photoacid generator (J) to the above d) to f), It is not susceptible to polymerization inhibition by oxygen, and can be suitably used as a coating agent.

The coating agent in the present embodiment is not particularly limited as long as it forms a coating film on the surface of the material, and the main purpose of use is as follows, and the coating agent may be used as necessary. It is blended with pigments or pigments and used as a coating or ink.

(1) Protection of coating or substrate, durability and aesthetics (protection of UV, infrared, oxidation, corrosion, damage, dust, dirt, temperature, humidity, etc.)

(2) Coating or imparting luster to the substrate

(3) Painting or water-repellent processing of the substrate

(4) Anti-skid processing of flooring

(5) Sealing and insulation of electronic parts

It is generally considered that although the polymerization of the epoxy compound starts quickly, the subsequent polymerization reaction is not fast. However, the present inventors have unexpectedly found that by blending an oxetane compound in the resin composition having an epoxy group, the polymerization rate can be accelerated, and a photosensitive resin excellent in photocurability and adhesion can be obtained. Composition. Further, by selecting an oxetane compound, the viscosity of the resin composition can be lowered.

The viscosity of the photosensitive resin composition of the present embodiment is preferably 1000 Pa ‧ or less, more preferably 0.05 or more and 50 Pa ‧ or less, and more preferably 0.2 or more and 30 Pa ‧ or less in terms of fluidity. . When the viscosity of the photosensitive resin composition exceeds 1000 Pa ‧ , the fluidity may be impaired, and it may be unsuitable.

The coating agent of the present embodiment is applied by a conventional method, and secondly, a coating film can be formed by curing. At this time, the coating method includes brush coating, roll coating, blow coating, bar coater, roll coater, burn coating, dip coating, electrodeposition coating, electrostatic coating Coating techniques such as powder coating, evaporation, electroplating, inkjet, laser printing, rotary printing, gravure printing, screen printing, etc. On the other hand, the method of forming a coating film is by heating The method of hardening or the method of hardening by irradiation of light is applicable.

The application of the coating agent and the coating film of the present embodiment is not particularly limited. For example, it can be used as a coating agent (coating, resin, plastic, metal, steel pipe, automobile, building, optical fiber, etc.), optical disk. Coating or subsequent printing (DVD, CD, Blu-ray Disc, etc.), ink (inkjet printing, gravure printing, flexographic printing, photoresist for printed wiring boards, UV printing applications, etc.), printing plate material (PS plate, photosensitive) Resin, stencil, etc.), photoresist (resist for semiconductors, resist for printed wiring boards, resist for photofabrication, etc.), printed wiring boards, and various electronic products including IC and LSI Pattern formation of parts, color filter forming material for liquid crystal or PDP display, sealing material for liquid crystal or organic EL, semiconductor ‧ LED peripheral material (sealing material, lens material, base material, die bonding material, wafer coating material) , laminates, optical fibers, optical waveguides, filters, adhesives for electronic parts, coating materials, sealing materials, insulating materials, photoresists, encap materials, potting materials, optical discs Light transmission layer or interlayer insulation Coatings such as layers, printed wiring boards, laminates, light guides, anti-reflective films, etc. (anti-corrosion coatings, maintenance, ship coating, corrosion resistant linings, automotive, home appliance primers, beverages, beer cans, exterior coatings) Paint, extrusion tube coating, general anti-corrosion coating, maintenance coating, woodworking products, automotive electroplating primer, other industrial electroplating coating, beverage, beer can inner surface painting, coil coating (Coil Coating), drum (drum), inner surface coating, woodworking coating, acid lining, wire enamel, insulating coating, automotive primer, beauty and anti-corrosion coating of various metal products, in pipeline Exterior coating, electrical parts, insulation coating, etc., composite materials (chemical plant pipelines, tanks, aircraft materials, automotive materials, various sporting goods, carbon fiber composites, aromatic polyamides (aramid) Fiber composite materials, etc., civil construction materials (floor materials, paving materials, film, non-slip and thin layer paving, concrete joints, ‧ heightening works, anchor filling, concrete concrete joints, tile joints, concrete Structural crack repair Grouting of the base, coating, corrosion protection of the waterway or sewer facilities, waterproof coating, corrosion-resistant laminated lining of storage tanks, anti-corrosion coating of iron structures, clay coating on the outer wall of buildings, etc. Metal ‧ glass ‧ ceramic ‧ cement concrete ‧ wood ‧ plastic equivalent or adhesive of different materials, automotive, railway vehicles, aircraft assembly adhesives, prefabricated composite sheet manufacturing adhesives, etc.: contains one liquid type, two Liquid type, sheet type), aircraft, car, plastic forming tool (pressure mold, stretched die, matched die), resin mold, vacuum forming, blow molding mold, main Model (master model), pattern for castings, laminated tools, various inspection tools, etc.), modifiers, stabilizers (resin processing of fibers, stabilizers for polyvinyl chloride, additives for synthetic rubber, etc.) . Among them, it is useful for the use of a coating agent, a coating material, an adhesive, and a photo-forming resin.

[Examples]

The examples of the present embodiment will be specifically described below, but the present embodiment is not limited to the following examples as long as it does not exceed the scope of the gist.

The evaluation of the physical properties in Examples 1 to 26 and Comparative Examples 1 to 9 was carried out as follows.

<epoxy equivalent (WPE)>

It is measured according to "JIS K 7236:2001 (method for calculating epoxy equivalent of epoxy resin)".

<viscosity>

The measurement was carried out under the following conditions.

Rotary E-shaped viscometer: Dongji Industry Co., Ltd., "TV-22"

Rotator: 3° × R14 (other rotators can be selected if necessary)

Measuring temperature: 25 ° C

Sample size: 0.4ml

<Calculation of mixing index α>

The mixing index α is calculated by the following general formula (2).

Mixed index α=(αc)/(αb) (2)

here,

Αb: (B) In the general formula (1), n = 1 or 2 and at least one cyclic ether group as the mol% of the alkoxydecane compound of R ¹

αc: (C) in the general formula (1), n = 1 or 2 and having at least one aromatic organic group as an alkoxy compound of silicon oxy mol alkoxy of ^1% R.

<Calculation of Mixed Index β>

The mixing index β is calculated by the following general formula (3).

Mixed index β={(βn2)/(βn0+βn1)} (3)

here,

Nn2: mol% of alkoxydecane compound of n=2 in the general formula (1)

Nn0: mol% of alkoxydecane compound of the formula (1), n=0

Nn1: mol% of the alkoxydecane compound of n=1 in the general formula (1),

But satisfy 0≦{(βn0)/(βn0+βn1+βn2)}≦0.1

<Calculation of Mixed Index γ>

The mixing index γ is calculated by the following general formula (4).

Mixed index γ=(γa)/(γs) (4)

here,

Γa: the mass of the epoxy resin (g),

Γs: the mass (g) of the alkoxydecane compound of the formula (1), n = 0 to 2.

<Calculation of mixing index δ>

The mixing index δ is calculated by the following general formula (5).

Mixed index δ=(δe)/(δs) (5)

here,

Δe: the amount of addition of the hydrolysis condensation catalyst (mol number),

Δs: the amount (mol number) of (OR ² ) in the general formula (1).

<Calculation of mixing index ε>

The mixing index ε is calculated by the following general formula (6).

Mixed index ε=(εw)/(εs) (6)

here,

Εw: the amount of water added (mol number),

Εs: the amount (mol number) of (OR ² ) in the general formula (1).

<Calculation of Mixed Indicators>

The mixed index ζ is calculated by the following general formula (7).

Mixed indicator ζ=(ζf)/(ζk) (7)

here,

Ζf: the amount of hardener added (mol number),

Ζk: The amount (mol number) of the cyclic ether group contained in the epoxy resin and the alkoxydecane compound.

<Calculation of mixed index η>

The mixing index η is calculated by the following general formula (8).

Mixed index η = (ηg) / (ηk) × 100 (8)

here,

Ηg: the mass (g) of the hardening accelerator,

Ηk: mass (g) of epoxy resin and alkoxydecane compound.

<Calculation of preservation stability index θ, and preservation stability of resin composition>

The storage stability in the resin composition is evaluated by the storage stability index θ shown by the following general formula (9).

Preservation stability index θ=(preservation viscosity)/(starting viscosity) (9)

The container of the resin composition immediately after the production was sealed, and the temperature was adjusted at 25 ° C for 2 hours, and then the viscosity at 25 ° C was measured, and this was referred to as "initial viscosity".

Further, the container in which the resin composition was placed was sealed, and then stored in an incubator at 25 ° C for 2 weeks. After storage, the viscosity at 25 ° C was measured, and this was taken as "preservation viscosity".

When the resin composition has fluidity (viscosity of 1000 Pa ‧ or less) and the storage stability index θ is 4 or less, it is judged to have storage stability.

<H-NMR measurement of intermediates>

The condensation rate of the intermediate is determined by H-NMR measurement of the sample solution (intermediate) taken after the completion of the refluxing step, according to the following procedure.

(1) In the sample bottle, 30 mg of the sample solution after the completion of the refluxing step was weighed, and chloroform-d (manufactured by Wako Pure Chemical Industries, Ltd.) was added to adjust to 1 g.

(2) The solution of the above (1) was transferred to an NMR tube having a diameter of 5 mmφ, and H-NMR was measured under the following conditions.

Fourier transform nuclear magnetic resonance device: "α-400 type" manufactured by Nippon Electronics Co., Ltd.

Nuclear species: H

Cumulative number: 200 times

<Calculation of the amount of residual alkoxy groups in the modified resin composition: H-NMR measurement>

The measurement of H-NMR was carried out by the following procedure.

(1) In the sample bottle, 10 mg of the modified resin composition and 20 mg of the internal standard substance (1,1,2,2-tetrabromoethane; Tokyo Chemical Industry Co., Ltd.) were weighed, and chloroform-d (Wako Pure Chemicals) was added. Industrial (stock) company) 970mg dissolution modulation.

(2) The solution of the above (1) was transferred to an NMR tube having a diameter of 5 mmφ, and H-NMR was measured under the following conditions.

Fourier transform nuclear magnetic resonance device: "α-400 type" manufactured by Nippon Denshi Co., Ltd.

Nuclear species: H

Cumulative number: 200 times

From the above measurement results, the amount (%) of residual alkoxy groups was calculated in the following procedure.

(3) From the H-NMR chart, the area value of the peak derived from the residual alkoxy group was calculated.

(4) From the H-NMR chart, the area value of the peak derived from the internal standard substance was calculated.

(5) The above (3) and (4) were read, and the area value was substituted into the following formula to calculate the amount (%) of the residual alkoxy group.

The amount of residual alkoxy group (%) = (area value derived from the peak of the residual alkoxy group) / (area value derived from the peak of the internal standard substance) × 100

Here, the area value of the peak derived from the residual alkoxy group is calculated by the following method.

<When the peak derived from the residual alkoxy group is a single peak>

The area of the portion enclosed by the baseline and the peak is taken as the area value derived from the peak of the residual alkoxy group.

Depending on the type of residual alkoxy group, the peak derived from the residual alkoxy group may be present in plural. In this case, the area value derived from the peak of the residual alkoxy group in the present embodiment is the sum of the areas of the plurality of peaks derived from the residual alkoxy group.

<When the peak derived from the residual alkoxy group is a composite peak>

Starting from the point where the slope between the peak derived from the residual alkoxy group and the peak derived from the residual alkoxy group is 0, the wiring is made to minimize the area of the peak derived from the residual alkoxy group. The area value of the portion surrounded by the wiring and the peak derived from the residual alkoxy group is taken as the area value derived from the peak of the residual alkoxy group.

Here, when the peak derived from the residual alkoxy group is the main component of the peak, and there is no point where the slope is 0 between the peak derived from the residual alkoxy group and the peak derived from the residual alkoxy group The peak derived from the residual alkoxy group is not regarded as a peak, and the peak is all regarded as a peak derived from the residual alkoxy group. Further, when the peak other than the residual alkoxy group is the main component of the peak, and the peak derived from the residual alkoxy group and the peak derived from the residual alkoxy group do not have a slope of 0, the source The peak from the residual alkoxy group is not considered to be a peak.

<Light resistance test of hardened material>

The light resistance of the cured product was evaluated by the following method.

(1) The cured product prepared by the method described later was hardened with a solution to prepare a cured product of 20 mm × 10 mm × 3 mm in thickness.

(2) The cured product was covered with a black mask of 25 mm × 15 mm × 1.2 mm thick having a hole having a diameter of 5.5 mm, and was used as a sample for light resistance test.

(3) A preparation device was used to irradiate the UV light from the UV irradiation device ("Spot Cure SP7-250DB" manufactured by Ushio Electric Co., Ltd.) to the above-mentioned sample in an incubator set to a constant temperature of 50 °C via an optical fiber.

(4) The above sample was placed in an incubator at 50 ° C in a state where the black mask was placed on the upper surface.

(5) UV light of 2 W/cm ^{2 was} irradiated from the upper portion of the black mask for 96 hours so that the UV light was irradiated to the hole having a diameter of 5.5 mm.

(6) A spectroscopic color meter ("SD5000" manufactured by Nippon Denshoku Industries Co., Ltd.) having a diameter of 10 mm was used to measure a sample irradiated with UV.

(7) Yellowness (YI) is determined in accordance with "ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics".

When this YI is 13 or less, it is judged that it has light resistance.

<Cold and thermal shock test of hardened material>

The thermal shock resistance of the cured product was evaluated in the following manner.

(1) A substrate and a germanium wafer as shown below are prepared.

(1-1) Substrate: "AMODEL A-4122NL WH 905" manufactured by Solvay Advanced Polymers Co., Ltd. (a hole having a diameter of 10 mm × a depth of 1.2 mm in the center of a flat plate of 15 mm × 15 mm × 2 mm thick)

(1-2) 矽 wafer

(2) Each of the ten cured solutions prepared by the method described later is introduced into the substrate, and one wafer is placed therein, and the cured one is used as a sample for the thermal shock test.

(3) Mount the above sample in a thermal shock device ("TSE-11-A", manufactured by Espec Co., Ltd.) at "(-40 ° C to 120 ° C) / cycle: exposure time 14 minutes, temperature rise and fall The thermal cycle is performed under the condition of 1 minute.

(4) The sample was taken out after 50 cycles of heat, and a permeate ("MICRO-CHECK" manufactured by KOHZAI Co., Ltd.) was sprayed to observe the presence or absence of abnormality (peeling or cracking) and the number thereof was recorded.

(5) The above-mentioned (4) sample confirmed as no abnormality is placed in the apparatus again, and after 50 cycles of thermal cycling, the same operation is performed and evaluated, and then, 100 thermal cycles are performed, and the same method is used for evaluation. . Repeat these operations for evaluation.

(6) When it is seen that two of the ten samples are abnormal, the evaluation is interrupted, and the number of times of thermal shock resistance = (the number of thermal cycles interrupted) - (50 times) is obtained. When the number of thermal shock resistance is 50 or more, it is determined that the thermal shock resistance is high, and the following is determined.

More than 50 times and less than 100 times: ○

More than 100 times: ◎

The raw materials used in Examples 1 to 26 and Comparative Examples 1 to 9 are shown in the following (1) to (9).

(1) Epoxy resin

(1-1) Epoxy Resin A1: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as Bis-A1 epoxy resin)

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER2600"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 187g/eq

‧ Viscosity (25 ° C): 14.3 Pa‧ s

(1-2) Epoxy Resin A2: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A2 epoxy resin)

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER2500"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 186g/eq

‧ Viscosity (25 ° C): 10.2 Pa‧ s

(1-3) Epoxy Resin A3: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A3 epoxy resin)

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER6071"

Further, the epoxy equivalent (WPE) measured by the above method is as follows. However, since the epoxy resin A3 was solid at 25 ° C, the viscosity could not be measured.

‧Epoxy equivalent (WPE): 470g/eq

(1-4) Epoxy resin B: 3,4-epoxycyclohexyl-methyl-3',4'-epoxycyclohexylcarboxylate (hereinafter referred to as alicyclic epoxy resin)

‧trade name: manufactured by Daicel Chemical Industry Co., Ltd., "Celloxide 2021P"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy content (WPE): 131g/eq

‧ Viscosity (25 ° C): 227 mPa ‧ s

(2) alkoxydecane compounds

(2-1) alkoxydecane compound H: 3-glycidoxypropyltrimethoxydecane (hereinafter referred to as GPTMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-403"

(2-2) alkoxydecane compound I: phenyltrimethoxydecane (hereinafter referred to as PTMS)

‧Product Name: Shin-Etsu Chemical Co., Ltd., "KBM-103"

(2-3) alkoxydecane compound J: dimethyldimethoxydecane (hereinafter referred to as DMDMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-22"

(2-4) Alkoxydecane Compound K: Tetraethoxydecane (hereinafter referred to as TEOS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBE-04"

(2-5) alkoxydecane compound L: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (hereinafter referred to as ECETMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-303"

(3) decane partial condensate

(3-1) Tetramethoxydecane partial condensate (alias: polymethoxy oxirane) (hereinafter referred to as P-MS)

‧Trade name: Fusang Chemical Industry Co., Ltd., "Methyl citrate 51"

(3-2) methyltrimethoxydecane partial condensate (alias: poly(methyltrimethoxydecane) (hereinafter referred to as P-MTMS)

‧Trade name: Tama Chemical Industry Co., Ltd., "MTMS-A"

(4) Solvent

(4-1) Tetrahydrofuran: manufactured by Wako Pure Chemical Industries Co., Ltd., without stabilizer (hereinafter referred to as THF)

(4-2) Ethanol: Wako Pure Chemical Industries Co., Ltd. (hereinafter referred to as EtOH)

(4-3) Isopropyl Alcohol: Wako Pure Chemical Industries Co., Ltd. (hereinafter referred to as i-PrOH)

(5) Hydrolysis condensation catalyst

(5-1) Dibutyltin dilaurate: Wako Pure Chemical Industries Co., Ltd. (hereinafter referred to as DBTDL)

(5-2) Dibutyltin diacetate: Tokyo Chemical Industry Co., Ltd. (hereinafter referred to as DBTDA)

(5-3) Dioctyltin diacetate: Nissan Chemical Co., Ltd., "Neostann U-820" (hereinafter referred to as DOTDA)

(6) Hardener: "4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30"

‧Trade name: New Japan Physical and Chemical Co., Ltd., "RIKACID MH-700G"

(7) Hardening accelerator: amine hardener

‧Trade name: San-apro (share) company, "U-CAT 18X"

(8) Polyoxyl resin: manufactured by Shin-Etsu Chemical Co., Ltd., "SCR-1012 (A liquid and B liquid)"

(9) Inorganic filling materials: colloidal cerium oxide

‧trade name: Nissan Chemical Industry Co., Ltd., "Methanol cerium oxide sol"

(SiO ₂ : 30%, particle diameter: 10 to 20 nm)

(10) Internal reference materials

1,1,2,2-tetrabromoethane: manufactured by Tokyo Chemical Industry Co., Ltd.

[Example 1]

The resin composition was manufactured and evaluated in the following steps.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an 80 ° C oil bath was placed on a magnetic stirrer.

(2) According to the composition ratio of Table 1, the Bis-A1 epoxy resin, the alkoxydecane compound and THF were added to the flask to which the stirrer was placed under the environment of 25 ° C, and the mixture was stirred and further added with water. The catalyst is condensed with hydrolysis and mixed and stirred.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 7 hours while refluxing (reflow step).

(4) After completion of the reaction, the mixture was cooled to 25 ° C, and then the cooling tube was removed from the flask, and after the completion of the reflux step, a sample solution (intermediate) was taken.

(5) After completion of the refluxing step, H-NMR of the sample solution (intermediate) was measured, and it was confirmed that (OR ² ) of the following formula (1) was hydrolyzed to (OH).

(R ¹ ) _n -Si-(OR ² ) _4-n (1)

(6) The solution after completion of the refluxing step was distilled off at 400 Pa and 50 ° C for 1 hour using an evaporator, and further distilled at 80 ° C for 5 hours to carry out a dehydration condensation reaction (dehydration condensation step).

(7) After completion of the reaction, the mixture was cooled to 25 ° C to obtain a resin composition. When the H-NMR of the resin composition was measured and calculated together with the internal standard substance, the amount of residual alkoxy groups was 0% ≦ 5%.

(8) The mixing index α1 to ε1 of this resin composition is shown in Table 3.

(9) Further, the epoxy equivalent (WPE), the initial viscosity, and the storage viscosity of the resin composition obtained in the above (6) were measured by the above method. Furthermore, the preservation stability index θ1 is obtained, and these values are indicated in Table 3.

The epoxy resin equivalent (WPE) of the resin composition of the above Example 1 was 230 g/eq, which showed an appropriate value. Further, the initial viscosity = 32.7 Pa ‧ S < 1000 Pa ‧ S, and the storage viscosity = 46.4 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ1 = 1.42 ≦ 4 was stored, and it was judged that the resin composition having the stability was stored.

Next, using the above resin composition stored at 25 ° C for 2 weeks, a cured product was produced and evaluated according to the following procedure.

(10) The resin composition, the curing agent, and the hardening accelerator were mixed and stirred at a composition ratio of Table 2 in an environment of 25 ° C, and deaerated under vacuum to obtain a solution for a cured product.

(11) The thickness will be 3mm The glyph 矽 rubber 挟 is formed between two stainless steel plates coated with a release agent to form a molding jig.

(12) For the molding jig and the substrate for the above-mentioned thermal shock test, the above-mentioned solution for the hardened material was injected, and one wafer was placed in each of the substrates.

(13) The above-mentioned molding jig and the substrate for thermal shock test were placed in an oven, and hardened at 120 ° C for 1 hour and further at 150 ° C for 1 hour to prepare a cured product.

(14) After the internal temperature of the oven was lowered to 30 ° C or lower, the cured product was taken out, and the sample for light resistance test and the sample for thermal shock test were prepared by the above method.

(15) The results of the light resistance test and the thermal shock test using the above samples in the above manner are shown in Table 3. The indicator YI of the light resistance test of the cured product was YI = 10.1 to 13, and it was judged to have light resistance. Furthermore, the number of thermal shock tests was 450 times ≧ 50 times, and it was judged that there was resistance to thermal shock.

As a result of the above, the resin composition of Example 1 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged to be satisfactory.

[Embodiment 2]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α2 to ε2, and the storage stability index θ2 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated by the resin composition and the internal standard substance is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 2 was 231 g/eq, which showed an appropriate value. Further, the initial viscosity was 11.8 Pa s < 1000 Pa s, and the storage viscosity was 17.0 Pa s < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ2 = 1.44 ≦ 4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 8.3 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 500 or more and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 2 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Example 3]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing index α3 to ε3, and the storage stability index θ3 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 3 was 253 g/eq, which showed an appropriate value. Further, the initial viscosity = 27.3 Pa s < 1000 Pa s, and the storage viscosity = 39.6 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ3=1.45≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 9.2 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 500 or more and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 3 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Example 4]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α4 to ε4, and the storage stability index θ4 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 4 was 208 g/eq, which showed a suitable value. Further, the initial viscosity was 11.7 Pa ‧ < 1000 Pa s, and the storage viscosity was = 16.7 Pa s < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ4=1.43≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 8.7≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 450 times ≧ 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 4 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Example 5]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1 and the mixing indexes α5 to ε5 and the storage stability index θ5 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy equivalent (WPE) of the resin composition = 245 g/eq, which showed a suitable value. Further, the initial viscosity = 13.2 Pa s < 1000 Pa ‧ and the storage viscosity = 18.7 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ5=1.42≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 8.5 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 250 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 5 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Embodiment 6]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α6 to ε6, and the storage stability index θ6 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 6 was 221 g/eq, which showed an appropriate value. Further, the initial viscosity = 18.2 Pa.s < 1000 Pa.s, and the storage viscosity = 26.6 Pa.s < 1000 Pa.s, both of which are fluid liquids. Further, the storage stability index θ6=1.46≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 8.1 ≦13, and it was judged that it had light resistance. In addition, the number of thermal shock tests was 350 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 6 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Embodiment 7]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α7 to ε7, and the storage stability index θ7 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy equivalent (WPE) of the resin composition of Example 7 was 217 g/eq, which showed an appropriate value. Further, the initial viscosity was 10.3 Pa s < 1000 Pa s, and the storage viscosity was 14.5 Pa s < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ7=1.41≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 8.3 ≦13, and it was judged that it had light resistance. In addition, the number of thermal shock tests was 450 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 7 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Embodiment 8]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α8 to ε8, and the storage stability index θ8 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy equivalent (WPE) of the resin composition of Example 8 was 213 g/eq, which showed an appropriate value. Further, the initial viscosity = 10.6 Pa s < 1000 Pa ‧ and the storage viscosity = 15.3 Pa s < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ8=1.45≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 7.6 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 150 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 8 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Embodiment 9]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α9 to ε9, and the storage stability index θ9 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 9 was 235 g/eq, which showed an appropriate value. Further, the initial viscosity = 27.8 Pa s < 1000 Pa s, and the storage viscosity = 28.6 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ9=1.03≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 8.0 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 350 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 9 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Embodiment 10]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing index α10 to ε10, and the storage stability index θ10 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy equivalent (WPE) of the resin composition of Example 10 was 214 g/eq, which showed an appropriate value. Further, the initial viscosity = 13.2 Pa ‧ < 1000 Pa ‧ and the storage viscosity = 13.7 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ10=1.04≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 7.8 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 450 times ≧ 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 10 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Example 11]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α11 to ε11, and the storage stability index θ11 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 11 was 228 g/eq, which showed an appropriate value. Further, the initial viscosity = 41.1 Pa ‧ < 1000 Pa s, and the storage viscosity = 65.8 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ11=1.60≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 7.5 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 450 times ≧ 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 11 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged to be satisfactory.

[Embodiment 12]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α12 to ε12, and the storage stability index θ12 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 12 was 230 g/eq, which showed an appropriate value. Further, the initial viscosity = 33.7 Pa ‧ < 1000 Pa s, and the storage viscosity = 48.5 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ12=1.44≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the index YI of the light resistance test of this cured product was 9.8 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 450 times ≧ 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 12 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged to be a comprehensive one.

[Example 13]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α13 to ε13, and the storage stability index θ13 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 13 was 253 g/eq, which showed an appropriate value. Further, the initial viscosity = 27.5 Pa ‧ < 1000 Pa s, and the storage viscosity = 40.8 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ13=1.48≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 9.9 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 450 times ≧ 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 13 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged to be qualified.

[Embodiment 14]

A resin composition was prepared in the same manner as in Example 1 except that the curing temperature of (12) of Example 1 was changed to 110 ° C, 4 hours, and further 150 ° C for 1 hour. With hardened matter. The results of evaluation in the same manner as in Example 1, the mixing indexes α14 to ε14, and the storage stability index θ14 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 14 was 192 g/eq, which showed an appropriate value. Further, the initial viscosity = 1.77 Pa s < 1000 Pa s, and the storage viscosity = 3.08 Pa s < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ14=1.74≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 5.2 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 150 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 14 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance.

[Example 15]

A resin composition and a cured product were produced in the same manner as in Example 1 except that the curing temperature of (13) of Example 1 was changed to 110 ° C for 4 hours. The results of evaluation in the same manner as in Example 1, the mixing indexes α15 to ε15, and the storage stability index θ15 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 15 was 214 g/eq, which showed an appropriate value. Further, the initial viscosity = 4.80 Pa s < 1000 Pa s, and the storage viscosity = 9.23 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ15=1.92≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 8.8 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 250 times and 50 times, and it was judged to have thermal shock resistance.

From the above results, the resin composition of Example 15 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged to be qualified.

[Example 16]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing index α16 to ε16, and the storage stability index θ16 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 16 = 214 g/eq, which showed an appropriate value. Further, the initial viscosity = 12.7 Pa ‧ < 1000 Pa ‧ and the storage viscosity = 15.4 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ 16 = 1.21 ≦ 4 was stored, and it was judged that the resin composition having the stability was stored.

Moreover, the indicator YI = 12.4 ≦ 13 of the light resistance test of the cured product was judged to have light resistance. Further, the number of thermal shock tests was 450 times ≧ 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 16 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged to be qualified.

[Example 17]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α 17 to ε 17 , and the storage stability index θ 17 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 17 was 238 g/eq, which showed an appropriate value. Further, the initial viscosity = 18.9 Pa s < 1000 Pa s, and the storage viscosity = 28.9 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ 17 = 1.53 ≦ 4 was stored, and it was judged that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 7.2 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 150 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 17 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged as a pass.

[Embodiment 18]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α18 to ε18, and the storage stability index θ18 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 18 was 245 g/eq, which showed an appropriate value. Further, the initial viscosity was 18.2 Pa s < 1000 Pa s, and the storage viscosity was 30.5 Pa ‧ < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ23=1.68≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 7.9 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 150 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 18 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged to be qualified.

[Embodiment 19]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α19 to ε19, and the storage stability index θ19 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 19 was 235 g/eq, which showed an appropriate value. Further, the initial viscosity was = 16.2 Pa s < 1000 Pa s, and the storage viscosity was 24.3 Pa s < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ24=1.50≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 7.3 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 150 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 19 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance.

[Example 20]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing index α20 to ε20, and the storage stability index θ20 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 20 was 296 g/eq, which showed an appropriate value. Further, the initial viscosity = 25.2 Pa s < 1000 Pa s, and the storage viscosity = 100.8 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ20=4≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 7.8 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 50 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 20 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged to be a comprehensive one.

[Example 21]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α21 to ε21, and the storage stability index θ21 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 21 was 270 g/eq, which showed an appropriate value. Further, the initial viscosity = 20.3 Pa ‧ < 1000 Pa ‧ and the storage viscosity = 75.1 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ21 = 3.7 ≦ 4 was determined, and it was judged that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 8.4 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 50 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 21 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged as a pass.

[Example 22]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α22 to ε22, and the storage stability index θ22 are shown in Table 3 ^. Further ^{, it was} confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 22 was 208 g/eq, which showed an appropriate value. Further, the initial viscosity = 21.9 Pa ‧ < 1000 Pa s, and the storage viscosity = 87.6 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ22=4≦4 was stored, and it was determined that the resin composition having the stability was stored.

Moreover, the indicator YI of the light resistance test of this cured product was 8.2 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 50 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 22 has fluidity and storage stability. Further, since the cured product of the resin composition has light resistance and thermal shock resistance, it is judged that it is qualified.

[Example 23]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The results of evaluation in the same manner as in Example 1, the mixing indexes α23 to ε23, and the storage stability index θ23 are shown in Table 3. Further, it was confirmed that (OR ² ) in the above formula (1) of the intermediate was hydrolyzed to (OH).

The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 0% ≦ 5%.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Example 23 was 190 g/eq, which showed an appropriate value. The initial viscosity is 14.4 Pa ‧ S < 1000 Pa ‧ S, and the storage viscosity = 100.8 Pa ‧ S < 1000 Pa ̇ S, both of which are fluid liquids. Further, the storage stability index θ23 = 1.2 ≦ 4 was stored, and it was judged that the resin composition having the stability was stored.

Further, the index YI of the light resistance test of the cured product was judged to have light resistance. In addition, the number of hot and cold shock test times was 500 or more and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 23 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Example 24]

The resin composition was produced and evaluated according to the following procedure.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an oil bath of 80 ° C was placed on a magnetic stirrer.

(2) According to the composition ratio of Table 1, an alkoxydecane compound and THF are added to a flask to which a stir bar is placed under an environment of 25 ° C, and after mixing and stirring, water and a hydrolysis condensation catalyst are further added. Mix and stir.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 7 hours while refluxing (reflow step).

(4) After completion of the reaction, the mixture was cooled to 25 ° C, and then the cooling tube was removed from the flask, and after the completion of the reflux step, a sample solution (intermediate) was taken.

(5) After completion of the refluxing step, H-NMR of the sample solution (intermediate) was measured, and it was confirmed that (OR ² ) of the following formula (1) was hydrolyzed to (OH).

(6) Add the Bis-A epoxy resin of Table 1 to the intermediate and mix until it is homogeneous, then place it in the evaporator, distill off at 400 Pa, 50 ° C for 1 hour, and further, at 80 ° C. After decanting for 5 hours, a dehydration condensation reaction (dehydration condensation step) was carried out.

(7) After completion of the reaction, the mixture was cooled to 25 ° C to obtain a resin composition. The amount of residual alkoxy groups calculated by the resin composition and the internal standard material was 0% ≦ 5%.

(8) The mixing index α24 to ε24 of this resin composition is shown in Table 3.

(9) Further, the epoxy equivalent (WPE), the initial viscosity, and the storage viscosity of the resin composition obtained in the above (6) were measured by the above method. Further, the preservation stability index θ24 is obtained, which is shown in Table 3.

The epoxy resin equivalent (WPE) of the resin composition of the above Example 24 was 233 g/eq, which showed an appropriate value. Further, the initial viscosity was 11.8 Pa s < 1000 Pa s, and the storage viscosity was 10.68 Pa s < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ24=1.42≦4 was stored, and it was determined that the resin composition having the stability was stored.

A resin composition and a cured product were produced in the same manner as in Example 1 according to Table 2. As a result of evaluation in the same manner as in Example 1, as shown in Table 3, the indicator YI of the light resistance test of the cured product was 8.3 ≦13, and it was judged to have light resistance. Further, the number of thermal shock tests was 500 or more and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 24 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Example 25]

The resin composition was produced and evaluated according to the following procedure.

(1) Preparation: The circulation thermostat was set to 5 ° C to reflux to the cooling tube. Further, an oil bath of 80 ° C was placed on a magnetic stirrer.

(2) According to the composition ratio of Table 1, a mass equivalent to one half of the total amount of Bis-Al epoxy resin and alkoxydecane compound and THF are added to the flask to which the stirrer has been placed in an environment of 25 ° C. After mixing and stirring, water and a hydrolysis condensation catalyst are further added, and mixing and stirring are carried out.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 7 hours while refluxing (reflow step).

(4) After completion of the reaction, the mixture was cooled to 25 ° C, and then the cooling tube was removed from the flask, and after the completion of the reflux step, a sample solution (intermediate) was taken.

(5) After completion of the refluxing step, H-NMR of the sample solution (intermediate) was measured, and it was confirmed that (OR ² ) of the following formula (1) was hydrolyzed to (OH).

(6) Adding half of the amount of Bis-A epoxy resin equivalent to the residue of Table 1 to the intermediate and mixing and stirring until uniform, and then placing it in an evaporator, and distilling off at 400 Pa at 50 ° C for 1 hour, Further, the mixture was subjected to a dehydration condensation reaction (dehydration condensation step) while distilling off at 80 ° C for 5 hours.

(7) After completion of the reaction, the mixture was cooled to 25 ° C to obtain a resin composition. The amount of residual alkoxy groups calculated by the resin composition and the internal standard substance is 0% ≦ 5%.

(8) The mixing index α25 to ε25 of this resin composition is shown in Table 3.

(9) Further, the epoxy equivalent (WPE), the initial viscosity, and the storage viscosity of the resin composition obtained in the above (6) were measured by the above method. Further, the storage stability index θ25 was obtained, and these are shown in Table 3.

The epoxy resin equivalent (WPE) of the resin composition of the above Example 25 was 232 g/eq, which showed an appropriate value. Further, the initial viscosity was 11.8 Pa s < 1000 Pa s, and the storage viscosity was = 16.7 Pa s < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ25=1.42≦4 was stored, and it was determined that the resin composition having the stability was stored.

A resin composition and a cured product were produced in the same manner as in Example 1 according to Table 2. As a result of evaluation in the same manner as in Example 1, as shown in Table 3, the indicator YI of the light resistance test of the cured product was 8.3 ≦13, and it was judged to have light resistance. Further, the number of thermal shock tests was 500 or more and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 25 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Example 26]

The resin composition was produced and evaluated according to the following procedure.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an oil bath of 80 ° C was placed on a magnetic stirrer.

(2) The P-MS component was removed, and the Bis-A1 epoxy resin, the alkoxydecane compound and the THF component were added to the flask to which the stirrer was placed and mixed at 25 ° C according to the composition ratio of Table 1. After stirring, water and a hydrolysis condensation catalyst were further added to carry out mixing and stirring.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 7 hours while refluxing (reflow step).

(4) After completion of the reaction, the mixture was cooled to 25 ° C, and then the cooling tube was removed from the flask, and after the completion of the reflux step, a sample solution (intermediate) was taken.

(5) After completion of the refluxing step, H-NMR of the sample solution (intermediate) was measured, and it was confirmed that (OR ² ) of the following formula (1) was hydrolyzed to (OH).

(6) The solution after completion of the refluxing step was distilled off at 400 Pa and 50 ° C for 1 hour using an evaporator, and further, while being distilled off at 80 ° C for 5 hours, a dehydration condensation reaction (dehydration condensation step) was carried out.

(7) After completion of the reaction, the mixture was cooled to 25 ° C, and the mass corresponding to the total amount of P-MS was added in accordance with the composition ratio of Table 1, and the mixture was stirred and homogenized to obtain a resin composition. The amount of residual alkoxy groups calculated from the resin composition and the internal standard material was 4.5% ≦ 5%.

(8) The mixing index α26 to ε26 of this resin composition is shown in Table 3.

(9) Further, the epoxy equivalent (WPE), the initial viscosity, and the storage viscosity of the resin composition obtained in the above (7) were measured by the above method. Further, the storage stability index θ26 is obtained, and these are shown in Table 3.

The epoxy resin equivalent (WPE) of the resin composition of the above Example 26 was 230 g/eq, which showed an appropriate value. Further, the initial viscosity = 14.5 Pa s < 1000 Pa s, and the storage viscosity = 49.3 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Moreover, the storage stability index θ26=3.4≦4 was stored, and it was judged that there was a resin composition which preserved stability.

A resin composition and a cured product were produced in the same manner as in Example 1 according to Table 2. As a result of evaluation in the same manner as in Example 1, as shown in Table 3, the light resistance test index YI = 10.6 ≦ 13 of the cured product was judged to have light resistance. Further, the number of thermal shock tests was 50 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, the resin composition of Example 26 has fluidity and storage stability, and the cured product of the resin composition has light resistance and thermal shock resistance.

[Comparative Example 1]

A resin composition was prepared in the same manner as in Example 1 according to Table 1. The amount of residual alkoxy groups thus calculated from the resin composition and the internal standard material was 17% > 5%.

The results of evaluation in the same manner as in Example 1, the mixing indexes α27 to ε27, and the storage stability index θ27 are shown in Table 3.

As shown in Table 3, the epoxy equivalent (WPE) of the resin composition of Comparative Example 1 was 368 g/eq, and an appropriate value was shown. Further, the initial viscosity was >1000 Pa‧s, and the storage viscosity was >1000 Pa‧s, neither of which showed fluidity, and the storage stability index θ27 could not be calculated.

Further, since the above-mentioned resin composition has a storage viscosity of >1000 Pa‧s and no fluidity, it is impossible to produce a cured product.

From the above results, it was found that the resin composition of Comparative Example 1 had no fluidity, was not able to calculate the storage stability, and was impossible to produce a cured product.

[Comparative Example 2]

A resin composition and a cured product were produced in the same manner as in Example 1 in accordance with Tables 1 and 2. The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 8% > 5%.

The results of evaluation in the same manner as in Example 1, the mixing index α 28 to ε 28 , and the storage stability index θ 28 are shown in Table 3.

As shown in Table 3, the epoxy equivalent (WPE) of the resin composition of Comparative Example 2 was 295 g/eq, which showed an appropriate value. Further, the initial viscosity = 30.5 Pa ‧ < 1000 Pa s, and the storage viscosity = 45.1 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ 28 = 1.48 ≦ 4 was observed, and it was found that there was a resin composition which preserved stability.

Moreover, the indicator YI of the light resistance test of this cured product was 8.4 ≦13, and it was judged that it had light resistance. Further, the number of thermal shock tests was 0 times < 50 times, and it was judged that there was no cold and hot resistance.

From the above results, the resin composition of Comparative Example 2 has fluidity and storage stability. However, the cured product prepared from the resin composition has no resistance to thermal shock, even if it has light resistance, so it is judged as comprehensive. Qualified.

[Comparative Example 3]

A resin composition was prepared in the same manner as in Example 1 according to Table 1. The results of evaluation in the same manner as in Example 1, the mixing index α 29 to ε 29, and the storage stability index θ29 are shown in Table 3.

As shown in Table 3, the epoxy equivalent (WPE) of the resin composition of Comparative Example 3 = 233 g/eq, which showed an appropriate value. Further, the initial viscosity was 3.8 Pa ‧ < 1000 Pa s, and the storage viscosity was > 1000 Pa ‧ , showing no fluidity. Further, the storage stability index θ28 = 263 or more > 4, and it was found that there was no preservation stability.

Further, since the above-mentioned resin composition has a storage viscosity of >1000 Pa‧s and no fluidity, it is impossible to produce a cured product.

From the above results, it was found that the resin composition of Comparative Example 3 had no fluidity and storage stability, and it was impossible to produce a cured product, so that it was judged to be unacceptable.

[Comparative Example 4]

A resin composition was prepared in the same manner as in Example 1 according to Table 1. The results of evaluation in the same manner as in Example 1, the mixing index α30 to ε30, and the storage stability index θ30 are shown in Table 3.

As shown in Table 3, the epoxy resin equivalent (WPE) of the resin composition of Comparative Example 4 was 184 g/eq, which showed an appropriate value. Further, the initial viscosity was 10.5 Pa‧s < 1000 Pa‧s, and the storage viscosity was >1000 Pa‧s, showing no fluidity. Further, the storage stability index θ30 = 95 or more > 4, and it was found that there was no preservation stability.

Further, since the above-mentioned resin composition has a storage viscosity of >1000 Pa‧s and no fluidity, it is impossible to produce a cured product.

From the above results, it was found that the resin composition of Comparative Example 4 had no fluidity or storage stability, and it was impossible to produce a cured product, so that it was judged to be unacceptable.

[Comparative Example 5]

A resin composition was prepared in the same manner as in Example 1 according to Table 1. The results of evaluation in the same manner as in Example 1, the mixing indexes α31 to ε31, and the storage stability index θ31 are shown in Table 3.

As shown in Table 3, the epoxy equivalent (WPE) of the resin composition of Comparative Example 5 could not be measured. Further, the initial viscosity was 24.0 Pa.s < 1000 Pa.s, and the storage viscosity was >1000 Pa.s, showing no fluidity. Further, the storage stability index θ30=41 or more>4, and it was found that there was no preservation stability.

Further, since the above resin composition has a storage viscosity of >1000 Pa.s and no fluidity, it is impossible to produce a cured product.

From the above results, it was found that the resin composition of Comparative Example 5 had no fluidity or storage stability, and it was impossible to produce a cured product, so that it was judged to be unacceptable.

[Comparative Example 6]

In the same manner as in Example 1, according to Table 2, a cured product was produced. The results of evaluation in the same manner as in Example 1 are shown in Table 3.

The index of the light resistance test of the cured product was YI=16.9>13, and it was judged that there was no light resistance. Further, the number of thermal shock tests was 500 or more and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, it is understood that the cured product of Comparative Example 6 has thermal and thermal shock resistance, but has no light resistance, so that it was judged to be unacceptable.

[Comparative Example 7]

The solution of the polyacetal resin was mixed with the liquid A and the liquid B at a mass ratio of 1:1, and a solution for a cured product was produced in the same manner as in Example 1 according to Table 2.

The above-mentioned curing solution was injected into a molding jig and ten substrates for the above-described thermal shock test in the same manner as in Example 1, and one wafer was placed in each of the substrates.

The above-mentioned molding jig and the substrate for thermal shock test were placed in an oven, and hardened at 70 ° C for 1 hour and further at 150 ° C for 5 hours to prepare a cured product.

The results of evaluation in the same manner as in Example 1 are shown in Table 3.

The index of the light resistance test of the cured product was YI=2.0≦13, and it was judged to have light resistance. However, the number of thermal shock tests was 0 times < 50 times, and it was judged that there was no cold shock resistance.

From the above results, it was found that the cured product of Comparative Example 7 had light resistance but was not resistant to thermal shock resistance, and was judged to be unacceptable.

[Comparative Example 8]

According to Table 1, epoxy resin A2 and epoxy resin A3 were placed in a reaction vessel, immersed in an oil bath at 85 ° C, stirred/dissolved, and further P-MTMS and DBTDL were added and mixed.

Further, while performing nitrogen purge, the oil bath temperature was raised to 105 ° C, and the dealcoholization reaction was carried out for 8 hours.

Next, after cooling to 60 ° C, the pressure was reduced to 12000 Pa, and the dissolved alcohol was removed to obtain a resin composition. The amount of residual alkoxy groups calculated from the resin composition and the internal standard material was 11% > 5%.

The results of evaluation in the same manner as in Example 1 and the storage stability index θ32 are shown in Table 3.

The epoxy equivalent (WPE) of the resin composition of Comparative Example 8 was 282 g/eq, which showed an appropriate value. Further, the initial viscosity was 0.15 Pa ‧ < 1000 Pa s, and the storage viscosity was 0.27 Pa ‧ < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ32=1.80≦4 was stored, and it was found that there was a resin composition which preserved stability.

Further, according to the blending method of Table 2, a cured product was produced in the same manner as in Example 1. When the evaluation was carried out, the number of thermal shock tests of the cured product of Comparative Example 8 was 0 times < 50 times, and it was found that there was no cold shock resistance. . Moreover, the sample produced in the light resistance test produced minute cracks and could not be measured.

From the above results, it was found that the cured product of Comparative Example 8 was judged to be unacceptable.

[Comparative Example 9]

A resin composition was prepared in the same manner as in Example 1 according to Table 1. The results of evaluation in the same manner as in Example 1 and the mixing indexes α33 to ε33 are shown in Table 3. Further, the (OR ² ) in the above formula (1) of the intermediate is not largely hydrolyzed, and the hydrolysis reaction cannot be carried out normally. Therefore, the normal resin composition could not be obtained, and it was judged that it was unqualified. The amount of residual alkoxy groups calculated from the resin composition and the internal standard material is 100% or more and >5%.

From the results of Tables 1 to 3, it is understood that the resin composition (Examples 1 to 26) obtained by mixing an epoxy resin with a specific alkoxydecane compound at a specific ratio and performing cohydrolysis condensation is excellent. Liquidity and preservation stability. Further, the cured product obtained by using these resin compositions has excellent light resistance and thermal shock resistance.

Hereinafter, the condensation ratio of the alkoxysilane of the modified resin composition and the condensation ratio of the intermediate will be specifically described by way of examples and comparative examples.

First, the evaluation methods of the physical properties in Examples 27 to 35 and Comparative Examples 10 to 14 are shown below.

The amount of residual alkoxy group, epoxy equivalent (WPE), viscosity, and mixing index α to η of the modified resin composition were determined in the same manner as above.

<Calculation of Condensation Rate of Intermediates>

The condensation ratio of the intermediate is determined by Si-NMR measurement of the sample solution (intermediate) taken after the completion of the refluxing step, according to the following procedure.

(1) Preparation of Cr solution: Chloroform-d (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 6.3 mass% of acetonitrile (III) (manufactured by Sigma-Aldrich Co., Ltd.), and dissolved.

(2) In the sample bottle, 200 mg of the sample solution after the completion of the refluxing step was weighed, and the above Cr solution was added to adjust to 1 g.

(3) The solution of the above (2) was transferred to an NMR tube having a diameter of 5 mmφ, and Si-NMR was measured under the following conditions.

Fourier transform nuclear magnetic resonance device: "α-400 type" manufactured by JEOL,

Nuclear species: Si,

Cumulative number: 4000 times

(4) According to the following formula, the condensation ratio K of the intermediate is obtained. Condensation rate (%) = (D1 × 1 + D2 × 2 + T1 × 1 + T2 × 2 + T3 × 3) / {(D0 + D1 + D2) × 2 + (T0 + T1 + T2 + T3) × 3} × 100 ... (10)

here,

D0: In the formula (1), the integral value of the signal derived from the DO structure represented by the following formula (11) derived from the alkoxydecane compound of n=1 is obtained.

D1: In the formula (1), the integral value of the signal derived from the D1 structure represented by the following formula (12) derived from the alkoxydecane compound of n=1 is obtained.

D2: In the formula (1), the integral value of the signal derived from the D2 structure represented by the following formula (12) derived from the alkoxydecane compound of n=1 is obtained.

T0: Formula (1), the total of the integrated values of the signals derived from the T0 structure represented by the following formula (13) derived from the alkoxydecane compound of n=2.

T1: In the formula (1), the integral value of the signal derived from the T1 structure represented by the following formula (14) derived from the alkoxydecane compound of n=2 is total.

T2: In the formula (1), the integral value of the signal derived from the T2 structure represented by the following formula (14) derived from the alkoxydecane compound of n=2 is total.

T3: In the formula (1), the integral value of the signal derived from the T3 structure represented by the following formula (14) derived from the alkoxydecane compound of n=2 is total.

In the above formula (11), R is an arbitrary organic group or H.

In the above formula (12), R is an arbitrary organic group or H.

In the above formula (13), R is an arbitrary organic group or H.

In the above formula (14), R is an arbitrary organic group or H.

<Calculation of Condensation Rate of Alkoxydecane Compound of Modified Resin Composition>

The condensation rate of the alkoxydecane compound of the modified resin composition is determined by Si-NMR measurement of the sample solution taken after completion of the dehydration condensation step, and the condensation is obtained in the same manner as the calculation method of the condensation ratio of the intermediate. Rate L (%).

<The calculation of the storage stability index θ and the storage stability of the resin composition>

The storage stability of the resin composition is expressed by the following formula (9), and is evaluated by preserving the stability index θ.

Preservation stability index θ = (preservation viscosity) / (starting viscosity) ... (9)

The container in which the resin composition immediately after the preparation was placed was sealed, and the temperature was adjusted at 25 ° C for 2 hours, and then the viscosity at 25 ° C was measured, and this was regarded as "initial viscosity".

Further, the container was placed in a resin composition and sealed, and stored in an incubator at 60 ° C for 16.5 days. After storage, the viscosity at 25 ° C was measured, and this was regarded as "preservation viscosity".

When the resin composition has fluidity (viscosity of 1000 Pa·s or less) and the storage stability index θ is 6 or less, it is determined that storage stability is determined, and it is determined as follows.

0≦θ≦4 ◎

4<θ≦6 ○

<Light resistance test of hardened material>

The light resistance of the cured product of the resin composition was evaluated by the following method.

(1) The cured product prepared by the method described later was hardened with a solution to prepare a cured product of 20 mm × 10 mm × 3 mm in thickness.

(2) The cured product was covered with a black mask of 25 mm × 15 mm × 1.2 mm thick having a hole having a diameter of 5.5 mm as a sample for light resistance test.

(3) A preparation device was used to irradiate the UV light from the UV irradiation device ("Spot Cure SP7-250DB" manufactured by Ushio Electric Co., Ltd.) to the above-mentioned sample in an incubator set to a constant temperature of 50 °C via an optical fiber.

(4) The above sample was placed in an incubator at 50 ° C in a state where the black mask was placed on the upper surface.

(5) UV light of ² W/cm ^{2 was} irradiated from the upper portion of the black mask for 96 hours so that light was irradiated to a hole having a diameter of 5.5 mm.

(6) A sample irradiated with UV was measured by a spectrophotometer ("SD5000" manufactured by Nippon Denshoku Industries Co., Ltd.) which has been modified into a 10 mm-diameter aperture.

(7) Yellowness (YI) is determined according to "ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics".

When the YI was 13 or less, it was judged to have light resistance.

<Cold and thermal shock test of hardened material>

The thermal shock resistance of the cured product of the resin composition was evaluated by the following method.

(1) Prepare the following substrate and germanium wafer.

(1-1) Substrate: "AMODEL A-4122NL WH 905" manufactured by Solvay Advanced Polymers Co., Ltd. (a hole having a diameter of 10 mm × a depth of 1.2 mm in the center of a flat plate of 15 mm × 15 mm × 2 mm thick)

(1-2) 矽 wafer (cutting a commercially available 矽 wafer into 5 mm × 5 mm × thickness 200 μm)

(2) Ten samples of the cured product solution which was produced by the method described later were poured into the substrate, and one of the above-mentioned silicon wafers was placed therein to be cured, and it was used as a sample for thermal shock test.

(3) The above sample was placed in a thermal shock device ("TSE-11-A", manufactured by Espec Co., Ltd.), with "(-40 ° C to 120 ° C) / cycle: exposure time of 14 minutes, temperature rise and fall time The thermal cycle is carried out under the conditions of 1 minute.

(4) The sample was taken out at the time of the 50th thermal cycle, and the permeate ("MICRO-CHECK" manufactured by KOHZAI Co., Ltd.) was sprayed, and the presence or absence of abnormality (peeling or cracking) was visually observed under a magnifying glass. , record the number.

(5) The sample confirmed as the no abnormality in the above (4) was again placed in the apparatus, and after the 50th thermal cycle, the same operation was evaluated, and then the thermal cycle was performed 100 times in the same manner and evaluated. Repeat these operations and evaluate them.

(6) When it is seen that two of the ten samples are abnormal, the evaluation is interrupted, and the number of times of thermal shock resistance = (the number of thermal cycles interrupted) - (50 times) is obtained.

When the number of thermal shock resistance is 50 or more, it is judged that it has practically sufficient thermal shock resistance.

Next, the raw materials used in Examples 27 to 35 and Comparative Examples 10 to 14 are shown in the following (1) to (10).

(1) Epoxy resin

(1-1) Epoxy Resin A: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as Bis-A epoxy resin)

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER2600"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Oxygen equivalent (WPE): 187g/eq

‧ degrees (25 ° C): 14.3 Pa ‧ s

(1-2) Epoxy resin B: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate (hereinafter, referred to as alicyclic epoxy resin)

‧trade name: manufactured by Daicel Chemical Industry Co., Ltd., "Celloxide 2021P"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Oxygen equivalent (WPE): 131g/eq

‧ degrees (25 ° C): 227mPa‧S

(2) alkoxydecane compound H: 3-glycidoxypropyltrimethoxydecane (hereinafter referred to as GPTMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-403"

(3) alkoxydecane compound I: phenyltrimethoxydecane (hereinafter referred to as PTMS)

‧Product Name: Shin-Etsu Chemical Co., Ltd., "KBM-103"

(4) alkoxydecane compound J: dimethyldimethoxydecane (hereinafter referred to as DMDMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-22"

(5) alkoxy decane compound K: tetraethoxy decane (hereinafter referred to as TEOS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBE-04"

(6) Solvent

(6-1) Tetrahydrofuran: manufactured by Wako Pure Chemical Industries Co., Ltd., without stabilizer (hereinafter referred to as THF)

(6-2) Tertiary butanol: Wako Pure Chemical Industries Co., Ltd. (hereinafter referred to as t-BuOH)

(7) Hydrolysis condensation catalyst

(7-1) Dibutyltin Dimethoxide (hereinafter referred to as DBTDM): manufactured by Sigma-Aldrich

(7-2) Dioctyltin diacetate (hereinafter referred to as DOTDA): manufactured by Nitto Chemical Co., Ltd., "Neostann U-820"

(7-3) Dibutyltin dilaurate (hereinafter referred to as DBTDL): manufactured by Wako Pure Chemical Industries Co., Ltd.

(8) Hardener: "4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30"

‧Trade name: New Japan Physical and Chemical Co., Ltd., "RIKACID MH-700G"

(9) Hardening accelerator: amine hardener

‧Trade name: San-apro (share) company, "U-CAT 18X"

(10) Polyoxyl resin: manufactured by Shin-Etsu Chemical Co., Ltd., "SCR-1012 (A liquid and B liquid)"

(11) Internal reference materials

1,1,2,2-tetrabromoethane: manufactured by Tokyo Chemical Industry Co., Ltd.

[Example 27]

The resin composition was produced by the following procedure.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an 80 ° C oil bath was placed on a magnetic stirrer.

(2) According to the composition ratio shown in Table 4, the above BiS-A epoxy resin, alkoxydecane compound, and THF were placed in a flask to which a stirrer was placed, and stirred and mixed under an environment of 25 ° C, and then stirred and stirred. Further, water and a hydrolysis condensation catalyst are further added and mixed and stirred.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 25 hours while refluxing (reflow step).

(4) After completion of the reaction, the mixture was cooled to 25 ° C, and then the cooling tube was removed from the flask, and after the completion of the reflux step, a sample solution (intermediate) was taken.

(5) After completion of the refluxing step, Si-NMR of the sample solution (intermediate) was measured, and the condensation ratio K1 of the intermediate was determined according to the above formula (10). The condensation ratio of the intermediate K1 (%) = 80.1% ≧ 78%%.

(6) The solution after the completion of the refluxing step was distilled off at 400 Pa and 50 ° C for 1 hour using an evaporator, and further subjected to a dehydration condensation reaction (dehydration condensation step) while distilling off at 80 ° C for 10 hours.

(7) After the completion of the dehydration condensation reaction, the mixture was cooled to 25 ° C to obtain a resin composition, and a sample solution was taken.

(8) After completion of the dehydration condensation step, Si-NMR of the sample solution is measured, and the condensation ratio L1 of the modified resin composition is obtained from the above formula (10). The condensation ratio of the modified resin composition L1 (%) = 86.6% ≧ 80%. Further, the amount of residual alkoxy groups of the modified resin composition was 0% ≦ 5%.

(9) The above-mentioned mixing indexes α34 to ε34 of the resin composition are shown in Table 6 below.

(10) Further, the epoxy equivalent (WPE), the initial viscosity, and the storage viscosity of the resin composition obtained in the above (6) were measured according to the above method. Further, the storage stability index θ34 was obtained and shown in Table 6.

The epoxy resin equivalent (WPE) of the resin composition of the above Example 27 was 220 g/eq, which showed an appropriate value. Further, the initial viscosity = 12.7 Pa ‧ < 1000 Pa s, and the storage viscosity = 32.5 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. In addition, the storage stability index θ34=2.6≦4 was obtained, and the fluidity was excellent, and it was judged that the resin composition having improved storage stability was determined.

Next, using the above resin composition, the cured product was produced by the following procedure and evaluated.

(11) The resin composition, the curing agent, and the curing accelerator described above were mixed and stirred at a composition ratio shown in the following Table 5 under an environment of 25 ° C, and deaerated under vacuum to obtain a solution for a cured product.

(12) The thickness will be 3mm The shape 矽 rubber 制作 is formed between two stainless steel sheets coated with a release agent to form a molding jig, and the cured product produced by the molding jig is about 50 mm × about 20 mm × thickness 3 mm.

(13) The above-mentioned curing solution and the above-mentioned substrate for the thermal shock test were injected into the above-mentioned hardened material solution, and one of the above-mentioned tantalum wafers was placed in each of the substrates.

(14) The above-mentioned forming jig and the substrate for thermal shock test were placed in an oven, and hardened at 120 ° C for 1 hour and further at 150 ° C for 1 hour to prepare a cured product.

(15) After the internal temperature of the oven was lowered to 30 ° C or lower, the cured product was taken out, and the sample for light resistance test and the sample for thermal shock test were prepared by the above method.

(16) The results of the light resistance test and the thermal shock test according to the above method using the above samples are shown in Table 6 below. The index of the light resistance test of the cured product YI = 11.9 ≦ 13 was judged to have practically sufficient light resistance. Further, the number of thermal shock tests was 350 times and 50 times, and it was judged to have practically sufficient cold shock resistance.

From the above results, it was found that the resin composition of Example 27 has good fluidity and excellent storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance.

[Example 28]

In the same manner as in the above Example 27, a resin composition and a cured product thereof were produced in accordance with Tables 4 and 5 below.

The resin composition and the cured product thereof were evaluated in the same manner as in the above Example 27. The evaluation results, the mixing index α35 to ε35, and the storage stability index θ35 are shown in Table 6 below.

The condensation rate of the intermediate K2 (%) = 78.2% ≧ 78%.

The condensation rate of the modified resin composition was L2 (%) = 81.8% ≧ 80%.

The amount of residual alkoxy groups of the modified resin composition is 0% ≦ 5%.

As shown in the following Table 6, the epoxy equivalent (WPE) of the resin composition of Example 28 was 233 g/eq, which showed an appropriate value.

Further, the initial viscosity = 15.9 Pa ‧ < 1000 Pa ‧ S, and the storage viscosity = 53.8 Pa ‧ < 1000 Pa ‧ has good fluidity. In addition, the storage stability index θ35=3.4≦4 is excellent in fluidity, and it is known that the resin composition having improved storage stability is improved.

Further, the index of the light resistance test of the cured product was YI = 8.1 ≦ 13, and it was judged that there was practically sufficient light resistance. The number of thermal shock tests was 250 times and 50 times, and it was judged that there was practically sufficient cold shock resistance.

From the above results, it is understood that the resin composition of Example 28 is excellent in fluidity and improved in storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance, so comprehensive judgment To be qualified.

[Example 29]

In the same manner as in the above Example 27, a resin composition and a cured product thereof were produced in accordance with Tables 4 and 5 below.

The resin composition and the cured product thereof were evaluated in the same manner as in the above Example 27. The evaluation results, the mixing index α 36 to ε 36, and the storage stability index θ 36 are shown in Table 6.

The condensation rate of the intermediate K3 (%) = 85.3% ≧ 78%.

The condensation rate of the modified resin composition was L3 (%) = 86.8% ≧ 80%.

The amount of residual alkoxy groups of the modified resin composition is 0% ≦ 5%.

As shown in the following Table 6, the epoxy equivalent (WPE) of the resin composition of Example 29 was 242 g/eq, which showed an appropriate value.

Further, the initial viscosity = 14.3 Pa s < 1000 Pa ‧ and the storage viscosity = 41.0 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. In addition, the storage stability index θ 36 = 2.9 ≦ 4 was excellent in fluidity, and it was found that the resin composition having improved storage stability was obtained.

The index YI of the light resistance test of the cured product was 8.9 ≦13, and it was judged that the light resistance was practically sufficient.

The number of thermal shock tests was 250 times and 50 times, and it was judged that there was practically sufficient cold shock resistance.

From the above results, it is understood that the resin composition of Example 29 is excellent in fluidity and has improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance, so comprehensive judgment To be qualified.

[Example 30]

In the same manner as in the above Example 27, a resin composition and a cured product thereof were produced in accordance with Tables 4 and 5 below.

The resin composition and the cured product thereof were evaluated in the same manner as in the above Example 37. The evaluation results, the mixing index α37 to ε37, and the storage stability index θ37 are shown in Table 6.

The condensation rate of the intermediate K4 (%) = 87.4% ≧ 78%.

The condensation rate of the modified resin composition was L4 (%) = 88.8% ≧ 80%.

The amount of residual alkoxy groups of the modified resin composition is 0% ≦ 5%.

As shown in the following Table 6, the epoxy resin equivalent (WPE) of the resin composition of Example 30 was 238 g/eq, which showed an appropriate value.

Further, the initial viscosity = 15.6 Pa s < 1000 Pa s, and the storage viscosity = 24.9 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids.

In addition, the storage stability index θ37=1.6≦4 is excellent in fluidity, and it is known that the resin composition having improved storage stability is improved.

The index YI of the light resistance test of the cured product was 8.8 ≦13, and it was judged that the light resistance was practically sufficient.

The number of thermal shock tests was 150 times and 50 times, and it was judged that there was a practically sufficient resistance to thermal shock.

From the above results, the resin composition of Example 30 is excellent in fluidity and improved in storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance, so that comprehensive judgment is made. To be qualified.

[Example 31]

In the same manner as in the above Example 27, a resin composition and a cured product thereof were produced in accordance with Tables 4 and 5 below.

The resin composition and the cured product thereof were evaluated by the same method as in the above Example 27. The evaluation results, the mixing index α38 to ε38, and the storage stability index θ38 are shown in Table 6 below.

The condensation rate of the intermediate K5 (%) = 82.6% ≧ 78%.

The condensation rate of the modified resin composition was L5 (%) = 87.2% ≧ 80%.

The amount of residual alkoxy groups of the modified resin composition is 0% ≦ 5%.

As shown in the following Table 6, the epoxy resin equivalent (WPE) of the resin composition of Example 31 was 245 g/eq, which showed an appropriate value.

Further, the initial viscosity was 17.3 Pa s < 1000 Pa s, and the storage viscosity was 50.2 Pa ‧ < 1000 Pa ‧ , both of which were fluid liquids. In addition, the storage stability index θ38 = 2.9 ≦ 4 was excellent in fluidity, and it was found that the resin composition having improved storage stability was obtained.

The index of the light resistance test of the cured product was YI = 8.2 ≦ 13, and it was judged that there was practically sufficient light resistance.

The number of thermal shock tests was 150 times ≧ 50 times, and it was judged that there was practically sufficient cold shock resistance.

From the above results, it is understood that the resin composition of Example 31 is excellent in fluidity and improved in storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance, so comprehensive judgment is made. To be qualified.

[Example 32]

In the same manner as in the above Example 27, a resin composition and a cured product thereof were produced in accordance with Tables 4 and 5 below.

The resin composition and the cured product thereof were evaluated in the same manner as in the above Example 27. The evaluation results, the mixing indexes α39 to ε39, and the storage stability index θ39 are shown in Table 6 below.

The condensation rate of the intermediate K6 (%) = 82.8% ≧ 78%.

The condensation rate of the modified resin composition was L6 (%) = 83.2% ≧ 80%.

The amount of residual alkoxy groups of the modified resin composition is 0% ≦ 5%.

As shown in the following Table 6, the epoxy resin equivalent (WPE) of the resin composition of Example 32 was 253 g/eq, which showed an appropriate value.

Further, the initial viscosity = 24.3 Pa s < 1000 Pa s, and the storage viscosity = 86.3 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. In addition, the storage stability index θ39=3.6≦4 is excellent in fluidity, and it is known that the resin composition having improved storage stability is improved.

The index of the light resistance test of the cured product was YI = 9.7 ≦ 13, and it was judged that there was practically sufficient light resistance. Further, the number of thermal shock tests was 250 times and 50 times, and it was judged that there was practically sufficient cold shock resistance.

From the above results, it is understood that the resin composition of Example 32 is excellent in fluidity and has improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance, so comprehensive judgment is made. To be qualified.

[Example 33]

In the same manner as in the above Example 27, a resin composition and a cured product thereof were produced in accordance with Tables 4 and 5 below.

The resin composition and the cured product thereof were evaluated in the same manner as in the above Example 27. The evaluation results, the mixing index α40 to ε40, and the storage stability index θ40 are shown in Table 6 below.

The condensation ratio of the intermediate K7 (%) = 83.5% ≧ 78%.

The condensation ratio of the modified resin composition was L7 (%) = 84.4% ≧ 80%.

The amount of residual alkoxy groups of the modified resin composition is 0% ≦ 5%.

As shown in the following Table 6, the epoxy resin equivalent (WPE) of the resin composition of Example 33 was 210 g/eq, which showed an appropriate value.

Further, the initial viscosity was 12.8 Pa s < 1000 Pa s, and the storage viscosity was 39.8 Pa ‧ < 1000 Pa ‧ , both of which were fluid liquids. In addition, the storage stability index θ33=3.1≦4 is excellent in fluidity, and it is known that the resin composition having improved storage stability is improved.

The index YI of the light resistance test of the cured product was 7.5 ≦13, and it was judged that the light resistance was practically sufficient. Further, the number of thermal shock tests was 350 times and 50 times, and it was judged that there was practically sufficient cold shock resistance.

From the above results, the resin composition of Example 33 is excellent in fluidity and improved in storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance. To be qualified.

[Example 34]

In the same manner as in the above Example 27, a resin composition and a cured product thereof were produced in accordance with Tables 4 and 5 below.

The resin composition and the cured product thereof were evaluated in the same manner as in the above Example 27, and the evaluation results, the mixing indexes α41 to ε41, and the storage stability index θ41 are shown in Table 6 below.

The condensation rate of the intermediate K8 (%) = 84.2% ≧ 78%.

The condensation ratio of the modified resin composition was L8 (%) = 84.4% ≧ 80%.

The amount of residual alkoxy groups of the modified resin composition is 0% ≦ 5%.

As shown in the following Table 6, the epoxy resin equivalent (WPE) of the resin composition of Example 33 was 233 g/eq, which showed an appropriate value.

Further, the initial viscosity = 13.2 Pa s < 1000 Pa ‧ and the storage viscosity = 46.8 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. In addition, the storage stability index θ41=3.5≦4 is excellent in fluidity, and it is known that the resin composition having improved storage stability is improved.

The index of the light resistance test of the cured product was YI = 7.3 ≦ 13, and it was judged to have light resistance. Further, the number of thermal shock tests was 150 times and 50 times, and it was judged that there was resistance to thermal shock.

From the above results, it is understood that the resin composition of Example 34 is excellent in fluidity and has improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance, so comprehensive judgment To be qualified.

[Example 35]

The distillation time of the dehydration condensation step at 80 ° C for 5 hours was changed to 2.5 hours. The rest of the conditions were the same as in Example 27, and a resin composition was produced according to Table 4, and evaluated in the same manner as in Example 27.

The evaluation results, the mixing indexes α42 to ε42, and the storage stability index θ42 are shown in Table 6 below.

The condensation ratio of the intermediate K9 (%) = 78.2% ≧ 78%.

The condensation ratio of the modified resin composition was L9 (%) = 79.0% < 80%.

The amount of residual alkoxy groups of the modified resin composition was 4% ≦ 5%.

As shown in the following Table 6, the epoxy resin equivalent (WPE) of the resin composition of Example 35 was 230 g/eq, which showed an appropriate value. Further, the initial viscosity was 15.1 Pa s < 1000 Pa s, and the storage viscosity was 68.0 Pa ‧ < 1000 Pa ‧ , both of which were fluid liquids. In addition, the storage stability index θ 42 = 4.5 ≦ 6 , and the condensation ratio of the modified resin is less than 80%, but the fluidity is excellent, and it is known that the resin composition having improved storage stability is improved.

The index of the light resistance test of the cured product was YI = 8.1 ≦ 13, and it was judged to have light resistance. Moreover, the number of hot and cold smashing tests was 250 times ≧ 50 times, and it was judged that there was resistance to cold and heat.

From the above results, it is understood that the resin composition of Example 35 is excellent in fluidity and has improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and cold and heat resistance, so that comprehensive judgment is made. To be qualified.

[Comparative Example 10]

The curing temperature of (14) shown in the above Example 27 was changed to 110 ° C for 4 hours, and further to 150 ° C for 1 hour. Other conditions were the same as in Example 27, and a resin composition and a cured product were produced in the following Tables 4 and 5, and evaluated in the same manner as in Example 27.

The evaluation results, the mixing indexes α 43 to ε 43 , and the storage stability index θ 43 are shown in Table 6 below.

The condensation ratio of the intermediate K10 (%) = 71.1% < 78%.

The condensation ratio of the modified resin composition was L10 (%) = 75.4% < 80%.

The amount of residual alkoxy groups of the modified resin composition was 21% > 5%.

The epoxy equivalent of the resin composition of Comparative Example 10 is shown in Table 6 below. (WPE) = 200 g/eq, showing the appropriate value.

Also, the initial viscosity = 11.7 Pa ‧ < 1000 Pa ‧. However, the preservation viscosity was >1000 Pa‧s, showing no fluidity, and the preservation stability index θ 43>85, and the preservation stability was poor.

As shown in Table 6, although the cured product obtained by using the resin composition of Comparative Example 10 was excellent in light resistance and thermal shock resistance, the storage stability of the resin composition was poor, and the overall judgment was unacceptable.

[Comparative Example 11]

In the same manner as in the above Example 27, a cured product was produced in accordance with the following Table 5. The cured product was evaluated in the same manner as in Example 27. The evaluation results are shown in Table 6 below.

The index YI=16.9>13 of the light resistance test of the cured product was judged to have no practically sufficient light resistance. Further, the number of thermal shock tests was 500 or more and 50 times, and it was judged that there was practically sufficient cold and heat resistance.

From the above results, it was found that the cured product of Comparative Example 11 was resistant to cold and heat, but had no light resistance, and was judged to be unacceptable.

[Comparative Example 12]

By using a polyoxyxylene resin (SCR-1012 (A liquid and B liquid)), a mixture of the A liquid and the B liquid in a mass ratio of 1:1, according to the following, In Table 5, a solution for a cured product was produced in the same manner as in Example 27.

In the same manner as in Example 27, a solution for the hardened material was injected into the forming jig and the ten substrates for the thermal shock test, and one wafer was placed in each of the substrates. .

The above-mentioned forming jig and the substrate for thermal shock test were placed in an oven, and hardened at 70 ° C for 1 hour and further at 150 ° C for 5 hours to prepare a cured product.

The cured product was evaluated in the same manner as in Example 27. The evaluation results are shown in Table 6 below.

The index of the light resistance test of the cured product was YI=2.0≦13, and it was judged that the light resistance was practically sufficient. However, the number of thermal shock tests was 0 times < 50 times, and it was judged that there was no practically sufficient cold shock resistance.

From the above results, it was found that the cured product of Comparative Example 12 had light resistance but was not resistant to thermal shock resistance, and was judged to be unacceptable.

[Comparative Example 13]

The reflux step was changed to 7 hours, and the dehydration condensation step was carried out for 25 hours. Other conditions were the same as in Example 27, and a resin composition was produced according to Table 4, and evaluated in the same manner as in Example 27.

The evaluation results, the mixing indexes α44 to ε44, and the storage stability index θ44 are shown in Table 6 below.

The condensation ratio of the intermediate K11 (%) = 64.8% < 78%.

The condensation ratio of the modified resin composition was L11 (%) = 68.0% < 80%.

The amount of residual alkoxy groups of the modified resin composition is 7% > 5%.

As shown in the following Table 6, the epoxy equivalent (WPE) of the resin composition of Comparative Example 13 was 233 g/eq, and an appropriate value was shown. Also, the initial viscosity = 15.2 Pa.s < 1000 Pa.s. However, the storage viscosity was >1000 Pa.s, showing no fluidity, the storage stability index θ44>66, and the storage stability was poor, so the comprehensive judgment was unqualified.

As described above, even if the time for carrying out the dehydration condensation step is prolonged, the storage stability of the resin composition does not reach the acceptable line, so that the characteristics of the resin composition and the condensation ratio (chemical structure) of the intermediate in the reflux step are known. Great dependence.

[Comparative Example 14]

The oil bath temperature in the reflux step was changed to 60 °C. Other conditions were the same as in Example 27, and a resin composition was produced according to Table 4, and evaluated in the same manner as in Example 27.

The evaluation results, the mixing index α45 to ε45, and the storage stability index θ45 are shown in Table 6 below.

The condensation rate of the intermediate K12 (%) = 63.6% < 78%.

The condensation ratio of the modified resin composition was L12 (%) = 65.4% < 80%.

The amount of residual alkoxy groups of the modified resin composition was 12% > 5%.

As shown in the following Table 6, the epoxy resin equivalent (WPE) of the resin composition of Comparative Example 14 was 238 g/eq, which showed an appropriate value. Also, the initial viscosity was = 16.4 Pa s < 1000 Pa ‧ s. However, the storage viscosity was >1000 Pa‧s, showing no fluidity, the storage stability index θ44>61, and the preservation stability was poor, so the comprehensive judgment was unqualified.

As shown in Tables 4 to 6, it is understood that the epoxy resin and the specific alkoxydecane compound are mixed at a specific ratio, and the condensation ratio of the intermediate in the reflux step of the co-hydrolysis condensation is specified, and then, The resin composition of Examples 27 to 35 produced by dehydrating condensation and imparting a specific condensation ratio of the modified resin composition has excellent fluidity and storage stability, and the cured product of the resin composition has Excellent light resistance and thermal shock resistance.

Next, a resin composition obtained by adding an oxetane compound to the modified resin composition of the present embodiment will be specifically described by way of examples and comparative examples.

The epoxy equivalent (WPE), viscosity, and mixing index α to η were obtained in the same manner as above.

The evaluation of the physical properties in Examples 36 to 38 and Comparative Examples 15 to 16 was carried out as follows.

<Measurement of viscosity of composition>

The container immediately after the composition was sealed, and the temperature was adjusted at 25 ° C for 1 hour, and then the viscosity at 25 ° C was measured.

When the viscosity was 1000 Pa‧s or less, it was judged to have fluidity.

<Light resistance test of hardened material>

The light resistance of the cured product was evaluated in the following manner.

(1) The cured product prepared by the method described later was hardened with a solution to prepare a cured product of 20 mm × 10 mm × 3 mm in thickness.

(2) The cured product was covered with a black mask of 25 mm × 15 mm × 1.2 mm thick having a hole having a diameter of 5.5 mm, and was used as a sample for light resistance test.

(3) The preparation device was used to irradiate the UV light from the UV irradiation device ("Spst Cure SP7-250DB" manufactured by Ushio Electric Co., Ltd.) to the above-mentioned sample in an incubator set to a constant temperature of 50 °C via an optical fiber.

(4) The above sample was placed in an incubator at 50 ° C in a state where the black mask was placed on the upper surface.

(5) UV light of 2 W/cm ^{2 was} irradiated from the upper portion of the black mask for 96 hours so that the UV light was irradiated to the hole having a diameter of 5.5 mm.

(6) A sample irradiated with UV was measured by a spectrophotometer ("SD5000" manufactured by Nippon Denshoku Industries Co., Ltd.) which has been modified into a 10 mm-diameter aperture.

(7) Yellowness (YI) is determined according to "ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics". When the YI is 11 or less, it is judged to have light resistance.

<Cracking test of hardened material>

The hardened matter was evaluated for cracking by the following method.

(1) Prepare a substrate as shown below.

‧Substrate: "AMODEL A-4122NL WH 905" manufactured by Solvay Advanced Polymers Co., Ltd. (a hole having a diameter of 10 mm × a depth of 1.2 mm in the center of a flat plate of 15 mm × 15 mm × 2 mm thickness)

(2) Five of the hardened material solutions prepared by the method described later are introduced into the substrate, and the cured one is used as a sample for the crack test.

(3) For the above sample, a permeate ("MICRO-CHECK" manufactured by KOHZAI Co., Ltd.) was sprayed, and the presence or absence of cracking was visually observed under a magnifying glass, and the number was recorded.

(4) When four of the five samples did not show cracking, it was judged to have crack resistance.

<Surface adhesion test of hardened material>

The surface adhesion of the cured product was evaluated by the following method.

(1) The cured product prepared by the method described later was cured with a solution to prepare a cured product of 20 mm × 10 mm × 3 mm in thickness.

(2) The surface of the obtained cured product was lightly pressed with the thumb of the latex glove, and when the adhesion was not confirmed, the surface adhesion was judged to be good.

The raw materials used in Examples 36 to 38 and Comparative Examples 15 to 16 are shown in the following (1) to (12).

(1) Epoxy resin

(1-1) Epoxy Resin A: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as Bis-A epoxy resin)

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 187g/eq

‧ Viscosity (25 ° C): 14.3 Pa‧ S

(1-2) Epoxy resin B: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate (hereinafter, referred to as alicyclic epoxy resin)

‧trade name: manufactured by Daicel Chemical Industry Co., Ltd., "Celloxide 2021P"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 131g/eq

‧ Viscosity (25 ° C): 227 mPa ‧ s

(2) alkoxydecane compound H: 3-glycidoxypropyltrimethoxydecane (hereinafter referred to as GPTMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-403"

(3) alkoxydecane compound I: phenyltrimethoxydecane (hereinafter referred to as PTMS)

‧Product Name: Shin-Etsu Chemical Co., Ltd., "KBM-103"

(4) alkoxydecane compound J: dimethyldimethoxydecane (hereinafter referred to as DMDMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-22"

(5) alkoxy decane compound K: tetraethoxy decane (hereinafter referred to as TEOS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBE-04"

(6) Solvent

(6-1) Tetrahydrofuran: manufactured by Wako Pure Chemical Industries Co., Ltd., without stabilizer (hereinafter referred to as THF)

(7) Hydrolysis condensation catalyst: Dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries Co., Ltd., hereinafter referred to as DBTDL)

(8) Oxetane compound: 3-ethyl-{[3-ethyloxetan-3-yl]methoxy}methyl}oxetane (East Asia Synthetic Co., Ltd.) System, "Aron oxetane OXT-221")

(9) Cationic polymerization initiator

‧Trade name: Sanxin Chemical Industry Co., Ltd., "San-aid Si-100L"

(10) Hardener: "4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30"

‧Trade name: New Japan Physical and Chemical Co., Ltd., "RIKACID MH-700G"

(11) Hardening accelerator: amine hardener

‧Trade name: San-apro (share) company, "U-CAT 18X"

(12) Polyoxyl resin

‧Trade name: Toray‧Dowcorning Co., Ltd., "EG6301 (A liquid / B liquid)"

(Synthesis Example 1)

Resin Composition A: Resin Composition A was produced in the following procedure and evaluated.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an 80 ° C oil bath was placed on a magnetic stirrer.

(2) According to the composition ratio shown in Table 7, an alicyclic epoxy resin, an alkoxydecane compound, and THF were placed in a flask to which a stir bar was placed, and stirred under an environment of 25 ° C, and then, after stirring, Further, water and a hydrolysis condensation catalyst are added and mixed and stirred.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 8 hours while refluxing.

(4) After completion of the reaction, the mixture was cooled to 25 ° C, and then the cooling tube was removed from the flask, and after the refluxing step was completed, the sample solution was taken.

(5) The solution after the completion of the refluxing step was distilled off at 400 Pa and 50 ° C for 1 hour using an evaporator, and further subjected to dehydration condensation reaction while distilling off at 80 ° C for 5 hours.

(6) After completion of the reaction, the mixture was cooled to 25 ° C to obtain a resin composition A.

(7) The mixing index α46 to ε46 of this resin composition is shown in Table 9.

(8) Further, the epoxy equivalent (WPE) of the resin composition A obtained in the above (6) was measured by the above method.

The epoxy resin equivalent (WPE) of the above resin composition was 158 g/eq, which showed an appropriate value.

(Synthesis Example 2)

Resin Composition B: According to the composition ratio of Table 7, the resin composition B was synthesized and evaluated in the same manner as in Synthesis Example 1. The mixing index α47 to ε47 is shown in Table 9.

The epoxy equivalent (WPE) of the above resin composition B was 163 g/eq, which showed an appropriate value.

(Synthesis Example 3)

Resin composition C: According to the composition ratio of Table 7, the resin composition C was synthesized and evaluated in the same manner as in Synthesis Example 1. . The mixing index α48 to ε48 is shown in Table 9.

The epoxy equivalent (WPE) of the above resin composition C was 160 g/eq, which showed an appropriate value.

(Example 36)

Composition 1 was produced and evaluated according to the following procedure.

(1) 75 mass% of the resin composition A of the above Synthesis Example 1 and a 25% by mass of an oxetane compound were mixed and stirred, and further degassed under vacuum to obtain the composition 1. The viscosity of the composition 1 was 1.82 Pa ‧ and it was a liquid excellent in fluidity.

(2) In the composition 1 of 99.2% by mass, 0.8% by mass of a cationic polymerization initiator was added and mixed, and degassing treatment was carried out under the same conditions as in (1) to prepare a solution for a cured product.

(3) The thickness will be 3mm The shape 矽 rubber 制作 was formed between two stainless steel sheets coated with a release agent to form a molding jig, and the cured product produced by the molding jig was made into a shape of about 50 mm × about 20 mm × thickness 30 mm.

(4) It is prepared to inject the above-mentioned hardened solution into the forming jig and the five substrates for the above-mentioned crack test.

(5) The above-mentioned molding jig and the substrate for cracking test were placed in an oven, and hardened at 85 ° C for 1 hour and further at 150 ° C for 3 hours to prepare a cured product.

(6) The results of the light resistance test, the crack resistance test, and the surface tackiness test by the above methods using the above samples are shown in Table 9. The index of the light resistance test of the cured product was YI=6.8≦11, and it was judged to have light resistance. Further, none of the five samples was cracked, and it was judged to have crack resistance. Further, since the adhesion was not confirmed, the surface adhesion was also good.

From the above results, it was found that the composition 1 of Example 36 had fluidity, and the cured product of the composition had light resistance and crack resistance, and the surface tackiness was also good.

(Example 37)

Composition 2 was produced and evaluated according to the following procedure.

(1) 70% by mass of the resin composition B of the above Synthesis Example 2 and 30% by mass of an oxetane compound were mixed and stirred, and degassed in the same manner as in Example 36, and was regarded as Composition 2. The viscosity of the composition 2 was 2.78 Pa·s, which was a liquid excellent in fluidity.

(2) In the composition 2 of 99.4% by mass, 0.6% by mass of a cationic polymerization initiator was added and mixed, and degassing treatment was carried out under the same conditions as in (1) to prepare a solution for a cured product.

(3) Using the above-mentioned solution for a cured product, a hardening treatment was carried out in the same manner as in Example 36 to prepare a cured product.

The index of the light resistance test of the cured product was YI=7.9≦11, and it was judged to have light resistance. Further, none of the five samples was cracked, and it was judged to have crack resistance. Further, since the adhesion was not confirmed, the surface adhesion was also good.

From the above results, it was found that the composition 2 of Example 37 had fluidity, and the cured product of the composition had light resistance and crack resistance, and the surface tackiness was also good.

(Example 38)

Composition 3 was produced and evaluated according to the following procedure.

(1) 80% by mass of the resin composition C of the above Synthesis Example 3 and 20% by mass of an oxetane compound were mixed and stirred, and degassed in the same manner as in Example 36, and was regarded as Composition 3. The viscosity of the composition 3 was 2.27 Pa s, which was a liquid excellent in fluidity.

(2) In the composition 3 of 99.3% by mass, 0.7% by mass of a cationic polymerization initiator was added and mixed, and degassing treatment was carried out under the same conditions as in (1) to prepare a solution for a cured product.

(3) Using the above-mentioned solution for a cured product, a hardening treatment was carried out in the same manner as in Example 36 to prepare a cured product.

The index of the light resistance test of the cured product was YI=8.8≦11, and it was judged that it had light resistance. Further, four of the five samples did not undergo cracking, and it was judged to have crack resistance. Further, since the adhesion was not confirmed, the surface adhesion was also good.

From the above results, it was found that the composition 3 of Example 38 had fluidity, and the cured product of the composition had light resistance and crack resistance, and the surface tackiness was also good.

(Comparative Example 15)

In the above Bis-A epoxy resin and alicyclic epoxy resin, a hardener and a hardening accelerator are added in accordance with the composition ratio of Table 8 to replace the cationic polymerization initiator, and the mixture is stirred, and then degassed under vacuum. Think of it as a solution for hardening. Then, the above-mentioned cured solution was injected into the molding jig and the five fracture test substrates in the same manner as in Example 36, and the hardened material was cured at 110 ° C for 4 hours to prepare a cured product.

The results of evaluation in the same manner as in Example 36 are shown in Table 9.

When the index YI=13.9>11 of the light resistance test of the cured product was judged to be no light resistance. Further, four of the five samples were not cracked and had crack resistance. Further, the adhesion was not confirmed, and the surface adhesion was good.

From the above results, it was found that the cured product of Comparative Example 15 was not light-resistant, and was generally judged to be unacceptable.

(Comparative Example 16)

The mixture of the A liquid and the liquid B was mixed at a mass ratio of 1:1 using the above polyoxyxylene resin, and the mixture was stirred and degassed under vacuum to obtain a solution for the hardened material.

Then, the above-mentioned cured solution was injected into the molding jig and the five fracture test substrates in the same manner as in Example 36, and the cured product was cured at 150 ° C for 1 hour to prepare a cured product.

The results of evaluation in the same manner as in Example 36 are shown in Table 9.

YI=2.3≦11, which is an index of the light resistance test of the cured product, was judged to have light resistance. Further, five of the five samples were not cracked, and thus had crack resistance. However, it was confirmed that there was a feeling of adhesion, so the surface adhesion was poor. From the above results, it was found that the cured product of Comparative Example 16 had light resistance and crack resistance, but the surface adhesion was poor, so that it was judged to be unacceptable.

As shown in Tables 7 to 9, a resin composition obtained by mixing an epoxy resin with a specific alkoxydecane compound in a specific ratio and performing cohydrolysis condensation, and a resin having an oxetane compound The composition system is excellent in fluidity. Moreover, the cured product obtained by using these resin compositions is light resistant and crack resistant. Excellent in properties and surface adhesion.

Next, a photosensitive resin composition obtained by adding a photoacid generator to the modified resin composition of the present embodiment will be specifically described by way of examples and comparative examples.

The epoxy equivalent (WPE), viscosity, and mixing index α to η were obtained in the same manner as above.

The physical property evaluations of Examples 39 to 41 and Comparative Examples 17 to 19 were carried out as follows.

<Measurement of Viscosity of Photosensitive Resin Composition>

The container in which the composition immediately after the production was placed was sealed, and the temperature was adjusted at 25 ° C for 1 hour, and then the viscosity at 25 ° C was measured.

When the viscosity is 1000 Pa‧s or less, it is judged to have fluidity.

<Method for producing coating film a>

The coating film was prepared under the following conditions in the air, at a temperature of 23 ° C, and at a humidity of 55% RH.

(1) The following substrates were prepared, and the surface was wiped with ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) to dry.

Substrate: Polyethylene terephthalate resin (hereinafter abbreviated as PET) polycarbonate resin (hereinafter referred to as PC) polymethyl methacrylate resin (hereinafter referred to as PMMA)

(2) The photosensitive composition of the example or the composition of the comparative example was applied onto the above substrate using a bar coater (#3).

(3) The above substrate was placed in a UV curing device (manufactured by Fusion UV Systems, Japan), and the operation was repeated three times under the following conditions to be hardened. Light source and amount of light: High pressure mercury lamp (120W/cm ² ) Conveyor speed: 10m/min

(4) Further, the substrate was heat-treated at 100 ° C for 1 hour to carry out post-hardening.

<Method for producing coating film b>

The coating film was prepared in the air under the conditions of a temperature of 23 ° C and a humidity of 55% RH according to the following procedure.

(1) The following substrates were prepared, and the surface was wiped with ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) to dry.

Substrate: PET

(2) The photosensitive composition of the example or the composition of the comparative example was applied onto the above substrate using a bar coater (#3).

(3) The above substrate was placed on a UV curing device (manufactured by Fusion UV Systems, Japan), and the operation was repeated five times under the following conditions to be hardened.

Light source and amount of light: high pressure mercury lamp (120W/cm ² )

Conveyor speed: 5m/min

<Photocuring hardenability of coating film>

The above coating film is determined according to [JIS K 5600-5-4:1999 General Test Method for Coatings - Part 5: Mechanical Properties of Coating Film - Section 4: Scratch Resistance (Pencil Method)], when it is 3B to When it was 6H, it was judged that the photocurability was good.

<Adhesiveness of coating film>

The above coating film was measured in accordance with [JIS K 5600-5-6: 1999 General Test Method for Coatings - Part 5: Mechanical Properties of Coating Films - Section 6: Adhesion (cross cut test).

The results are evaluated in the following three stages:

○: almost no peeling

△: partial peeling

×: almost all peeled off

When the result which is better than the standard is displayed, it is judged that the adhesiveness is good.

<Comprehensive judgment>

When the photosensitive resin composition has fluidity and the photocurability and adhesion of the coating film are good, it is judged to be satisfactory.

The raw materials used in Examples 39 to 41 and Comparative Examples 17 to 19 are shown in the following (1) to (9).

(1) Epoxy resin

(1-1) Epoxy Resin A: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as Bis-A epoxy resin)

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 187g/eq

‧ Viscosity (25 ° C): 14.3 Pa‧ s

(1-2) Epoxy resin B: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate (hereinafter, referred to as alicyclic epoxy resin)

‧trade name: manufactured by Daicel Chemical Industry Co., Ltd., "Celloxide 2021P"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 131g/eq

‧ Viscosity (25 ° C): 227 mPa ‧ s

(2) alkoxydecane compound H: 3-glycidoxypropyltrimethoxydecane (hereinafter referred to as GPTMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-403"

(3) alkoxydecane compound I: phenyltrimethoxydecane (hereinafter referred to as PTMS)

‧Product Name: Shin-Etsu Chemical Co., Ltd., "KBM-103"

(4) alkoxydecane compound J: dimethyldimethoxydecane (hereinafter referred to as DMDMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-22"

(5) alkoxy decane compound K: tetraethoxy decane (hereinafter referred to as TEOS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBE-04"

(6) Solvent

(6-1) Tetrahydrofuran: manufactured by Wako Pure Chemical Industries Co., Ltd., without stabilizer (hereinafter referred to as THF)

(7) Hydrolysis condensation catalyst: Dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as DBTDL).

(8) Photoacid generator:

(8-1) Triallyl sulfonium hexafluorophosphate mixture

‧ Product name: "UVI-6990" (hereinafter referred to as UVI-6900) manufactured by Union Carbide

(8-2) Aromatic quinone hexafluoroantimonate

‧ Product name: Sanshin Chemical Industry Co., Ltd., "San-AidSI-80L" (hereinafter referred to as SI-80L)

(9) Oxetane compounds

(9-1) 3-ethyl-3-(phenoxymethyl)oxetane

‧Trade name: East Asia Synthetic Co., Ltd., "OXT-211" (hereinafter referred to as POX)

(Synthesis Example 4)

Resin Composition D: Resin Composition D was produced and evaluated in the following procedure.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an 80 ° C oil bath was placed on a magnetic stirrer.

(2) According to the composition ratio of Table 10, an alicyclic epoxy resin, an alkoxydecane compound, and THF are added to a flask to which a stirrer has been placed under an environment of 25 ° C, mixed and stirred, and further added. The water and the hydrolysis condensation catalyst are mixed and stirred.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 8 hours while refluxing.

(4) After completion of the reaction, it was cooled to 25 ° C, and then the cooling tube was removed from the flask to take a solution.

(5) The above solution was distilled off at 400 Pa and 50 ° C for 1 hour using an evaporator, and further subjected to dehydration condensation reaction while distilling off at 80 ° C for 5 hours.

(6) After completion of the reaction, the mixture was cooled to 25 ° C to obtain a resin composition D.

(7) The mixing index α49 to ε49 of this resin composition is shown in Table 12.

(8) Further, the epoxy equivalent (WPE) of the resin composition D obtained in the above (6) was measured by the above method.

The epoxy equivalent (WPE) of the above resin composition was 193 g/eq, which showed an appropriate value. Further, the viscosity was 12.7 Pa.s < 1000 Pa s, which showed good fluidity.

(Synthesis Example 5)

Resin Composition E: The resin composition E was synthesized and evaluated in the same manner as in Synthesis Example 4 according to the composition ratio of Table 10. The mixing index α50 to ε50 is shown in Table 12.

The epoxy equivalent (WPE) of the above resin composition E was 152 g/eq, which showed an appropriate value. Further, the viscosity was 0.93 Pa ‧ < 1000 Pa ‧ and showed good fluidity.

(Example 39)

The photosensitive resin composition 1 and its coating film were produced and evaluated in the following procedures.

(1) The resin composition D of the above Synthesis Example 4 was mixed and stirred according to the blending method of Table 11, and further degassed under vacuum to obtain the photosensitive resin composition 1. The photosensitive resin composition 1 has a viscosity of 12.6 Pa s < 1000 Pa s and is a liquid excellent in fluidity.

(2) The photosensitive resin composition 1 was applied to the above-mentioned three types of substrates (PET, PC, PMMA) in accordance with the above [Method for Producing Coating Film a], and a coating film was produced using a UV curing device.

(3) The above coating film is expressed in accordance with [JIS K5600-5-4:1999 General Test Method for Coatings - Part 5: Mechanical Properties of Coating Films - Section 4: Scratch Resistance (Pencil Method)] In Table 12.

(4) The above coating film is expressed in accordance with [JIS K5600-5-6:1999 General Test Method for Coatings - Part 5: Mechanical Properties of Coating Films - Section 6: Adhesion (Transverse Method)] In Table 12.

As described above, the photosensitive resin composition 1 was excellent in fluidity, and the photocuring property of the coating film was good, and the adhesion was better than that of the comparative example 17 as a standard.

(Embodiment 40)

The photosensitive resin composition 2 was produced in the same manner as in Example 39 according to the blending method of Table 11. However, the conveyor speed of the UV curing device was set to 10 m/min. The evaluation results are shown in Table 12.

The viscosity of the photosensitive resin composition 2 is 3.2 Pa ‧ < 1000 Pa s, and it is a liquid excellent in fluidity.

As described above, the photosensitive resin composition 2 was excellent in fluidity, and the photocuring property of the coating film was good, and the adhesion was better than that of Comparative Example 17 as a standard.

(Example 41)

The photosensitive resin composition 3 was produced in accordance with the blending method of Table 11, and evaluated in the same manner as in Example 39. The viscosity of the photosensitive resin composition 3 is 1.0 Pa ‧ < 1000 Pa s, and is a liquid excellent in fluidity.

Next, using the photosensitive resin composition 3 described above, PET is used as a substrate, and a coating film is produced in accordance with the above [Method for Producing Coating Film b]. The results are shown in Table 12.

As described above, the photosensitive resin composition 3 was excellent in fluidity, and the photocurability of the coating film was good, and the adhesion was better than that of Comparative Example 19 as a standard.

(Comparative Example 17)

The photosensitive resin composition 4 was produced in the same manner as in Example 39, according to the blending method of Table 11. The evaluation results are shown in Table 12.

The photosensitive resin composition 4 has a viscosity of 13.8 Pa s < 1000 Pa s, and is a liquid excellent in fluidity.

However, as shown in Table 12, the photosensitive resin composition 4 was excellent in fluidity, but the adhesion of the coating film was poor, so that it was judged to be unacceptable.

(Comparative Example 18)

The photosensitive resin composition 5 was produced in the same manner as in Example 39 according to the blending method of Table 11. GPTMS was used as the decane coupling agent. The evaluation results are shown in Table 12.

The viscosity of the photosensitive resin composition 5 is 12.1 Pa s < 1000 Pa s, and is a liquid excellent in fluidity.

However, as shown in Table 12, the photosensitive resin composition 5 was excellent in fluidity, but the effect of improving the adhesion of the coating film was not observed.

(Comparative Example 19)

The photosensitive resin composition 6 was produced in the same manner as in Example 39 according to the blending method of Table 11. The evaluation results are shown in Table 12.

The viscosity of the photosensitive resin composition 6 is 0.3 Pa ‧ < 1000 Pa s, and is a liquid excellent in fluidity.

However, as shown in Table 12, the photosensitive resin composition 6 was excellent in fluidity, but the adhesion of the coating film was poor, so that it was judged to be unacceptable.

From the results of Tables 10 to 12, it is understood that the resin composition obtained by co-hydrolyzing and condensing an epoxy resin with a specific alkoxydecane compound and the photosensitive resin composition of the photoacid generator have excellent fluidity. The coating agent and the coating film which are obtained by using such a photosensitive resin composition are excellent in photocurability and adhesion.

Next, a fluorescent resin composition in which a phosphor is added to the modified resin composition of the present embodiment will be specifically described by way of examples and comparative examples.

The evaluation of the physical properties of Examples 42 to 44 and Comparative Examples 20 to 23 was carried out as follows.

The epoxy equivalent (WPE), viscosity, and mixing index α to η were obtained in the same manner as above.

<Calculation of preservation stability index θ, and preservation stability of resin composition>

The storage stability in the resin composition was evaluated by the storage stability index θ shown by the following general formula (9).

Preservation stability index θ=(preservation viscosity)/(starting viscosity)...(9)

The container in which the resin composition immediately after the production was placed was sealed, and after adjusting the temperature at 25 ° C for 2 hours, the viscosity at 25 ° C was measured, and this was regarded as [starting viscosity].

Further, the container in which the resin composition was placed was sealed, and then stored in an incubator kept at a constant temperature of 25 ° C for 2 weeks. After storage, the viscosity at 25 ° C was measured and this was taken as [preservation viscosity].

When the resin composition has fluidity (viscosity of 1000 Pa ‧ or less) and the storage stability index θ is 4 or less, it is determined that there is storage stability.

<Dispersion stability test of fluorescent resin composition>

After the fluorescent resin composition was produced, it was placed in a 50 ml glass bottle and sealed, and stored in an incubator at a constant temperature of 25 ° C for 5 hours. After storage, the appearance was observed to visually confirm the precipitation or uniformity of the phosphor. When the precipitation of the phosphor was not observed and the phosphor was uniformly dispersed, it was judged that the dispersion stability was acceptable.

<Light resistance test of cured product (hardened product of resin composition)>

The hardened matter in which the solid matter (fluorescent body) is dispersed has a large deviation in yellowness (YI). Therefore, a cured product was produced from a resin composition to which no phosphor was added by the following method, and the evaluation results were evaluated as light resistance.

(1) The cured product prepared by the method described later was hardened with a solution to prepare a cured product of 20 mm × 10 mm × 3 mm in thickness.

(2) The cured product was covered with a black mask of 25 mm × 15 mm × 1.2 mm thick having a hole having a diameter of 5.5 mm, and was used as a test sample for light resistance test.

(3) A preparation device was used to irradiate the UV light from the UV irradiation device ("Spot Cure SP7-250DB" manufactured by Ushio Electric Co., Ltd.) to the above-mentioned sample in an incubator set to a constant temperature of 50 °C via an optical fiber.

(4) The sample was placed in an incubator at a constant temperature of 50 ° C in a state where the black mask was placed on the upper surface.

(5) UV light of 2 W/cm ² was irradiated for 96 hours from the upper portion of the black mask so that the UV light was irradiated to the hole having a diameter of 5.5 mm.

(6) A sample irradiated with UV was measured by a spectrophotometer ("SD5000" manufactured by Nippon Denshoku Industries Co., Ltd.) which has been modified into a 10 mm-diameter aperture.

(7) Yellowness (YI) is determined in accordance with "ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics".

Here, when YI is 13 or less, it is judged as pass.

<LED luminescence test>

When the LED is lit, the color tone is visually confirmed, and when the color tone changes from blue to white with respect to the LED which is not blended with the phosphor, it is considered that the luminosity is acceptable.

<Luminescence test of light-storing material (measurement of afterglow time)>

For the sample, a conventional light source fluorescent lamp D65 prescribed in [JIS Z9107:2008 Safety Marking - Performance Classification, Performance Standards and Test Methods] was used, and was irradiated with 200 lux for 20 minutes. After the irradiation, the residual light luminance was measured with a luminance meter, and the time until it reached 0.3 mcd/m ² or less was regarded as the afterglow time. When the afterglow time was 120 minutes or more, it was judged that the luminosity was acceptable.

<Creditworthiness test of LED (1) (continuous action test: hereinafter referred to as [L test])>

10 LEDs according to [MIL-STD-750E (Test Methods For Semiconductor Devices)] METHOD 1026.5 (Steady-State Operation Life) and [MIL-STD-883G (Microcircuits)] METHOD 1005.8 (Steady-State Life) was evaluated under the following conditions.

The light was lit with [IF = 20 mA, Ta = 25 ° C, 960 hours], and the full beam (1 m) before and after the lighting was measured. In addition, the [full beam maintenance rate (%) = (full beam after lighting) / (full beam before lighting) × 100] is obtained for each LED, and the total beam maintenance rate (%) of the full LED is the lowest. When the value is 90% or more, it is judged as pass.

<Creditworthiness test of LED (2) (thermal shock test: hereinafter referred to as [TS test])>

Ten LEDs were evaluated according to the following conditions [Test Method 307 (Heat Impact Test) of [EIAJ ED-4701/300 (Environment and Durability Test Method for Semiconductor Devices (Strength Test 1))].

[10 ° C (5 minutes) to 100 ° C (5 minutes)] as a single cycle, after performing 100 cycles of thermal shock, confirm the number of LED lights, when all 10 are lit, it is judged as qualified.

<Creditworthiness Test of LED (3) (Temperature Cycle Test: Hereinafter referred to as [TC] Test)>

Ten LEDs were evaluated according to the following conditions [Test Method 105 (Temperature Cycle Test) of [EIAJ ED-4701/100 (Environment and Durability Test Method for Semiconductor Devices (Life Test I))].

[-40 ° C (30 minutes) to 85 ° C (5 minutes) to 100 ° C (30 minutes) to 25 ° C (5 minutes)] as a single cycle, after performing 100 cycles of temperature cycle, confirm the brightness of the LED When the number of lamps is all 10, it is judged as pass.

In the evaluation of the above LEDs, when the light resistance and reliability tests (1) to (3) were all qualified, the overall judgment was a pass.

The raw materials used in Examples 42 to 44 and Comparative Examples 20 to 23 are shown in the following (1) to (10).

(1) Epoxy resin

(1-1) Epoxy Resin A: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as "Bis-A epoxy resin")

‧ Trade name: Asahi Kasei Epoxy Co., Ltd., "AER" In addition, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 188g/eq

‧ Viscosity (25 ° C): 14.8 Pa‧ s

(1-2) Epoxy resin B: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate (hereinafter referred to as "alicyclic epoxy resin")

‧trade name: manufactured by Daicel Chemical Industry Co., Ltd., "Celloxide 2021P"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 131g/eq

‧ Viscosity (25 ° C): 227 mPa ‧ s

(2) alkoxydecane compounds

(2-1) alkoxydecane compound H: 3-glycidoxypropyltrimethoxydecane (hereinafter referred to as GPTMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-403"

(2-2) alkoxydecane compound I: phenyltrimethoxydecane (hereinafter referred to as PTMS)

‧Product Name: Shin-Etsu Chemical Co., Ltd., "KBM-103"

(2-3) alkoxydecane compound J: dimethyldimethoxydecane (hereinafter referred to as DMDMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-22"

(2-4) Alkoxydecane Compound K: Tetraethoxydecane (hereinafter referred to as TEOS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBE-04"

(3) Solvent: tetrahydrofuran: manufactured by Wako Pure Chemical Industries Co., Ltd., without stabilizer (hereinafter referred to as "THF")

(4) Hydrolysis condensation catalyst: Dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as "DBTDL")

(5) Hardener: [4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30]

‧Trade name: New Japan Physical and Chemical Co., Ltd., "RIKACID MH-700G"

(6) Hardening accelerator: amine compound

‧Trade name: San-apro (share) company, "U-CAT 18X"

(7) Reactive diluent: "1,2:8,9 epoxide limonene"

‧Trade name: Daicel Chemical Industry Co., Ltd., "Celloxide 3000"

(8) Polymerization initiator: aromatic sulfonium salt

‧trade name: Sanshin Chemical Industry Co., Ltd., "San Aid SI-100L" (9) phosphor

(9-1) Phosphor A: "YAG: Ce ³⁺ phosphor" (manufactured by Optnics Co., Ltd.)

(9-2) Phosphor B (light-storing phosphor): "SrAl ₂ O ₄ : EU, Dy phosphor" (manufactured by Basic Specialty Chemicals Co., Ltd.)

(10) Polyoxyl resin

‧Trade name: Toray‧Dow corning Co., Ltd., "EG6301 (A liquid / B liquid)

[Synthesis Example 6]

The resin composition was produced by the following procedure.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an 80 ° C oil bath was placed on a magnetic stirrer.

(2) According to the composition ratio shown in Table 13, the above Bis-A1 epoxy resin, alkoxydecane compound, and THF were placed in a flask to which a stir bar was placed, and mixed and stirred under an environment of 25 ° C, Further, water and a hydrolysis condensation catalyst are added and mixed and stirred.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 20 hours while refluxing (reflow step).

(4) After completion of the reaction, it was cooled to 25 ° C, and then the cooling tube was removed from the flask.

(5) The solution after the completion of the refluxing step was distilled off at 400 Pa and 50 ° C for 1 hour using an evaporator, and further subjected to a dehydration condensation reaction (dehydration condensation step) while distilling off at 80 ° C for 10 hours.

(6) After completion of the above dehydration condensation reaction, the mixture was cooled to 25 ° C to obtain a resin composition.

(7) The mixing indexes α51 to ε51 of the resin composition are shown in Table 16 below, respectively.

(8) Further, the epoxy equivalent (WPE), the initial viscosity, and the storage viscosity of the resin composition obtained in the above (6) were measured by the above method. Furthermore, the preservation stability index θ51 is obtained, which is shown in Table 16.

The epoxy resin equivalent (WPE) of the resin composition of the above Synthesis Example 6 was 228 g/eq, and showed an appropriate value. Further, the initial viscosity was 38.2 Pa s < 1000 Pa s, and the storage viscosity = 61.1 Pa ‧ < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ51=1.6≦4 was determined, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 7]

A resin composition was produced in the same manner as in Synthesis Example 6 except that the reflux step was changed to 6 hours, in accordance with Tables 13 and 14. The results of evaluation in the same manner as in Synthesis Example 6, the mixing indexes α52 to ε52, and the storage stability index θ52 are shown in Table 16.

As shown in Table 16, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 7 was 158 g/eq, which showed an appropriate value. Further, the initial viscosity = 1.8 Pa ‧ < 1000 Pa s, and the storage viscosity = 3.1 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ52=1.72≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Example 42]

The cured product was produced using the resin composition of the above Synthesis Example 6 after storage at 25 ° C for 2 weeks, and the light resistance test was carried out. The results are shown in Table 16.

(1) The resin composition, the curing agent, and the hardening accelerator described above were mixed and stirred at a composition ratio of Table 14 in an environment of 25 ° C, and deaerated under vacuum to obtain a solution for a cured product.

(2) The thickness will be 3mm The glyph 矽 rubber 挟 is formed between two stainless steel plates coated with a release agent to form a molding jig.

(3) The solution for the hardened material was poured into the molding jig, and hardened at 120 ° C for 1 hour and further at 150 ° C for 1 hour to prepare a cured product.

(4) After the temperature in the oven was lowered to 30 ° C or lower, the cured product was taken out, and a sample for light resistance test was prepared by the above method.

(5) The results of the light resistance test conducted by the above method using the above samples are shown in Table 16. The index YI of the light resistance test of the cured product was 7.5 ≦13, and it was judged that the light resistance was acceptable.

(6) Next, 10% by mass of the phosphor A was blended in 90% by mass of the resin composition of Synthesis Example 6, and mixed by a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) for 10 minutes, and then under vacuum. The defoaming treatment was carried out, and this was regarded as a fluorescent resin composition.

(7) The above fluorescent resin composition was poured into a 50 mL sample bottle and stored at 25 ° C for 5 hours.

(8) After the storage, the side surface and the bottom surface were visually observed to be free from precipitation, and the phosphor was uniformly dispersed. Therefore, the dispersion stability of the fluorescent resin composition was judged to be acceptable. The results of the evaluation are shown in Table 16.

Further, using the above-described fluorescent resin composition stored at 25 ° C for 2 weeks, a cannonball type LED was produced in the following procedure, and reliability tests (1) to (3) were performed. The results are shown in Table 16.

The structure of the bullet-type LED has two lead frames, and at one of the upper ends, a cup portion for mounting the LED chip is formed.

(9) Further, the above-mentioned fluorescent resin composition, curing agent, and curing accelerator were mixed and stirred according to the composition ratio of Table 15, and deaerated under vacuum to obtain an LED sealing material.

(10) Inject the (9) LED sealing material into the cup portion of the 5 mm diameter shell type mold frame.

(11) Here, an LED wafer having an emission wavelength of 400 nm is die-bonded with a silver paste), a bonding wire (copper wire) is connected, and the lead frame is immersed.

(12) After defoaming in a vacuum, the hardening treatment was performed at 90 ° C for 1 hour and further at 110 ° C for 5 hours.

(13) Further, as the outer layer resin, 46.6 mass% of the hardener and 0.2 mass% of the hardening accelerator are added to the 53.2% by mass of the Bis-A epoxy resin, mixed and stirred, and degassed under vacuum to The mold frame was injected, and hardened at 130 ° C for 1 hour and further at 150 ° C for 6 hours to obtain a bullet-type LED. The evaluation results are shown in Table 16.

As a result of the above-mentioned [luminescence test], the LED of Comparative Example 20 was blue light emission, and the LED of Example 42 was white light emission, and it was judged that it was acceptable.

As a result of the above-mentioned [confidence test (1) (L test)], the lowest value of the entire LED was the total beam maintenance ratio (%) = 94% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned [confidence test (2) (TS test)], after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Further, as a result of the above-mentioned [confidence test (3) (TC test)], after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged as pass.

From the above results, it was found that the dispersion resin stability test, the light resistance test, the luminescence test, and the reliability test (1) to (3) of the fluorescent resin composition of Example 42 were all acceptable, and the overall judgment was a pass.

[Example 43]

The resin composition of Synthesis Example 6 was used instead of the resin composition of Synthesis Example 6, and the curing temperature of (3) and (12) of Example 41 was changed to 110 ° C for 4 hours, and further 150 ° C for 1 hour. The resin composition, the cured product, the fluorescent resin composition, and the LED were produced in the same manner as in Example 40 in accordance with Tables 13 to 15, and the evaluation results are shown in Table 16.

The light resistance test index YI=6.8≦13, and it was judged that the light resistance was acceptable.

Moreover, since the fluorescent resin composition after 5 hours of storage at 25 ° C was not precipitated, and the phosphor was uniformly dispersed, it was judged that the dispersion stability was acceptable.

Next, the result of performing the [luminescence test] of the LED was white light emission, and it was judged as pass.

Further, as a result of the [confidence test (1) (L test)], the lowest value of the entire LED was the total beam maintenance ratio (%) = 95% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned [confidence test (2) (TS test)], after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Then, as a result of the above-mentioned [confidence test (3) (TC test)], after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged as pass.

From the above results, it was found that the dispersion resin stability test, the light resistance test, the luminosity test, and the reliability test (1) to (3) of the fluorescent resin composition of Example 43 were all acceptable, so that the comprehensive judgment was qualified. .

[Example 44]

In a resin composition of Synthesis Example 7 of 60% by mass, 40% by mass of the phosphor B was blended in the same manner as in Example 42 to prepare a fluorescent resin composition, which was evaluated. When the dispersion resin stability test of the fluorescent resin composition of Example 44 was carried out without precipitation, it was judged to be acceptable.

Therefore, the fluorescent resin composition was mixed with the reaction diluent and the polymerization initiator at the ratio shown in Table 17, and defoamed under vacuum, further in the following steps, in air, at a temperature of 23 ° C, and a humidity of 55%. A light storage material (coating film) was produced under the conditions of RH.

(1) A slide glass having a size of 5 cm × 5 cm was prepared, and the surface was wiped with ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) and dried.

(2) The above fluorescent resin composition was applied onto the above-mentioned slide glass using a bar coater (#3).

(3) The carrier glass was cured at 140 ° C for 10 minutes to form a coating film.

In the luminosity test of the above-mentioned light-storing material (coating film), the residual light time was measured by the above method to be 600 minutes or longer, and it was judged to be acceptable.

From the above results, it was found that the dispersion resin composition of Example 44 had passed the dispersion stability test and the luminescence test, and was comprehensively judged to be acceptable. This result is shown in Table 18.

[Reference example]

The resin composition of Synthesis Example 6 was used instead of the fluorescent resin composition of Example 42, and a resin composition, a cured product, and an LED were produced according to Tables 13 to 15, and the evaluation results are shown in Table 16.

The light resistance test index YI=7.5≦13, and it was judged that the light resistance was acceptable.

Next, as a result of performing the [luminescence test] of the LED, it was blue light emission, and it was judged that the luminosity was unacceptable.

Further, as a result of the [confidence test (1) (L test)], the lowest value of all the LEDs was the total beam maintenance ratio (%) = 95% ≧ 90%, and it was judged to be acceptable.

Next, as a result of the above-mentioned [confidence test (2) (TS test)], after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Then, as a result of the above-mentioned [confidence test (3) (TC test)], after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged as pass.

[Comparative Example 20]

The resin composition of Synthesis Example 6 was replaced with an alicyclic epoxy resin to prepare a fluorescent resin composition, and the results of the evaluation are shown in Table 16.

After the fluorescent resin composition of Comparative Example 20 was stored at 25 ° C for 5 hours, the phosphor precipitated to be uneven, and the dispersion stability was judged to be unacceptable. Therefore, since the normal fluorescent resin composition could not be produced, the cured cured product and the LED were not produced, and the overall judgment was unacceptable.

[Comparative Example 21]

The resin composition of Synthesis Example 6 was replaced with a Bis-A epoxy resin, and a resin composition, a cured product, a fluorescent resin composition, and an LED were produced in the same manner as in Example 42 according to Tables 13 to 15, and evaluated. The results are shown in Table 16.

The light resistance test index YI = 17.2>13, and it was judged that the light resistance was unacceptable.

Further, the phosphor resin composition after storage at 25 ° C for 5 hours was free from precipitation, and the phosphor was uniformly dispersed, and the dispersion stability was judged to be acceptable.

Next, as a result of performing the [luminescence test] of the LED, it was white light emission, and it was judged as pass.

Further, as a result of the [confidence test (1) (L test)], the lowest value of all the LEDs was the total beam maintenance ratio (%) = 97% ≧ 90%, and it was judged to be acceptable.

Next, the results of the above-mentioned [confidence test (2) (TS test)] were carried out, and after the thermal shock of 100 cycles was performed, all the LEDs were turned on, and it was judged as pass.

Then, as a result of the above-mentioned [confidence test (3) (TC test)], after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged as pass.

From the above results, the fluorescent resin composition of Comparative Example 21 was qualified in the dispersion stability test, the luminosity test, and the reliability test (1) to (3), but the light resistance was poor, so the overall judgment was Not qualified.

[Comparative Example 22]

The resin composition of Synthesis Example 6 was replaced with the above polyfluorinated resin obtained by mixing and stirring the liquid A and the liquid B at a mass ratio of 1:1. A resin composition and a cured product were produced in the same manner as in Example 42 except that the curing temperature of the cured product of the cured product and the LED was changed to 70 ° C for 1 hour and further 150 ° C for 5 hours. The fluorescent resin composition, and the LED, the results of the evaluation are shown in Table 16.

The light resistance test index YI=2.0≦13, and it was judged that the light resistance was acceptable.

Next, as a result of performing the [luminescence test] of the LED, it was white light emission, and it was judged as pass.

As a result of the above-mentioned [confidence test (1) (L test)], three of the ten LEDs were not lit, and the total beam maintenance ratio (%) could not be measured, and it was judged to be unacceptable.

Next, the results of the above-mentioned [confidence test (2) (TS test)] were carried out, and after performing thermal shock of 100 cycles, only four of the 10 LEDs were turned on, and it was judged to be unacceptable.

Further, as a result of the above-mentioned [confidence test (3) (TC test)], after performing a temperature cycle of 100 cycles, only 6 of the 10 LEDs were turned on, and it was judged to be unacceptable.

From the above results, it was found that the refractive resin composition of Comparative Example 22 was qualified as the dispersion stability test, the light resistance test, and the luminosity test, but the results of the reliability tests (1) to (3) were unacceptable. Therefore, the comprehensive judgment is unqualified.

[Comparative Example 23]

A fluorescent resin composition and a light-storing material (coating film) were produced in the same manner as in Example 44 except that the alicyclic epoxy resin was used instead of the resin composition of Synthesis Example 7, in the same manner as in Example 44. A dispersion stability test and a luminescence test were carried out. The results are shown in Table 18.

When the dispersion resin test of Comparative Example 23 was subjected to the dispersion stability test, precipitation was caused to be uneven, and it was judged to be unacceptable.

In the luminosity test of the above-described light-storing material (coating film), the afterglow time was measured by the above method to be 600 minutes or longer, and it was judged to be acceptable.

From the above results, it was found that the fluorescent resin composition of Comparative Example 23 was qualified in the luminescence test, but the dispersion stability was unacceptable, so that the overall judgment was unacceptable.

As is clear from the results of Tables 13 to 18, the fluorescent resin compositions of Examples 42 and 43 were excellent in dispersion stability, and the cured product was excellent in light resistance. Further, the LEDs using the fluorescent resin compositions of Examples 42 and 43 as the sealing material were excellent in the luminosity test, and were also excellent in the reliability test. Further, the fluorescent resin composition of Example 44 was excellent in dispersion stability, and the light-storing material was excellent in luminosity test. On the other hand, the fluorescent resin compositions of Comparative Examples 20 and 23 were inferior in dispersion stability. Further, at least one of the light resistance at the time of forming a cured product, the luminosity test and the reliability test of an LED used as a sealing material was defective.

In the above, the fluorescent resin composition of the present embodiment is excellent in dispersion stability, and the sealing material obtained by using the fluorescent resin composition is excellent in reliability, and the light-storing material is excellent in light-emitting property.

Next, an insulating resin composition obtained by adding an insulating powder to the modified resin composition of the present embodiment will be specifically described by way of examples and comparative examples.

The evaluation of the physical properties in Examples 45 to 48 and Comparative Examples 24 to 25 was carried out as follows.

The epoxy equivalent (WPE), viscosity, and mixing index α to η were obtained in the same manner as above.

<Measurement of average particle size of molten cerium oxide>

The average particle diameter was measured in a dry mode using a laser diffraction type particle size distribution measuring apparatus (manufactured by SYMPATEC, [HELOS system]) ^.

<Measurement of Viscosity of Resin Composition>

The container immediately after the composition was sealed, and the temperature was adjusted at 25 ° C for 1 hour, and then the viscosity at 25 ° C was measured.

When the viscosity was 1000 Pa‧S or less, it was judged that there was fluidity.

<Measurement of Volume Resistivity of Insulating Resin Composition>

The insulating resin composition was applied to a carrier glass to a thickness of 40 μm by a bar coater, and heated at 200 ° C for 60 minutes to form a coating film.

The coating film was measured by a resistivity meter ("Loresta" manufactured by Dia Instruments Co., Ltd.), and when the volume resistivity was 1 × 10 ¹⁰ Ω ‧ cm or more, the insulation property was judged to be good.

<Measurement of adhesion strength and adhesion evaluation of insulating resin composition>

The adhesion strength before and after the moisture absorption treatment was measured by the following procedure.

(1) An insulating resin composition was applied to a die pad portion (9 mm × 9 mm) of a copper lead frame.

(2) Next, a ruthenium wafer (8 mm × 16 mm) was mounted on the die pad portion, and heated in an oven at 200 ° C for 1 hour (sample before moisture absorption treatment).

(3) The sample prepared in (2) was absorbed by a constant temperature and humidity machine set to a temperature of 85 ° C and a humidity of 85% for 72 hours (sample after moisture absorption treatment).

(4) The above-mentioned [pre-hygroscopic treatment sample] and [moisture-absorbing-treated sample] are placed on the hot plate at 250 ° C for 20 seconds while the crucible wafer is placed below, and the lead wire of the lead frame is pulled up. The adhesion strength at the time of peeling off the ruthenium wafer and the die pad was measured using a push-pull gauge (manufactured by IMADA Co., Ltd.).

(5) When the residual strength residual ratio represented by the following formula is 80% or more, it is judged that the adhesion is good.

Then, the residual rate of strength (%) = (the strength after the moisture absorption treatment) / (the strength before the moisture absorption treatment) × 100

<Void evaluation of insulating resin composition>

As described above, an insulating resin composition was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. Visually confirm the presence or absence of voids in the sample under a magnifying glass.

In the insulating resin compositions of the examples and the comparative examples, when the insulating properties and the adhesion were good, and it was confirmed that no voids were formed, the overall judgment was passed.

The raw materials used in the examples and comparative examples are shown in the following (1) to (10).

(1) Epoxy resin

(1-1) Epoxy Resin A: Bisphenol A type epoxy resin (hereinafter, referred to as Bis-A epoxy resin)

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 187g/eq

‧ Viscosity (25 ° C): 14.3 Pa‧ s

(1-2) Epoxy Resin F: Bisphenol F-type epoxy resin (hereinafter, referred to as "Bis-F epoxy resin" for short)

‧Trade name: Japan Ep Resin Co., Ltd., "jER807"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 169g/eq

‧ Viscosity (25 ° C): 3.2 Pa‧ S

(2) alkoxydecane compound H: 3-glycidoxypropyltrimethoxydecane (hereinafter referred to as GPTMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-403"

(3) alkoxydecane compound I: phenyltrimethoxydecane (hereinafter referred to as PTMS)

‧Product Name: Shin-Etsu Chemical Co., Ltd., "KBM-103"

(4) alkoxydecane compound J: dimethyldimethoxydecane (hereinafter referred to as DMDMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-22"

(5) alkoxy decane compound K: tetraethoxy decane (hereinafter referred to as TEOS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBE-04"

(6) Solvent

(6-1) Tetrahydrofuran: manufactured by Wako Pure Chemical Industries Co., Ltd., without stabilizer (hereinafter referred to as THF)

(7) Hydrolysis condensation catalyst: Dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries Co., Ltd., hereinafter referred to as DBTDL)

(8) Hardener: dicyandiamide (Maruzen Pharmaceutical Industry Co., Ltd.)

(9) Diluent: o-Cresyl glycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name "SY-OCG") (epoxy equivalent: 181 g/eq, viscosity: 8 mPa) ‧s)

(10) Insulating powder

(10-1) Molten cerium oxide (manufactured by Dongshin Chemical Co., Ltd., average particle diameter 6.1 μM)

(10-2) Hydrophobic cerium oxide ("H18" manufactured by Asahi Kasei WACKER Silicone Co., Ltd.)

(Synthesis Example 8)

Resin Composition F: Resin Composition F was produced and evaluated in the following procedure.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an oil bath of 80 ° C was placed on a magnetic stirrer.

(2) According to the composition ratio of Table 19, an epoxy resin, an alkoxydecane compound and THF are added to a flask which has been stirred with a stirring agent at 25 ° C, and after mixing and stirring, water and hydrolysis are further added. Condensation catalyst, mixing and stirring.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 10 hours while refluxing.

(4) After completion of the reaction, the mixture was cooled to 25 ° C, and then the cooling tube was removed from the flask, and after the refluxing step was completed, the sample solution was taken.

(5) The solution after the completion of the refluxing step was distilled off at 400 Pa and 50 ° C for 1 hour using an evaporator, and further distilled at 80 ° C for 5 hours to carry out a dehydration condensation reaction.

(6) After completion of the reaction, the mixture was cooled to 25 ° C to obtain a resin composition F.

(7) The mixing index α54 to ε54 of this resin composition is shown in Table 21.

(8) Further, the epoxy equivalent (WPE) of the resin composition F obtained in the above (6) was measured by the above method.

The epoxy equivalent (WPE) of the above resin composition = 195 g/eq, which showed an appropriate value. Further, the viscosity is 12.7 Pa‧s, which is a fluid liquid.

(Synthesis Example 9)

Resin composition G: According to the composition ratio of Table 19, the resin composition G was synthesized and evaluated in the same manner as in Synthesis Example 8. The mixing index α55 to ε55 is shown in Table 21.

The epoxy equivalent (WPE) of the above resin composition was 228 g/eq, which showed an appropriate value. Further, the viscosity is 13.8 Pa s, which is a fluid liquid.

(Synthesis Example 10)

Resin composition H: According to the composition ratio of Table 19, the resin composition H was synthesized and evaluated in the same manner as in Synthesis Example 8. The mixing index α56 to ε56 is shown in Table 21.

The epoxy equivalent (WPE) of the above resin composition was 206 g/eq, which showed an appropriate value. Further, the viscosity is 18.2 Pa s, which is a liquid having fluidity.

(Synthesis Example 11)

Resin Composition I: According to the composition ratio of Table 19, the resin composition I was synthesized and evaluated in the same manner as in Synthesis Example 8. The mixing index α57 to ε57 is shown in Table 21.

The epoxy equivalent (WPE) of the above resin composition was 208 g/eq, which showed an appropriate value. Further, the viscosity is 10.2 Pa s, which is a fluid liquid.

(Example 45)

The insulating resin composition 1 was produced by the following procedure and evaluated. The evaluation results and the mixing indexes α54 to ε54 are shown in Table 21.

Using the resin composition F of the above-mentioned Synthesis Example 8, the raw materials were blended according to the composition of Table 20, and uniformly kneaded by a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd.). Further, it was defoamed at 400 Pa for 30 minutes using a vacuum chamber, and this was regarded as the insulating composition 1.

The insulating resin composition 1 was applied onto a slide glass by a bar coater to a thickness of 40 μm, and heated at 200 ° C for 60 minutes to form a coating film. The volume resistivity of this coating film was measured by a resistivity meter ("Loresta", manufactured by Dia Instruments Co., Ltd.), and when the volume resistivity was 1 × 10 ¹⁰ Ω ‧ cm or more, the insulation property was judged to be good.

The residual strength residual ratio of the insulating resin composition 1 was determined by the following procedure.

(1) Four insulating resin compositions 1 were coated on a die pad portion (9 mm × 9 mm) of a copper lead frame.

(2) Next, a ruthenium wafer (8 mm × 16 mm) was mounted on the die pad portion, and heated at 200 ° C for 1 hour in an oven.

(3) Two of the samples prepared in (2) were used as "pre-hygroscopic treatment samples".

(4) The remaining two of the samples prepared in (2) were absorbed for 72 hours in a constant temperature and humidity machine set to a temperature of 85 ° C and a humidity of 85%, and these were used as "samples after moisture absorption treatment".

(5) Using the above "pre-hygroscopic treatment sample" and "moisture-absorbing sample", the crucible wafer is placed underneath, heated on a hot plate at 250 ° C for 20 seconds, and the lead wire of the lead frame is pulled up. The tensile strength (manufactured by IMADA Co., Ltd.) was measured for the adhesion strength when the tantalum wafer and the die pad were peeled off. The measurement was performed at n=2, and the average value was obtained.

(6) The average value of the subsequent strengths of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" obtained above was substituted into the following formula, and the residual strength was determined to evaluate the adhesion.

Then, the strength residual ratio (%) = (the strength after the moisture absorption treatment) / (the adhesion strength before the moisture absorption treatment) × 100 = 95% ≧ 80%, and the adhesion of the insulating resin composition 1 was judged to be good.

Next, the insulating resin composition 1 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. It was visually confirmed under a magnifying glass that no void was formed in this sample.

As a result of the above, it was found that the insulating resin composition 1 was excellent in insulation and adhesion, and no void was formed.

(Example 46)

The insulating resin composition 2 was produced and evaluated in the same manner as in Example 45, using the resin composition G described above. The evaluation results and the mixing indexes α55 to ε55 are shown in Table 21.

When the volume resistivity of the insulating resin composition 2 is 1 × 10 ¹⁰ Ω ‧ cm or more, it is judged that the insulation property is good.

The average value of the subsequent strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the insulating resin composition 2 was substituted into the following formula to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the strength residual ratio (%) = (the strength after the moisture absorption treatment) / (the adhesion strength before the moisture absorption treatment) × 100 = 92% ≧ 80%, and the adhesion of the insulating resin composition 2 was judged to be good.

Next, the insulating resin composition 2 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. It was visually confirmed under a magnifying glass that no void was generated in this sample.

As a result of the above, it was found that the insulating resin composition 2 was excellent in insulation and adhesion, and voids were not formed.

(Example 47)

The insulating resin composition 3 was produced and evaluated in the same manner as in Example 45 using the above-mentioned resin composition H according to the composition of Table 20. The evaluation results and the mixing indexes α56 to ε56 are shown in Table 21.

When the volume resistivity of the insulating resin composition 3 is 1 × 10 ¹⁰ Ω ‧ cm or more, it is judged that the insulation property is good.

The average value of the subsequent strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the insulating resin composition 3 was substituted into the following formula to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the strength residual ratio (%) = (the strength after the moisture absorption treatment) / (the adhesion strength before the moisture absorption treatment) × 100 = 89% ≧ 80%, and the adhesion property of the insulating resin composition 3 was judged to be good.

Next, the insulating resin composition 3 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. It was visually confirmed under a magnifying glass that the sample did not produce a void.

As a result of the above, it was found that the insulating resin composition 3 was excellent in insulation and adhesion, and no voids were formed.

(Example 48)

The insulating resin composition 4 was produced and evaluated in the same manner as in Example 43 using the above-mentioned resin composition I according to the composition of Table 20. The evaluation results and the mixing indexes α57 to ε57 are shown in Table 21.

The volume resistivity of the insulating resin composition 4 was 1 × 10 ¹⁰ Ω ‧ cm or more, and it was judged that the insulation property was good.

The average value of the subsequent strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the insulating resin composition 4 was substituted into the following formula to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the strength residual ratio (%) = (the strength after the moisture absorption treatment) / (the adhesion strength before the moisture absorption treatment) × 100 = 86% ≧ 80%, and the adhesion property of the insulating resin composition 4 was judged to be good.

Next, the insulating resin composition 4 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. It was visually confirmed under a magnifying glass that no void was generated in this sample.

As a result of the above, it was found that the insulating resin composition 4 was excellent in insulation and adhesion, and voids were not formed.

(Comparative Example 24)

The insulating resin composition 5 was produced and evaluated in the same manner as in Example 45 except that the resin composition F was replaced with a Bis-A epoxy resin and a Bis-F epoxy resin according to the composition of Table 20. The results are shown in Table 21.

The volume resistivity of the insulating resin composition 5 was 1 × 10 ¹⁰ Ω ‧ cm or more, and it was judged that the insulation property was good.

The average value of the subsequent strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the insulating resin composition 5 was substituted into the following formula to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the strength residual ratio (%) = (the strength after the moisture absorption treatment) / (the adhesion strength before the moisture absorption treatment) × 100 = 63% < 80%, and the adhesion property of the insulating resin composition 5 was judged to be defective.

Next, the insulating resin composition 5 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. It was visually confirmed under a magnifying glass that no void was generated in this sample.

As a result of the above, the insulating resin composition 5 was excellent in insulation, and no voids were formed. However, the adhesion was poor, and the overall judgment was unacceptable.

(Comparative Example 25)

The insulating resin composition 6 was produced and evaluated in the same manner as in Example 43 except that the resin composition F was replaced with Bis-A epoxy resin, GPTMS, and PTMS. The results are shown in Table 21.

The volume resistivity of the insulating resin composition 6 was 1 × 10 ¹⁰ Ω ‧ cm or more, and it was judged that the insulation property was good.

The average value of the subsequent strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the insulating resin composition 6 was substituted into the following formula to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the strength residual ratio (%) = (the strength after the moisture absorption treatment) / (the adhesion strength before the moisture absorption treatment) × 100 = 89% ≧ 80%, and the adhesion of the insulating resin composition 6 was judged to be good.

Next, an insulating resin composition 6 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. Visually confirm that this sample has voids under a magnifying glass.

As a result of the above, the insulating resin composition 6 was excellent in insulation property and adhesion, but it was confirmed that voids were formed, and it was judged that it was unacceptable.

As shown in Tables 19 to 21, the insulating composition of the resin composition, the insulating powder, and the hardener obtained by mixing an epoxy resin and a specific alkoxydecane compound in a specific ratio and performing cohydrolysis condensation The resin composition is excellent in insulation and adhesion, and voids are not generated.

Next, a semiconductor device in which the modified resin composition of the present embodiment is used will be specifically described by way of examples and comparative examples.

The evaluation of the physical properties in Examples 49 to 58 and Comparative Examples 26 to 30 was carried out as follows.

The epoxy equivalent (WPE), viscosity, and mixing index α to η were obtained in the same manner as described above.

<Calculation of preservation stability index θ, and preservation stability of resin composition>

The storage stability in the resin composition was evaluated based on the storage stability index θ represented by the following general formula (9).

Preservation stability index θ=(preservation viscosity)/(starting viscosity) (9)

The container in which the resin composition immediately after the preparation was placed was sealed, and the temperature was adjusted at 25 ° C for 2 hours, and then the viscosity at 25 ° C was measured, and this was regarded as "initial viscosity".

Further, the container in which the resin composition was placed was sealed, and then stored in an incubator kept at a constant temperature of 25 ° C for 2 weeks. After storage, the viscosity at 25 ° C was measured, and this was regarded as "preservation viscosity".

When the resin composition has fluidity (viscosity of 1000 Pa ‧ or less) and the storage stability index θ is 4 or less, it is determined that there is storage stability ^.

<LED (hardened) light resistance test>

It is difficult to cut out the sample after the LED is manufactured. Therefore, the cured product was produced by the following method, and the evaluation result was substituted for the light resistance evaluation of the LED.

(1) The cured product prepared by the method described later was hardened with a solution to prepare a cured product of 20 mm × 10 mm × 3 mm in thickness.

(2) The cured product was covered with a black mask of 25 mm × 15 mm × 1.2 mm thick having a hole having a diameter of 5.5 mm as a sample for light resistance test.

(3) The preparation device was used to irradiate the UV light from the UV irradiation device ("Spot Cure SP7-250DB" manufactured by Ushio Electric Co., Ltd.) to the above-mentioned sample in an incubator set to a constant temperature of 50 °C via an optical fiber.

(4) The sample was placed in an incubator at a constant temperature of 50 ° C in a state where the black mask was placed on the upper surface.

(5) UV light of 2 W/cm ² was irradiated for 96 hours from the upper portion of the black mask so that the UV light was irradiated to the hole having a diameter of 5.5 mm.

(6) A sample irradiated with UV was measured by a spectrophotometer ("SD5000" manufactured by Nippon Denshoku Industries Co., Ltd.) which has been modified into a 10 mm-diameter aperture.

(7) Yellowness (YI) is determined in accordance with "ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics".

When the YI was 13 or less, it was judged to be acceptable.

<Creditworthiness test of LED (1) (continuous action test: hereinafter referred to as [L test])>

10 LEDs, according to "MIL-STD-750E (Test Method for Semiconductor Devices)", METHOD 1026.5 (steady state operational life) and "MIL-STD-883G (microcircuit)", METHOD 1005.8 (steady state lifetime), Evaluate using the following conditions.

The lighting was performed under the conditions of forward current (IF) = 20 mA, ambient temperature (TA) = 25 ° C, and 960 hours, and the total light beam (LM) before and after lighting was measured. In addition, the "full beam maintenance rate (%) = (full beam after lighting) / (full beam before lighting) × 100" of each LED is obtained, and the total beam maintenance rate (%) of the entire LED is the lowest. When the value is 90% or more, it is judged as pass.

<Creditworthiness test of LED (2) (thermal shock test: hereinafter, referred to as [TS test] for short)

Ten LEDs were evaluated according to the following conditions [Test Method 307 (Heat Impact Test) of EIAJ ED-4701/300 (Environment and Durability Test Method for Semiconductor Devices (Strength Test I)).

[10 ° C (5 minutes) to 100 ° C (5 minutes)] was used as one cycle, and after performing 100 cycles of thermal shock, it was confirmed that the LED was turned on, and when all of the ten were turned on, it was judged to be acceptable.

<Creditworthiness Test of LED (3) (Temperature Cycle Test: Hereinafter referred to as [TC] Test)>

Ten LEDs were evaluated according to the following conditions [Test Method 105 (Temperature Cycle Test) of [EIAJ ED-4701/100 (Environment and Durability Test Method for Semiconductor Devices (Life Test I))].

[-40 ° C (30 minutes) to 85 ° C (5 minutes) to 100 ° C (30 minutes) to 25 ° C (5 minutes)] as a single cycle, after performing 100 cycles of temperature cycle, confirm the brightness of the LED When the number of lamps is 10, all of them are lit, and it is judged as pass.

In the evaluation of the above LEDs, when the light resistance and reliability tests (1) to (3) are all qualified, the overall judgment is qualified.

The raw materials used in Examples 49 to 59 and Comparative Examples 26 to 30 are shown in the following (1) to (12).

(1) Epoxy resin

(1-1) Epoxy Resin A1: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as "Bis-A1 Epoxy Resin")

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER2600"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 188g/eq

‧ Viscosity (25 ° C): 14.8 Pa‧ s

(1-2) Epoxy Resin A2: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as "Bis-A2 Epoxy Resin")

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER2500"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 186g/eq

‧ Viscosity (25 ° C): 10.2Pa‧S

(1-3) Epoxy Resin A3: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as "Bis-A3 Epoxy Resin")

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER6071"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows. However, since the epoxy resin A3 was solid at 25 ° C, the viscosity could not be measured.

‧Epoxy equivalent (WPE): 470g/eq

(2) alkoxydecane compound H: 3-glycidoxypropyltrimethoxydecane (hereinafter referred to as "GPTMS")

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-403"

(3) Alkoxydecane compound L: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (hereinafter referred to as "ECETMS")

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-303"

(4) Alkoxydecane Compound I: Phenyltrimethoxydecane (hereinafter, abbreviated as "PTMS")

‧Product Name: Shin-Etsu Chemical Co., Ltd., "KBM-103"

(5) Alkoxydecane compound J: trimethyldimethoxydecane (hereinafter, abbreviated as "DMDMS")

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-22"

(6) alkoxydecane compound K: tetraethoxy decane (hereinafter, referred to as "TEOS")

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBE-04"

(7) Solvent

(7-1) Tetrahydrofuran: manufactured by Wako Pure Chemical Industries Co., Ltd., which does not contain a stabilizer (hereinafter referred to as "THF")

(7-2) Tertiary butanol: manufactured by Wako Pure Chemical Industries Co., Ltd., which does not contain a stabilizer (hereinafter referred to as "t-BuOH")

(8) Hydrolysis condensation catalyst

(8-1) Dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as "DBTDL")

(8-2) Dibutyltin dimethoxide (manufactured by Sigma-Aldrich Co., Ltd., hereinafter referred to as "DBTDM")

(9) Hardener: [4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30]

‧Trade name: New Japan Physical and Chemical Co., Ltd., "RIKACID MH-700G"

(10) Hardening accelerator: amine compound

‧trade name: San-apro (share) company, "U-CAT 18x" (11) polyoxyl resin

‧Trade name: Toray‧Dow Corning Co., Ltd., "EG6301 (A liquid / B liquid)"

[Synthesis Example 12]

The resin composition was produced by the following procedure.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an 80 ° C oil bath was placed on a magnetic stirrer.

(2) According to the composition ratio shown in Table 22, the above Bis-A1 epoxy resin, alkoxydecane compound, and THF were placed in a flask to which a stir bar was placed, and mixed and stirred under an environment of 25 ° C, and then, after stirring, Further, water and a hydrolysis condensation catalyst are added and mixed and stirred.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 20 hours while refluxing (reflow step).

(4) After completion of the reaction, it was cooled to 25 ° C, and then the cooling tube was removed from the flask.

(5) The solution after the completion of the refluxing step was distilled off at 400 Pa and 50 ° C for 1 hour using an evaporator, and further subjected to a dehydration condensation reaction (dehydration condensation step) while distilling off at 80 ° C for 10 hours.

(6) After completion of the above dehydration condensation reaction, the mixture was cooled to 25 ° C to obtain a resin composition.

(7) The mixing indexes α58 to ε58 of the resin composition are shown in Table 24, respectively.

(8) Further, the epoxy equivalent (WPE), the initial viscosity, and the storage viscosity of the resin composition obtained in the above (6) were measured by the above method. Further, the storage stability index θ58 was obtained and shown in Table 24.

The epoxy resin equivalent (WPE) of the resin composition of the above Synthesis Example 12 was 230 g/eq, and showed an appropriate value. Further, the initial viscosity was 33.7 Pa s < 1000 Pa s, and the storage viscosity was 47.0 Pa ‧ < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ58=1.39≦4 was determined, and it was judged that there was a resin composition for preserving stability.

[Synthesis Example 13]

A resin composition was produced in the same manner as in Synthesis Example 12 in accordance with Tables 22 and 23. The results of evaluation in the same manner as in Synthesis Example 12, the mixing index α59 to ε59, and the storage stability index θ59 are shown in Table 24.

As shown in Table 24, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 13 was 231 g/eq, which showed an appropriate value. Further, the initial viscosity was = 13.2 Pa s < 1000 Pa s, and the storage viscosity was 11.1 Pa s < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ59=1.45≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 14]

A resin composition was produced in the same manner as in Synthesis Example 12 in accordance with Tables 22 and 23. The results of evaluation in the same manner as in Synthesis Example 12, the mixing index α60 to ε60, and the storage stability index θ60 are shown in Table 24.

As shown in Table 24, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 14 was 242 g/eq, which showed an appropriate value. Further, the initial viscosity = 14.5 Pa.s < 1000 Pa.s, and the storage viscosity = 16.2 Pa.s < 1000 Pa.s, both of which are fluid liquids. Further, the storage stability index θ60=1.12≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 15]

A resin composition was produced in the same manner as in Synthesis Example 12 in accordance with Tables 22 and 23. The results of evaluation in the same manner as in Synthesis Example 12, the mixing indexes α61 to ε61, and the storage stability index θ61 are shown in Table 24.

As shown in Table 24, the epoxy resin equivalent (WPE) of the resin composition of Synthesis Example 15 = 245 g/eq, which showed an appropriate value. Further, the initial viscosity = 14.8 Pa.s < 1000 Pa.s, and the storage viscosity = 21.0 Pa.s < 1000 Pa.s, both of which are fluid liquids. Further, the storage stability index θ61=1.42≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 16]

A resin composition was produced in the same manner as in Synthesis Example 12 in accordance with Tables 22 and 23. The results of evaluation in the same manner as in Synthesis Example 12, the mixing indexes α62 to ε62, and the storage stability index θ62 are shown in Table 24.

As shown in Table 24, the epoxy resin equivalent (WPE) of the resin composition of Synthesis Example 16 was 228 g/eq, which showed an appropriate value. Further, the initial viscosity = 44.0 Pa.s < 1000 Pa.s, and the storage viscosity = 61.1 Pa.s < 1000 Pa.s, both of which are fluid liquids. Further, the storage stability index θ62=1.39≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 17]

A resin composition was produced in the same manner as in Synthesis Example 12 except for the time of the reflux step, except that the time of the reflux step was set to 7 hours. The results of evaluation in the same manner as in Synthesis Example 12, the mixing index α 63 to ε 63 , and the storage stability index θ 63 are shown in Table 24.

As shown in Table 24, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 17 was 214 g/eq, which showed an appropriate value. Further, the initial viscosity = 4.9 Pa ‧ < 1000 Pa s, and the storage viscosity = 9.4 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ 63 = 1.91 ≦ 4 was stored, and it was judged that the resin composition having the stability was stored.

[Synthesis Example 18]

A resin composition was produced in the same manner as in Synthesis Example 12 in accordance with Tables 22 and 23. The results of the evaluation in the same manner as in Synthesis Example 12, the mixing index α 64 to ε 64 , and the storage stability index θ 64 are shown in Table 24.

As shown in Table 24, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 18 = 214 g/eq, which showed an appropriate value. Further, the initial viscosity = 15.9 Pa ‧ < 1000 Pa s, and the storage viscosity = 15.9 Pa s < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ 64=1.21≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 19]

A resin composition was produced in the same manner as in Synthesis Example 12 in accordance with Tables 22 and 23. The results of evaluation in the same manner as in Synthesis Example 12, the mixing index α 65 to ε 65 , and the storage stability index θ 65 are shown in Table 24.

As shown in Table 24, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 19 was 238 g/eq, which showed an appropriate value. Further, the initial viscosity = 18.9 Pa s < 1000 Pa s, and the storage viscosity = 28.7 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ65=1.52≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 20]

A resin composition was produced in the same manner as in Synthesis Example 12 in accordance with Tables 22 and 23. The results of evaluation in the same manner as in Synthesis Example 12, the mixing index α66 to ε66, and the storage stability index θ66 are shown in Table 24.

As shown in Table 24, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 20 was 213 g/eq, and an appropriate value was shown. Further, the initial viscosity was 11.2 Pa s < 1000 Pa s, and the storage viscosity was 11.16 Pa s < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ66=1.44≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 21]

A resin composition was produced in the same manner as in Synthesis Example 12 in accordance with Tables 22 and 23. The results of evaluation in the same manner as in Synthesis Example 12, the mixing index α67 to ε67, and the storage stability index θ67 are shown in Table 24.

As shown in Table 24, the epoxy resin equivalent (WPE) of the resin composition of Synthesis Example 21 was 253 g/eq, which showed an appropriate value. Further, the initial viscosity = 26.8 Pa ‧ < 1000 Pa s, and the storage viscosity = 39.1 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ67=1.46≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Comparative Synthesis Example 1]

A resin composition was produced in the same manner as in Synthesis Example 12 in accordance with Tables 22 and 23. The results of evaluation in the same manner as in Synthesis Example 12, the mixing index α68 to ε68, and the storage stability index θ68 are shown in Table 24.

As shown in Table 24, the epoxy equivalent (WPE) of the resin composition of Comparative Example 1 was compared to 295 g/eq, and an appropriate value was shown. Further, the initial viscosity = 33.4 Pa ‧ S < 1000 Pa s, and the storage viscosity is 48.2 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ68=1.44≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Comparative Synthesis Example 2]

A resin composition was produced in the same manner as in Synthesis Example 12 in accordance with Tables 22 and 23. The results of evaluation in the same manner as in Synthesis Example 12, the mixing indexes α69 to ε69, and the storage stability index θ69 are shown in Table 24.

As shown in Table 24, the epoxy equivalent (WPE) of the resin composition of Comparative Example 2 was compared to 295 g/eq, and an appropriate value was shown. Further, the initial viscosity = 29.0 Pa ‧ < 1000 Pa ‧ is a fluid liquid, but the storage viscosity is > 1000 Pa ‧ and it is fluid-free. Since the storage stability index θ69>35 was stored, it was judged that the resin composition of the synthesis example 2 was poor in storage stability, and the sample for LED evaluation could not be produced.

[Comparative Synthesis Example 3]

According to Table 22, epoxy resin A2 and epoxy resin A3 were added to the reaction vessel, immersed in an oil bath at 85 ° C, stirred, dissolved, and further P-MS and DBTDL were added and mixed.

Then, while performing nitrogen purge, the temperature of the oil bath was raised to 105 ° C, and the dealcoholization reaction was carried out for 8 hours.

Next, after cooling to 60 ° C, the pressure was reduced to 12000 Pa, and the dissolved alcohol was removed to obtain a resin composition. The results of evaluation in the same manner as in Synthesis Example 12 and the storage stability index θ70 are shown in Table 24.

The epoxy equivalent (WPE) of the resin composition of Synthesis Example 3 was compared to 282 g/eq, and an appropriate value was shown. Further, the initial viscosity was 1.89 Pa s < 1000 Pa s, and the storage viscosity was 2.03 Pa s < 1000 Pa ‧ , both of which were fluid liquids. Further, the storage stability index θ70=1.07≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Example 49]

After storing at 25 ° C for 2 weeks, the resin composition of the above Synthesis Example 12 was used to produce a cured product, and the light resistance test was carried out. The results are shown in Table 24.

(1) The resin composition, the curing agent, and the hardening accelerator described above were mixed and stirred at a composition ratio of Table 23 in an environment of 25 ° C, and deaerated under vacuum to obtain a solution for a cured product.

(2) The thickness will be 3mm The glyph 矽 rubber 挟 is formed between two stainless steel plates coated with a release agent to form a molding jig.

(3) The solution for the hardened material was poured into the molding jig, and hardened at 120 ° C for 1 hour and further at 150 ° C for 1 hour to prepare a cured product.

(4) After the internal temperature of the oven was lowered to 30 ° C or lower, the cured product was taken out, and a sample for light resistance test was prepared by the above method.

(5) The results of the light resistance test conducted by the above method using the above samples are shown in Table 24. The indicator YI of the light resistance test of the cured product was YI = 10.1 to 13, and it was judged that the light resistance was acceptable.

Next, using the resin composition of Synthesis Example 12, a bullet-type LED having the structure shown in Fig. 1 was produced by the following procedure, and reliability tests (1) to (3) were performed. The results are shown in Table 24.

(6) A solution for a cured product of (1) as a sealing resin is injected into a cup portion of a mold frame of a diameter of 5 mm.

(7) Here, the LED wafer having an emission wavelength of 400 nm is die-bonded with a silver paste, and the bonding wires (gold wires) are connected to each other to immerse the lead frame.

(8) After defoaming in a vacuum, the hardening treatment was performed at 90 ° C for 1 hour and further at 110 ° C for 5 hours.

(9) Further, in the case of the outer layer resin, 46.6 mass% of the hardener and 0.2 mass% of the hardening accelerator are added to the 53.2% by mass of the Bis-A1 epoxy resin, and the mixture is stirred and degassed under vacuum. This was poured into a mold frame, and hardened at 130 ° C for 1 hour and further at 150 ° C for 6 hours to obtain a bullet-type LED.

As a result of the above-mentioned "confidence test (1) (L test)", the lowest value of all the LEDs was the total beam maintenance ratio (%) = 94% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after 100 cycles of thermal shock, all of the LEDs were turned on, and it was judged as pass.

Further, as a result of the above-mentioned "credibility test (3) (TC test)", after performing the temperature cycle of 100 cycles, all of the LEDs were turned on, and it was judged as pass.

From the above results, it was found that the LED light resistance test and the reliability test (1) to (3) of Example 49 were all acceptable, and the overall judgment was a pass.

[Example 50]

The resin composition of Synthesis Example 13 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, and the light resistance test and the reliability test (1) to (3) were carried out. The results are shown in Table 24.

The light resistance test index YI=8.1≦13, and it was judged that the light resistance was acceptable.

As a result of the above-mentioned "confidence test (1) (L test)", the lowest value of all the LEDs was the total beam maintenance ratio (%) = 96% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Moreover, as a result of the above-mentioned "confidence test (3) (TC test)", after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged that it was pass.

From the above results, it was found that the LED light resistance test and the reliability test (1) to (3) of Example 50 were all acceptable, and the overall judgment was acceptable.

[Example 51]

The resin composition of Synthesis Example 14 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, and the light resistance test and the reliability test (1) to (3) were carried out. The results are shown in Table 24.

The light resistance test index YI=8‧9≦13, and the light resistance was judged to be acceptable.

As a result of the above-mentioned "confidence test (1) (L test)", the lowest value of all the LEDs was the total beam maintenance ratio (%) = 95% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Moreover, as a result of the above-mentioned "confidence test (3) (TC test)", after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged that it was pass.

From the above results, it was found that the LED light resistance test and the reliability test (1) to (3) of Example 51 were all acceptable, and the overall judgment was a pass.

[Example 52]

The resin composition of Synthesis Example 15 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, and a light resistance test and a reliability test (1) to (3) were carried out. The results are shown in Table 24.

The light resistance test index YI=8.3≦13, and the light resistance was judged to be acceptable.

As a result of the above-mentioned "credibility test (1) (L test)", the lowest value of all the LEDs, the total beam maintenance ratio (%) = 92% ≧ 90%, and it was judged as pass.

Next, after performing the above-mentioned "trustworthiness test (2) (TS test)", after performing 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as pass.

Further, after the results of the above-mentioned "credibility test (3) (TC test)", after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged as pass.

From the above results, it was found that all of the LEDs of Example 52, the light resistance test and the reliability test (1) to (3) were qualified, and the overall judgment was a pass.

[Example 53]

The resin composition of Synthesis Example 16 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, and the light resistance test and the reliability test (1) to (3) were carried out. The results are shown in Table 24.

The light resistance test index YI=7.5≦13, and it was judged that the light resistance was acceptable.

As a result of the above-mentioned "confidence test (1) (L test)", the lowest value of all the LEDs was the total beam maintenance ratio (%) = 96% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Further, as a result of the above-mentioned "confidence test (3) (TC test)", after performing the temperature cycle of 100 cycles, all of the LEDs were turned on, and it was judged as pass.

From the above results, it was found that the LED light resistance test and the reliability test (1) to (3) of Example 53 were all acceptable, and the overall judgment was a pass.

[Example 54]

The same procedure as in Example 49 was carried out, except that the resin composition of Synthesis Example 17 was used instead of the resin composition of Synthesis Example 12, and the curing temperature of the cured product and the sealing resin of the LED was changed to 110 ° C for 4 hours. The cured product and the LED were produced, and the light resistance test and the reliability test (1) to (3) were performed. The results are shown in Table 24.

The light resistance test index YI=8.8≦13, and it was judged that the light resistance was acceptable.

As a result of the above-mentioned "confidence test (1) (L test)", the lowest value of all the LEDs was the total beam maintenance ratio (%) = 96% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Moreover, as a result of the above-mentioned "confidence test (3) (TC test)", after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged that it was pass.

From the above results, it was found that the LED light resistance test and the reliability test (1) to (3) of Example 54 were all acceptable, and the overall judgment was a pass.

[Example 55]

The resin composition of Synthesis Example 18 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, and the light resistance test and the reliability test (1) to (3) were carried out. The results are shown in Table 24.

The light resistance test index YI = 12.4 ≦ 13 was judged to be acceptable for light resistance.

As a result of the above-mentioned "confidence test (1) (L test)", the lowest value of all the LEDs was the total beam maintenance ratio (%) = 97% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Moreover, as a result of the above-mentioned "confidence test (3) (TC test)", after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged that it was pass.

From the above results, it was found that the LED light resistance test and the reliability test (1) to (3) of Example 55 were all acceptable, and the overall judgment was a pass.

[Example 56]

The resin composition of Synthesis Example 19 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, and the light resistance test and the reliability test (1) to (3) were carried out. The results are shown in Table 24.

The light resistance test index YI=7.2≦13, and it was judged that the light resistance was acceptable.

As a result of the above-mentioned "confidence test (1) (L test)", the lowest value of all LEDs was the total beam maintenance ratio (%) = 92% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Moreover, as a result of the above-mentioned "confidence test (3) (TC test)", after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged that it was pass.

From the above results, it was found that the LED light resistance test and the reliability test (1) to (3) of Example 56 were all acceptable, and the overall judgment was a pass.

[Example 57]

The resin composition of Synthesis Example 20 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, and the light resistance test and the reliability test (1) to (3) were carried out. The results are shown in Table 24.

The light resistance test index YI=7.8≦13, and it was judged that the light resistance was acceptable.

As a result of the above-mentioned "confidence test (1) (L test)", the lowest value of all LEDs was the total beam maintenance ratio (%) = 93% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Moreover, as a result of the above-mentioned "confidence test (3) (TC test)", after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged that it was pass.

From the above results, it was found that the LED light resistance test and the reliability test (1) to (3) of Example 57 were all acceptable, and the overall judgment was a pass.

[Example 58]

The resin composition of Synthesis Example 21 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, and the light resistance test and the reliability test (1) to (3) were carried out. The results are shown in Table 24.

The light resistance test index YI=9.2≦13, and the light resistance was judged to be acceptable.

As a result of the above-mentioned "confidence test (1) (L test)", the lowest value of all LEDs was the total beam maintenance ratio (%) = 92% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Further, as a result of the above-mentioned "confidence test (3) (TC test)", after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged as pass.

From the above results, it was found that the LED light resistance test and the reliability test (1) to (3) of Example 58 were all acceptable, and the overall judgment was a pass.

[Example 59]

Using the resin composition of Synthesis Example 13, an SMD type LED having a structure shown in Fig. 2 having a size of 2.5 mm × 2.5 mm was produced by the following procedure, and it was confirmed that the LED was turned on.

(1) A metal pattern is formed, and a silver paste is applied onto a glass epoxy substrate to bond the LED wafers.

(2) The substrate is placed in an electric furnace to be hardened.

(3) A bonding circuit (gold wire) is connected to the die-bonded LED wafer to form a circuit.

(4) A substrate was placed on the mold, and the resin composition of Synthesis Example 13 was poured, and the hardening treatment was performed at 90 ° C for 1 hour and further at 110 ° C for 5 hours.

(5) Separate and cut each LED on the substrate to manufacture an SMD type LED.

From the above results, it was found that the LEDs of Examples 49 to 59 were excellent in light resistance and reliability, and were comprehensively judged to be acceptable.

[Comparative Example 26]

The resin composition of Comparative Synthesis Example 1 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, and the light resistance test and the reliability test (1) to (3) were carried out. The results are shown in Table 24.

The light resistance test index YI=8.4≦13, and it was judged that the light resistance was acceptable.

As a result of the above-mentioned "confidence test (1) (L test)", two of the ten LEDs were not lit, and the total beam maintenance ratio (%) could not be measured, and it was judged to be unacceptable.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after performing 100 cycles of thermal shock, only 6 of the 10 LEDs were turned on, and it was judged to be unacceptable.

Further, as a result of the above-mentioned "confidence test (3) (TC test)", after performing a temperature cycle of 100 cycles, only 6 of the 10 LEDs were turned on, and it was judged to be unacceptable.

From the above results, it was found that the LED of Comparative Example 26 had good light resistance, but the reliability tests (1) to (3) were all unacceptable, and therefore the overall judgment was unacceptable.

[Comparative Example 27]

The resin composition of Comparative Synthesis Example 2 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, although attempts to carry out the light resistance test and the reliability test (1) to (3) were attempted. However, the storage stability of the resin composition is poor, and it is impossible to manufacture a cured product and an LED. Therefore, the overall judgment is unqualified.

[Comparative Example 28]

The resin composition of Synthesis Example 12 was replaced with a Bis-Al epoxy resin, and a cured product and an LED were produced in the same manner as in Example 49, and the light resistance test and the reliability test (1) to (3) were carried out. The results are shown in Table 24.

The light resistance test index YI = 17.2>13, and it was judged that the light resistance was unacceptable.

As a result of the above-mentioned "confidence test (1) (L test)", the lowest value of all the LEDs was the total beam maintenance ratio (%) = 97% ≧ 90%, and it was judged as pass.

Next, as a result of the above-mentioned "trustworthiness test (2) (TS test)", after performing the thermal shock of 100 cycles, all the LEDs were turned on, and it was judged as pass.

Moreover, as a result of the above-mentioned "confidence test (3) (TC test)", after performing the temperature cycle of 100 cycles, all the LEDs were turned on, and it was judged that it was pass.

From the above results, it was found that the reliability of the LED of Comparative Example 28 was excellent, but the light resistance was poor, so that the overall judgment was unacceptable.

[Comparative Example 29]

The polyoxyl resin of the liquid A and the liquid B was mixed and stirred at a mass ratio of 1:1, and the resin composition of the synthesis example 12 was replaced. A cured product and an LED were produced in the same manner as in Example 49 except that the curing temperature of the cured resin and the sealing resin of the LED was changed to 70 ° C for 1 hour and further 150 ° C for 5 hours, and the light resistance test was performed. Credibility tests (1) to (3). The results are shown in Table 24.

The light resistance test index YI-2.0≦13 was judged to be acceptable for light resistance.

As a result of the above-mentioned "confidence test (1) (L test)", only three of the ten LEDs were turned on, and the total beam maintenance ratio (%) could not be measured, and it was judged to be unacceptable.

Next, as a result of the above-mentioned "credibility test (2) (TS test)", after performing thermal shock of 100 cycles, only four of the ten LEDs were turned on, and it was judged that it was unqualified.

Further, as a result of the above-mentioned "confidence test (3) (TC test)", after performing a temperature cycle of 100 cycles, only 6 of the 10 LEDs were turned on, and it was judged to be unacceptable.

From the above results, it was found that the LED of Comparative Example 29 was excellent in light resistance, but the reliability tests (1) to (3) were all unacceptable, so that the overall judgment was unacceptable.

[Comparative Example 30]

The resin composition of Comparative Example 3 was used instead of the resin composition of Synthesis Example 12, and a cured product and an LED were produced in the same manner as in Example 49, and the light resistance test and the reliability test (1) to (3) were carried out. The results are shown in Table 24.

Although it was possible to produce a cured product for light resistance test, it was broken and could not be measured. Therefore, it was judged that the light resistance was unacceptable.

As a result of the above-mentioned "confidence test (1) (L test)", only four of the ten LEDs were turned on, and the total beam maintenance ratio (%) could not be measured, and it was judged as unacceptable.

Next, as a result of the above-mentioned "credibility test (2) (TS test)", after performing 100 cycles of thermal shock, only five of the ten LEDs were turned on, and it was judged to be unacceptable.

Further, as a result of the above-mentioned "confidence test (3) (TC test)", after performing a temperature cycle of 100 cycles, only 7 of the 10 LEDs were turned on, and it was judged to be unacceptable.

From the above results, it was found that the LED of Comparative Example 30 was excellent in light resistance, but the reliability tests (1) to (3) were all unacceptable, so that the overall judgment was unacceptable.

From the results of Tables 22 to 24, it is understood that the LEDs of Examples 49 to 59 are excellent results in any of the light resistance, the L test, the TS test, and the TC test. On the other hand, in Comparative Examples 26 to 30, at least one of storage stability, light resistance, L test, TS test, and TC test was defective.

According to the above, it is shown that the LED manufactured by using the modified resin composition of the present embodiment is excellent in light resistance and reliability.

Next, an optical lens manufactured using the modified resin composition of the present embodiment will be specifically described by way of examples and comparative examples.

The evaluation of the physical properties in Examples 60 to 63 and Comparative Examples 31 to 35 was carried out as follows.

<Calculation of preservation stability index θ, and preservation stability of resin composition>

The storage stability of the resin composition was evaluated by the storage stability index θ shown by the following general formula (9).

Preservation stability index θ=(preservation viscosity)/(starting viscosity) (9)

The container of the resin composition immediately after the production was sealed, and the temperature was adjusted at 25 ° C for 2 hours, and then the viscosity at 25 ° C was measured, and this was regarded as "initial viscosity".

Further, the container in which the resin composition was placed was sealed, and stored in an incubator kept at a constant temperature of 25 ° C for 2 weeks. After storage, the viscosity at 25 ° C was measured, and this was regarded as "preservation viscosity".

When the resin composition has fluidity (viscosity of 1000 Pa ‧ or less) and the storage stability index θ is 4 or less, it is determined that there is storage stability.

<Light resistance test of optical lens (hardened material)>

Since it was difficult to cut the sample after manufacturing the optical lens, the cured product was produced by the following method, and the evaluation result was evaluated as the light resistance of the optical lens.

(1) The cured product prepared by the method described later was hardened with a solution to prepare a cured product of 20 mm × 10 mm × 3 mm in thickness.

(2) The cured product was covered with a black mask of 25 mm × 15 mm × 1.2 mm thick having a hole having a diameter of 5.5 mm, and was used as a sample for light resistance test.

(3) The preparation device was irradiated with UV light from a UV irradiation device (manufactured by Ushio Electric Co., Ltd., [Spot cure SP7-250DB]) via an optical fiber to the above-mentioned sample set in an incubator at a constant temperature of 50 °C.

(4) The sample was placed in an incubator at a constant temperature of 50 ° C in a state where the black mask was placed on the upper surface.

(5) UV light of 2 W/cm ² was irradiated for 96 hours from the upper portion of the black mask so that the UV light was irradiated to the hole having a diameter of 5.5 mm.

(6) A sample irradiated with UV was measured by a spectrophotometer (manufactured by Nippon Denshoku Industries Co., Ltd., [SD5000]) in which the opening portion of the integrating sphere was modified to have a diameter of 10 mm.

(7) Yellowness (YI) is determined in accordance with "ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics". When the YI was 13 or less, it was judged to be acceptable.

<Cold and thermal shock test of optical lens>

(1) Ten optical lenses manufactured by the method described later are placed in a thermal shock device ("TSE-11-A", manufactured by Espec Co., Ltd.), and "(-40 ° C to 120 ° C) / cycle: exposure) The heating cycle was carried out under the conditions of a time of 14 minutes and a temperature rise and fall time of 1 minute.

(2) The sample was taken out after 100 cycles of heat, and sprayed with a permeate ("Micro Check" manufactured by KOHZAI Co., Ltd.) under a magnifying glass to visually observe whether there was an abnormality (peeling or cracking). , record the number.

(3) The sample confirmed as the no abnormality in the above (4) was placed in the apparatus again, and after 100 cycles of thermal cycling, it was evaluated in the same manner. Repeat these operations for evaluation.

(4) When one of the 10 samples is abnormal, the evaluation is aborted, and the number of times of thermal shock resistance = (the number of thermal cycles to be stopped) - (100 times) is obtained.

When the number of cold shock resistance is 200 or more, the thermal shock resistance is judged to be acceptable.

<Surface adhesion test of optical lens>

The surface of the optical lens manufactured by the method described later was lightly pressed with a thumb wearing a latex glove, and when the adhesion was not confirmed, the surface adhesion was judged to be acceptable.

<Void test of optical lens>

Ten optical lenses manufactured by the method described later were visually confirmed under a magnifying glass, and when all of the ten optical lenses were void-free, it was judged to be acceptable.

When the above-mentioned light resistance test, cold shock resistance test, surface adhesion test, and void test are all acceptable, the overall judgment is acceptable.

The raw materials used in Examples 60 to 63 and Comparative Examples 31 to 35 are shown in the following (1) to (7).

(1) Epoxy resin

(1-1) Epoxy Resin A: Poly(bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as Bis-A epoxy resin)

‧Product Name: Asahi Kasei Epoxy Co., Ltd., "AER"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 187g/eq

‧ Viscosity (25 ° C): 14.3 Pa‧ s

(1-2) Epoxy resin B: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate (hereinafter, referred to as alicyclic epoxy resin)

‧trade name: manufactured by Daicel Chemical Industry Co., Ltd., "Celloxide 2021P"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 131g/eq

‧ Viscosity (25 ° C): 227 mPa ‧ s

(2) alkoxydecane compounds

(2-1) alkoxydecane compound H: 3-glycidoxypropyltrimethoxydecane (hereinafter referred to as GPTMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-403"

(2-2) alkoxydecane compound I: phenyltrimethoxydecane (hereinafter referred to as PTMS)

‧Product Name: Shin-Etsu Chemical Co., Ltd., "KBM-103"

(2-3) alkoxydecane compound J: dimethyldimethoxydecane (hereinafter referred to as DMDMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-22"

(2-4) Alkoxydecane Compound K: Tetraethoxydecane (hereinafter referred to as TEOS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBE-04"

(3) Solvent: tetrahydrofuran: manufactured by Wako Pure Chemical Industries Co., Ltd., without stabilizer (hereinafter referred to as THF)

(4) Hydrolysis condensation catalyst:

(4-1) Dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as DBTDL)

(4-2) Dibutyltin dimethoxide (manufactured by Sigma-Aldrich Co., Ltd., hereinafter referred to as DBTDM)

(5) Hardener: "4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30"

‧Trade name: New Japan Physical and Chemical Co., Ltd., "RIKACID MH-700G"

(6) Hardening accelerator: amine compound

‧Trade name: San-apro (share) company, "U-CAT 18X"

(7) Polyoxyl resin

‧trade name: manufactured by Toray‧Dow Corning, "EG6301 (A liquid / B liquid)"

[Synthesis Example 22]

The resin composition was produced by the following procedure.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an 80 ° C oil bath was placed on a magnetic stirrer.

(2) According to the composition ratio shown in Table 25 below, the above Bis-A1 epoxy resin, alkoxydecane compound, and THF were placed in a flask to which a stirrer was placed, and mixed and stirred at 25 ° C. Thereafter, water and a hydrolysis condensation catalyst are further added and mixed and stirred.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 20 hours while refluxing (reflow step).

(4) After completion of the reaction, it was cooled to 25 ° C, and then the cooling tube was removed from the flask.

(5) The solution after completion of the refluxing was distilled off at 400 Pa and 50 ° C for 1 hour using an evaporator, and further subjected to a dehydration condensation reaction (dehydration condensation step) while distilling off at 80 ° C for 10 hours.

(6) After completion of the above dehydration condensation reaction, the mixture was cooled to 25 ° C to obtain a resin composition.

(7) The mixing index α71 to ε71 of the resin composition is shown in Table 27 below.

(8) Further, the epoxy equivalent (WPE), the initial viscosity, and the storage viscosity of the resin composition obtained in the above (6) were measured by the above method. Further, the storage stability index θ71 was obtained, which is shown in Table 27.

As shown in Table 27, the epoxy resin equivalent (WPE) of the resin composition of the above Synthesis Example 22 was 230 g/eq, which showed an appropriate value. Further, the initial viscosity = 33.7 Pa ‧ < 1000 Pa s, and the storage viscosity = 47.0 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ71=1.39≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 23]

A resin composition was produced in accordance with Tables 25 and 26 in the same manner as in Synthesis Example 22 except that the time of the reflux step was changed to 25 hours. The evaluation was carried out in the same manner as in Synthesis Example 22. The evaluation results, the mixing indexes α72 to ε72, and the storage stability index θ72 are shown in Table 27.

As shown in Table 27, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 23 was 238 g/eq, which showed an appropriate value. Further, the initial viscosity = 15.2 Pa s < 1000 Pa s, and the storage viscosity = 20.3 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ72=1.33≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 24]

A resin composition was produced in the same manner as in Synthesis Example 22 in accordance with Tables 25 and 26. The evaluation was carried out in the same manner as in Synthesis Example 22. The evaluation results, the mixing indexes α73 to ε73, and the storage stability index θ73 are shown in Table 27.

As shown in Table 27, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 24 was 228 g/eq, which showed an appropriate value. Further, the initial viscosity = 38.2 Pa ‧ < 1000 Pa s, and the storage viscosity = 61.1 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ73=1.60≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Synthesis Example 25]

A resin composition was produced in accordance with Tables 25 and 26 in the same manner as in Synthesis Example 22 except that the time of the reflux step was changed to 7 hours. The evaluation was carried out in the same manner as in Synthesis Example 22. The evaluation results, the mixing indexes α74 to ε74, and the storage stability index θ74 are shown in Table 27.

As shown in Table 27, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 25 = 214 g/eq, which showed an appropriate value. Further, the initial viscosity = 4.9 Pa ‧ < 1000 Pa s, and the storage viscosity = 9.4 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. Further, the storage stability index θ74=1.91≦4 was stored, and it was determined that the resin composition having the stability was stored.

[Comparative Synthesis Example 4]

A resin composition was produced in the same manner as in Synthesis Example 22 in accordance with Tables 25 and 26. The evaluation was carried out in the same manner as in Synthesis Example 22. The evaluation results, the mixing indexes α75 to ε75, and the storage stability index θ75 are shown in Table 27.

As shown in Table 27, the epoxy equivalent (WPE) of the resin composition of Synthesis Example 4 was compared to 295 g/eq, and an appropriate value was shown. Further, the initial viscosity = 33.4 Pa ‧ < 1000 Pa s, and the storage viscosity = 48.2 Pa ‧ < 1000 Pa ‧ , both of which are fluid liquids. also. The stability index θ75=1.44≦4 was stored, and it was judged that there was a resin composition for preserving stability.

[Comparative Synthesis Example 5]

A resin composition was produced in the same manner as in Synthesis Example 22 in accordance with Tables 25 and 26. The evaluation was carried out in the same manner as in Synthesis Example 22. The evaluation results, the mixing indexes α76 to ε76, and the storage stability index θ76 are shown in Table 27.

As shown in Table 27, the epoxy equivalent (WPE) of the resin composition of Comparative Example 5 was compared to 295 g/eq, and an appropriate value was shown. Further, the initial viscosity = 29.0 Pa ‧ < 1000 Pa ‧ is a fluid liquid. However, when the storage viscosity is >1000 Pa·s, the fluidity is not satisfied, and when the storage stability index θ76>35, the storage stability is poor, so that the sample for optical lens evaluation cannot be produced.

[Example 60]

The resin composition of the above Synthesis Example 22, which was stored at 25 ° C for 2 weeks, was subjected to the following procedure to produce a cured product, and the light resistance test was carried out. The results are shown in Table 27.

(1) The resin composition, the curing agent, and the hardening accelerator were mixed and stirred at a composition ratio of Table 26 in an environment of 25 ° C, and degassed under vacuum to obtain a solution for the cured product.

(2) The thickness will be 3mm The glyph 矽 rubber 挟 is formed between two stainless steel plates coated with a release agent to form a molding jig.

(3) The solution for the hardened material was poured into the molding jig, and hardened at 120 ° C for 1 hour and further at 150 ° C for 1 hour to prepare a cured product.

(4) After the temperature in the oven was lowered to 30 ° C or lower, the cured product was taken out, and the sample for light resistance test was prepared by the above method.

(5) The results of the light resistance test by the above method using the above samples are shown in Table 27. The index of the light resistance test of the cured product was YI = 10.1 ≦ 13, and it was judged that the light resistance was acceptable.

Next, using the resin composition of Synthesis Example 22, an optical lens was produced by the following procedure, and subjected to a thermal shock test, a surface adhesion test, and a void test. The results are shown in Table 27.

(6) The raw materials were mixed according to the blending method of Table 26, and after defoaming in a vacuum, they were placed in an injection molding machine (manufactured by Sodick Co., Ltd.).

(7) Further, it was hardened at 140 ° C for 15 minutes, and allowed to release to room temperature, and then released to obtain an optical lens having a diameter of about 1 cm.

As a result of the thermal shock test by the above method, the number of thermal shock tests was 400 times 200 times, and it was judged that the thermal shock resistance was acceptable.

As a result of the surface adhesion test by the above method, the adhesion was not confirmed, and it was judged to be acceptable.

As a result of the hole test by the above method, no void was confirmed, and it was judged to be acceptable.

From the above results, it was found that the optical lens of Example 60 was qualified for the light resistance test, the thermal shock test, the surface adhesion test, and the void test, and was comprehensively judged to be acceptable.

[Example 61]

The resin composition of Synthesis Example 23 was used instead of the resin composition of Synthesis Example 22, and a cured product and an optical lens were produced in the same manner as in Example 60, and subjected to a light resistance test, a thermal shock test, a surface adhesion test, and a void test. . The results are shown in Table 27.

The light resistance test index YI=8.1≦13, and it was judged that the light resistance was acceptable.

As a result of the thermal shock test by the above method, the number of thermal shock tests was 300 times 200 times, and it was judged that the cold shock resistance was acceptable.

As a result of the surface adhesion test by the above method, the adhesion was not confirmed, and it was judged to be acceptable.

As a result of the void test by the above method, no void was confirmed, and it was judged as pass.

From the above results, it was found that all of the optical lenses of Example 61 were tested for light resistance, thermal shock test, surface adhesion test, and void test, and were judged to be acceptable.

[Example 62]

The resin composition of Synthesis Example 24 was used instead of the resin composition of Synthesis Example 22, and a cured product and an optical lens were produced in the same manner as in Example 60, and subjected to a light resistance test, a thermal shock test, a surface adhesion test, and a void test. . The results are shown in Table 27.

The light resistance test index YI=8.9≦13, and it was judged that the light resistance was acceptable.

As a result of the above-described thermal shock resistance test, the number of thermal shock tests was 500 or more and 200 times, and it was judged that the thermal shock resistance was acceptable.

As a result of the surface adhesion test by the above method, the adhesion was not confirmed, and it was judged to be acceptable.

As a result of the void test by the above method, no void was confirmed, and it was judged to be acceptable.

From the above results, the optical lens of Example 62 was tested for light resistance, thermal shock test, surface adhesion test, and void test, and was judged to be acceptable.

[Example 63]

The resin composition of Synthesis Example 25 was used instead of the resin composition of Synthesis Example 22, and a cured product and an optical lens were produced in the same manner as in Example 60, and subjected to a light resistance test, a thermal shock test, a surface adhesion test, and a void test. . The results are shown in Table 27.

The index of the light resistance test YI=8.3≦13, and it was judged that the light resistance was acceptable.

As a result of the thermal shock test by the above method, the number of thermal shock tests was 300 times 200 times, and it was judged that the cold shock resistance was acceptable.

As a result of the surface adhesion test by the above method, the adhesion was not confirmed, and it was judged to be acceptable.

As a result of the void test by the above method, no void was confirmed, and it was judged as pass.

From the above results, it was found that the optical lens of Example 63 was qualified for the light resistance test, the thermal shock test, the surface adhesion test, and the void test, and was comprehensively judged to be acceptable.

[Comparative Example 31]

The resin composition of Comparative Example 4 was used instead of the resin composition of Synthesis Example 22, and a cured product and an optical lens were produced in the same manner as in Example 60, and subjected to a light resistance test, a thermal shock test, a surface adhesion test, and a cavity. test. The results are shown in Table 27.

The light resistance test index YI=8.4≦13, and it was judged that the light resistance was acceptable.

As a result of the thermal shock test by the above method, the number of thermal shock tests was 100 times <200 times, and it was judged that the thermal shock resistance was unacceptable.

As a result of the surface adhesion test by the above method, the adhesion was not confirmed, and it was judged to be acceptable.

As a result of the void test by the above method, no void was confirmed, and it was judged as pass.

As a result of the above, although the optical lens of Comparative Example 31 was satisfactory in the light resistance test, the surface adhesion test, and the void test, the thermal shock test failed, and the overall judgment was unacceptable.

[Comparative Example 32]

The resin composition of Comparative Example 5 was used instead of the resin composition of Synthesis Example 22, and a cured product and an optical lens were produced in the same manner as in Example 60, although attempts were made to perform light resistance test, thermal shock test, and surface adhesion test. In the void test, the storage stability of the resin composition was poor, and it was impossible to manufacture a cured product and an optical lens. Therefore, the overall judgment was unacceptable.

[Comparative Example 33]

The resin composition of Synthesis Example 22 was replaced with a Bis-A epoxy resin, and a cured product and an optical lens were produced in the same manner as in Example 60, and subjected to a light resistance test, a surface adhesion test, and a void test. The results are shown in Table 27.

The index of the light resistance test YI=17.2<13, and it was judged that the light resistance was unacceptable.

As a result of the thermal shock resistance test by the above method, the number of thermal shock tests was 500 times or more and 200 times, and it was judged that the thermal shock resistance was acceptable.

As a result of the surface adhesion test by the above method, the adhesion was not confirmed, and it was judged to be acceptable.

As a result of the void test by the above method, no void was confirmed, and it was judged as pass.

From the above results, the optical lens of Comparative Example 33 was qualified for the thermal shock test, the surface adhesion test, and the void test. However, since the light resistance test failed, the overall judgment was unacceptable.

[Comparative Example 34]

The cured resin and the optical lens were produced in the same manner as in Example 60, and the light resistance was carried out in the same manner as in Example 60, except that the resin composition of Synthesis Example 22 was mixed with the above-mentioned polyoxyl resin in a mass ratio of 1:1. Test, surface adhesion test, cavity test. The results are shown in Table 27.

The index of the light resistance test YI=2.0≦13, and it was judged that the light resistance was acceptable.

As a result of the thermal shock test by the above method, the number of thermal shock tests was 100 times <200 times, and it was judged that the thermal shock resistance was unacceptable.

As a result of the surface adhesion test by the above method, the adhesion was not confirmed, and it was judged to be acceptable.

As a result of the void test by the above method, no void was confirmed, and it was judged as pass.

As a result of the above, although the optical lens of Comparative Example 34 was qualified in the light resistance test, the surface adhesion test, and the void test, the thermal shock test failed, and the overall judgment was unacceptable.

[Comparative Example 35]

A cured product and an optical lens were produced in the same manner as in Example 60, except that the composition obtained by mixing Bis-A epoxy resin, GPTMS, and PTMS was replaced with the resin composition of Synthesis Example 22 according to the blending method of Table 25. , light resistance test, surface adhesion test, cavity test. The results are shown in Table 27.

In the light resistance test, the test sample produced a plurality of voids, and the light resistance could not be measured.

As a result of the thermal shock test by the above method, the number of thermal shock tests was 200 times 200 times, and it was judged that the thermal shock resistance was acceptable.

As a result of the surface adhesion test by the above method, the adhesion was confirmed and it was judged to be unacceptable.

As a result of the void test by the above method, voids were confirmed in 8 of the 10 samples, and it was judged to be unacceptable.

As a result of the above, it was found that the optical lens of Comparative Example 35 was qualified for the thermal shock test, but the light resistance test, the surface adhesion test, and the void test were unacceptable, so that the overall judgment was unacceptable.

Next, a conductive resin composition obtained by adding a conductive metal powder to the modified resin composition of the present embodiment will be specifically described by way of examples and comparative examples.

The physical properties of Examples 64 to 67 and Comparative Examples 36 to 38 were evaluated as follows.

The epoxy equivalent (WPE), viscosity, and mixing index α to η were obtained by the same method as above.

<Measurement of average particle diameter of conductive metal powder>

The average particle diameter was measured in a dry mode using a laser diffraction type particle size distribution measuring apparatus ("HELOS system" manufactured by SYMPATEC Co., Ltd.).

<Measurement of Viscosity of Conductive Resin Composition>

The container in which the composition immediately after the production was placed was sealed, and the temperature was adjusted at 25 ° C for 1 hour, and then the viscosity at 25 ° C was measured.

When the viscosity was 100 Pa‧s or less, it was judged that there was fluidity.

<Measurement of softening point of phenolic phenol resin>

The measurement was carried out in accordance with 5.8 of JIS K6910:2007 (Phenol Resin Test Method).

<Measurement of hydroxyl equivalent of phenolic phenol resin>

The hydroxyl value is measured in accordance with "JIS K0070: 1002 (Test method for acid value, saponification price, ester value, iodine value, hydroxyl value, and unsaponifiable matter of chemical products), and is converted into a hydroxyl group equivalent.

<Measurement of Volume Resistivity of Conductive Resin Composition>

The conductive resin composition was applied to a thickness of 40 μm on a carrier glass by a bar coater, and heated at 200 ° C for 60 minutes to form a coating film.

The coating film was measured by a resistivity meter ("Loresta" manufactured by Dia Instruments Co., Ltd.), and when the volume resistivity was 9 × 10 ^-4 Ω‧ cm or less, it was judged that the conductivity was good.

<Measurement of adhesion strength and adhesion evaluation of conductive resin composition>

The adhesion strength before and after the moisture absorption treatment was measured by the following procedure.

(1) A conductive resin composition was applied to a die pad portion (9 mm × 9 mm) of a copper lead frame.

(2) Next, a ruthenium wafer (8 mm × 16 mm) was mounted on the die pad portion, and heated in an oven at 200 ° C for 1 hour (sample before moisture absorption treatment).

(3) The sample prepared in (2) was absorbed by a constant temperature and humidity machine set to a temperature of 85 ° C and a humidity of 85% for 72 hours (sample after moisture absorption treatment).

(4) The above [pre-hygroscopic treatment sample] and [moisture-absorbing sample] are placed so that the crucible wafer is placed underneath, heated on a hot plate at 250 ° C for 20 seconds, and the lead wire of the lead frame is pulled up, and push-pull is used. The film (manufactured by IMADA Co., Ltd.) measures the adhesion strength when the ruthenium wafer and the die pad are peeled off.

(5) When the subsequent strength residual ratio expressed by the following formula is 80% or more, it is judged that the adhesion is good.

Then, the residual rate of strength (%) = (the strength after the moisture absorption treatment) / (the strength before the moisture absorption treatment) × 100

<Void evaluation of conductive resin composition>

As described above, a conductive resin composition was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. The sample was visually confirmed under a magnifying glass to see if there was a void.

When the resin composition of the examples and the comparative examples was excellent in fluidity, conductivity, and adhesion, and no void was observed, the overall judgment was a pass.

The raw materials used in the examples and comparative examples are shown in the following (1) to (10).

(1) Epoxy resin

(1-1) Epoxy Resin A: Bisphenol A type epoxy resin (hereinafter referred to as "Bis-A epoxy resin")

‧Trade name: Asahi Kasei Epoxy Co., Ltd., [AER]

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 187g/eq

‧ Viscosity (25 ° C): 14.3 Pa‧ s

(1-2) Epoxy Resin F: Bisphenol F-type epoxy resin (hereinafter, referred to as "Bis-F epoxy resin" for short)

‧Product Name: Japan Epoxy Resin Co., Ltd., "jER807"

Further, the epoxy equivalent (WPE) and viscosity measured by the above method are as follows.

‧Epoxy equivalent (WPE): 169g/eq

‧ Viscosity (25 ° C): 3.2 Pa‧ s

(2) alkoxydecane compound H: 3-glycidoxypropyltrimethoxydecane (hereinafter referred to as GPTMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-403"

(3) alkoxydecane compound I: phenyltrimethoxydecane (hereinafter referred to as PTMS)

‧Product Name: Shin-Etsu Chemical Co., Ltd., "KBM-103"

(4) alkoxydecane compound J: dimethyldimethoxydecane (hereinafter referred to as DMDMS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBM-22"

(5) alkoxy decane compound K: tetraethoxy decane (hereinafter referred to as TEOS)

‧Trade name: Shin-Etsu Chemical Co., Ltd., "KBE-04"

(6) Solvent

(6-1) Tetrahydrofuran: manufactured by Wako Pure Chemical Industries Co., Ltd., without stabilizer (hereinafter referred to as THF)

(7) Hydrolysis condensation catalyst: Dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as DBTDL).

(8) Hardener

(8-1) Hardener A: a novolac type phenol resin (manufactured by DIC Co., Ltd., trade name "PHENOLITE"; hydroxyl equivalent: 104 g/eq, softening point: 100 ° C) (hereinafter referred to as "NP resin")

(8-2) Hardener B: 1,8-diazabicyclo[5.4.0]undecene-7 (manufactured by San-apro Co., Ltd., trade name "DBU") (hereinafter, referred to as "DBU" ")

(9) Diluent: o-cresol-glycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name "SY-OCG"; epoxy equivalent 181 g/eq, viscosity 8 mPa‧s)

(10) Silver powder

(10-1) scaly silver powder (average particle size 6.3 μm)

(10-2) Spherical silver powder (average particle size 1.2 μm)

(Synthesis Example 26)

Resin Composition J: Resin Composition J was produced and evaluated according to the following procedure.

(1) Preparation: The circulating constant temperature water tank was set to 5 ° C to return to the cooling pipe. Further, an 80 ° C oil bath was placed on a magnetic stirrer.

(2) According to the composition ratio of Table 28, an epoxy resin, an alkoxydecane compound, and THF are added to a flask which has been stirred with a stirring agent at 25 ° C, and after mixing and stirring, water is added and hydrolyzed and condensed. Catalyst and mix and stir.

(3) Next, a cooling tube was attached to the flask, and it was quickly immersed in an oil bath of 80 ° C to start stirring, and reacted for 10 hours while refluxing.

(4) After completion of the reaction, the mixture was cooled to 25 ° C, and then the cooling tube was removed from the flask, and after the refluxing step was completed, the sample solution was taken.

(5) The solution after the completion of the refluxing step was distilled off at 400 Pa and 50 ° C for 1 hour using an evaporator, and further, while being distilled off at 80 ° C for 5 hours, the dehydration condensation reaction was carried out.

(6) After completion of the reaction, the mixture was cooled to 25 ° C to obtain a resin composition J.

(7) The mixing index α77 to ε77 of this resin composition is shown in Table 30.

(8) Further, the epoxy equivalent (WPE) of the resin composition J obtained in the above (6) was measured by the above method.

The epoxy equivalent (WPE) of the above resin composition = 195 g/eq, which showed an appropriate value. Further, the viscosity is 12.7 Pa ‧ and it is a liquid having fluidity.

(Synthesis Example 27)

Resin composition K: According to the composition ratio of Table 28, the resin composition K was synthesized and evaluated in the same manner as in Synthesis Example 26. The mixing index α78 to ε78 is shown in Table 30.

The above resin composition was an epoxy equivalent (WPE) = 228 g/eq, and showed an appropriate value. Further, the viscosity is 13.8 Pa s, which is a fluid liquid.

(Synthesis Example 28)

Resin Composition L: The resin composition L was synthesized and evaluated in the same manner as in Synthesis Example 26 in accordance with the composition ratio of Table 28. The mixing index α79 to ε79 is shown in Table 30.

The above resin composition was an epoxy equivalent (WPE) = 206 g/eq, and showed an appropriate value. Further, the viscosity is 18.2 Pa s, which is a liquid having fluidity.

(Synthesis Example 29)

Resin Composition M: According to the composition ratio of Table 28, the resin composition M was synthesized and evaluated in the same manner as in Synthesis Example 26. The mixing index α80 to ε80 is shown in Table 30.

The above resin composition was an epoxy equivalent (WPE) = 208 g/eq, and showed an appropriate value. The viscosity is 10.2 Pa‧ s, which is a liquid with fluidity.

(Example 64)

The conductive resin composition 1 was produced by the following procedure and evaluated. The evaluation results and the mixing indexes α77 to ε77 are shown in Table 30.

Using the resin composition J of the above Synthesis Example 26, the raw materials were blended according to the composition of Table 29, and uniformly kneaded by a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd.). Further, a person who defoamed at 400 Pa for 30 minutes was used as the conductive resin composition 1 using a vacuum chamber. The conductive resin composition 1 has a viscosity of 21.5 Pa s and is a liquid excellent in fluidity.

On the carrier glass, the conductive resin composition 1 was applied in a bar coater to a thickness of 40 μm, and heated at 200 ° C for 60 minutes to form a coating film. When the volume resistivity of this coating film was measured with a resistance meter ("Loresta" manufactured by Dia Instruments Co., Ltd.), the volume resistivity was 2 × 10 ^-4 Ω ‧ cm, and it was judged that the conductivity was good.

The residual strength residual ratio of the conductive resin composition 1 was determined by the following procedure.

(1) Four conductive resin compositions 1 were coated on a die pad portion (9 mm × 9 mm) of a copper lead frame.

(2) Next, a ruthenium wafer (8 mm × 16 mm) was mounted on the die pad portion, and heated in an oven at 200 ° C for 1 hour.

(3) In the sample prepared in (2), two were regarded as "samples before moisture absorption treatment"

(4) After the two samples of the sample prepared in (2) were absorbed for 72 hours in a constant temperature and humidity machine set to a temperature of 85 ° C and a humidity of 85%, the samples were regarded as "samples after moisture absorption treatment". .

(5) Using the above "pre-hygroscopic treatment sample" and "moisture-absorbing sample", the crucible wafer is placed underneath, heated on a hot plate at 250 ° C for 20 seconds, and the lead wire of the lead frame is pulled up, using push-pull The film (manufactured by IMADA Co., Ltd.) measures the adhesion strength when the ruthenium wafer and the die pad are peeled off. The measurement was performed by n=2 each, and the average value was obtained.

(6) The average value of the subsequent strengths of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" obtained above was substituted into the following formula, and the residual strength was determined to evaluate the adhesion.

Then, the residual rate of strength (%) = (the strength after the moisture absorption treatment) / (the strength after the moisture absorption treatment) × 100 = (148 mN) / (151 mN) × 100 = 98% ≧ 80%, the composition of the conductive resin The adhesion of the substance 1 was judged to be good.

Next, the conductive resin composition 1 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. The sample was visually confirmed under a magnifying glass and no void was produced.

As a result of the above, the conductive resin composition 1 was excellent in fluidity, conductivity, and adhesion, and no voids were formed.

(Example 65)

The conductive resin composition 2 was produced in the same manner as in Example 64 using the above-mentioned resin composition K according to the composition of Table 29, and evaluated. The evaluation results and the mixing indexes α78 to ε78 are shown in Table 30.

The viscosity of the conductive resin composition 2 was 23.7 Pa·s, which was a liquid excellent in fluidity.

The volume resistivity of the conductive resin composition 2 was 3 × 10 ^-4 Ω ‧ cm, and it was judged that the conductivity was good.

The average value of the subsequent strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the conductive resin composition 2 was substituted into the following formula to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the residual rate of strength (%) = (the strength after the moisture absorption treatment) / (the strength after the moisture absorption treatment) × 100 = (138 mN) / (145 mN) × 100 = 95% ≧ 80%, the composition of the conductive resin The adhesion of the substance 2 was judged to be good.

Next, the conductive resin composition 2 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. The sample was visually confirmed under a magnifying glass and no void was produced.

As a result of the above, the conductive resin composition 2 was excellent in fluidity, conductivity, and adhesion, and no voids were formed.

(Example 66)

The conductive resin composition 3 was produced in the same manner as in Example 64 using the resin composition L described above, and evaluated according to the composition of Table 29. The evaluation results and the mixing indexes α 79 to ε 79 are shown in Table 30.

The viscosity of the conductive resin composition 3 is 28.2 Pa s, which is a liquid excellent in fluidity.

The volume resistivity of the conductive resin composition 3 was 3 × 10 ^-4 Ω ‧ cm, and it was judged that the conductivity was good.

The average value of the joint strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the conductive resin composition 3 was substituted into the following equation to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the residual rate of strength (%) = (the strength after the moisture absorption treatment) / (the strength after the moisture absorption treatment) × 100 = (124 mN) / (136 mN) × 100 = 91% ≧ 80%, the composition of the conductive resin The adhesion of the object 3 was judged to be good. Further, since the conductive resin composition of Example 65 produced in the same composition except that the ratio of the NP resin to the DBU was changed, the present Example 66 showed better adhesion, and it was estimated that two kinds were used in combination. The hardener will exhibit a multiplier effect.

Next, the conductive resin composition 3 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. The sample was visually confirmed under a magnifying glass and no void was produced.

As a result of the above, the conductive resin composition 3 was excellent in fluidity, conductivity, and adhesion, and no voids were formed.

(Example 67)

The conductive resin composition 4 was produced and evaluated in the same manner as in Example 64, using the resin composition M described above. The evaluation results and the mixing indexes α80 to ε80 are shown in Table 30.

The viscosity of the conductive resin composition 4 was 19.1 Pa·s, which was a liquid excellent in fluidity.

The volume resistivity of the conductive resin composition 4 was 3 × 10 ^-4 Ω ‧ cm, and it was judged that the conductivity was good.

The average value of the subsequent strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the conductive resin composition 4 was substituted into the following equation to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the residual rate of strength (%) = (the strength after the moisture absorption treatment) / (the strength after the moisture absorption treatment) × 100 = (108 mN) / (128 mN) × 100 = 84% ≧ 80%, the composition of the conductive resin The adhesion of the object 4 was judged to be good.

Next, the conductive resin composition 4 was applied to the die pad portion of the copper lead frame, and a glass piece (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. It was visually confirmed under a magnifying glass that the sample was free of voids.

As a result of the above, the conductive resin composition 4 was excellent in fluidity, conductivity, and adhesion, and no voids were formed.

(Comparative Example 36)

The conductive resin composition 5 was produced in the same manner as in Example 64 using a Bis-A epoxy resin and a Bis-F epoxy resin in place of the resin composition J according to the composition of Table 29, and evaluated. The evaluation results are shown in Table 30.

The viscosity of the conductive resin composition 5 is 26.4 Pa·s, which is a liquid excellent in fluidity.

The volume resistivity of the conductive resin composition 5 was 3 × 10 ^-4 Ω ‧ cm, and it was judged that the conductivity was good.

The average value of the subsequent strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the conductive resin composition 5 was substituted into the following equation to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the residual rate of strength (%) = (the strength after the moisture absorption treatment) / (the strength after the moisture absorption treatment) × 100 = (81 mN) / (132 mN) × 100 = 61% < 80%, the composition of the conductive resin The adhesion of the substance 5 was judged to be defective.

Next, the conductive resin composition 5 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. The sample was visually confirmed under a magnifying glass and no void was formed.

As a result of the above, the conductive resin composition 5 was excellent in fluidity and conductivity, and no voids were formed. However, it was judged to be unacceptable because of poor adhesion.

(Comparative Example 37)

The conductive resin composition 6 was produced in the same manner as in Example 1 except that the resin composition J was replaced with Bis-A epoxy resin, PTMS, or TMS, and evaluated. The evaluation results are shown in Table 30.

The viscosity of the conductive resin composition 6 is 18.2 Pa s, which is a liquid excellent in fluidity.

The volume resistivity of the conductive resin composition 6 was 42 × 10 ^-4 Ω ‧ cm, and it was judged that the conductivity was poor.

The average value of the subsequent strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the conductive resin composition 6 was substituted into the following equation to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the residual rate of strength (%) = (the strength after the moisture absorption treatment) / (the strength after the moisture absorption treatment) × 100 = (120 mN) / (134 mN) × 100 = 89% ≧ 80%, the composition of the conductive resin The adhesion of the substance 6 was judged to be good.

Next, the conductive resin composition 6 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. Visually confirm that this sample has voids under a magnifying glass.

As a result of the above, the conductive resin composition 6 was excellent in fluidity and adhesion, but it was confirmed that voids were formed due to poor conductivity, and therefore it was judged to be unacceptable.

(Comparative Example 38)

The conductive resin composition 7 was produced in the same manner as in Example 62 except that the resin composition J was replaced with Bis-A epoxy resin, Bis-F epoxy resin and TEOS, and evaluated. The results are shown in Table 30.

The viscosity of the conductive resin composition 7 is 16.3 Pa s, which is a liquid excellent in fluidity.

The volume resistivity of the conductive resin composition 7 was 3 × 10 ^-4 Ω ‧ cm, and it was judged that the conductivity was good.

The average value of the subsequent strengths of the "pre-hygroscopic treatment sample" and the "moisture-absorbing sample" of the conductive resin composition 7 was substituted into the following formula to determine the residual strength residual ratio, and the adhesion was evaluated.

Then, the residual rate of strength (%) = (the strength after the moisture absorption treatment) / (the strength after the moisture absorption treatment) × 100 = (131 mN) / (140 mN) × 100 = 94% ≧ 80%, the composition of the conductive resin The adhesion of the substance 7 was judged to be good.

Next, the conductive resin composition 7 was applied to the die pad portion of the copper lead frame, and a glass wafer (8 mm × 8 mm) was attached and heated in an oven at 200 ° C for 1 hour. Visually confirm that this sample has voids under a magnifying glass.

As a result of the above, the conductive resin composition 7 was excellent in fluidity, conductivity, and adhesion. However, it was confirmed that voids were formed, and it was judged that it was unacceptable.

As shown in Table 28 to Table 30, a resin composition obtained by mixing an epoxy resin and a specific alkoxydecane compound at a specific ratio in the present embodiment and performing cohydrolysis condensation, and a conductive metal powder are contained. The conductive resin composition of the curing agent is excellent in fluidity.

Further, the conductive resin composition of the present embodiment is excellent in conductivity and adhesion, and voids are not generated.

This application is based on a Japanese patent application filed on July 3, 2008 to the Japanese Patent Office (Japanese Patent Application No. 2008-175096), and a Japanese patent filed on December 10, 2008 for the Japanese Patent Office. The application (Japanese Patent Application No. 2008-314273) is hereby incorporated by reference.

[Industry use possibility]

According to the present invention, it is possible to provide a modified resin composition having good storage stability, which can be formed with good transparency, and also has excellent heat resistance, heat discoloration resistance, light resistance, and thermal shock resistance. Hardened material.

Further, by using the modified resin composition of the present invention, it is possible to provide:

<a> Excellent light-emitting parts such as LEDs that are excellent in adhesion to components or packaging materials, do not break, and have a low degree of brightness reduction for a long period of time; and can be injection-molded, hardened after hardening, and dimensionally stable. An optical lens excellent in light resistance and light-resistant; and a semiconductor device using the above-described light-emitting component and/or optical lens;

<b> a photosensitive composition excellent in adhesion of polymerization due to oxygen; a coating agent containing the composition; and a coating film obtained by curing the coating agent;

<c> a fluorescent resin composition excellent in dispersion stability of a phosphor; and a light-storing material obtained by using the fluorescent resin composition;

<d> a conductive resin composition excellent in fluidity, conductivity, and adhesion and having no voids;

<e> An insulating resin composition which is excellent in fluidity, insulation, and adhesion and which does not cause voids.

10, 20. . . Light-emitting diode (LED)

10A, 20A. . . LED chip

10A, 20A. . . anode

10C, 20C. . . cathode

12, 22. . . Sealing material

14, 24. . . Bonding wire

16. . . Outer layer resin

18. . . Lead frame

26. . . Package substrate

28. . . Reflective plate

Figure 1 is a cross-sectional view showing a bullet-type LED.

Fig. 2 is a cross-sectional view showing an SMD type LED.

10. . . Light-emitting diode (LED)

10a. . . LED chip

10A. . . anode

10C. . . cathode

12. . . Sealing material

14. . . Bonding wire

16. . . Outer layer resin

18. . . Lead frame

Claims (32)

A modified resin composition obtained by reacting an epoxy resin (A) with an alkoxydecane compound represented by the following formula (1), (R ¹ ) _n -Si-(OR ² ) _4-n ( 1) (wherein n represents an integer of 0 or more and 3 or less; and R ¹ each independently represents at least one or more organic groups selected from the group consisting of a) to c): a) An aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 4 or more and 24 or less and oxygen An organic group having a cyclic ether group having 1 or more and 5 or less atoms; b) having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups a monovalent aliphatic organic group having a carbon number of 1 or more and 24 or less and an oxygen atom number of 0 or more and 5 or less; c) having an unsubstituted or substituted aromatic hydrocarbon unit, and if necessary And an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups, and having a carbon number of 6 or more 24 or less and a monovalent aromatic organic group having an oxygen atom number of 0 or more and 5 or less; on the other hand, R ² each independently represents a hydrogen atom, and one or more organic groups selected from the group consisting of d): d) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, or cyclic groups, and having a carbon number of 1 or more and 8 or less The alkoxydecane compound contains at least one alkoxydecane having the following (B) and (C): (B) n = 1 or 2 and having at least one cyclic ether group as R ¹ a compound, and (C) n = 1 or 2 and at least one aromatic organic group as at least one alkoxydecane compound of R ¹ ; a mixture of the alkoxydecane compound represented by the following general formula (2) The index α is 0.001 or more and 19 or less: the mixing index α = (α c) / (α b) (2) (here, in the formula (2), α b represents an alkoxydecane compound represented by the general formula (1) In the content (mol%) of the component (B), α c represents the content (mol%) of the component (C) in the alkoxydecane compound represented by the general formula (1); and the modified resin Residual alkoxy group in the composition 5% or less based; Further, condensation of the silane-alkoxy compounds of 80% or more. The modified resin composition of claim 1, wherein the modified resin composition has a viscosity at 25 ° C of 1000 Pa ‧ or less. The modified resin composition according to claim 1 or 2, wherein the modified resin composition has an epoxy equivalent of from 100 g/eq to 700 g/eq. The modified resin composition according to claim 1 or 2, wherein the epoxy resin (A) has a viscosity at 25 ° C of 500 Pa ‧ or less. The modified resin composition according to claim 1 or 2, wherein the epoxy resin (A) has an epoxy equivalent of from 100 g/eq to 300 g/eq. The modified resin composition according to claim 1 or 2, wherein the epoxy resin (A) is a polyfunctional epoxy resin composed of a glycidyl etherate of a polyphenol compound. The modified resin composition according to claim 1 or 2, wherein the epoxy resin (A) is a bisphenol A type epoxy resin. The modified resin composition of the first or second aspect of the invention, wherein the alkoxydecane compound represented by the following general formula (3) has a mixing index β of 0.01 or more and 1.4 or less: a mixing index β={( β n2)/(β n0+β n1)} (3) (In the formula (3), β n2 represents an alkoxydecane of n=2 in the alkoxydecane compound represented by the general formula (1). The content (mol%) of the compound, β n0 represents the content (mol%) of the alkoxydecane compound of n=0 in the alkoxydecane compound represented by the general formula (1), and β n1 represents the general formula (1). The content (mol%) of the alkoxydecane compound of n = 1 in the alkoxydecane compound, and the values satisfy the following formula: 0 ≦ {(β n0) / (β n0 + β n1 + β n2)}≦0.1). The modified resin composition of the first or second aspect of the invention, wherein the mixing index γ of the epoxy resin (A) represented by the following general formula (4) and the alkoxydecane compound is 0.02 to 15 : mixing index γ = (γ a) / (γ s) (4) (here, in the formula (4), γ a represents the mass (g) of the epoxy resin (A), γ s represents the mass (g) of the alkoxydecane compound of n = 0 to 2 in the alkoxydecane compound represented by the general formula (1). A method for producing a modified resin composition by reacting an alkoxydecane compound containing at least (B) and (C) represented by the following general formula (1) in the presence of an epoxy resin (A); The method for producing a modified resin composition according to any one of claims 1 to 9, which comprises the following steps (a) and (b): (a) step: in epoxy resin (A) In the presence of the alkoxydecane compound containing at least (B) and (C) represented by the general formula (1), a step of producing an intermediate by co-hydrolysis without a reflux step with dehydration; (b) Step: a step of subjecting the intermediate produced in the step (a) to a dehydration condensation reaction; (R ¹ ) _n -Si-(OR ² ) _4-n (1) (here, n represents an integer of 0 or more and 3 or less) Further, R ¹ each independently represents a hydrogen atom, at least one or more organic groups selected from the group consisting of a) to c): a) having a chain or a group selected from unsubstituted or substituted An aliphatic hydrocarbon unit composed of one or more types of structures in a branched or cyclic structure, and a cyclic ether group having a carbon number of 4 or more and 24 or less and an oxygen atom of 1 or more and 5 or less of (b) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups, and having a carbon number of 1 or more a monovalent aliphatic organic group having 24 or less and an oxygen atom number of 0 or more and 5 or less; c) having an unsubstituted or substituted aromatic hydrocarbon unit, and having a chain selected from unsubstituted or substituted, if necessary a monovalent aromatic organic group formed by one or more kinds of structures having a branched or cyclic structure; and having a carbon number of 6 or more and 24 or less and an oxygen atom number of 0 or more and 5 or less; On the other hand, R ² each independently represents a hydrogen atom or one or more organic groups selected from the group consisting of d): d) having a chain, a branch, or a ring selected from unsubstituted or substituted An aliphatic hydrocarbon unit composed of one or more types of structures in a group, and a monovalent organic group having a carbon number of 1 or more and 8 or less; (B) n = 1 or 2 and at least one ring R ¹ is an ether group, at least one kind of alkyl alkoxy silicon compound; (C) n = 1 or 2 and having at least one aromatic organic groups for R ¹ is at least one kind of alkoxy group And the mixing index α of the alkoxydecane compound represented by the following general formula (2) is 0.001 or more and 19 or less: a mixing index α=(α c)/(α b) (2) (here) In the formula (2), α b represents the content (mol%) of the component (B), and α c represents the content (mol%) of the component (C). A method for producing a modified resin composition by reacting an alkoxydecane compound containing at least (B) and (C) represented by the following general formula (1) in the presence of an epoxy resin (A); The method for producing a modified resin composition according to any one of claims 1 to 9, which comprises the following steps (c) and (d): (c): at least containing a general formula (1) The alkoxydecane compound of (B) and (C), wherein the step of producing an intermediate by co-hydrolysis without a reflux step with dehydration; (d) the step of: (c) a step of performing a dehydration condensation reaction in the presence of an intermediate and an epoxy resin (A); (R ¹ ) _n -Si-(OR ² ) _4-n (1) (here, n represents an integer of 0 or more and 3 or less, Further, R ¹ each independently represents a hydrogen atom, at least one or more organic groups selected from the group consisting of a) to c): a) having a chain or branch selected from unsubstituted or substituted groups An aliphatic hydrocarbon unit composed of one or more types of structures in a group or a ring-shaped structure, and a cyclic ether group composed of a carbon number of 4 or more and 24 or less and an oxygen atom number of 1 or more and 5 or less Have (b) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted or substituted chain, branched, and cyclic groups, and having a carbon number of 1 or more and 24 The following is a monovalent aliphatic organic group having an oxygen atom number of 0 or more and 5 or less; c) having an unsubstituted or substituted aromatic hydrocarbon unit, and having a chain or sub-group selected from unsubstituted or substituted, if necessary An aliphatic hydrocarbon unit composed of one or more kinds of structures of a branched or cyclic structure, and a monovalent aromatic organic group having a carbon number of 6 or more and 24 or less and an oxygen atom number of 0 or more and 5 or less; In one aspect, R ² each independently represents a hydrogen atom, one or more organic groups selected from the group consisting of d): d) having a chain, a branch, or a ring selected from unsubstituted or substituted An aliphatic hydrocarbon unit composed of one or more types of structures in a group, and a monovalent organic group having a carbon number of 1 or more and 8 or less; (B) n = 1 or 2 and at least one ring R ¹ is an ether group, at least one kind of alkyl alkoxy silicon compound; (C) n = 1 or 2 and having at least one aromatic organic groups for R ¹ is at least one kind of alkoxy group And the mixing index α of the alkoxydecane compound represented by the following general formula (2) is 0.001 or more and 19 or less: a mixing index α=(α c)/(α b) (2) (here) In the formula (2), α b represents the content (mol%) of the component (B), and α c represents the content (mol%) of the component (C). The method for producing a modified resin composition according to claim 10, wherein the mixing index β of the alkoxydecane compound represented by the following general formula (3) is 0.01 to 1.4: a mixing index β={ (β n2) / (β n0 + β n1)} (3) (In the formula (3), β n2 represents an alkoxy group of n=2 in the alkoxydecane compound represented by the general formula (1). The content (mol%) of the decane compound, β n0 represents the content (mol%) of the alkoxydecane compound of n=0 in the alkoxydecane compound represented by the general formula (1), and β n1 represents the general formula (1). The content (mol%) of the alkoxydecane compound of n = 1 in the alkoxydecane compound shown, and the values satisfy the following formula: 0 ≦ {(β n0) / (β n0 + β n1 +β n2)}≦0.1). The method for producing a modified resin composition according to claim 10, wherein the mixing index γ of the epoxy resin (A) represented by the following general formula (4) and the alkoxydecane compound is 0.02. To 15: mixing index γ = (γ a) / (γ s) (4) (here, in the formula (4), γ a represents the mass (g) of the epoxy resin (A), and γ s represents the general formula ( 1) The mass (g) of the alkoxydecane compound of n = 0 to 2 in the alkoxydecane compound shown. The method for producing a modified resin composition according to claim 10 or 11, wherein the temperature of the reflux step without dehydration is from 50 to 100 °C. The method for producing a modified resin composition according to claim 10 or 11, wherein the condensation ratio of the intermediate obtained by co-hydrolysis without a reflux step with dehydration is 78% or more. The method for producing a modified resin composition according to claim 10, wherein an alkoxide-based organotin is used as a catalyst when the co-hydrolysis is carried out. A resin composition obtained by adding an oxetane compound (D) to the modified resin composition of claim 1 of the patent application. A fluorescent resin composition obtained by adding a phosphor (E) to a modified resin composition of the first application of the patent application. A conductive resin composition obtained by adding a conductive metal powder (F) to a modified resin composition of the first application of the patent application. An insulating resin composition is modified in the first item of the patent application scope The insulating resin powder (G) is added to the resin composition. A resin composition obtained by adding an epoxy resin (A') to a modified resin composition of the first application of the patent application. A curable resin composition obtained by adding a curing agent (H) to a resin composition according to any one of claims 1, 17, and 18. A curable resin composition obtained by adding a hardening accelerator (I) to a resin composition of claim 22 of the patent application. A photosensitive resin composition obtained by adding a photo-acid generator (J) to a resin composition according to any one of claims 1, 17, and 18. A light-emitting component produced by using the resin composition of claim 23 or 24. An optical lens obtained by using the resin composition of claim 23 or 24. A light-storing material obtained by using the resin composition of claim 23 or 24. A semiconductor device comprising the light-emitting component of claim 25 and/or the optical lens of claim 26 of the patent application. A curable resin composition obtained by adding a hardening accelerator (I) to a resin composition according to any one of claims 19 to 21. A photosensitive resin composition obtained by adding a photoacid generator (J) to a resin composition according to any one of claims 19 to 21; Adult. A coating agent containing the resin composition of any one of claims 23, 24, 29, and 30. A coating film obtained by using the coating agent of claim 31.