CN102076734A - Modified resin composition, method for producing the same, and curable resin composition containing the same - Google Patents

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

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CN102076734A
CN102076734A CN2009801247757A CN200980124775A CN102076734A CN 102076734 A CN102076734 A CN 102076734A CN 2009801247757 A CN2009801247757 A CN 2009801247757A CN 200980124775 A CN200980124775 A CN 200980124775A CN 102076734 A CN102076734 A CN 102076734A
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resin composition
group
alkoxysilane compound
organic group
general formula
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CN102076734B (en
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秋元光代
中村光武
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Asahi Kasei Corp
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Asahi Kasei Chemicals Corp
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
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    • H01L2224/48151Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
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    • H01L2224/48257Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
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    • H01L2224/49105Connecting at different heights
    • H01L2224/49107Connecting at different heights on the semiconductor or solid-state body
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  • Polymers & Plastics (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)

Abstract

Disclosed is a modified resin composition obtained by reacting an epoxy resin (A) and an alkoxysilane compound represented by the following general formula (1): (R1)n-Si-(OR2)4-n. The alkoxysilane compound contains (B) at least one kind of an alkoxysilane compound wherein n is 1 or 2 and at least one cyclic ether group is contained as R1 and (C) at least one kind of an alkoxysilane compound wherein n is 1 or 2 and at least one aromatic organic group is contained as R1. The mixing index a of the alkoxysilane compound, which is represented by the following general formula (2): mixing index alpha = (alpha*c)/( alpha*b), is not less than 0.001 but not more than 19, and the amount of remaining alkoxy groups in the modified resin composition is not more than 5%.

Description

Modified resin composition, method for producing same, and curable resin composition containing same
Technical Field
The present invention relates to a modified resin composition obtained by reacting an epoxy resin with an alkoxysilane compound, a method for producing the same, a curable resin composition containing the modified resin composition, and uses thereof.
Background
Conventionally, an epoxy resin composition using an acid anhydride curing agent is suitably used as a sealing resin for an optical semiconductor such as a light emitting diode (hereinafter, abbreviated as LED) or a photodiode because it can provide a transparent cured product and has high heat resistance and adhesiveness. However, in recent years, the performance of optoelectronic semiconductors has been improved, and as a resin for sealing LED, in addition to excellent transparency, high heat resistance and adhesiveness, which have been conventionally required, a cured product excellent in heat discoloration resistance, light resistance, crack resistance at the time of thermal cycle, and no surface tackiness (タック property) has been desired, and in actuality, a composition comprising an epoxy resin such as a bisphenol a-based epoxy resin or a bisphenol F-based epoxy resin, which has been conventionally used, has not been able to obtain sufficient heat properties.
As a resin for sealing a light-emitting element, a silicone resin having a siloxane skeleton which is stable to heat or light as a repeating unit has been studied in a large number. However, the silicone resin is actually excellent in light resistance and heat resistance, but has low adhesiveness and peeling from a substrate, and in some cases, the cured product has low hardness and surface tackiness, and thus the performance is not satisfactory, and a large amount of improvement is required.
On the other hand, many studies have been made on a modified resin composition compound having a siloxane skeleton as a repeating unit and an epoxy group in an organic group. The modified resin composition has excellent transparency and heat resistance of an epoxy resin, and can provide a cured product having no surface tackiness, and the cured product can be expected to have light resistance, oxidation resistance, and flexibility of silicone.
For example, patent document 1 proposes the following: a modified resin composition contains a T structure as an essential repeating unit and contains an epoxy group-containing organic group in an amount of 0.1 to 40 mol% based on all organic groups bonded to silicon atoms in 1 molecule.
Patent document 2 describes a composition containing a silicone compound having a molecular weight within a specific range and at least 2 epoxy groups in 1 molecule, and its use in an optoelectronic semiconductor encapsulating material.
Patent documents 3 to 5 disclose a resin composition obtained by mixing an epoxy resin and a silicone resin which has been previously condensed.
Patent documents 6 to 11 disclose a resin composition obtained by mixing an epoxy resin and alkoxysilanes or partial condensates thereof, followed by dealcoholization reaction.
Patent document 12 discloses a resin composition comprising a modified phenoxy resin containing an alkoxy group having 2 times the number of Si atoms in the molecule and an epoxy resin.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3263177
Patent document 2: japanese patent laid-open publication No. 2005-171021
Patent document 3: japanese laid-open patent publication No. 2006-225515
Patent document 4: japanese laid-open patent publication No. 2006-241230
Patent document 5: japanese patent laid-open No. 2008-120843
Patent document 6: japanese patent laid-open No. 2001 and 059011
Patent document 7: japanese patent laid-open No. 2001 and 059013
Patent document 8: japanese laid-open patent publication No. 2002-179762
Patent document 9: japanese laid-open patent publication No. 2002-249539
Patent document 10: japanese patent laid-open publication No. 2003-246838
Patent document 11: japanese patent application laid-open No. 2005-179401
Patent document 12: japanese laid-open patent publication No. 2007-321130
Disclosure of Invention
Problems to be solved by the invention
However, the resin compositions described in patent documents 1 and 2 are insufficient in light resistance, and satisfactory levels of crack resistance and adhesiveness have not yet been achieved. Further, the modified resin composition described above is low in storage stability in some cases, and tends to increase the viscosity of the resin significantly during storage, and thus cannot be said to have sufficient practicability.
The compositions described in patent documents 3 to 5 are obtained by mixing a silicone resin condensed in advance with an epoxy resin in the absence of the epoxy resin, and have low storage stability and tend to significantly increase the viscosity of the resin during storage. In addition, the epoxy resin and the silicone resin cannot be uniformly mixed in some cases, and thus the epoxy resin and the silicone resin cannot be said to have sufficient practicability.
Further, in the case of producing silicone by dealcoholization, alkoxy groups tend to remain in silicone, and cured products obtained by curing resin compositions containing alkoxysilane residues as described in patent documents 6 to 12 tend to have reduced crack resistance and adhesiveness during thermal cycles because alcohol is generated by hydrolysis with time and the cured products are vaporized.
In view of the above circumstances, an object of the present invention is to provide a modified resin composition which can form a cured product having good transparency and excellent heat resistance, thermal discoloration resistance, light resistance, and crack resistance during thermal cycles, and which has good storage stability.
Another object of the present invention is to provide an excellent light-emitting component such as an LED which has excellent adhesion to an element or a sealing material, does not crack, and has a small decrease in long-term luminance; an optical lens which can be injection molded, has a hard texture after curing and excellent dimensional stability, and has light resistance; and a semiconductor device using the light emitting component and/or the optical lens.
Further, an object of the present invention is to provide a photosensitive composition which can suppress a polymerization inhibiting effect by oxygen and has excellent adhesion, a coating agent containing the composition, and a coating film obtained by curing the coating agent.
Another object of the present invention is to provide a fluorescent resin composition having excellent dispersion stability of a fluorescent material, and a light storage material using the fluorescent resin composition.
Another object of the present invention is to provide a conductive resin composition which is excellent in fluidity, conductivity and adhesiveness and does not generate voids (void).
Another object of the present invention is to provide an insulating resin composition which is excellent in fluidity, insulating properties and adhesion properties and does not generate voids.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by adjusting the amount of residual alkoxy groups in a resin composition to a specific range, in a modified resin composition obtained by reacting an epoxy resin with a specific alkoxysilane compound at a specific ratio, and have completed the present invention.
Namely, the present invention is as follows.
[1]
A modified resin composition obtained by reacting an epoxy resin (A) with an alkoxysilane compound represented by the following general formula (1),
(R1)n-Si-(OR2)4-n (1)
(it isWherein n represents an integer of 0 to 3 inclusive; in addition, R1Each independently represents at least 1 or more organic groups selected from the group consisting of hydrogen atoms, the following a), the following b), the following c), and R2Each independently represents 1 or more organic groups selected from the group consisting of a hydrogen atom and d),
a) An organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms,
b) a 1-valent aliphatic organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more kinds of structures selected from the group consisting of a chain, a branched chain and a ring, the 1-valent aliphatic organic group having 1 or more carbon atoms and 24 or less and an oxygen atom number of 0 or more and 5 or less,
c) a 1-valent aromatic organic group, wherein the 1-valent aromatic organic group is an unsubstituted or substituted aromatic hydrocarbon unit, and optionally has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 to 24 carbon atoms and 0 to 5 oxygen atoms,
d) a 1-valent organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, wherein the number of carbon atoms in the 1-valent organic group is 1 to 8. )
The alkoxysilane compound includes:
(B) n is 1 or 2 and has at least 1 cyclic ether group as R1At least 1 alkoxysilane compound, and
(C) n is 1 or2. And having at least 1 aromatic organic group as R1At least 1 kind of alkoxysilane compound of (a),
the alkoxysilane compound represented by the general formula (2) has a mixing index alpha of 0.001 to 19 inclusive,
mixing index α ═ (α c)/(α b) … (2)
(wherein, in the formula (2), α B represents the content (mol%) of the component (B) in the alkoxysilane compound represented by the general formula (1), and α C represents the content (mol%) of the component (C) in the alkoxysilane compound represented by the general formula (1))
And the modified resin composition has a residual alkoxy group content of 5% or less.
[2]
The modified resin composition according to [1], which has a viscosity of 1000 pas or less at 25 ℃.
[3]
The modified resin composition according to [1] or [2], wherein the epoxy equivalent of the modified resin composition is 100g/eq or more and 700g/eq or less.
[4]
The modified resin composition according to any one of the above [1] to [3], wherein the condensation rate of the alkoxysilane compound is 80% or more.
[5]
The modified resin composition according to any one of the above [1] to [4], wherein the epoxy resin (A) has a viscosity of 500 pas or less at 25 ℃.
[6]
The modified resin composition according to any one of the above [1] to [5], wherein the epoxy equivalent of the epoxy resin (A) is 100g/eq or more and 300g/eq or less.
[7]
The modified resin composition according to any one of the above [1] to [6], wherein the epoxy resin (A) is a polyfunctional epoxy resin comprising a glycidyl ether compound of a polyphenol compound.
[8]
The modified resin composition according to any one of the above [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 mixing index β of the alkoxysilane compound represented by the following general formula (3) is 0.01 or more and 1.4 or less.
Mixing index β { (β n2)/(β n0+ β n1) } (3)
(wherein, in formula (3), β n2 represents the content (mol%) of the alkoxysilane compound of formula (1) in which n is 2, β n0 represents the content (mol%) of the alkoxysilane compound of formula (1) in which n is 0, β n1 represents the content (mol%) of the alkoxysilane compound of formula (1) in which n is 1, and β n2, β n0, and β n1 are values satisfying 0 ≦ { (β n0)/(β n0+ β n1+ β n2) } ≦ 0.1.)
[10]
The modified resin composition according to any one of the above [1] to [9], wherein the mixing index γ of the epoxy resin (A) represented by the following general formula (4) and the alkoxysilane compound is 0.02 to 15.
Mixing index γ ═ (γ a)/(γ s) (4)
(wherein in formula (4), γ a represents the mass (g) of the epoxy resin (a), and γ s represents the mass (g) of an alkoxysilane compound having n of 0 to 2 among the alkoxysilane compounds represented by general formula (1))
[11]
A method for producing a modified resin composition described in any one of the above [1] to [10] by reacting an alkoxysilane compound including at least (B) and (C) represented by the following general formula (1) in the presence of an epoxy resin (A), the method comprising the following steps (a) and (B):
a step (a): a step of co-hydrolyzing an alkoxysilane compound containing at least (B) and (C) represented by the general formula (1) in the presence of an epoxy resin (A) through a reflux step without dehydration to produce an intermediate;
a step (b): and (c) a step of subjecting the intermediate produced in the step (a) to dehydration condensation reaction.
(R1)n-Si-(OR2)4-n (1)
(wherein n represents an integer of 0 to 3; and R represents 1Each independently represents at least 1 or more organic groups selected from the group consisting of hydrogen atoms, the following a), the following b), the following c), and R2Each independently represents 1 or more organic groups selected from the group consisting of a hydrogen atom and d),
a) an organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms,
b) a 1-valent aliphatic organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more kinds of structures selected from the group consisting of a chain, a branched chain and a ring, the 1-valent aliphatic organic group having 1 or more carbon atoms and 24 or less and an oxygen atom number of 0 or more and 5 or less,
c) a 1-valent aromatic organic group, wherein the 1-valent aromatic organic group is an unsubstituted or substituted aromatic hydrocarbon unit, and optionally has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 to 24 carbon atoms and 0 to 5 oxygen atoms,
d) A 1-valent organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, wherein the number of carbon atoms in the 1-valent organic group is 1 to 8. )
(B) n is 1 or 2 and has at least 1 cyclic ether group as R1At least 1 alkoxysilane compound.
(C) n is 1 or 2 and has at least 1 aromatic organic group as R1At least 1 alkoxysilane compound.
And the mixing index alpha of the alkoxysilane compound represented by the general formula (2) is 0.001 to 19.
Mixing index α ═ (α c)/(α b) … (2)
(wherein, 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))
[12]
A process for producing a modified resin composition according to any one of the above [1] to [10] by reacting an alkoxysilane compound comprising at least (B) and (C) represented by the following general formula (1) in the presence of an epoxy resin (A), the process comprising the following steps (C) and (d):
a step (c): a step of co-hydrolyzing an alkoxysilane compound containing at least (B) and (C) represented by the general formula (1) in a reflux step without dehydration to produce an intermediate.
Step (d): and (c) allowing the intermediate produced in the step (c) to coexist with the epoxy resin (a) and allowing the mixture to undergo a dehydration condensation reaction.
(R1)n-Si-(OR2)4-n (1)
(wherein n represents an integer of 0 to 3; and R represents1Each independently represents at least 1 or more organic groups selected from the group consisting of hydrogen atoms, the following a), the following b), the following c), and R2Each independently represents 1 or more organic groups selected from the group consisting of a hydrogen atom and d),
a) an organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms,
b) a 1-valent aliphatic organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more kinds of structures selected from the group consisting of a chain, a branched chain and a ring, the 1-valent aliphatic organic group having 1 or more carbon atoms and 24 or less and an oxygen atom number of 0 or more and 5 or less,
c) a 1-valent aromatic organic group, wherein the 1-valent aromatic organic group is an unsubstituted or substituted aromatic hydrocarbon unit, and optionally has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 to 24 carbon atoms and 0 to 5 oxygen atoms,
d) A 1-valent organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, wherein the number of carbon atoms in the 1-valent organic group is 1 to 8. )
(B) n is 1 or 2 and has at least 1 cyclic ether group as R1At least 1 alkoxysilane compound.
(C) n is 1 or 2 and has at least 1 aromatic organic group as R1At least 1 alkoxysilane compound.
And the mixing index alpha of the alkoxysilane compound represented by the general formula (2) is 0.001 to 19.
Mixing index α ═ (α c)/(α b) … (2)
(wherein, 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))
[13]
The process for producing a modified resin composition as described in the above [11] or [12], wherein the alkoxysilane compound represented by the following general formula (3) has a mixing index β of 0.01 to 1.4.
Mixing index β { (β n2)/(β n0+ β n1) } (3)
(wherein, in formula (3), β n2 represents the content (mol%) of the alkoxysilane compound of formula (1) in which n is 2, β n0 represents the content (mol%) of the alkoxysilane compound of formula (1) in which n is 0, β n1 represents the content (mol%) of the alkoxysilane compound of formula (1) in which n is 1, and β n2, β n0, and β n1 are values satisfying 0 ≦ { (β n0)/(β n0+ β n1+ β n2) } ≦ 0.1.)
[14]
The process for producing a modified resin composition according to any one of the above [11] to [13], wherein the mixing index γ between the epoxy resin (A) represented by the following general formula (4) and the alkoxysilane compound is 0.02 to 15.
Mixing index γ ═ (γ a)/(γ s) (4)
(wherein in formula (4), γ a represents the mass (g) of the epoxy resin (a), and γ s represents the mass (g) of an alkoxysilane compound having n of 0 to 2 among the alkoxysilane compounds represented by general formula (1))
[15]
The method for producing a modified resin composition as described in any one of the above [11] to [14], wherein the temperature in the reflux step without dehydration is 50 to 100 ℃.
[16]
The method for producing a modified resin composition according to any one of the above [11] to [15], wherein a condensation rate of an intermediate obtained by cohydrolysis in a reflux step without dehydration is 78% or more.
[17]
The process according to any one of the above [11] to [16], wherein an alkoxide-based organotin is used as a catalyst in the cohydrolysis.
[18]
A resin composition obtained by further adding an oxetane compound (D) to the modified resin composition described in [1 ].
[19]
A fluorescent resin composition, which is obtained by further adding a fluorescent material (E) to the modified resin composition according to [1 ].
[20]
A conductive resin composition, which is obtained by adding a conductive metal powder (F) to the modified resin composition described in [1 ].
[21]
An insulating resin composition, which is obtained by further adding an insulating powder (G) to the modified resin composition according to [1 ].
[22]
A resin composition obtained by further adding an epoxy resin (A') to the modified resin composition according to [1 ].
[23]
A curable resin composition obtained by further adding a curing agent (H) to the resin composition according to any one of [1], [18] and [19 ].
[24]
A curable resin composition obtained by further adding a curing accelerator (I) to the resin composition according to [23 ].
[25]
A photosensitive resin composition, which is obtained by further adding a photoacid generator (J) to the resin composition according to any one of [1], [18] and [19 ].
[26]
A light-emitting component produced using the resin composition according to [24] or [25 ].
[27]
An optical lens produced by using the resin composition according to [24] or [25 ].
[28]
A light-storing material produced using the resin composition according to [24] or [25 ].
[29]
A semiconductor device comprising the light-emitting component according to [26] above and/or the optical lens according to [27 ].
[30]
A curable resin composition obtained by adding a curing accelerator (I) to the resin composition according to any one of [20] to [22 ].
[31]
A photosensitive resin composition obtained by further adding a photoacid generator (J) to the resin composition according to any one of [20] to [22 ].
[32]
A coating agent comprising the resin composition according to any one of [24], [25], [30] and [31 ].
[33]
A coating film produced by using the coating agent according to [32 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a modified resin composition which can form a cured product having excellent light resistance and thermal shock resistance (crack resistance in thermal cycles) and which has good storage stability.
Drawings
Fig. 1 is a sectional view of a shell type LED.
Fig. 2 shows a cross-sectional view of an SMD type LED.
Description of the reference numerals
10. 20: luminous diode (LED)
10a, 20 a: LED chip
10A, 20A: anode electrode
10C, 20C: cathode electrode
12. 22: sealing material
14. 24: bonding wire
16: outer resin
18: lead frame
26: package substrate
28: reflecting plate
Detailed Description
Hereinafter, a specific embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following modes.
The modified resin composition in the present embodiment is a modified resin composition obtained by reacting an epoxy resin (a) with an alkoxysilane compound represented by the following general formula (1),
(R1)n-Si-(OR2)4-n (1)
(wherein n represents an integer of 0 to 3, or less; R1Each independently represents at least 1 or more organic groups selected from the group consisting of hydrogen atoms, the following a), the following b), the following c): a) an organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms; b) a 1-valent aliphatic organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, the 1-valent aliphatic organic group having 1 or more carbon atoms and 24 or less and 0 or more oxygen atoms and 5 or less; c) a 1-valent aromatic organic group, wherein the 1-valent aromatic organic group is an unsubstituted or substituted aromatic hydrocarbon unit, and optionally has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 to 24 carbon atoms and an oxygen atom The number is 0 to 5 inclusive. In another aspect, R2Each independently represents 1 or more organic groups selected from the group consisting of a hydrogen atom and d) below: d) a 1-valent organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, wherein the number of carbon atoms in the 1-valent organic group is 1 to 8. )
The alkoxysilane compound includes:
(B) n is 1 or 2 and has at least 1 cyclic ether group as R1At least 1 alkoxysilane compound, and
(C) n is 1 or 2 and has at least 1 aromatic organic group as R1At least 1 kind of alkoxysilane compound of (a),
the alkoxysilane compound represented by the general formula (2) has a mixing index alpha of 0.001 to 19 inclusive,
mixing index α ═ (α c)/(α b) … (2)
(wherein, in the formula (2), α B represents the content (mol%) of the component (B) in the alkoxysilane compound represented by the general formula (1), and α C represents the content (mol%) of the component (C) in the alkoxysilane compound represented by the general formula (1))
And the modified resin composition has a residual alkoxy group content of 5% or less.
The epoxy resin (a) used in the present embodiment is not particularly limited, and examples thereof include alicyclic epoxy resins, aliphatic epoxy resins, polyfunctional epoxy resins composed of glycidyl etherate of polyphenol compounds, polyfunctional epoxy resins which are glycidyl etherate of novolac resins, hydrogenated products (nuclear hydrated products) of aromatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, and the like. These epoxy resins may be used alone or in combination of two or more.
The alicyclic epoxy resin that 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 epoxy resins such as an epoxycyclohexane group, an epoxytricyclodecane group, and an epoxycyclopentyl group. As specific examples of the alicyclic epoxy resin, the monofunctional alicyclic epoxy compound may include 4-vinylcyclohexane, dioctylphthalate oxide and di-2-ethylhexyl hexahydrophthalate oxide. Examples of the 2-functional alicyclic epoxy compound include 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxycyclohexyloctyl-3, 4-epoxycyclohexanecarboxylate, 2- (3, 4-epoxycyclohexyl-5, 5-spiro-3, 4-epoxy) cyclohexane-1, 3-dioxane, bis (3, 4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3, 4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3, 4-epoxycyclohexane), Dicyclopentadiene dioxide, ethylene glycol di (3, 4-epoxycyclohexylmethyl) ether, ethylenebis (3, 4-epoxycyclohexanecarboxylate), 1, 2, 8, 9-diepoxy limonene. Examples of the polyfunctional alicyclic epoxy compound include 1, 2-epoxy-4- (2-oxiranyl) cyclohexene adducts of 2, 2-bis (hydroxymethyl) -1-butanol, and the like. Further, as commercially available products of the polyfunctional alicyclic epoxy compound, EPOLEAD GT401, EHPE3150 (manufactured by Daicel Chemical Industries, ltd.) and the like are exemplified.
Representative examples of the alicyclic epoxy resin are shown below.
Chemical formula 1
Figure BDA0000041312520000131
Figure BDA0000041312520000141
The aliphatic epoxy resin that can be used in the present embodiment is not particularly limited, and specific examples thereof include glycidyl ethers of polyhydric alcohols such as 1, 4-butanediol, 1, 6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, and xylene glycol derivatives.
Representative examples of the aliphatic epoxy resin are shown below.
Chemical formula 2
Figure BDA0000041312520000151
The polyfunctional epoxy resin composed of a glycidyl ether compound of a polyphenol compound that can be used in the present embodiment is not particularly limited, and specific examples thereof include bisphenol a, bisphenol F, bisphenol S, 4 ' -biphenol, tetramethylbisphenol a, dimethyl bisphenol a, tetramethylbisphenol F, dimethyl bisphenol F, tetramethylbisphenol S, dimethyl bisphenol S, tetramethyl-4, 4 ' -biphenol, dimethyl-4, 4 ' -biphenol, 1- (4-hydroxyphenyl) -2- [4- (1, 1-bis- (4-hydroxyphenyl) ethyl) phenyl ] propane, 2 ' -methylene-bis (4-methyl-6-tert-butylphenol), 4 ' -butylidene-bis (3-methyl-6-tert-butylphenol), And polyfunctional epoxy resins such as trishydroxyphenylmethane, resorcinol, hydroquinone, 2, 6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1, 1-di (4-hydroxyphenyl) fluorene, and glycidyl etherate compounds which are polyphenol compounds of phenolated polybutadiene.
Representative examples of the polyfunctional epoxy resin as a glycidyl etherate of a phenol having a bisphenol skeleton are shown below.
Chemical formula 3
Figure BDA0000041312520000152
When a polyfunctional epoxy resin which is a glycidyl etherate of a polyphenol compound is used, these repeating units (n in the chemical formula representing the above representative example) are not particularly limited, and are 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 possibility that a problem may occur in practical use. From the viewpoint of improving reactivity with alkoxysilane compounds, and further from the viewpoint of improving fluidity of the resulting modified resin composition, the range of the repeating unit is preferably 0.001 or more and 10 or less, and more preferably 0.01 or more and 2 or less.
The polyfunctional epoxy resin which is a glycidyl etherate of the novolak resin is not particularly limited, and examples thereof include glycidyl etherates of various novolak resins such as a novolak resin using various phenols such as phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenol a, bisphenol F, bisphenol S, naphthol and the like as raw materials, a novolak resin containing a xylylene skeleton, a novolak resin containing a dicyclopentadiene skeleton, a novolak resin containing a biphenyl skeleton, a novolak resin containing a fluorene skeleton and the like.
Representative examples of the polyfunctional epoxy resin as the glycidyl etherate of the novolak resin are shown below.
Chemical formula 4
Figure BDA0000041312520000161
The hydrogenated product (hydrated product) of the aromatic epoxy resin that can be used in the present embodiment is not particularly limited, and examples thereof include a glycidyl etherate of a phenol compound (bisphenol a, bisphenol F, bisphenol S, 4' -biphenol, etc.), a hydrogenated product of an aromatic ring of various phenols (phenol, cresol, ethylphenol, butylphenol, octylphenol, bisphenol a, bisphenol F, bisphenol S, naphthol, etc.), a hydrogenated product of a glycidyl etherate of a novolac resin, and the like.
The heterocyclic epoxy resin is not particularly limited, and examples thereof include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanurate ring and a hydantoin ring.
The glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include carboxylic acid-based epoxy resins such as diglycidyl hexahydrophthalate and diglycidyl tetrahydrophthalate.
The glycidyl amine-based epoxy resin is not particularly limited, and examples thereof include epoxy resins obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivatives, and diaminomethylbenzene derivatives.
The epoxy resin obtained by glycidylating a halogenated phenol is not particularly limited, and examples thereof include epoxy resins obtained by glycidylating a halogenated phenol such as brominated bisphenol a, brominated bisphenol F, brominated bisphenol S, brominated novolak, brominated cresol novolak, chlorinated bisphenol S, and chlorinated bisphenol a.
Among the above, the modified resin composition of the present embodiment is easily available, and the cured product obtained by curing the intended modified resin composition tends to have excellent transparency, heat resistance, thermal discoloration resistance, light resistance, and crack resistance during thermal cycling, and therefore, an alicyclic epoxy resin, an aliphatic epoxy resin, and a polyfunctional epoxy resin composed of a glycidyl etherate of a polyphenol compound are preferable, an alicyclic epoxy resin and a polyfunctional epoxy resin composed of a glycidyl etherate of a polyphenol compound are more preferable, a polyfunctional epoxy resin composed of a glycidyl etherate of a polyphenol compound is further preferable, and a bisphenol a type epoxy resin is particularly preferable.
The viscosity of the epoxy resin (a) used in the present embodiment at 25 ℃ is not particularly limited, but is preferably 1000Pa · s or less, more preferably 500Pa · s or less, further preferably 300Pa · s or less, and particularly preferably 100Pa · s or less, because fluidity as a liquid is ensured and compatibility with the alkoxysilane compound is improved.
The epoxy equivalent Weight (WPE) of the epoxy resin (a) used in the present embodiment is not particularly limited, but is preferably 100g/eq or more from the viewpoint of improving the storage stability of the modified resin composition of the present embodiment, and is preferably 700g/eq or less, more preferably 100g/eq or more and 500g/eq or less, and even more preferably 100g/eq or more and 300g/eq or less from the viewpoint of improving the crack resistance of a cured product obtained by curing the modified resin composition of the present embodiment.
The alkoxysilane compound that can be used in the present embodiment is a silicon compound having 1 to 4 alkoxy groups, and is represented by the following general formula (1).
(R1)n-Si-(OR2)4-n (1)
(wherein n represents an integer of 0 to 3, or less; R1Each independently represents at least 1 or more organic groups selected from the group consisting of hydrogen atoms, the following a), the following b), the following c): a) an organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms; b) a 1-valent aliphatic organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing at least 1 structure selected from the group consisting of a chain, a branched chain and a ring, wherein the 1-valent aliphatic organic group has 1 to 24 carbon atoms and 0 to 5 oxygen atoms The following steps of (1); c) a 1-valent aromatic organic group, wherein the 1-valent aromatic organic group is an unsubstituted or substituted aromatic hydrocarbon unit, and optionally has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 to 24 carbon atoms and 0 to 5 oxygen atoms. In another aspect, R2Each independently represents 1 or more organic groups selected from the group consisting of a hydrogen atom and d) below, and d) a 1-valent organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched chain and cyclic structures, and the number of carbon atoms of the 1-valent organic group is 1 or more and 8 or less. )
In this embodiment, a cyclic ether group will be described. The cyclic ether group in the present embodiment refers to an organic group having an ether obtained by substituting carbon of a cyclic hydrocarbon with oxygen, and generally refers to a cyclic ether group having a structure of a 3 to 6-membered ring. Among them, a 3-or 4-membered cyclic ether group having a large ring strain energy and high reactivity is preferable, and a 3-membered cyclic ether group is particularly preferable.
Next, R in the present embodiment is1The description is given. R in the present embodiment1Each independently represents at least 1 or more organic groups selected from the group consisting of hydrogen atoms, the following a), the following b), the following c): a) an organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms; b) a 1-valent aliphatic organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, the 1-valent aliphatic organic group having 1 or more carbon atoms and 24 or less and 0 or more oxygen atoms and 5 or less; c) a 1-valent aromatic organic group, the 1-valent aromatic organic groupIs an unsubstituted or substituted aromatic hydrocarbon unit, optionally having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more kinds of structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 to 24 carbon atoms and 0 to 5 oxygen atoms.
The above-mentioned a) organic group has an unsubstituted or substituted aliphatic hydrocarbon unit containing at least 1 kind of structure selected from the group consisting of a chain, a branched chain and a ring, and the organic group contains a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms, and examples of the above-mentioned a) organic group include a glycidoxyalkyl group having an oxycarbidlyl group having 4 carbon atoms or less bonded thereto, such as β -glycidoxyethyl group, γ -glycidoxypropyl group and γ -glycidoxybutylyl group, a glycidyl group, β - (3, 4-epoxycyclohexyl) ethyl group, γ - (3, 4-epoxycyclohexyl) propyl group, β - (3, 4-epoxycycloheptyl) ethyl group, β - (3, 4 epoxycyclohexyl) propyl group, And alkyl groups substituted with a cycloalkyl group having 5 to 8 carbon atoms and having an oxirane group, such as a β - (3, 4-epoxycyclohexyl) butyl group and a β - (3, 4-epoxycyclohexyl) pentyl group.
The b) 1-valent aliphatic organic group described above has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more kinds of structures selected from the group consisting of a chain, a branched chain and a ring, and the 1-valent aliphatic organic group has 1 or more and 24 or less carbon atoms and 0 or more and 5 or less oxygen atoms, and examples of the b) 1-valent aliphatic organic group described above include:
(b-1) a chain organic group composed of an aliphatic hydrocarbon such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl,
(b-2) an organic group composed of a hydrocarbon containing a cyclic unit, such as a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, or a norbornyl group,
(b-3) an ether bond-containing organic group such as methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, etc.,
(b-4) vinyl, allyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, and the like.
The c) 1-valent aromatic organic group is an unsubstituted or substituted aromatic hydrocarbon unit, and optionally has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 or more and 24 or less carbon atoms and 0 or more and 5 or less oxygen atoms. Examples of the c) 1-valent aromatic organic group include a phenyl group, a tolyl group, a xylyl group, a benzyl group, an α -methylstyrene group, a 3-methylstyrene group, and a 4-methylstyrene group.
The alkoxysilane compound may be a mixture of 2 or more different organic groups from a) to c) described above.
In addition, as long as the number of carbon atoms and the number of oxygen atoms are within the above range, the organic group may include a hydroxyl unit, an alkoxy unit, an acyl unit, a carboxyl unit, an alkenyloxy unit, an acyloxy unit, a halogen atom such as fluorine or chlorine, an ester bond, and a hetero atom such as nitrogen, phosphorus, or sulfur other than an oxygen atom or a silicon atom. The a) to c) may be 1 or 2 or more organic groups mixed.
As organic radicals R1Since a cured product obtained by curing the modified resin composition of the present embodiment tends to have good light resistance or improved stability during storage, the total number of moles of silicon atoms to which the following organic groups are bonded is preferably 10% or less, more preferably 1% or less, and even more preferably completely, based on the total number of moles of all Si unitsThe organic group includes a hydroxyl group unit, an alkoxy group unit, an acyl group unit, a carboxyl group unit, an alkenyloxy group unit, an acyloxy group unit, a halogen atom such as fluorine or chlorine, an ester bond, and a hetero atom such as nitrogen, phosphorus, or sulfur other than an oxygen atom or a silicon atom.
On the other hand, in the production of a cured product using the modified resin composition of the present embodiment, since there is a tendency that the cured product can be cured stably with good reproducibility, the total number of moles of (b-4) a 1-valent aliphatic organic group such as a vinyl group, an allyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, or a hexenyl group is preferably 10% or less, more preferably 5% or less, further preferably 1% or less, and particularly preferably not contained at all, relative to the total number of moles of all Si units.
The modified resin composition of the present embodiment is excellent in light resistance and tends to have improved heat discoloration resistance, and therefore is used as the organic group R of the general formula (1) in the present embodiment1Preferably selected from the group consisting of a), b-1), b-2) and c) described above, and a) is more preferably selected from the group consisting of glycidoxyalkyl groups to which an oxyglycidyl group having not more than 4 carbon atoms is bonded, such as β -glycidoxyethyl, γ -glycidoxypropyl and γ -glycidoxybutyl, glycidyl, β - (3, 4-epoxycyclohexyl) ethyl, 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 a group selected from b-1) and b-2) in which the number of carbon atoms is not less than 1 and not more than 8, An organic group having an oxygen atom number of 0, and a group consisting of a phenyl group and a benzyl group; the group a) is particularly preferably one selected from the group consisting of glycidoxyalkyl to which an oxyglycidyl group having 4 or less carbon atoms is bonded, such as β -glycidoxyethyl, γ -glycidoxypropyl and γ -glycidoxybutyl, glycidyl, β - (3, 4-epoxycyclohexyl) ethyl, and an organic group selected from the group consisting of b-1) and b-2) wherein the number of carbon atoms is 1 to 3 and the number of oxygen atoms is 0, and a phenyl group.
Next, R in the present embodiment is2The description is given. R in the present embodiment2Each independently represents 1 or more organic groups selected from the group consisting of a hydrogen atom and d) below: d) a 1-valent organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, wherein the number of carbon atoms in the 1-valent organic group is 1 to 8. Examples of the organic group of d) include chain organic groups composed of aliphatic hydrocarbons such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl; and organic groups composed of hydrocarbons containing cyclic units, such as cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, and norbornyl groups.
The alkoxysilane compound may be a mixture of 2 or more species different in the organic group of d) described above. Further, they may be 1 or 2 or more organic groups mixed.
Among these organic groups, methyl, ethyl, n-propyl, and isopropyl groups are preferable, and methyl and ethyl groups are more preferable, because the reactivity of the alkoxysilane compound tends to be improved.
In the present embodiment, the alkoxysilane compound represented by at least the general formula (1) contains the following (B) and (C): (B) n is 1 or 2 and has at least 1 cyclic ether group as R1At least 1 alkoxysilane compound of (a); (C) n is 1 or 2 and has at least 1 aromatic organic group as R1At least 1 alkoxysilane compound. When (B) n is not 1 or 2, and at least 1 cyclic ether group is contained as R1In the case of at least 1 alkoxysilane compound of (2), the modified resin composition of the present embodiment is usedThe cured product obtained by curing was insufficient in crack resistance and adhesiveness. On the other hand, when (C) n is not 1 or 2, and at least 1 aromatic organic group is contained as R1In the case of at least 1 alkoxysilane compound (2), the modified resin composition undergoes phase separation, and the cold and hot shock resistance and adhesiveness with reproducibility cannot be obtained.
Specific examples of the component (B) used in the present embodiment include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2, 3-epoxypropyl (methyl) dimethoxysilane, 2, 3-epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 2, 3-epoxypropyltrimethoxysilane, 2, 3-epoxypropyltriethoxysilane, etc. They may be used in 1 kind or as a mixture of 2 or more kinds.
Specific examples of the component (C) used in the present embodiment include dimethoxymethylphenylsilane, diethoxymethylphenylsilane, phenyltriethoxysilane, trimethoxy [3- (phenylamino) propyl ] silane, dimethoxydiphenylsilane, diphenyldiethoxysilane, and phenyltrimethoxysilane. They may be used in 1 kind or as a mixture of 2 or more kinds.
In addition, the modified resin composition of the present embodiment can use, as other components, the R represented by the general formula (1) as well as the components (a) to (C) described above1N is 0, specifically 4 (OR) are bonded2) The alkoxysilane compound of (1). Examples of the alkoxysilane compound include tetramethoxysilane and tetraethoxysilaneSilane, tetrapropoxysilane, and the like. They may be used as 1 species or as a mixture of 2 or more species.
Here, the mixing index α used in the present embodiment will be described.
In the alkoxysilane used in the present embodiment, the (B) general formula (1) in which n is 1 or 2 and at least 1 cyclic ether group is provided as R1And (C) general formula (1), wherein n is 1 or 2, and has at least 1 aromatic organic group as R 1The mixing ratio of the at least 1 alkoxysilane compound "of (a) is defined as a mixing index α calculated from the following formula (2).
Mixing index α ═ (α c)/(α b) (2)
(wherein in formula (2),. alpha.b represents the content (mol%) of the component (B) in the alkoxysilane represented by general formula (1) and. alpha.c represents the content (mol%) of the component (C) in the alkoxysilane represented by general formula (1))
In the present embodiment, the mixing index α needs to be 0.001 or more in order to ensure the fluidity and storage stability of the modified resin composition, and needs to be 19 or less in order to ensure the fluidity of the modified resin composition and the crack resistance of the cured product. The value of α is more preferably in the range of 0.2 to 5, and still more preferably 0.3 to 2.
The modified resin composition of the present embodiment has a residual alkoxy group content of 5% or less. When the residual alkoxy group content exceeds 5%, the crack resistance and adhesiveness during thermal cycling of a cured product obtained by curing the composition are insufficient. The amount of residual alkoxy groups in the modified resin composition is more preferably 3% or less, still more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably not contained at all.
Further, as for the quantitative value of the amount of residual alkoxy group, the quantitative value of the amount of residual alkoxy group can be obtained by calculating the area ratio of the obtained internal standard peak and the residual alkoxy group peak by H-NMR measurement using 1, 1, 2, 2-tetrabromoethane as an internal standard substance.
Specifically, the measurement can be obtained by the following method and analysis method.
< H-NMR measurement >
(1) 10mg of the modified resin composition, 20mg of an internal standard (1, 1, 2, 2-tetrabromoethane; Tokyo chemical industry), and 970mg of deuterated chloroform were uniformly mixed to prepare an H-NMR measurement solution.
(2) The solution of the above (1) was subjected to H-NMR spectroscopy under the following conditions.
The device comprises the following steps: "alpha-400 type" manufactured by Nippon electronic Co., Ltd "
And (4) nuclear seed: h
Cumulative number of times: 200 times (one time)
< analysis of measurement results >
(3) The peak area value of the residual alkoxy peak in the H-NMR spectrum was calculated.
(4) The peak area value of the internal standard substance peak in the H-NMR spectrum was calculated.
(5) The area values obtained in (3) and (4) above were substituted into the following formula, and the obtained result was defined as the residual alkoxy group amount (%).
Residual alkoxy group amount (%) - (peak area value of residual alkoxy group peak)/(peak area value of internal standard substance peak) × 100
The viscosity of the modified resin composition of the present embodiment at 25 ℃ is not particularly limited, but is preferably a liquid of 1,000Pa · s or less, more preferably 500Pa · s or less, further preferably 300Pa · s or less, and particularly preferably 100Pa · s or less, because the modified resin composition tends to ensure fluidity as a liquid and to improve handling properties, and also tends to be easily mixed with an additive added as needed.
The epoxy equivalent Weight (WPE) of the modified resin composition of the present embodiment is not particularly limited, and from the viewpoint of improving the storage stability of the modified resin composition, the functional group is preferably selected so as to be 100g/eq or more, and from the viewpoint of improving the crack resistance of a cured product obtained by curing the modified resin composition, the functional group is preferably selected so as to be 700g/eq or less. More preferably, the content is in the range of 100 to 500g/eq, and still more preferably in the range of 100 to 300 g/eq.
Next, the mixing index β used in the present embodiment will be described.
The mixing ratio of the "n-2 alkoxysilane compound", the "n-1 alkoxysilane compound", and the "n-0 alkoxysilane compound" in the alkoxysilane compounds used in the present embodiment is defined as a mixing index β calculated from the following formula (3).
Mixing index β { (β n2)/(β n0+ β n1) } (3)
(wherein, in formula (3), β n2 represents the content (mol%) of the alkoxysilane compound of formula (1) in which n is 2, β n0 represents the content (mol%) of the alkoxysilane compound of formula (1) in which n is 0, β n1 represents the content (mol%) of the alkoxysilane compound of formula (1) in which n is 1, and β n2, β n0, and β n1 are values satisfying 0 ≦ { (β n0)/(β n0+ β n1+ β n2) } ≦ 0.1.)
In the present embodiment, the mixing index β is preferably 0.01 or more because the modified resin composition tends to have improved fluidity and improved handling properties, and is preferably 1.4 or less, more preferably 0.03 or more and 1.2 or less, and even more preferably 0.05 or more and 1.0 or less because the modified resin composition tends to have improved crack resistance of a cured product obtained by curing the modified resin composition.
Next, the mixing index γ used in the present embodiment will be described.
The mixing ratio of the epoxy resin (a) and the alkoxysilane compound having "n is 0 to 2" in the alkoxysilane compound used in the present embodiment is defined as a mixing index γ calculated from the following formula (4).
Mixing index γ ═ (γ a)/(γ s) (4)
(wherein in formula (4), γ a represents the mass (g) of the epoxy resin (a), and γ s represents the mass (g) of the alkoxysilane compound in which n is 0 to 2 in the alkoxysilane represented by general formula (1))
In the present embodiment, the mixing index γ is preferably 0.02 or more because there is a tendency that the crack resistance of a cured product obtained by curing the modified resin composition is improved during thermal cycling, and is preferably in the range of 15 or less, more preferably in the range of 0.04 to 7, and even more preferably in the range of 0.08 to 5 because there is a tendency that the light resistance of a cured product obtained by curing the modified resin composition is improved.
In the modified resin composition of the present embodiment, the condensation rate of the alkoxysilane compound is preferably 80% or more, more preferably 82% or more, further preferably 85% or more, and particularly preferably 88% or more, from the viewpoint of 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 handling properties.
The condensation rate of the alkoxysilane compound of the present embodiment is determined by the ratio of (OR) to (OR) contained in the alkoxysilane compound represented by the general formula (1)2) (OR) of the Silicone component present in the modified resin composition, the number of moles of the group (U)2) The number of moles (V) of the base group is represented by a molar percentage represented by the following formula (5).
Condensation rate (%) of alkoxysilane compound [ (U-V)/U ] x 100 (5)
Next, a specific example of the method for producing the modified resin composition of the present embodiment will be described.
The modified resin composition of the present embodiment can be produced by reacting an alkoxysilane compound which comprises at least (B) and (C) represented by the following general formula (1) and in which the mixing index α of the alkoxysilane compound represented by the following general formula (2) is 0.001 to 19 in the presence of an epoxy resin (a) by the following [ production method 1] or [ production method 2 ].
(R1)n-Si-(OR2)4-n (1)
(wherein n represents an integer of 0 to 3, or less; R1Each independently represents at least 1 or more organic groups selected from the group consisting of hydrogen atoms, the following a), the following b), the following c): a) an organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms; b) a 1-valent aliphatic organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, the 1-valent aliphatic organic group having 1 or more carbon atoms and 24 or less and 0 or more oxygen atoms and 5 or less; c) a 1-valent aromatic organic group, wherein the 1-valent aromatic organic group is an unsubstituted or substituted aromatic hydrocarbon unit, and optionally has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 to 24 carbon atoms and 0 to 5 oxygen atoms. In another aspect, R 2Each independently represents 1 or more organic groups selected from the group consisting of a hydrogen atom and d) below; d) a 1-valent organic group having 1 valenceThe organic group has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched, and cyclic structures, and the number of carbon atoms of the 1-valent organic group is 1 to 8. )
(B) n is 1 or 2 and has at least 1 cyclic ether group as R1At least 1 alkoxysilane compound.
(C) n is 1 or 2 and has at least 1 aromatic organic group as R1At least 1 alkoxysilane compound.
And the mixing index alpha of the alkoxysilane compound represented by the general formula (2) is 0.001 to 19.
Mixing index α ═ (α c)/(α b) … (2)
(wherein, 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))
[ production method 1] is a method for producing a modified resin composition comprising the following two steps, namely, step (a) and step (b).
A step (a): a step of co-hydrolyzing an alkoxysilane compound containing at least (B) and (C) represented by the general formula (1) in the presence of an epoxy resin (A) in a reflux step without dehydration to produce an intermediate.
A step (b): and (c) a step of subjecting the intermediate produced in the step (a) to dehydration condensation reaction.
[ production method 2] is a method for producing a modified resin composition comprising the following two steps, namely, step (c) and step (d).
A step (c): a step of co-hydrolyzing an alkoxysilane compound containing at least (B) and (C) represented by the general formula (1) in a reflux step without dehydration to produce an intermediate.
Step (d): and (c) allowing the intermediate produced in the step (c) to coexist with the epoxy resin (a) and allowing the mixture to undergo a dehydration condensation reaction.
The "step of producing an intermediate by cohydrolysis in a reflux step without dehydration" and the "step of dehydration condensation reaction" will be described.
The "step of producing an intermediate by cohydrolysis in a reflux step without dehydration" refers to a step of reacting water or a solvent mixed for the cohydrolysis and water or a solvent derived from an alkoxysilane compound generated in the reaction while returning the reaction solution. The reaction system is not particularly limited, and may be carried out by 1 or 2 or more kinds in various reaction systems such as a batch system, a semi-batch system, or a continuous system. As specific examples, the following methods can be cited: a method in which a cooling tube is installed in the upper part of the reaction vessel and the reaction is carried out while refluxing the generated water or solvent; or a method in which the reaction is carried out while stirring and/or circulating the reaction solution in a closed vessel; and so on.
On the other hand, the "step of dehydration condensation reaction" refers to a step of performing condensation reaction while removing added water or solvent and water or solvent generated in the above-mentioned "reflux step without dehydration". For example, 1 or 2 or more of the following devices may be combined: a rotary evaporator, a vertical agitation tank provided with a distillation-out pipe, a surface renewal type agitation tank, a thin film evaporator, a surface renewal type twin-screw kneader, a twin-screw horizontal agitator, a wet wall type reactor, a free-fall type porous plate type reactor, a reactor for distilling off volatile components while dropping a compound along a support, and the like.
The modified resin composition of the present embodiment can be produced by any of the above-described [ production method 1] and [ production method 2 ]. The method of reacting the alkoxysilane compound in the production of the modified resin composition of the present embodiment is not particularly limited, and the alkoxysilane compound may be added at once in the initial stage to be reacted, or may be added to the reaction system sequentially or continuously to be reacted.
In addition, the epoxy resin (a) may be added at once or may be added in several times in each of [ production method 1] and [ production method 2 ].
In the case of [ production method 1], the steps (a) and (b) may be performed continuously, or the step (b) may be performed after the reaction mixture obtained in the step (a) is separated or recovered.
On the other hand, in the case of [ production method 2], the step (c) and the step (d) may be continuously performed, or the step (d) may be performed after the reaction mixture obtained in the step (c) is collected.
Among them, examples of the epoxy resin (a) and the alkoxysilane compound used in [ production method 1] and [ production method 2] include the same epoxy resin (a) and alkoxysilane compound as listed above.
The preferable range of the mixing index α to γ of the alkoxysilane compound in [ production method 1] and [ production method 2] is the same as described above.
In the [ production method 1] or [ production method 2] of the present embodiment, the condensation rate of the intermediate at the end of the step of producing the intermediate by cohydrolysis in the reflux step without dehydration is preferably 78% or more, more preferably 80% or more, and still more preferably 83% or more. When the condensation rate of the intermediate is less than 78%, a large amount of OH groups derived from silicone remain in the produced resin composition even after the subsequent dehydration condensation step, and the residual OH groups condense during storage, which causes significant thickening or gelation of the resin composition, and tends to deteriorate storage stability.
In addition, the condensation rate of the intermediate at the end of the step of producing the intermediate by cohydrolysis in the present embodiment is based On (OR) contained in the alkoxysilane compound represented by general formula (1)2) (OR) of the Silicone component present in the modified resin composition, the number of moles of the group (R)2) The number of moles (S) of the base group is represented by the following formula (6)And (4) percent.
Condensation rate (%) of alkoxysilane compound [ (R-S)/R ] x 100 (6)
In the method for producing the modified resin composition of the present embodiment, the condensation rate of the alkoxysilane compound is preferably 80% or more, more preferably 82% or more, further preferably 85% or more, and particularly preferably 88% or more, from the viewpoint of 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 handling properties.
The condensation rate of the alkoxysilane compound of the present embodiment is determined by the ratio of (OR) to (OR) contained in the alkoxysilane compound represented by the general formula (1)2) (OR) of the Silicone component present in the modified resin composition, the number of moles of the group (U)2) The number of moles (V) of the base group is represented by a molar percentage represented by the following formula (5).
Condensation rate (%) of alkoxysilane compound [ (U-V)/U ] x 100 (5)
In the method for producing a modified resin composition according to the present embodiment, the amount of residual alkoxy groups in the obtained modified resin composition is 5% or less. When the residual alkoxy group content exceeds 5%, the crack resistance and adhesiveness during thermal cycle of a cured product obtained by curing the composition may be insufficient. The amount of residual alkoxy groups in the resulting modified resin composition is preferably 3% or less, more preferably 1% or less, even more preferably 0.5% or less, and particularly preferably no residual alkoxy groups are contained at all.
In the step (a) or the step (c) of the present embodiment, water is shared in the reaction system in order to hydrolyze the alkoxysilane compound. For the addition of water, hydrolysis of the alkoxysilane compound is the main objective. The time for adding water is not particularly limited, and may be any time until the end of the step of producing an intermediate by cohydrolysis, and any of a method of adding water at once in the initial stage of the reaction, a method of adding water sequentially during the reaction, and a method of adding water continuously during the reaction may be used. Among them, a method of adding the reaction solution at once at the initial stage of the reaction is preferably used.
Here, the amount of water added will be explained. The amount (mole number) of water added is equal to (OR) in the above formula (1)2) The ratio of the amount (mole number) of (c) is defined as a mixing index ε represented by the following formula (7).
Mixing index ε ═ ε w)/(ε s) … (7)
(wherein in the formula (7),. epsilon.w represents the amount of water added (mol number), and. epsilon.s represents (OR) in the general formula (1)2) Amount (mol number). )
In the present embodiment, the mixing index ∈ is preferably in a range of 0.1 or more and 5 or less, more preferably in a range of 0.2 or more and 3 or less, and still more preferably in a range of 0.3 or more and 1.5 or less. If the mixing index ε is less than 0.1, the hydrolysis reaction may not proceed, and if it exceeds 5, the storage stability of the modified resin composition may be lowered.
The step (a) or the step (c) may be carried out in the absence of a solvent or in a solvent. When the solvent is used, a known solvent can be used as long as it is an organic solvent which can dissolve the epoxy resin and the alkoxysilane compound and is inert to them.
Examples of the solvent to be used include ether solvents such as dimethyl ether, diethyl ether, diisopropyl ether, 1, 4-dioxane, 1, 3-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, and anisole; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as hexane, cyclohexane, heptane, octane, and isooctane; aromatic hydrocarbon solvents such as toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene; ester solvents such as ethyl acetate and butyl acetate; and alcohol solvents such as methanol, ethanol, butanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol. These solvents may be used in 1 kind or as a mixture of 2 or more kinds. Among them, from the viewpoint of suppressing the ring opening of the epoxy group in the reaction, an ether-based solvent, a ketone-based solvent, an aliphatic hydrocarbon-based solvent, and an aromatic hydrocarbon-based solvent are preferable, a solvent containing 50 mass% or more of an ether-based solvent is more preferable, a mixed solvent of at least 1 or 2 or more selected from the group consisting of 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and propylene glycol dimethyl ether is further preferable, and 1, 4-dioxane and tetrahydrofuran are particularly preferable.
The amount of the solvent to be added is preferably 0.01 to 20 times, more preferably 0.02 to 15 times, and even more preferably 0.03 to 10 times the total mass of the epoxy resin (a) and the alkoxysilane compound added up to the end of the step of producing the intermediate by cohydrolysis in a reflux step without dehydration in the case of the step (a), and on the other hand, the amount of the solvent to be added is preferably 0.01 to 20 times, more preferably 0.02 to 15 times, and even more preferably 0.03 to 10 times the total mass of the alkoxysilane compound added up to the end of the step of producing the intermediate by cohydrolysis in a reflux step without dehydration in the case of the step (c). Since the molecular weight of the resin composition of the present embodiment can be controlled by the amount of the solvent to be added, the resin composition having an appropriate molecular weight and, therefore, an appropriate viscosity tends to be obtained by setting the amount of the solvent to be added to the above range.
The reaction temperature in the step (a) or the step (c) is usually in the range of 0 ℃ to 200 ℃. If the reaction temperature is below 0 ℃, the water may solidify. On the other hand, if it exceeds 200 ℃, the resin composition may be colored. The reaction temperature is preferably in the range of 20 ℃ to 150 ℃, more preferably in the range of 40 ℃ to 120 ℃, and still more preferably in the range of 50 ℃ to 100 ℃ from the viewpoint of improving the reaction rate and suppressing the modification of the resin such as the ring-opening of the epoxy group. The reaction temperature is not necessarily a constant value as long as it is within the above range, and may be varied during the reaction.
The reaction time in the step (a) OR the step (c) is not particularly limited, but is increased from (OR) in the above formula (1)2) From the viewpoint of suppressing the modification of the resin,preferably 0.1 hour or more and less than 100 hours, more preferably 1 hour or more and less than 80 hours, still more preferably 3 hours or more and less than 60 hours, and particularly preferably 5 hours or more and less than 50 hours.
On the other hand, the reaction temperature in the step (b) or the step (d) is usually in the range of 0 ℃ to 200 ℃. If the reaction temperature is less than 0 ℃, the reaction rate may be decreased and the reaction time may be increased, and if it exceeds 200 ℃, the resin composition may be colored. The reaction temperature is preferably in the range of 20 ℃ to 150 ℃, more preferably in the range of 40 ℃ to 120 ℃, and still more preferably in the range of 50 ℃ to 100 ℃ from the viewpoint of improving the reaction rate and suppressing the modification of the resin such as the ring-opening of the epoxy group. The reaction temperature is not necessarily a constant value as long as it is within the above range, and may be changed at the initial stage of the reaction or during the reaction.
The reaction time in the step (b) or the step (d) is not particularly limited, but is preferably in the range of 0.1 hour or more and less than 100 hours, more preferably in the range of 0.5 hour or more and less than 80 hours, even more preferably in the range of 1 hour or more and less than 50 hours, and particularly preferably in the range of 3 hours or more and less than 50 hours, from the viewpoint of improving the reaction rate and suppressing the modification of the resin.
The modified resin composition of the present embodiment can be produced in an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, or a lower saturated hydrocarbon, or in air. Among these gases, from the viewpoint of suppressing the modification of the resin, inert gases such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, or lower saturated hydrocarbons are preferable, nitrogen, helium, neon, argon, krypton, xenon, and carbon dioxide are more preferable, nitrogen and helium are further preferable, and nitrogen is particularly preferable.
The steps (a) to (d) of producing the modified resin composition of the present embodiment can be performed in the atmosphere of the gas, under the flow of the gas, under reduced pressure, under pressure, or a combination thereof. In addition, the pressure does not have to be a constant value and may vary on the way of the reaction.
Among these, the step (a) and the step (c) are preferably carried out under an atmospheric pressure atmosphere and/or under pressure of the above gas because it is necessary to carry out the reaction while returning water or a solvent mixed for the co-hydrolysis and water or a solvent derived from the alkoxysilane compound produced in the reaction to the reaction solution in an industrially easy manner.
On the other hand, since the condensation reaction is required to be carried out while removing the water or solvent added in the step (a) or (c) and the water or solvent produced in the above-mentioned "reflux step without dehydration", the steps (b) and (d) are preferably carried out under inert gas flow and/or under reduced pressure.
In the present embodiment, the cohydrolysis of the epoxy resin (a) and the alkoxysilane compound may be carried out by adding a hydrolysis condensation catalyst.
The hydrolysis condensation catalyst is not particularly limited as long as it is a conventionally known catalyst that promotes the hydrolysis condensation reaction, and examples thereof include metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, and the like), organic metals (organic oxides, organic acid salts, organic halides, alkoxides, and the like of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, and the like), inorganic bases (magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and the like), organic bases (ammonia, tetramethylammonium hydroxide, and the like), and the like.
Among the organic metals, organotin is preferable. Organotin means a substance in which at least one organic group is bonded to a tin atom, and examples of the structure include mono-organotin, di-organotin, tri-organotin, tetra-organotin, and the like. Examples of the organotin include tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra-n-octyltin, tetra-n-butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin di-tert-carbonate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dilaurate, dibutyltin stearate, dibutyltin dioleate, a reaction product of dibutyltin ethyl silicon (ケイ element エチル), a compound of a dibutyltin salt and a silicate, a compound of a dioctyltin salt and a silicate, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (2-ethylhexylmaleate), dibutyltin bis (benzylmaleate), dibutyltin bis (stearylmaleate), dibutyltin bis (oleylmaleate), dibutyltin monoxides, dibutyltin oxides, dibutyltin dioxides, dibutyltin oxides, dibutyltin maleate, dibutyltin bis (O-phenylphenoxy) dibutyltin, dibutyltin bis (2-ethylhexyl thioglycolate), dibutyltin bis (2-ethylhexyl mercaptopropionate), dibutyltin bis (isononyl 3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dioctanoate, dioctyltin dilaurylmercaptosuccinate, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethylmaleate), dioctyltin bis (octylmaleate), dioctyltin maleate, dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexyl thioglycolate), dibutyltin dibutyldimethoxytin, dibutyldiethoxytin, Dibutyl dipropoxy tin, dioctyl dimethoxy tin, dioctyl diethoxy tin, dioctyl dipropoxy tin, octoate tin, stearic acid tin, etc.
Among the above-mentioned organic metals, alkali-based organic metals which exhibit basicity when the ligand is free are suitable. By using an alkali organic metal as the hydrolysis condensation catalyst, the modified resin composition of the present embodiment tends to have good storage stability. Further, the use of an alkali-based organic metal tends to accelerate the progress of the condensation reaction, and therefore, it is very useful in the case of obtaining a resin composition having a condensation rate of an intermediate of 78% or more.
Among the alkali organic metals, alkali organic tin is preferable, and alkoxide organic tin is particularly preferable. Examples of the organotin alkoxide include dibutyl dimethoxytin, dibutyl diethoxytin, dibutyl dipropoxytin, dioctyl dimethoxytin, dioctyl diethoxytin, and dioctyl dipropoxytin.
On the other hand, when an acid-based organic metal which exhibits acidity when the ligand is free is used as the 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.
The above hydrolysis-condensation catalysts may be used alone, or 2 or more of them may be used in combination. For example, organic acid tin and alkali-based organic tin may be used in combination, or after the reaction with an organic acid salt such as tin, treatment with an inorganic base may be carried out. In this case, the inorganic base is preferably a hydroxide of a polyvalent cation such as magnesium hydroxide, calcium hydroxide, strontium hydroxide, or barium hydroxide.
The amount of the hydrolytic condensation catalyst added is not particularly limited, but is preferably an amount based On (OR) in the formula (1)2) The ratio of (d) is obtained as the following mixing index δ.
The mixing index δ is represented by the following formula (8).
Blending index δ (δ e)/(δ s) … (8)
(wherein in the formula (8), δ e represents the amount (mol number) of the hydrolytic condensation catalyst, and δ s represents (OR) in the formula (1)2) Amount (mol number). )
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 further preferably in the range of 0.005 or more and 0.5 or less.
Depending on the composition of the modified resin composition, if the blending index δ is less than 0.0005, the effect of promoting hydrolytic condensation may be difficult to obtain, and if it exceeds 5, ring opening of the cyclic ether group may be promoted or deterioration of storage stability may occur.
The modified resin composition of the present embodiment has good storage stability, and is a modified resin composition capable of forming a cured product having excellent transparency, heat resistance, thermal discoloration resistance, light resistance, and crack resistance during thermal cycling, and 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, and an insulating resin because a cured product is formed by heat or an energy ray.
The modified resin composition of the present embodiment may further contain an oxetane compound (D), a phosphor (E), a conductive metal powder (F), an insulating powder (G), an epoxy resin (a '), a curing agent (H), a curing accelerator (I), a photoacid generator (J), and if necessary, a cationic polymerization catalyst, a modifier, a vinyl ether compound, an organic resin other than the epoxy resin (a'), and a silane coupling agent.
A resin composition obtained by further adding the 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 examples thereof include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, bis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3- (phenoxymethyl) oxetane, and 3-ethyl-3- (2, 3-glycidoxymethyl) oxetane. Mixing these oxetane compounds tends to increase the polymerization rate and also tends to decrease the viscosity of the composition.
Representative examples of oxetane compounds are shown below.
Chemical formula 5
Figure BDA0000041312520000321
The amount of the oxetane compound is not particularly limited, and it is preferable to mix the resin composition and the oxetane compound in a mass ratio of 20: 80 to 95: 5 (total 100). More preferably 40: 60 to 80: 20. If the mixing ratio of the resin composition is less than 20, the curing reaction may not proceed normally, and if it exceeds 95, the adhesiveness of the cured product may be deteriorated.
In addition, in order to improve the compatibility of the resin composition with the oxetane compound, it is generally carried out to select an appropriate combination, for example, to combine an oxetane compound having an aromatic ring with a resin composition using an epoxy resin having a bisphenol skeleton as a raw material, or the like.
A fluorescent resin composition obtained by further adding a fluorescent material (E) to the modified resin composition of the present embodiment will be described.
The phosphor (E) in the present embodiment is not particularly limited as long as it is a substance that emits fluorescence, that is, a substance that absorbs energy of an electron beam, an X-ray, an ultraviolet ray, an electric field, or the like and emits (emits) a part of the absorbed energy as visible light rays with relatively high efficiency, and can be used in any of inorganic systems and organic systems. Among these, inorganic phosphors which generally exhibit excellent luminescence are preferable.
The size of the inorganic phosphor that can be used in the present embodiment is not particularly limited, and powder having a particle diameter of 1 to several tens μm is generally used. In order to develop the performance of the inorganic phosphor, a compound a called a matrix, into which an element B called an activator (emission center) is introduced, is generally used and is generally referred to as "matrix a: activator B".
In particular, when the fluorescent resin composition is used as an encapsulating material for an LED, it is preferable to use a cerium-activated yttrium aluminate phosphor (YAG: Ce phosphor) for the reasons described later, and when it is used as a light-storing material, it is preferable to use a light-storing phosphor. These may be used alone, or 2 or more of them may be used in combination.
The amount of the phosphor is preferably 30: 70 to 95: 5, more preferably 50: 50 to 80: 20 (total 100) in terms of the mass ratio of the resin composition to the phosphor. If the amount of the fluorescent material is more than 30: 70, the fluidity of the fluorescent resin composition may be deteriorated, and if the amount is less than 95: 5, the function as the fluorescent material may be insufficient.
The matrix a and the activator B are not particularly limited, and examples of the matrix a include an oxide phosphor and a nitride phosphor. Examples of the activator B include rare earth elements such as europium (Eu) and cerium (Ce).
As the oxide phosphor, for example, a "YAG: Ce phosphor" is known in which a matrix a is yttrium aluminate (Y3Al5O 12: hereinafter referred to as YAG) and an activator B is cerium (Ce). When blue light is irradiated (around 460 nm), yellow light emission is efficiently generated. This phosphor is very useful because it can shift the emission peak position to the long wavelength side or the short wavelength side by changing the structure of the matrix a by replacing a part of Y of "Y3 Al5O 12" with other Gd, Tb, or the like, or replacing a part of Al with Ga or the like.
That is, the "YAG: Ce phosphor" is not particularly limited as long as the host a is YAG, a part of Y is replaced with another Gd, Tb or the like, or a part of Al is replaced with Ga or the like, the structure of the host a is changed, and the activator B is Ce. Specific examples thereof include "Y3 Al5O12: Ce3 +" (Y3, Gd0.9) Al5O12: Ce3+ ".
In addition, as an example of the oxide phosphor, "(Sr, Ba)2SiO4: Eu phosphor" is known, in which a matrix a of the phosphor is strontium barium silicate (Sr, Ba)2SiO4, and europium (Eu) is introduced as an activator B. In this system, the emission color can be adjusted to green to orange by changing the composition ratio of Sr and Ba.
As the nitride phosphor, for example, the following phosphors can be exemplified.
α -SiAlON phosphor: the matrix A is a crystal in which metal ions such as Ca, aluminum and oxygen are dissolved in a solid solution in an α -type silicon nitride crystal, and is represented by "(Mp (Si, Al)12(O, N) 16", wherein 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".
beta-SiAlON phosphor: the matrix A was represented by a composition "Si 6-qALqOqN 8-q" obtained by dissolving aluminum and oxygen in a solid solution in a β -type silicon nitride crystal. Wherein q represents a solid solution amount. Specific examples thereof include "Si 6-qALqOqN8-q: Eu".
CaAlSiN3 phosphor: the matrix A is a nitride crystal obtained by reacting calcium nitride, aluminum nitride and silicon nitride at a high temperature of 1800 ℃, and specific examples thereof include "CaAlSiN 3: Eu".
Specific examples of the inorganic phosphor include, for example, "6 MgO. As2O5: Mn4+, Y (PV) O4: Eu", "CaLa0.1Eu0.9Ga3O7", "BaY0.9Sm0.1Ga3O7", "Ca (Y0.5Eu0.5) (Ga0.5In0.5)3O 7", "Y3O 3: Eu, YVO4: Eu", "Y2O 2: Eu", "3.5 MgO.50.5 MgF2GeO2: Mn4 +", "(Y. Cd) BO2: Eu", and the like, As a phosphor having a red emission color.
Examples of the phosphor having a blue emission color include "(Ba, Ca, Mg)5 (PO) 3Cl: Eu +", "(Ba, Mg)2Al 16O: Eu +", "Ba 3MgSi 2O: Eu +", "" BaMg2Al 16O: Eu + "," (Sr, Ca)10 (PO) 6Cl: Eu + "," (Sr, Ca)10 (PO) 6 Cl.nB 2O: Eu + "," "Sr (PO) 6Cl: Eu +", "(Sr, Ba, Ca)5 (PO) 3Cl: Eu +", "" Sr2P 2O: Eu "," Sr (PO) 3Cl: Eu "," "(Sr, Ca, Ba)3 (PO) 6Cl: Eu", "SrO.P 2 O.B 2" "," (BaCa)5 (PO) 3Cl: Eu "," SrLaGaGaGaGaGaTm0.957 "," MgSi + Ag 2O + Eu "," BaCa, Ga (Ca) 5 (PO) 3Cl: Eu "," GaxAg 2+ and "GaxAg 2+ are selected from BaCa, Ca, Eu, Ca, Mg, Ca, and Ca, and Ca, ca. At least 1 element of the group consisting of Sr and Ba) ", and the like.
Examples of the phosphor having a green emission color include "Y3 Al5O12: Ce3+ (YAG)", "Y2 SiO5: Ce3+, Tb3 +", "Sr 2Si3O 8.2 SrCl2: Eu", "BaMg 2Al16O27: Eu2+, Mn2 +", "ZnSiO 4: Mn", "Zn 2SiO4: Mn", "LaPO 4: Tb", "SrAl 2O4: Eu", "SrLa0.2Tb0.8Ga3O7", "CaY0.90.1Ga3O7", "ZnGd0.8Ho0.2Ga3O7", "SrLa0.6Tb0.6Al3O7", "ZnS: Cu, Al", "(Zn, Cd) S: Cu, Al", "ZnS: Cu, Al: SiO, Al 2: Mn", "ZnSiZniO 42: Tb", "GeiCu, Tb: 27: Tb", "GegO 27: Tb", "GenCu", "BaGnCu 2O 16: Tp 27: Eu, and" BaGnCu ".
Further, examples thereof include "YVO 4: Dy" having a white emission color, and "reli0.5dy0.5ga3o7" having a yellow emission color.
Specific examples of the organic phosphor include stilbene-based dyes such as 1, 4-Bis (2-methylstyrene) benzene (Bis-MSB) and trans-4, 4' -Diphenylstilbene (DPS) having a blue emission color, and coumarin-based dyes such as 7-hydroxy-4-methylcoumarin (coumarin 4).
Examples of commercially available phosphors having yellow to green fluorescent COLORs include Brilliant sulfoflavine FF, Basic yellow HG, and SINLOIHI COLOR FZ-5005 (manufactured by SINLOIHI).
Examples of commercially available phosphors having fluorescent colors of yellow to red include Eosine, Rhodamine6G, Rhodamine b, and the like.
When a general phosphor blocks irradiation with light or an electron beam, which is an excitation source, light emission is immediately attenuated and disappears. However, as an exception, there is a phosphor which exhibits afterglow for several seconds to several tens of hours after interruption of the excitation source, and is called a phosphorescent phosphor. The kind of the phosphor is not particularly limited as long as it exhibits such properties, and specific examples thereof include "CaS: Eu, Tm", "CaS: Bi", "CaAl 2O4: Eu, Nd", "CaSrS: Bi", "Sr 2MgSi2O7: Eu, Dy", "Sr 4Al14O25: Eu, Dy", "SrAl 2O4: Eu, Dy", "SrAl 2O4: Eu", "ZnS: Cu, Co", "Y2O 2S: Eu, Mg, Ti", "CaS: Eu, Tm", and the like, and among them, "Sr 2MgSi2O7: Eu, Dy", "Sr 4Al14O25: Eu, Dy", "SrAl 2O4: Eu, Dy", and "SrAl 2O4: Eu", which exhibit long afterglow are preferable.
The method for producing the fluorescent resin composition of the present embodiment is not particularly limited, and for example, the following methods can be exemplified: a method of stirring, mixing and dispersing the modified resin composition and the phosphor by a mixing device described later while heating them simultaneously or separately as necessary; or a method of further performing a defoaming treatment under reduced pressure as necessary, following the above-mentioned method. Further, a curing agent, a curing accelerator, a polymerization initiator, an additive, and the like, which will be described later, may be added in any of the above steps as appropriate.
The mixing apparatus is not particularly limited, and examples thereof include a kneader, a three-roll mill, a ball mill, a planetary mixer, a line mixer, a homogenizer, and a homogenizing disperser.
A conductive resin composition obtained by further adding a conductive metal powder (F) to the modified resin composition of the present embodiment will be described.
The conductive metal powder (F) that can be used in the present embodiment is not particularly limited as long as it is a metal powder containing silver, and it is not limited to silver powder, and may be a metal powder having silver attached to or coated on the surface thereof. Examples of the metal powder include powders of metal elements such as aluminum, silicon, boron, carbon, magnesium, nickel, copper, graphite, gold, palladium, and metal oxides or metal nitrides thereof. Among the above, aluminum, nickel, gold, and palladium are preferable from the viewpoint of conductivity.
Specific examples of the metal oxide and the metal nitride include alumina, magnesia, aluminum nitride, boron nitride, silicon nitride, fused silica, crystalline silica, magnesium silicate, an oxide of a composite metal of aluminum and silicon, an oxide of a composite metal of aluminum and magnesium, and the like.
The conductive metal powder may be one surface-coated with a polymer such as polyethyleneimine, polyvinylpyrrolidone, polyacrylic acid, carboxymethyl cellulose, polyvinyl alcohol, or a copolymer having a polyethyleneimine moiety and a polyethylene oxide moiety. By coating with these polymers, the dispersibility in the resin composition tends to be good.
Since silver is an element having a low volume resistivity and the conductivity of the metal powder depends on the surface state or the like to a greater extent than that of the carrier serving as the core thereof, even if the entire particles of the conductive metal powder are not silver, the metal powder having silver attached or coated on the surface thereof can be used.
The shape of the silver powder is not particularly limited, and examples thereof include a scale-like shape, a spherical shape, and a dendritic shape.
The scale-like silver powder has many contacts and is excellent in conductivity, and its orientation tends to exhibit thixotropy when prepared into a conductive resin composition, thereby being excellent in handling properties. On the contrary, when used for a precision member, a problem of poor electrical connection may occur due to its orientation. The size is not particularly limited, but the average particle diameter determined by a laser diffraction particle size distribution measuring apparatus is preferably 50 μm or less, and more preferably 1 to 20 μm. The use of the average particle diameter is preferable because the possibility of occurrence of electrical connection failure is reduced even when the particles are used for precision electronic components and the like.
The spherical silver powder has substantially no orientation and thus is less likely to cause a problem of electrical connection, but tends to have poor conductivity because of point contact between particles. The size is not particularly limited, but the average particle diameter is preferably 20 μm or less, and more preferably 5 μm or less. When the average particle diameter exceeds 20 μm, the conductivity tends to decrease. Further, the silver powder is used together with the scale-like silver powder to fill the pores and achieve conductivity, and when used for this purpose, the silver powder is preferably selected to be 5 μm or less.
The dendritic silver powder has a large specific surface area and excellent conductivity, but may have unstable quality due to its specific shape. The size is not particularly limited, but the average particle diameter is preferably 30 μm or less, and more preferably 5 μm or less. The use of the average particle diameter is preferable because the handling property (ハンドリング) tends to be excellent.
In the present embodiment, silver powders having different shapes are preferably used in consideration of these properties depending on the purpose or use.
The amount of the conductive metal powder to be mixed is preferably 60 to 85 mass%, more preferably 70 to 80 mass%, with respect to the resin composition. When the amount is 60% by mass or more, the conductivity tends to be more excellent, and when the amount is 85% by mass or less, the bleeding phenomenon tends to be prevented.
An insulating resin composition obtained by further adding an insulating powder (G) to the modified resin composition of the present embodiment will be described.
Specific examples of the insulating powder (G) that can be used in the present embodiment include non-oxide ceramic powders such as carbon, boron carbide, boron nitride, aluminum nitride, and titanium nitride; powders of oxides of beryllium, magnesium, aluminum, titanium, and the like; silicon oxide, silicon nitride, fused silica, crystalline silica, other siliceous fillers; magnesium silicate, an oxide of a composite metal of aluminum and silicon, an oxide of a composite metal of aluminum and magnesium; powders of muscovite, phlogopite, synthetic mica, saponite, alumina, soda glass, borosilicate glass, quartz glass, wood, and the like; silicone rubber, Teflon (registered trademark), and the like, and they may be used alone or in combination of a plurality. Among the above, from the viewpoint of insulation properties and ease of obtaining, silica, silicon nitride, fused silica, crystalline silica, and other silicon-containing fillers are preferable.
The insulating powder may be one having a surface coated with a polymer such as a silane compound, polyethyleneimine, polyvinylpyrrolidone, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, or a copolymer having a polyethyleneimine moiety and a polyethylene oxide moiety. By coating with these polymers, the dispersibility in the resin composition tends to be good.
The amount of the insulating powder to be mixed with the resin composition is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the amount is 5 mass% or more, the insulation property tends to be more excellent, and when the amount is 50 mass% or less, the stress relaxation effect tends to improve the reliability of the semiconductor device.
It is needless to say that the modified resin composition of the present embodiment may further contain an epoxy resin (a') other than the epoxy resin (a) contained in the modified resin composition of the present embodiment. In addition, as the organic resin other than the epoxy resin (a'), an organic resin such as a silicone resin, an acrylic resin, a urea resin, or an imide resin can be mixed.
The modified resin composition of the present embodiment can be further added with a curing agent (H) and/or a curing accelerator (I) to prepare a curable resin composition.
The curing agent (H) is not particularly limited as long as it is a substance for curing the resin composition.
As the curing agent, for example, an acid anhydride compound, an amine compound, an amide compound, a phenol compound, or the like can be used, and particularly, an acid anhydride compound such as an aromatic acid anhydride, a cyclic aliphatic acid anhydride, or an aliphatic acid anhydride is preferable, and carboxylic acid anhydride is more preferable.
The acid anhydride compound contains an alicyclic acid anhydride, and the alicyclic acid anhydride is preferable among the acid anhydrides. These cured products can be used alone, can also be used in combination of 2 or more.
Specific examples of the curing agent include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, norbornane-2, 3-dicarboxylic anhydride, methylnorbornane-2, 3-dicarboxylic anhydride, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyanodiamide, tetraethylenepentamine, dimethylbenzylamine, ketimine compounds, polyamide resins synthesized from a linolenic acid-2-mer and ethylenediamine, bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.), polycondensates of various aldehydes, and the like, Polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylol compounds, condensates of bismethoxymethylbiphenyl and naphthols or phenols, biphenols and modified products thereof, imidazoles, boron trifluoride-amine chelates, guanidine derivatives, and the like.
Specific examples of the alicyclic carboxylic acid anhydride include 1, 2, 3, 6-tetrahydrophthalic anhydride, 3, 4, 5, 6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, "4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride ═ 70/30", 4-methylhexahydrophthalic anhydride, "methylbicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride/bicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride" and the like.
Among these curing agents (H), alicyclic acid anhydrides and silicones having, as a substituent, 2 or more anhydride-containing functional groups in 1 molecule are more preferable, and methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2, 3-dicarboxylic anhydride and methylnorbornane-2, 3-dicarboxylic anhydride are still more preferable, because the light resistance of a cured product obtained by curing the modified resin composition of the present embodiment tends to be improved. These curing agents may be used in 1 kind or as a mixture of 2 or more kinds.
The amount of the curing agent (H) added is determined from the mixing index ζ, which is the ratio of the cyclic ether group contained in the epoxy resin and the alkoxysilane compound. The mixing index ζ is represented by the following formula (9).
The mixing index ζ is (ζ f/(ζ k) … (9)
(wherein, in the formula (9), ζ f represents the addition amount (mol number) of the curing agent (H), ζ k represents the amount (mol number) of the cyclic ether group contained in the epoxy resin and the alkoxysilane compound.)
The mixing index ζ is preferably in a range of 0.1 to 1.5, more preferably in a range of 0.2 to 1.3, and still more preferably in a range of 0.3 to 1.3. If the mixing index ζ is less than 0.1, the curing rate may be lowered, and if it exceeds 1.5, the moisture resistance as a cured product may be deteriorated.
The curing accelerator (I) refers to a curing catalyst for accelerating a curing reaction. The curing accelerator is preferably a tertiary amine or a salt thereof. Specific examples of the curing accelerator include the following.
Tertiary amines: benzyldimethylamine, 2, 4, 6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine, and the like.
Imidazoles: 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-benzyl-2-methylimidazole, 1-phenylimidazole, 2-cyanoethyl-2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-methyl, 2-phenyl-4, 5-bis (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4, 5-bis [ (2 '-cyanoethoxy) methyl ] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2, 4-diamino-6- [ 2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- (2' -n-undecylimidazolyl) ethyl-s-triazine, 2, 4-diamino-6- [ 2 ' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, an isocyanuric acid adduct of 2-methylimidazole, an isocyanuric acid adduct of 2-phenylimidazole, and the like.
An organophosphorus compound: diphenylphosphine, triphenylphosphine, triphenyl phosphite, and the like.
Quaternary phosphonium salts: benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-o, o-diethyldithiophosphate, tetra-n-butylphosphonium benzotriazole, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, and the like.
Diazabicyclo olefins: 1, 8-diazabicyclo [5.4.0] undec-7-ene and organic acid salts thereof and the like.
An organometallic compound: zinc octoate, tin octoate (アクチル acid ), aluminum acetylacetonate chelate, and the like.
Quaternary ammonium salts: tetraethylammonium bromide, tetra-n-butylammonium bromide, and the like.
Metal halide: boron compounds such as boron trifluoride and triphenylborate; zinc chloride, tin tetrachloride, and the like.
The amount of the curing accelerator (I) to be added is determined from the ratio of the amount of the epoxy resin and the amount of the alkoxysilane compound to the mass, i.e., the mixing index η. The mixing index η is represented by the following formula (10).
Mixing index η ═ (η g)/(η k) … (10)
(wherein, in the formula (10),. eta.g represents the mass (g) of the curing accelerator (I), and. eta.k represents the mass (g) of the epoxy resin and the alkoxysilane compound.)
The mixing index η is preferably in the range of 0.01 to 5, more preferably in the range of 0.05 to 3, and still more preferably in the range of 0.1 to 1. If the mixing index η is less than 0.01, curing may not proceed well, and if it exceeds 5, the cured product may be colored.
A photosensitive resin composition obtained by further adding a photoacid generator (J) to the modified resin composition of the present embodiment will be described.
The photoacid generator (J) that can be used in the present embodiment is not particularly limited as long as it is a compound that releases an acid upon irradiation with light and initiates polymerization, and among them, an onium salt is preferable. Specific examples thereof include diazonium salts, iodonium salts, sulfonium salts and the like, in which the cationic moiety is composed of aromatic diazonium, aromatic iodonium, aromatic sulfonium, and the anionic moiety is composed of BF4-、PF6-、SbF6-、[BX4]-(wherein X is a phenyl group substituted with at least 2 or more fluorine or trifluoromethyl), and the like. Representative examples of the photoacid generator are shown below.
Chemical formula 6
Figure BDA0000041312520000401
Wherein R, R 'and R' represent an arbitrary substituent.
More specific examples thereof include aryldiazonium salts of boron tetrafluoride, triarylsulfonium salts of phosphorus hexafluoride, diaryliodonium salts of phosphorus hexafluoride, triarylphosphonium salts of antimony hexafluoride, diaryliodonium salts of antimony hexafluoride, tris-4-methylphenylsulfonium salts of arsenic hexafluoride, tris-4-methylphenylsulfonium salts of antimony tetrafluoride, triarylsulfonium salts of tetrakis (pentafluorophenyl) borate, diaryliodonium salts of tetrakis (pentafluorophenyl) borate, mixtures of acetylacetonato aluminum salts and o-nitrobenzylsilyl ethers, phenylsulfurium salts, and phosphorus hexafluoride allene-iron chelate complexes. Commercially available products include CD-1012 (manufactured by SARTOMER), PCI-019, PCI-021 (manufactured by Nippon Kabushiki Kaisha), Optimer SP-150, Optimer SP-170 (manufactured by ADEKA CORPORATION), UVI-6990, UVI-6974 (manufactured by Dow Chemical Co., Ltd.), CPI-100P, CPI-100A, CPI-100L (manufactured by San-Apro Ltd.), TEPBI-S (manufactured by Nippon Kabushiki Kaisha), Rhodorsil2074 (manufactured by Rhodia). These may be used alone, or 2 or more of them may be used in combination. Among the above, sulfonium salts and iodonium salts are preferable from the viewpoint of less coloring of the cured product, and sulfonium salts are particularly preferable from the viewpoint of curability.
Further, the photosensitive resin composition may be mixed with a vinyl ether compound, if necessary. Examples of such compounds include vinyl ether compounds containing no hydroxyl group. Specific examples thereof include ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, and diethylene glycol divinyl ether.
In addition, a conventionally known cationic polymerization catalyst can be mixed in the modified resin composition of the present embodiment. As the cationic polymerization catalyst which can be used, BF may be mentioned3Amine chelate, PF5、BF3、AsF5、SbF5Lewis acid-based catalysts represented by the following general formula; with phosphonium or quaternary ammonium saltsThermosetting cationic polymerization catalysts typified by sulfonium salts, benzylammonium salts, benzylpyridinium salts, benzylsulfonium salts, hydrazine salts, carboxylic acid esters, sulfonic acid esters, and amineimides; ultraviolet-curable cationic polymerization catalysts typified by diaryliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate and the like. Among the above, a thermosetting cationic polymerization catalyst is preferably used because a transparent cured product having a high glass transition temperature and excellent solder heat resistance and adhesion and having less coloration tends to be obtained. Examples of commercially available products of such thermosetting cationic polymerization catalysts include SI-100L, SI-60L (manufactured by Sanxin chemical industries, Ltd.), CP-66 and CP-77 (manufactured by Asahi Denka Co., Ltd.) as a sulfonium salt-based cationic polymerization initiator.
The modified resin composition obtained in the present embodiment may contain a modifier as necessary, from the viewpoint of imparting flexibility to a cured product and improving peel adhesion. Examples of the modifier to be used include polyhydric alcohols having 2 or more hydroxyl groups in 1 molecule, and for example, aliphatic polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1, 2-butanediol, 1, 4-butanediol, neopentyl glycol, glycerin, erythrol, trimethylolpropane, and 1, 2, 4-butanetriol, polycarbonate diol, and silicones having a silanol group at the terminal are preferably used. These modifiers may be used in 1 kind or as a mixture of 2 or more kinds.
In order to improve physical properties such as adhesion, various silane coupling agents can be used for the modified resin composition of the present embodiment. In this case, the residual alkoxy group in the modified resin composition needs to be 5% or less. When the residual alkoxy group content exceeds 5%, the crack resistance and adhesiveness during thermal cycling of a cured product obtained by curing the composition are insufficient.
Examples of the silane coupling agent suitable for the modified resin composition of the present embodiment include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, and, N- (2-aminoethyl) aminomethyltrimethoxysilane, N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane, N- (2-aminoethyl) (3-aminopropyl) triethoxysilane, N- (2-aminoethyl) (3-aminopropyl) methyldimethoxysilane, N- [ N' - (2-aminoethyl) ] (3-aminopropyl) trimethoxysilane, 2- (2-aminoethyl) thioethyltriethoxysilane, 2- (2-aminoethyl) thioethylmethyldiethoxysilane, 3- (N-phenylamino) propyltrimethoxysilane, 3- (N-cyclohexylamino) propyltrimethoxysilane, N-aminopropyl-trimethoxysilane, N- (2-aminoethyl) methyldimethoxysilane, N- (2-aminopropyl) methyldiethoxysilane, N- (3-phenylamino) propyltrimethoxysilane, N- (2-cyclohexylamino) propyltrimethoxysilane, N- (2-aminoethyl) methyldimethoxysilane, N- (3-aminopropyl) trimethoxysilane, (N-phenylaminomethyl) trimethoxysilane, (N-phenylaminomethyl) methyldimethoxysilane, (N-cyclohexylaminomethyl) triethoxysilane, (N-cyclohexylaminomethyl) methyldiethoxysilane, piperazinylmethyltrimethoxysilane, piperazinylmethyltriethoxysilane, 3-piperazinylpropyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyldimethoxysilane, mercaptomethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, N-phenylaminomethyl-trimethoxysilane, N-cyclohexylaminomethyl-triethoxysilane, N-piperazinylmethyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3- (trimethoxysilyl) propylsuccinic anhydride, 3- (triethoxysilyl) propylsuccinic anhydride, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylcyclohexyldimethoxysilane, dimethylcyclohexyldimethoxysilane, dimethyltriethoxysilane, dimethylvinyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldimethoxysilane, and dimethylcyclohexyldimethoxysilane, Methylcyclohexyldiethoxysilane, methylcyclopentyldimethoxysilane, methylcyclopentyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and the like. In addition, partial condensates of these silane coupling agents may also be used.
In addition, in the modified resin composition of the present embodiment, inorganic fillers, colorants, leveling agents, lubricants, surfactants, antioxidants, light stabilizers, and the like other than those described above may be added as appropriate according to the purpose, within a range in which these functions are not impaired. In addition to these, plasticizers, flame retardants, stabilizers, antistatic agents, impact resistance enhancers, foaming agents, antibacterial/antifungal agents, conductive fillers, antifogging agents, crosslinking agents, and the like, which are generally used as additives for resins, can be mixed.
Examples of the inorganic filler include silica (fused silica, crystalline silica, spherical silica, fumed silica, colloidal silica, precipitated silica, and the like), silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, and molybdenum disulfide. Particularly, silica, calcium carbonate, alumina, aluminum hydroxide, calcium silicate and the like are preferable, and silica is more preferable in view of physical properties of a cured product. These inorganic fillers may be used alone, or 2 or more kinds may be used in combination.
The coloring agent is not particularly limited as long as it is used for coloring purposes, and examples thereof include various organic pigments of phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavanthrone, perinone, perylene, dioxazine, condensed azo, and azomethine; inorganic pigments such as titanium oxide, lead sulfate, chrome yellow, zinc yellow, chrome vermilion (chrome), red iron oxide, cobalt violet, prussian blue, ultramarine, carbon black, chrome green, chromium oxide, and cobalt green. These colorants may be used alone, or 2 or more of them may be used in combination.
The leveling agent is not particularly limited, and examples thereof include oligomers having a molecular weight of 4000 to 12000 and comprising acrylic esters such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized rosin alcohol, hydrogenated castor oil, and titanium-based coupling agent. These leveling agents may be used alone, or 2 or more kinds may be used in combination.
The lubricant is not particularly limited, and examples thereof include hydrocarbon-based lubricants such as paraffin wax, microcrystalline wax, and polyethylene wax; higher fatty acid-based lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid; higher fatty acid amide-based lubricants such as stearamide, palmitamide, oleamide, methylene bis stearamide, and ethylene bis stearamide; higher fatty acid ester-based lubricants such as cured castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri-, or tetra-) stearate, and the like; alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, and polyglycerin; metallic soaps as metal salts of magnesium, calcium, cadmium, barium, zinc, lead, etc. such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid, naphthenic acid, etc.; natural waxes such as carnauba wax, candelilla wax, beeswax, and montan wax. These lubricants may be used alone, or 2 or more of them may be used in combination.
The surfactant is an amphiphilic substance having a hydrophobic group having no affinity for a solvent and a solvophilic group (usually, a hydrophilic group) having an affinity for a solvent in its molecule. The type of the surfactant is not particularly limited, and examples thereof include silicone surfactants, fluorine surfactants, and the like. The surfactants may be used alone or in combination of 2 or more.
The antioxidant is not particularly limited, and examples thereof include organic phosphorus antioxidants such as triphenyl phosphate and phenylisodecyl phosphite; organic sulfur antioxidants such as dioctadecyl 3, 3' -thiodipropionate; and phenol-based antioxidants such as 2, 6-di-t-butyl-p-cresol.
The light stabilizer is not particularly limited, and examples thereof include ultraviolet absorbers such as benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based, and hindered amine-based light stabilizers.
The modified resin composition of the present embodiment can be formed into a cured product by a known method; alternatively, a curable resin composition obtained by mixing the modified resin composition of the present embodiment with the oxetane compound (D), the fluorescent material (E), the conductive metal powder (F), the insulating powder (G), the epoxy resin (a '), the curing agent (H), the curing accelerator (I), or the photoacid generator (J), and further, if necessary, with a cationic polymerization catalyst, a modifier, a vinyl ether compound, an organic resin other than the epoxy resin (a'), and a silane coupling agent can be formed into a cured product by a known method. Among these, a method of curing by heating or a method of curing by irradiating light is a method generally used as a curing method of an epoxy resin, and can be exemplified as a preferable method in the present embodiment. The temperature at the time of curing by heating is not particularly limited, depending on the epoxy resin, curing agent, etc. used, but is usually in the range of 20 to 200 ℃.
On the other hand, the light used for curing by irradiation with light is preferably ultraviolet light or visible light, and more preferably ultraviolet light. Examples of the light generating source include various light sources such as a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a UV lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, an excimer laser, a light emitting diode, a CRT light source, and a plasma light source.
The curing reaction may be carried out in air, or in an inert gas atmosphere such as nitrogen, helium, or argon, if necessary.
The modified resin composition of the present embodiment is, for example, a) a modified resin composition of the present embodiment, b) a resin composition obtained by further adding an oxetane compound (D) to the modified resin composition of the present embodiment, c) a fluorescent resin composition obtained by further adding a fluorescent material (E) to the modified resin composition of the present embodiment, or a resin composition obtained by further adding a curing agent (H) to the above-mentioned a) to c). The modified resin composition of the present embodiment is useful as a material for producing an excellent sealing material for a light-emitting element, which has excellent adhesion to an element or a sealing material, does not crack, and has little decrease in luminance over a long period of time; or as a material for a curable resin composition for an optical lens which can be injection-molded, has a hard texture after curing, has excellent dimensional stability, and has light resistance. Further, a curable resin composition obtained by further adding a curing accelerator (I) to a resin composition obtained by further adding a curing agent (H) to the above a) to c), or a photosensitive resin composition obtained by further adding a photoacid generator (J) to the above a) to c) is very useful as a curable resin composition or a photosensitive resin composition for producing the above light-emitting element sealing material or optical lens.
By sealing the light-emitting element with the curable resin composition containing the modified resin composition of the present embodiment, a light-emitting component such as a light-emitting diode can be manufactured. The light emitting diode and/or the optical lens can be suitably used as a semiconductor device such as a backlight (back light) of a liquid crystal display or the like, an illumination, various sensors, a light source of a printer, a copier or the like, a vehicle meter light source, a signal lamp, an indicator lamp, a display device, a light source of a planar light emitter, a display, a decoration, various lamps, and the like.
The light-emitting element, which is sealed with a sealing material for a light-emitting element comprising a curable resin composition containing the modified resin composition of the present embodiment, can be used in a wide range of emission wavelengths from infrared to red, green, blue, violet, and ultraviolet, and can be used even under light having a wavelength of 250nm to 550nm in practical use, and the conventional sealing material is deteriorated in light resistance due to insufficient light resistance under light having a wavelength of 250nm to 550 nm. Thus, a white light-emitting diode having a long lifetime, high energy efficiency, and high color reproducibility can be obtained. The emission wavelength is a main emission peak wavelength.
As a specific example of the light-emitting element to be used, for example, a light-emitting element formed by stacking a semiconductor material on a substrate is illustrated. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.
Examples of the substrate include sapphire, spinel, SiC, Si, ZnO, GaN single crystal, and the like. If necessary, a buffer layer may be formed between the substrate and the semiconductor material. Examples of the buffer layer include GaN and AlN.
The method for depositing the semiconductor material on the substrate is not particularly limited, and for example, MOCVD method, HDVPE method, liquid phase growth method, or the like can be used.
Examples of the structure of the light-emitting element include homojunction, heterojunction, and double-heterostructure having MIS junction, PN junction, and PIN junction. In addition, a single or multiple quantum well structure may also be formed.
A light-emitting diode can be manufactured by sealing a light-emitting element with a light-emitting element sealing material made of a curable resin composition containing the modified resin composition of the present embodiment. In this case, the light-emitting element may be sealed with only a light-emitting element sealing material, or may be sealed with another sealing material. In the case of using another sealing material in combination, the modified resin composition obtained in the present embodiment may be used, and after sealing with the light-emitting element sealing material thus obtained, the periphery thereof may be sealed with another sealing material; alternatively, after sealing with another sealing material, the modified resin composition obtained in the present embodiment may be used to seal the periphery of the light-emitting element with a sealing material for a light-emitting element obtained from the modified resin composition. Examples of the other sealing materials include epoxy resins, silicone resins, acrylic resins, urea resins, imide resins, and glass.
As a method for 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, the following methods can be mentioned: a method of injecting a light emitting element sealing material in advance into a mold case (モ - ルド (model No. h)), immersing a lead frame or the like having a light emitting element fixed thereto therein, and curing the lead frame or the like; a method of injecting a light emitting element sealing material into a mold case (type (best) of section (section)) having a light emitting element inserted therein and curing the material. In this case, examples of a method of injecting the light-emitting element sealing material include injection using a dispenser (dispenser), transfer molding, and injection molding. As another sealing method, the following methods can be mentioned: a method of dropping a light-emitting element sealing material onto a light-emitting element, and performing stencil printing, screen printing, or coating and curing through a mask; a method of pouring a light emitting element sealing material into a cup or the like in which a light emitting element is arranged at a lower portion with a dispenser or the like and curing the material.
The curable resin composition containing the modified resin composition of the present embodiment can also be used as a die-bonding material for fixing a light-emitting element to a lead terminal or a package (パッケ - ジ), a passivation film on a light-emitting element, or a package substrate. Examples of the shape of the sealing portion include a bullet-shaped lens shape, a plate shape, and a film shape.
The light-emitting diode obtained using the modified resin composition of the present embodiment can be improved in performance by a conventionally known method. Examples of the method for improving the performance include the following methods: a method of providing a light reflecting layer or a light condensing layer on the back surface of the light emitting element; a method of forming a complementary color coloring portion on the bottom; a method of providing a layer that absorbs light having a wavelength shorter than a main emission peak on a light-emitting element; a method of further molding with a hard material after sealing the light emitting element; a method of inserting and fixing the light emitting diode into the through hole; a method of connecting the light emitting element to a lead member or the like by flip chip connection or the like and extracting light from the substrate direction.
The light-emitting diode obtained using the modified resin composition of the present embodiment is useful as, for example, a backlight (back light) for a liquid crystal display or the like, a light source for lighting, various sensors, a printer, a copying machine or the like, a light source for a vehicle meter, a signal lamp, an indicator lamp, a display device, a light source for a planar light-emitting body, a display, a decoration, a light-emitting member for various lamps or the like.
On the other hand, a light-storing material having excellent light-emitting properties can be produced by curing a curable resin composition obtained by further adding a curing agent (H) to a fluorescent resin composition obtained by further adding a fluorescent material (E) to the modified resin composition of the present embodiment, or a photosensitive resin composition obtained by further adding a photoacid generator (J) to the modified resin composition of the present embodiment.
Next, the light storing material will be described. In general, a light-storing material is a material that emits light by being excited by light stimulation such as sunlight, a fluorescent lamp, or ultraviolet rays, and emits light while being excited by energy conversion, and that emits light slowly after excitation by the light stimulation is stopped, and that continuously emits light 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 displays at night and during power failure, disaster prevention and safety signs, clocks, wall papers, electric switches, signs, clothes, shoes, reflectors for bicycles and motorcycles, fishing gear such as tapes, crochet hooks and buoys, sporting goods, ornaments, and toys.
In addition, for example, d) the conductive resin composition obtained by further adding the conductive metal powder (F) to the modified resin composition of the present embodiment has excellent fluidity, conductivity and adhesiveness, and is useful as a raw material for a curable conductive resin composition capable of suppressing the generation of voids, while e) an insulating resin composition obtained by further adding an insulating powder (G) to the modified resin composition of the present embodiment, 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, or a resin composition obtained by further adding a curing agent (H) to the above-mentioned d) to f) has excellent insulating properties and adhesive properties, and is useful as a material for a curable insulating resin composition which can suppress the occurrence of voids. The curable resin composition obtained by further adding the curing accelerator (I) to the resin composition obtained by further adding the curing agent (H) to d) to f) or the photosensitive resin composition obtained by further adding the photoacid generator (J) to d) to f) is very useful as the above-mentioned various curable conductive resin compositions or curable insulating resin compositions.
The use of the conductive resin composition using the modified resin composition of the present embodiment is not particularly limited, and examples thereof include adhesion of a semiconductor element to a peripheral member, formation of a conductor wiring, and solder replacement in surface mounting; adhesives or die-bonding agents used for casting of insulators, crystal oscillators, ac transformers, switches, and the like, circuit units, packaging of various components, coils of rotary machines such as ICs, LEDs, and semiconductors, power generators, motors, and the like, coil impregnation, printed circuit boards, transparent substrates instead of glass, medium-sized insulators, coils, connectors, terminals, and the like, and wiring thereof; conductive paint, electrodes, printed circuits, conductive resin, and the like.
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 semiconductor chips in semiconductor devices (mounting); die solders and adhesives for bonding semiconductor chips (IC, LSI, and the like) to ceramic cases, lead frames, substrates, and the like. Further, the present invention can be applied to applications of insulating materials requiring high heat dissipation, such as an interposer (interposer) of a semiconductor package, a printed circuit board, a display, a solar cell, a board for a generator/motor, and a board for an automobile.
For example, a curable resin composition obtained by adding a curing agent (H) and a curing accelerator (I) to the following a) to c), or a photosensitive resin composition obtained by further adding a photoacid generator (J) to the above a) to c) can be effectively used as a coating agent which is less susceptible to polymerization inhibition by oxygen: a) a modified resin composition of the present embodiment, b) a resin composition obtained by further adding an oxetane compound (D) to the modified resin composition of the present embodiment, c) a fluorescent resin composition obtained by further adding a fluorescent material (E) to the modified resin composition of the present embodiment; further, for example, a curable resin composition obtained by adding a curing agent (H) and a curing accelerator (I) to the following d) to f), or a photosensitive resin composition obtained by further adding a photoacid generator (J) to the above d) to f) is very useful as a coating agent which is hardly affected by a polymerization inhibition effect by oxygen: d) a conductive resin composition obtained by further adding a conductive metal powder (F) to the modified resin composition of the present embodiment, e) an insulating resin composition obtained by further adding an insulating powder (G) to the modified resin composition of the present 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.
The coating agent in the present embodiment is not particularly limited as long as it is a material for forming and coating a coating film on the surface of a substance, and the main purpose of the coating agent is as follows.
(1) Protection of coating or substrate, durability imparting, maintenance of beauty (protection from ultraviolet rays, infrared rays, oxidation, corrosion, flaws, dust, dirt, temperature, humidity, etc.)
(2) Coating or imparting gloss to substrates
(3) Coating or hydrophobic finishing of substrates
(4) Anti-slip processing of flooring material and the like
(5) Sealing and insulating electronic parts
In general, epoxy compounds are considered to initiate polymerization relatively quickly, but the subsequent polymerization reaction is not rapid. However, the present inventors have unexpectedly found that by mixing an oxetane compound with the resin composition having an epoxy group, the polymerization rate can be accelerated, and a photosensitive resin composition excellent in photocurability and adhesiveness can be obtained. Further, by selecting the oxetane compound, the viscosity of the resin composition can be reduced.
The viscosity of the photosensitive resin composition of the present embodiment is preferably 1000Pa · s or less, more preferably in the range of 0.05 to 50Pa · s, and still more preferably in the range of 0.2 to 30Pa · s. If the viscosity of the photosensitive resin composition exceeds 1000 pas, the fluidity is impaired, and the composition may not be suitable for practical use.
The coating agent of the present embodiment is applied by a conventionally known method and then cured to form a coating film. In this case, as a method of coating, coating techniques such as brush coating, roll coating, spray coating, bar coating, roll coating, baking varnish, dip coating, electrodeposition coating, electrostatic coating, powder coating, vapor deposition, and plating, and printing techniques such as inkjet, laser printer, rotary printing, gravure printing, and screen printing are preferably used, and as a method of forming a coating film, a method of curing by heating or a method of curing by irradiation with light is preferably used.
The coating agent and the application of the coating film of the present embodiment are not particularly limited, and for example, the coating agent (coating, resin, plastic, metal, steel pipe, automobile, building, optical fiber application, etc.), coating or adhesion of optical disks (DVD, CD, blu-ray disk, etc.), inks (ink jet printer, gravure printing, flexographic printing, resist for printed wiring board, UV printing application, etc.), printing plate making materials (PS plate, photosensitive resin relief plate, photosensitive material for screen plate, etc.), photoresists (resist for semiconductor, resist for printed wiring board, resist for chemical Photo-etching production (Photo-etching), etc.), patterning of various electronic parts including printed wiring board, IC, LSI, color filter forming material for liquid crystal or PDP display, sealing material for liquid crystal or organic EL, semiconductor and LED peripheral materials (sealing material), Lens material, substrate material, die-bonding material, chip-coating material, laminate, optical fiber, optical waveguide, optical filter, adhesive for electronic parts, coating material, sealing material, insulating material, photoresist, sealing material, potting material, light-transmitting layer or interlayer insulating layer of optical disk, printed wiring board, laminate, light guide plate, antireflection film, etc.), and the like, paints (anticorrosive paint, maintenance, marine coating, corrosion-resistant coating (lining), primer for automobile and home electric appliances, beverage and beer cans, exterior surface coating, extrusion tube coating, general anticorrosive coating, maintenance coating, paint for carpentry products, electrodeposition primer for automobiles, electrodeposition coating for other industries, beverage and beer cans interior surface coating, coil coating, can and can interior surface coating, carpentry paint, acid-resistant coating, enameled wire paint, insulating paint, optical waveguide, optical filter, adhesive for electronic parts, coating material, sealing material, insulating material, photoresist, sealing material, sealing, Primer for automobile, coating of various metal products with aesthetic and anticorrosive properties, coating of interior and exterior surfaces of pipes, coating of electrical components for insulation, etc.), composite materials (pipes and tanks for chemical equipment, aircraft materials, automobile members, various sporting goods, carbon fiber composite materials, aramid fiber composite materials, etc.), civil engineering and construction materials (flooring materials, paving materials, films, non-slip and thin-layer paving, concrete construction joints and heightening, anchor embedding adhesion, precast concrete joining, tile adhesion, crack repairing of concrete structures, grouting and leveling of foundations, anticorrosive and waterproof coating of plumbing facilities, anticorrosive laminated coating of tanks, anticorrosive coating of iron structures, thick mortar (mastic) coating of building exterior walls, etc.), adhesives (adhesives of the same or different materials such as metal, glass, ceramics, cement concrete, wood, plastics, etc.), Adhesives for assembling automobiles, railway vehicles, aircrafts, and the like, adhesives for producing composite panels for prefabricated houses, and the like: including single liquid type, two liquid type, and thin sheet type. ) And jigs for aircraft, automobile, and plastic molding (resin molds such as compression molds, stretch-blow molds, and mixing extrusion molds, molds for vacuum molding and blow molding, master molds, patterns for castings, lamination jigs, various inspection jigs, and the like), modifiers and stabilizers (resin processing of fibers, stabilizers for polyvinyl chloride, additives for synthetic rubbers, and the like). Among them, the resin composition is useful for coating agents, paints, adhesives, and stereolithography resins.
Examples
The following examples specifically illustrate the present embodiment, but the present embodiment is not limited to the following examples as long as the gist thereof is not exceeded.
The evaluation of physical properties in examples 1 to 26 and comparative examples 1 to 9 was carried out as follows.
< epoxy equivalent Weight (WPE) >
In accordance with "JIS K7236: 2001 (method of calculating epoxy equivalent of epoxy resin) ".
< viscosity >
The measurement was performed under the following conditions.
Rotary E-viscometer: "TV-22 shape" manufactured by Dongyi industries Co., Ltd "
A rotor: 3 ° × R14 (other rotors may be selected as required.)
Measuring temperature: 25 deg.C
Sample amount: 0.4mL
< calculation of blending index α >
The mixing index α is calculated from the following general formula (2).
Mixing index α ═ (α c)/(α b) (2)
Wherein,
α b: (B) in the general formula (1), n is 1 or 2, and has at least 1 cyclic ether group as R1The molar% of the alkoxysilane compound of (4),
α c: (C) in the general formula (1), n is 1 or 2, and at least 1 aromatic organic group is used as R1Mol% of the alkoxysilane compound (b).
< calculation of blending index β >
The mixing index β is calculated from the following general formula (3).
Mixing index β { (β n2)/(β n0+ β n1) } (3)
Wherein,
β n 2: in the general formula (1), n is 2 mol% of the alkoxysilane compound,
β n 0: in the general formula (1), n is 0 mol% of the alkoxysilane compound,
β n 1: in the general formula (1), n is 1 mol% of the alkoxysilane compound,
wherein, 0 { (beta n 0)/(beta n0+ beta n1+ beta n2) } is less than or equal to 0.1.
< calculation of blending index γ >
The mixing index γ is calculated from the following general formula (4).
Mixing index γ ═ (γ a)/(γ s) (4)
Wherein,
γ a: the mass (g) of the epoxy resin,
γ s: in the general formula (1), n is 0-2 mass (g) of the alkoxysilane compound.
< calculation of blending index δ >
The mixing index δ is calculated by the following general formula (5).
Blending index δ (δ e)/(δ s) (5)
Wherein,
δ e: the amount (mol number) of the hydrolysis condensation catalyst,
δ s: (OR) in the formula (1)2) Amount (mol number).
< calculation of blending index ε >
The mixing index ε can be calculated by the following formula (6).
Mixing index ε ═ ε w)/(ε s) (6)
Wherein,
ε w: the amount (mol number) of water added,
ε s: (OR) in the formula (1)2) Amount (mol number).
< calculation of mixing index ζ >
The mixing index ζ was calculated by the following general formula (7).
Mixing index ζ ═ (ζ f)/(ζ k) (7)
Wherein,
ζ f: the amount (mol number) of the curing agent added,
ζ k: the amount (mol number) of the cyclic ether group contained in the epoxy resin and the alkoxysilane compound.
< calculation of blending index η >
The mixing index η is calculated by the following general formula (8).
Mixing index η ═ η g)/(η k) × 100 (8)
Wherein,
η g: the mass (g) of the curing accelerator,
η k: mass (g) of epoxy resin and alkoxysilane compound.
< calculation of storage stability index θ and storage stability of resin composition >
The storage stability of the resin composition was evaluated by a storage stability index θ represented by the following general formula (9).
Storage stability index θ ═ (storage viscosity)/(initial viscosity) (9)
The container containing the resin composition immediately after the production was sealed, and after adjusting the temperature at 25 ℃ for 2 hours, the viscosity at 25 ℃ was measured and used as the "initial viscosity".
Further, the container containing the resin composition was sealed and stored in a thermostatic incubator at 25 ℃ for 2 weeks. After storage, the viscosity at 25 ℃ was measured and used as "storage viscosity".
When the resin composition has fluidity (viscosity of 1000Pa · s or less) and the storage stability index θ is 4 or less, it is judged that the resin composition has storage stability.
< H-NMR measurement of intermediate >
The condensation rate of the intermediate was determined from the H-NMR measurement results of the collected sample solution (intermediate) after the completion of the reflux step in the following order.
(1) 30mg of the sample solution after the completion of the refluxing step was weighed into a sample bottle, and chloroform-d (manufactured by Wako pure chemical industries, Ltd.) was added thereto to adjust the amount to 1 g.
(2) Transferring the solution of (1) to the diameter
Figure BDA0000041312520000521
H-NMR was measured under the following conditions in the NMR tube (1).
Fourier transform nuclear magnetic resonance apparatus: "alpha-400 type" manufactured by Nippon electronic Co., Ltd "
And (4) nuclear seed: h
Cumulative number of times: 200 times (one time)
< calculation of the amount of residual alkoxy group in the modified resin composition: H-NMR measurement >
The H-NMR measurement was carried out in the following order.
(1) In a sample bottle, 10mg of the modified resin composition and 20mg of an internal standard (1, 1, 2, 2-tetrabromoethane; Tokyo chemical industry) were weighed, and 970mg of chloroform-d (Wako pure chemical industries) was added thereto and dissolved to prepare a solution.
(2) Transferring the solution of (1) to the diameter
Figure BDA0000041312520000531
H-NMR was measured under the following conditions in the NMR tube (1).
Fourier transform nuclear magnetic resonance apparatus: "alpha-400 type" manufactured by Nippon electronic Co., Ltd "
And (4) nuclear seed: h
Cumulative number of times: 200 times (one time)
The residual alkoxy group amount (%) was calculated from the above measurement results in the following order.
(3) The peak area value of the residual alkoxy peak was calculated from the H-NMR chart.
(4) The peak area value of the internal standard substance peak is calculated by an H-NMR chart.
(5) The residual alkoxy group amount (%) was determined by substituting the area values read in (3) and (4) into the following equation.
Residual alkoxy group amount (%) - (peak area value of residual alkoxy group peak)/(peak area value of internal standard substance peak) × 100
The peak area value of the residual alkoxy peak was calculated by the following method.
< case where the peak of the residual alkoxy group is a single peak >
The area of the portion surrounded by the baseline and the peak was taken as the peak area value of the residual alkoxy peak.
Depending on the kind of the residual alkoxy group, there may be a plurality of peaks of the residual alkoxy group. In this case, the peak area value of the residual alkoxy group peak in the present embodiment is the sum of the areas of the peaks of the plurality of residual alkoxy groups.
< case where the peak of the residual alkoxy group is a composite peak >
From the point where the slope enclosed between the peak of the residual alkoxy group and the peak of the group other than the residual alkoxy group is 0, a tangent is drawn so as to minimize the area of the peak of the residual alkoxy group, and the area of the portion enclosed by the tangent and the peak of the residual alkoxy group is taken as the peak area value of the peak of the residual alkoxy group.
In the case where the peak of the residual alkoxy group is a main component of the peak and there is no point having a slope of 0 between the peak of the residual alkoxy group and the peak of the group other than the residual alkoxy group, the peaks of the groups other than the residual alkoxy group are not regarded as peaks, and all of the peaks are peaks of the residual alkoxy group. When the peak of a group other than the residual alkoxy group is a main component of the peak and there is no point having a slope of 0 between the peak of the residual alkoxy group and the peak of a group other than the residual alkoxy group, the peak of the residual alkoxy group is not regarded as a peak.
< test on light resistance of cured product >
The light resistance of the cured product was evaluated by the following method.
(1) A cured product prepared by the method described below was cured in a solution to prepare a cured product having a thickness of 20 mm. times.10 mm. times.3 mm.
(2) The cured product was covered with a black mask having a hole diameter of 5.5mm of 25 mm. times.15 mm. times.1.2 mm thick to prepare a sample for light resistance test.
(3) An apparatus was prepared so that the above-mentioned sample in an incubator thermostatically maintained at 50 ℃ could be irradiated with UV light from a UV irradiation apparatus (manufactured by Ushio inc. "Spot Cure SP7-250 DB") via an optical fiber.
(4) The sample was placed in a 50 ℃ incubator with a black mask on top.
(5) 2W/cm was irradiated from the upper part of the black mask in such a manner that UV light could be irradiated into a hole having a diameter of 5.5mm2UV light for 96 hours.
(6) The sample after UV irradiation was measured by a spectrocolorimeter ("SD 5000", manufactured by Nippon Denshoku industries Co., Ltd.) in which the opening of the integrating sphere was modified to have a diameter of 10 mm.
(7) According to "ASTM D1925-70 (1988): the Test Method for Yellowness Index of Plastics (Test Method for Yellowness Index of Plastics) "determines the Yellowness Index (YI). When YI is 13 or less, it is judged to have light resistance.
< Cold thermal shock test of cured product >
The thermal shock properties of the cured product were evaluated by the following methods.
(1) The following substrates and silicon chips were prepared.
(1-1) substrate: manufactured by Solvay Advanced Polymers K.K. "AMODEL A-4122NL WH 905" (having a depression of diameter 10mm X depth 1.2mm in the center of a plate of 15mm X thickness 2 mm)
(1-2) silicon chip
(2) The solution for curing material prepared by the method described later was poured onto the substrate, and 10 samples each containing 1 silicon chip were prepared and cured to be samples for the cold thermal shock test.
(3) The above sample was set in a cold-hot impact device ("TSE-11-A" manufactured by ESPEC CORP. to obtain a cold-hot impact material having a temperature of "(-40 ℃ to 120 ℃)/cycle: the exposure time was 14 minutes and the warming and cooling time was 1 minute ".
(4) After 50 cycles of thermal cycles, the samples were taken out, and the number of samples was recorded by spraying a penetrant (MICRO CHECK, manufactured by KOHZAI CORPORATION) to observe whether or not an abnormality (separation or crack) occurred.
(5) The sample in which abnormality was not confirmed in (4) above was again placed in the apparatus, and the evaluation was performed in the same manner after 50 cycles of thermal cycling, and then the evaluation was performed in the same manner after 100 cycles of thermal cycling. These operations were repeated to evaluate.
(6) The evaluation was interrupted when abnormality was observed in 2 out of 10 samples, and the "number of thermal shock resistance" was obtained (number of interrupted thermal cycles) - (50) ". When the number of times of thermal shock resistance is 50 or more, it is determined that the thermal shock resistance is present, and the determination is performed as follows.
More than 50 times and less than 100 times; o-
More than 100 times; very good
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)
Trade name: "AER 2600" manufactured by Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described methods are as follows.
Epoxy equivalent (WPE): 187g/eq
Viscosity (25 ℃): 14.3 pas
(1-2) epoxy resin A2: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as Bis-A2 epoxy resin)
Trade name: "AER 2500" by Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described methods are as follows.
Epoxy equivalent (WPE): 186g/eq
Viscosity (25 ℃): 10.2 pas
(1-3) epoxy resin A3: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as Bis-A3 epoxy resin)
Trade name: "AER 6071" made by Ltd, Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) measured by the above method is as follows. Among them, the epoxy resin a3 was solid at 25 ℃, and thus the viscosity could not be measured.
Epoxy equivalent (WPE): 470g/eq
(1-4) epoxy resin B: 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate (hereinafter, referred to as alicyclic epoxy resin)
Trade name: "CEL 2021P" manufactured by Daicel Chemical Industries, Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described methods are as follows.
Epoxy equivalent (WPE): 131g/eq
Viscosity (25 ℃): 227mPa · s
(2) Alkoxysilane compound
(2-1) alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter, GPTMS)
Trade name: KBM-403 manufactured by shin-Etsu chemical industries, Ltd "
(2-2) alkoxysilane compound I: phenyltrimethoxysilane (hereinafter referred to as PTMS)
Trade name: KBM-103, manufactured by shin-Etsu chemical industries, Ltd "
(2-3) alkoxysilane compound J: dimethyldimethoxysilane (hereinafter referred to as DMDMS)
Trade name: KBM-22, manufactured by shin-Etsu chemical industries, Ltd "
(2-4) alkoxysilane compound K: tetraethoxysilane (hereinafter, referred to as TEOS)
Trade name: KBE-04, manufactured by shin-Etsu chemical industries, Ltd "
(2-5) alkoxysilane compound L: 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter, ECETMS)
Trade name: KBM-303, manufactured by shin-Etsu chemical industries, Ltd "
(3) Partial condensates of silanes
(3-1) partial condensate of tetramethoxysilane (also known as polymethoxysiloxane) (hereinafter, referred to as P-MS)
Trade name: "methyl silicate 51" manufactured by Hibiscus chemical industries Co., Ltd "
(3-2) partial condensate of methyltrimethoxysilane (alias: poly (methyltrimethoxysilane) (hereinafter, referred to as P-MTMS)
Trade name: "MTMS-A" manufactured by Moore chemical industries, Ltd "
(4) Solvent(s)
(4-1) tetrahydrofuran: wako pure chemical industries, Ltd., a stabilized form (hereinafter referred to as THF) was not contained
(4-2) ethanol: "Heguang pure chemical" manufactured by Heguang pure chemical industries, Ltd. (hereinafter referred to as EtOH)
(4-3) isopropyl alcohol: "Heguang pure chemical industries Co., Ltd." (hereinafter referred to as "i-PrOH")
(5) Hydrolytic condensation catalyst
(5-1) dibutyltin dilaurate: "Heguang pure chemical industry 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: "Neosantan U-820" (hereinafter referred to as DOTDA) manufactured by Nitto Kabushiki Kaisha
(6) Curing agent: "4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride ═ 70/30"
Trade name: manufactured by Nissan chemical and physical Co., Ltd. "RIKACID MH-700G"
(7) Curing accelerator: amine-based curing agent
Trade name: "U-CAT 18X" manufactured by San-Apro Ltd "
(8) Silicone resin: "SCR-1012 (solutions A and B)" manufactured by shin-Etsu chemical industries, Ltd "
(9) Inorganic filler: colloidal silicon dioxide
Trade name: "methanol silica sol" (SiO 2: 30%, particle size: 10 to 20nm) manufactured by Nissan chemical industries Co., Ltd
(10) Internal standard substance
1, 1, 2, 2-tetrabromoethane: manufactured by Tokyo chemical industry Co Ltd
[ example 1]
The resin composition was produced and evaluated in the following manner.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) In accordance with the composition ratio shown in Table 1, Bis-A1 epoxy resin, alkoxysilane compound and THF were charged into a flask charged with a stirrer in an atmosphere of 25 ℃ and mixed under stirring, and then water and a hydrolytic condensation catalyst were added thereto and mixed under stirring.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 7 hours while refluxing (refluxing step).
(4) After the reaction was completed, the temperature was cooled to 25 ℃, and then the cooling tube was removed from the flask, and after the reflux step was completed, a sample solution (intermediate) was collected.
(5) After the reflux step was completed, (OR) of the following formula (1) was confirmed by measuring H-NMR of the sample solution (intermediate)2) Is hydrolyzed to generate (OH).
Chemical formula 7
(R1)n-Si-(OR2)4-n (1)
(6) After the solution after the reflux step was distilled off at 400Pa and 50 ℃ for 1 hour using an evaporator, a dehydration condensation reaction was carried out while further distilling off at 80 ℃ for 5 hours (dehydration condensation step).
(7) After the reaction, the reaction mixture was cooled to 25 ℃ to obtain a resin composition. The H-NMR of the resin composition was measured and calculated together with an internal standard substance, and the amount of the residual alkoxy group was 0% to 5%.
(8) The mixing indices α 1 to ∈ 1 in the resin composition are shown in table 3.
(9) Further, the epoxy equivalent Weight (WPE), initial viscosity, and storage viscosity of the resin composition obtained in (6) were measured by the above-mentioned methods. Further, the storage stability index θ 1 was obtained and shown in table 3.
The epoxy equivalent Weight (WPE) of the resin composition of example 1 was 230g/eq, which is an appropriate value. The initial viscosity was 32.7Pa · s < 1000Pa · s, and the storage viscosity was 46.4Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 1 was 1.42. ltoreq.4, and it was confirmed that the resin composition had storage stability.
Then, using the above resin composition stored at 25 ℃ for 2 weeks, a cured product was produced in the following order and evaluated.
(10) The resin composition, the curing agent and the curing accelerator were mixed and stirred at the composition ratios shown in table 2 in an atmosphere of 25 ℃, and degassed under vacuum to obtain a solution for a cured product.
(11) A molding jig was prepared by holding silicone rubber 3mm thick and shaped like コ between 2 stainless steel plates coated with a release agent.
(12) The molding jig and the 10 substrates for the cold-hot impact test were filled with the solution for a cured product, and 1 silicon chip was put into each substrate.
(13) The molding jig and the substrate for the cold thermal shock test were placed in a furnace, and curing treatment was performed at 120 ℃ for 1 hour and further at 150 ℃ for 1 hour to prepare a cured product.
(14) After the temperature in the furnace was lowered to 30 ℃ or lower, the cured product was taken out, and a sample for light resistance test and a sample for cold thermal shock test were prepared according to the above-mentioned methods.
(15) Using the above samples, a light resistance test and a cold-heat shock test were performed by the above methods, and the results are shown in table 3. The cured product was judged to have light resistance when YI, which is an index for the light resistance test, was 10.1. ltoreq.13. The number of cold and hot impact tests was not less than 450 times and not less than 50 times, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 1 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus was judged to be acceptable in all cases.
[ example 2]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 2 to ∈ 2, and the storage stability index θ 2 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 2 was 231g/eq, which is an appropriate value. The initial viscosity was 11.8Pa · s < 1000Pa · s, and the storage viscosity was 17.0Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 2 was 1.44. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 8.3. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of cold and hot shock tests was 500 or more and 50 or more, and it was judged that the test had cold and hot shock resistance.
From the above results, it was confirmed that the resin composition of example 2 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus was judged to be acceptable in all cases.
[ example 3]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. Table 3 shows the results of evaluation by the same method as in example 1, the blend indices α 3 to ∈ 3, and the storage stability index θ 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed by waterTo form (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 3 was 253g/eq, which shows a suitable value. The initial viscosity was 27.3Pa · s < 1000Pa · s, and the storage viscosity was 39.6Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 3 was 1.45. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI, which is an index of the light resistance test of the cured product, was 9.2. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of cold and hot shock tests was 500 or more and 50 or more, and it was judged that the test had cold and hot shock resistance.
From the above results, it was confirmed that the resin composition of example 3 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus was judged to be acceptable in all cases.
[ example 4]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 4 to ∈ 4, and the storage stability index θ 4 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 4 was 208g/eq, which shows a suitable value. The initial viscosity was 11.7Pa · s < 1000Pa · s, and the storage viscosity was 16.7Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 4 was 1.43. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 8.7. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was not less than 450 times and not less than 50 times, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 4 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in total.
[ example 5]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 5 to ∈ 5, and the storage stability index θ 5 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition was 245g/eq, which shows a suitable value. The initial viscosity was 13.2Pa · s < 1000Pa · s, and the storage viscosity was 18.7Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 5 was 1.42. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 8.5. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of cold and hot impact tests was 250 or more and 50 or less, and it was judged that the test had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 5 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus was judged to be acceptable in all cases.
[ example 6]
Using the same method as in example 1, resin compositions were prepared according to tables 1 and 2And a cured product. The results of evaluation by the same method as in example 1, the blend indices α 6 to ∈ 6, and the storage stability index θ 6 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 6 was 221g/eq, which is an appropriate value. The initial viscosity was 18.2Pa · s < 1000Pa · s, and the storage viscosity was 26.6Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 6 was 1.46. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 8.1. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of cold and hot impact tests was 350 or more and 50 or less, and it was judged that the test had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 6 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 7]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 7 to ∈ 7, and the storage stability index θ 7 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 7 was 217g/eq, which shows a suitable value. The initial viscosity was 10.3Pa · s < 1000Pa · s, and the storage viscosity was 14.5Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 7 was 1.41. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 8.3. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was not less than 450 times and not less than 50 times, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 7 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 8]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 8 to ∈ 8, and the storage stability index θ 8 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 8 was 213g/eq, which is an appropriate value. The initial viscosity was 10.6Pa · s < 1000Pa · s, and the storage viscosity was 15.3Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 8 was 1.45. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 7.6. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was 150 or more and 50 or less, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 8 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 9]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 9 to ∈ 9, and the storage stability index θ 9 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 9 was 235g/eq, which shows a suitable value. The initial viscosity was 27.8Pa · s < 1000Pa · s, and the storage viscosity was 28.6Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 9 was 1.03. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 8.0. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of cold and hot impact tests was 350 or more and 50 or less, and it was judged that the test had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 9 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 10]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 10 to ∈ 10, and the storage stability index θ 10 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 10 was 214g/eq, which is an appropriate value. The initial viscosity was 13.2Pa · s < 1000Pa · s, and the storage viscosity was 13.7Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 10 was 1.04. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 7.8. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was not less than 450 times and not less than 50 times, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 10 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 11]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 11 to ∈ 11, and the storage stability index θ 11 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 11 was 228g/eq, which is an appropriate value. The initial viscosity was 41.1Pa · s < 1000Pa · s, and the storage viscosity was 65.8Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 11 was 1.60. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 7.5. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was not less than 450 times and not less than 50 times, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 11 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 12]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 12 to ∈ 12, and the storage stability index θ 12 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 12 was 230g/eq, which is an appropriate value. The initial viscosity was 33.7Pa · s < 1000Pa · s, and the storage viscosity was 48.5Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 12 was 1.44. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI, which is an index of the light resistance test of the cured product, was 9.8. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was not less than 450 times and not less than 50 times, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 12 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 13]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 13 to ∈ 13, and the storage stability index θ 13 are shown in table 3. In addition, the intermediates were confirmed(OR) in the above formula (1)2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 13 was 253g/eq, which shows a suitable value. The initial viscosity was 27.5Pa · s < 1000Pa · s, and the storage viscosity was 40.8Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 13 was 1.48. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI, which is an index of the light resistance test of the cured product, was 9.9. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was not less than 450 times and not less than 50 times, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 13 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 14]
Resin compositions and cured products were prepared in the same manner as in example 1, except that the curing temperature in (12) in example 1 was changed to 110 ℃ for 4 hours and further to 150 ℃ for 1 hour, and in tables 1 and 2. The results of evaluation by the same method as in example 1, the blend indices α 14 to ∈ 14, and the storage stability index θ 14 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 14 was 192g/eq, which is an appropriate value. The initial viscosity was 1.77Pa · s < 1000Pa · s, and the storage viscosity was 3.08Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 14 was 1.74 ≦ 4, and it was determined as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 5.2. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was 150 or more and 50 or less, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 14 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 15]
Resin compositions and cured products were prepared in the same manner as in example 1, except that the curing temperature in (13) in example 1 was changed to 110 ℃ for 4 hours, and in accordance with tables 1 and 2. The results of evaluation by the same method as in example 1, the blend indices α 15 to ∈ 15, and the storage stability index θ 15 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 15 was 214g/eq, which is an appropriate value. The initial viscosity was 4.80Pa · s < 1000Pa · s, and the storage viscosity was 9.23Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 15 was 1.92. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 8.8. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of cold and hot impact tests was 250 or more and 50 or less, and it was judged that the test had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 15 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 16]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 16 to ∈ 16, and the storage stability index θ 16 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 16 was 214g/eq, which shows a suitable value. The initial viscosity was 12.7Pa · s < 1000Pa · s, and the storage viscosity was 15.4Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 16 was 1.21. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI, which is an index of the light resistance test of the cured product, was 12.4. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was not less than 450 times and not less than 50 times, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 16 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 17]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 17 to ∈ 17, and the storage stability index θ 22 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 17 was 238g/eq, which shows a suitable value. The initial viscosity was 18.9Pa · s < 1000Pa · s, and the storage viscosity was 28.9Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 17 was 1.53. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 7.2. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was 150 or more and 50 or less, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 17 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 18]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 18 to ∈ 18, and the storage stability index θ 18 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 18 was 245g/eq, which shows a suitable value. The initial viscosity was 18.2Pa · s < 1000Pa · s, and the storage viscosity was 30.5Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 23 was 1.68. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 7.9. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was 150 or more and 50 or less, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 18 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 19]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 19 to ∈ 19, and the storage stability index θ 19 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 19 was 235g/eq, which shows a suitable value. The initial viscosity was 16.2Pa · s < 1000Pa · s, and the storage viscosity was 24.3Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 24 was 1.50. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 7.3. ltoreq.13, and it was judged that the cured product had light resistance. The number of cold and hot impact tests was 150 or more and 50 or less, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 19 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 20]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results evaluated by the same method as in example 1, and the mixing indexes α 20 to ∈ 20 were storedThe stability index θ 20 is shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 20 was 296g/eq, which shows a suitable value. The initial viscosity was 25.2Pa · s < 1000Pa · s, and the storage viscosity was 100.8Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 20 was 4 ≦ 4, and it was determined as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 7.8. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of cold and hot impact tests was 50 or more times, and it was judged that the test had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 20 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 21]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 21 to ∈ 21, and the storage stability index θ 21 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 21 was 270g/eq, which is an appropriate value. The initial viscosity was 20.3Pa · s < 1000Pa · s, and the storage viscosity was 75.1Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 21 was 3.7. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 8.4. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of cold and hot impact tests was 50 or more times, and it was judged that the test had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 21 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 22]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 22 to ∈ 22, and the storage stability index θ 22 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 22 was 208g/eq, which shows a suitable value. The initial viscosity was 21.9Pa · s < 1000Pa · s, and the storage viscosity was 87.6Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 22 was 4 ≦ 4, and was determined to be a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 8.2. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of cold and hot impact tests was 50 or more times, and it was judged that the test had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 22 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 23]
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The results of evaluation by the same method as in example 1, the blend indices α 23 to ∈ 23, and the storage stability index θ 23 are shown in table 3. In addition, it was confirmed that (OR) in the above formula (1) is an intermediate2) Is hydrolyzed to generate (OH).
The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of example 23 was 190g/eq, which is an appropriate value. The initial viscosity was 14.4Pa · s < 1000Pa · s, and the storage viscosity was 100.8Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 23 was 1.2. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI, which is an index of the light resistance test of the cured product, was 13.0. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of cold and hot shock tests was 500 or more and 50 or more, and it was judged that the test had cold and hot shock resistance.
From the above results, it was confirmed that the resin composition of example 23 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 24]
The resin composition was produced and evaluated in the following manner.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) According to the composition ratio shown in table 1, an alkoxysilane compound and THF were charged into a flask charged with a stirrer in an atmosphere of 25 ℃ and mixed and stirred, and then water and a hydrolytic condensation catalyst were added and mixed and stirred.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 7 hours while refluxing (refluxing step).
(4) After the reaction was completed, the temperature was cooled to 25 ℃, and then the cooling tube was removed from the flask, and after the reflux step was completed, a sample solution (intermediate) was collected.
(5) After the reflux step was completed, (OR) of the following formula (1) was confirmed by measuring H-NMR of the sample solution (intermediate)2) Is hydrolyzed to generate (OH).
(6) The Bis-a epoxy resin shown in table 1 was added to the intermediate, mixed and stirred until uniform, and then the mixture was placed on an evaporator, and distilled off at 400Pa and 50 ℃ for 1 hour, and further distilled off at 80 ℃ for 5 hours, and a dehydration condensation reaction was carried out (dehydration condensation step).
(7) After the reaction, the reaction mixture was cooled to 25 ℃ to obtain a resin composition. The amount of residual alkoxy groups calculated from the resin composition and an internal standard substance is 0% to 5%.
(8) The mixing indices α 24 to ∈ 24 in the resin composition are shown in table 3.
(9) Further, the epoxy equivalent Weight (WPE), initial viscosity, and storage viscosity of the resin composition obtained in (6) were measured by the above-mentioned methods. Further, the storage stability index θ 24 was obtained and shown in table 3.
The epoxy equivalent Weight (WPE) of the resin composition of example 24 was 233g/eq, which is an appropriate value. The initial viscosity was 11.8Pa · s < 1000Pa · s, and the storage viscosity was 16.8Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 24 was 1.42. ltoreq.4, and it was judged as a resin composition having storage stability.
Resin compositions and cured products were prepared in the same manner as in example 1, as shown in Table 2. As shown in table 3, the results of evaluation by the same method as in example 1 indicate that the cured product has light resistance, where YI, which is an index of the light resistance test, is 8.3. ltoreq.13. In addition, the number of cold and hot shock tests was 500 or more and 50 or more, and it was judged that the test had cold and hot shock resistance.
From the above results, it was confirmed that the resin composition of example 24 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 25]
The resin composition was produced and evaluated in the following manner.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) According to the composition ratio of table 1, Bis-a1 epoxy resin, alkoxysilane compound and THF in an amount equal to half the total mass were charged into a flask charged with a stirrer under an atmosphere of 25 ℃ and mixed with stirring, and then water and a hydrolytic condensation catalyst were further added and mixed with stirring.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 7 hours while refluxing (refluxing step).
(4) After the reaction was completed, the temperature was cooled to 25 ℃, and then the cooling tube was removed from the flask, and after the reflux step was completed, a sample solution (intermediate) was collected.
(5) After the reflux step was completed, (OR) of the following formula (1) was confirmed by measuring H-NMR of the sample solution (intermediate) 2) Is hydrolyzed to generate (OH).
(6) The intermediate was added with the Bis-A epoxy resin in an amount equal to the remaining half of Table 1 and mixed and stirred until uniform, and then placed on an evaporator, and after 1 hour of distillation at 400Pa and 50 ℃, further 5 hours of distillation at 80 ℃ were carried out while carrying out dehydration condensation reaction (dehydration condensation step).
(7) After the reaction, the reaction mixture was cooled to 25 ℃ to obtain a resin composition. The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 0% to 5%.
(8) The mixing indices α 25 to ∈ 25 in the resin composition are shown in table 3.
(9) Further, the epoxy equivalent Weight (WPE), initial viscosity, and storage viscosity of the resin composition obtained in (6) were measured by the above-mentioned methods. Further, the storage stability index θ 25 was obtained and shown in table 3.
The epoxy equivalent Weight (WPE) of the resin composition of example 25 was 232g/eq, which is an appropriate value. The initial viscosity was 11.8Pa · s < 1000Pa · s, and the storage viscosity was 16.7Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 25 was 1.42. ltoreq.4, and it was judged as a resin composition having storage stability.
Resin compositions and cured products were prepared in the same manner as in example 1, as shown in Table 2. As shown in table 3, the results of evaluation by the same method as in example 1 indicate that the cured product has light resistance, where YI, which is an index of the light resistance test, is 8.3. ltoreq.13. In addition, the number of cold and hot shock tests was 500 or more and 50 or more, and it was judged that the test had cold and hot shock resistance.
From the above results, it was confirmed that the resin composition of example 25 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
[ example 26]
The resin composition was produced and evaluated in the following manner.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) In addition to the P-MS component, Bis-A1 epoxy resin, an alkoxysilane compound and THF were charged in a flask charged with a stirrer in accordance with the composition ratio shown in Table 1 at 25 ℃ and mixed under stirring, and then water and a hydrolytic condensation catalyst were further added and mixed under stirring.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 7 hours while refluxing (refluxing step).
(4) After the reaction was completed, the temperature was cooled to 25 ℃, and then the cooling tube was removed from the flask, and after the reflux step was completed, a sample solution (intermediate) was collected.
(5) After the reflux step was completed, (OR) of the following formula (1) was confirmed by measuring H-NMR of the sample solution (intermediate)2) Is hydrolyzed to generate (OH).
(6) After the solution after the reflux step was distilled off at 400Pa and 50 ℃ for 1 hour using an evaporator, a dehydration condensation reaction was carried out while further distilling off at 80 ℃ for 5 hours (dehydration condensation step).
(7) After the reaction was completed, it was cooled to 25 ℃ and the total amount of mass equal to P-MS was added in accordance with the composition ratio of Table 1 and mixed and stirred until uniform to obtain a resin composition. The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance is 4.5% to 5%.
(8) The mixing indices α 26 to ∈ 26 in the resin composition are shown in table 3.
(9) Further, the epoxy equivalent Weight (WPE), initial viscosity, and storage viscosity of the resin composition obtained in (7) were measured by the above-mentioned methods. Further, the storage stability index θ 26 was obtained and shown in table 3.
The epoxy equivalent Weight (WPE) of the resin composition of example 26 was 230g/eq, which is an appropriate value. The initial viscosity was 14.5Pa · s < 1000Pa · s, and the storage viscosity was 49.3Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 26 was 3.4. ltoreq.4, and was judged to be a resin composition having storage stability.
Resin compositions and cured products were prepared in the same manner as in example 1, as shown in Table 2. As shown in table 3, the results of evaluation by the same method as in example 1 indicate that the cured product has a light resistance when YI, which is an index of the light resistance test, is 10.6. ltoreq.13. In addition, the number of cold and hot impact tests was 50 or more times, and it was judged that the test had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 26 had fluidity and storage stability, and the cured product of the resin composition had light resistance and thermal shock resistance, and thus the resin composition was judged to be acceptable in all cases.
Comparative example 1
Resin compositions were prepared in the same manner as in example 1, according to table 1. The amount of residual alkoxy groups calculated from the resin composition and the internal standard was 17% to 5%.
The results of the evaluation by the same method as in example 1, the blend indices α 27 to ∈ 27, and the storage stability index θ 27 are shown in table 3.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of comparative example 1 was 368g/eq, which is an appropriate value. Further, the initial viscosity was > 1000 pas and the storage viscosity was > 1000 pas, both of which did not exhibit fluidity, and the storage stability index θ 27 could not be calculated.
Further, the resin composition had a storage viscosity of > 1000 pas and had no fluidity, and thus a cured product could not be produced.
From the above results, it was judged that the resin composition of comparative example 1 had no flowability, storage stability could not be calculated, and a cured product could not be produced, and thus it was judged as a failure in total.
Comparative example 2
Resin compositions and cured products were prepared in accordance with tables 1 and 2 in the same manner as in example 1. The amount of residual alkoxy groups calculated from the resin composition and the internal standard was 8% > 5%.
The results of the evaluation by the same method as in example 1, the blend indices α 28 to ∈ 28, and the storage stability index θ 28 are shown in table 3.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of comparative example 2 was 295g/eq, which is an appropriate value. The initial viscosity was 30.5Pa · s < 1000Pa · s, and the storage viscosity was 45.1Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 13 was 1.48. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, YI as an index of the light resistance test of the cured product was 8.4. ltoreq.13, and it was judged that the cured product had light resistance. In addition, the number of hot and cold shock tests was 0 times < 50 times, and it was judged that the test had no hot and cold shock resistance.
From the above results, it was confirmed that the resin composition of comparative example 2 had fluidity and storage stability, but the cured product produced from the resin composition had light resistance but no thermal shock resistance, and was judged to be generally defective.
Comparative example 3
Resin compositions were prepared in the same manner as in example 1, according to table 1. The results of evaluation by the same method as in example 1, the blend indices α 29 to ∈ 29, and the storage stability index θ 29 are shown in table 3.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of comparative example 3 was 233g/eq, which is an appropriate value. Further, the initial viscosity was 3.8 pas < 1000 pas, the storage viscosity was > 1000 pas, and no fluidity was exhibited. The storage stability index θ 28 is 263 or more and > 4, and is judged not to have storage stability.
Further, the resin composition had a storage viscosity of > 1000 pas and had no fluidity, and thus a cured product could not be produced.
From the above results, it was judged that the resin composition of comparative example 3 had no flowability or storage stability, and further, a cured product could not be produced, and thus it was judged as a failure in total.
Comparative example 4
Resin compositions were prepared in the same manner as in example 1, according to table 1. The results of evaluation by the same method as in example 1, the blend indices α 30 to ∈ 30, and the storage stability index θ 30 are shown in table 3.
As shown in table 3, the epoxy equivalent Weight (WPE) of the resin composition of comparative example 4 was 184g/eq, which is an appropriate value. Further, the initial viscosity was 10.5 pas < 1000 pas, the storage viscosity was > 1000 pas, and no fluidity was exhibited. The storage stability index θ 30 is 95 or more and > 4, and is judged not to have storage stability.
Further, the resin composition had a storage viscosity of > 1000 pas and had no fluidity, and thus a cured product could not be produced.
From the above results, it was judged that the resin composition of comparative example 4 had no flowability or storage stability, and further, a cured product could not be produced, and thus it was judged as a failure in total.
Comparative example 5
Resin compositions were prepared in the same manner as in example 1, according to table 1. The results of evaluation by the same method as in example 1, the blend indices α 31 to ∈ 31, and the storage stability index θ 31 are shown in table 3.
As shown in Table 3, the epoxy equivalent Weight (WPE) of the resin composition of comparative example 5 could not be measured. Further, the initial viscosity was 24.0 pas < 1000 pas, the storage viscosity was > 1000 pas, and no fluidity was exhibited. The storage stability index θ 30 is greater than 41 and > 4, and is judged not to have storage stability.
Further, the resin composition had a storage viscosity of > 1000 pas and had no fluidity, and thus a cured product could not be produced.
From the above results, it was judged that the resin composition of comparative example 5 had no flowability or storage stability, and further, a cured product could not be produced, and therefore, it was judged to be a failure in total.
Comparative example 6
Cured products were prepared in the same manner as in example 1, and according to Table 2. The results of evaluation by the same method as in example 1 are shown in table 3.
YI, which is an index of the light resistance test of the cured product, is 16.9 > 13, and it is judged that the cured product has no light resistance. In addition, the number of cold and hot shock tests was 500 or more and 50 or more, and it was judged that the test had cold and hot shock resistance.
From the above results, it was found that the cured product of comparative example 6 was judged to be defective in its entirety because it had no light resistance although it had thermal shock resistance.
Comparative example 7
The solutions a and B of the silicone resin were mixed and stirred at a mass ratio of 1: 1, and the resulting mixture was prepared into a solution for a cured product according to table 2 in the same manner as in example 1.
The curing solution was injected into the molding jig and the 10 substrates for the cold-hot impact test in the same manner as in example 1, and 1 silicon chip was further put into each substrate.
The molding jig and the substrate for the cold thermal shock test were placed in a furnace, and curing was performed at 70 ℃ for 1 hour and at 150 ℃ for 5 hours to prepare a cured product.
The results of evaluation by the same method as in example 1 are shown in table 3.
When YI, which is an index of the light resistance test of the cured product, is 2.0. ltoreq.13, the cured product is judged to have light resistance. However, the number of hot and cold shock tests was 0 times < 50 times, and it was judged that the test had no hot and cold shock resistance.
From the above results, it was judged that the cured product of comparative example 7 was not heat and cold shock resistant although it had light resistance, and thus was judged to be a total failure.
Comparative example 8
According to Table 1, epoxy resin A2 and epoxy resin A3 were added to a reaction vessel, immersed in an oil bath at 85 ℃ and stirred to dissolve, and P-MTMS and DBTDL were added and mixed.
Further, while purging with nitrogen, the temperature of the oil bath was increased to 105 ℃ to carry out dealcoholization reaction for 8 hours.
Subsequently, the mixture was cooled to 60 ℃ and then reduced in pressure to 12000Pa to remove the dissolved alcohol, thereby obtaining a resin composition. The amount of residual alkoxy groups calculated from the resin composition and the internal standard was 11% > 5%.
The results of evaluation by the same method as in example 1 and the storage stability index θ 32 are shown in table 3.
The epoxy equivalent Weight (WPE) of the resin composition of comparative example 8 was 282g/eq, which showed a suitable value. Further, the initial viscosity was 0.15Pa · s < 1000Pa · s, and the storage viscosity was 0.27Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 32 was 1.80. ltoreq.4, and it was judged as a resin composition having storage stability.
Further, according to the compounding ratio shown in table 2, cured products were produced and evaluated in the same manner as in example 1, and as a result, the cured product of comparative example 8 was judged to have no thermal shock resistance when the number of thermal shock tests was 0 < 50. In addition, the sample prepared for the light resistance test had minute cracks and could not be measured.
From the above results, it was judged that the cured products of comparative example 8 were judged as failed in total.
Comparative example 9
Resin compositions were prepared in the same manner as in example 1, according to table 1. The results of evaluation by the same method as in example 1 and the mixing indices α 33 to ∈ 33 are shown in table 3. Further, (OR) of the intermediate in the above formula (1)2) The hydrolysis reaction did not proceed normally because much of the residue remained without being hydrolyzed. Therefore, a normal resin composition could not be obtained, and it was judged as defective. The amount of residual alkoxy groups calculated from the resin composition and an internal standard substance is 100% or more and > 5%.
From the results shown in tables 1 to 3, it is understood that the resin compositions (examples 1 to 26) obtained by mixing the epoxy resin and the specific alkoxysilane compound at a specific ratio and cohydrolytic condensation are excellent in fluidity and storage stability. Further, cured products using these resin compositions are excellent in light resistance and thermal shock resistance.
Figure BDA0000041312520000751
TABLE 2
Unit: mass%
Figure BDA0000041312520000761
Figure BDA0000041312520000771
The condensation rate of the alkoxysilane and the condensation rate of the intermediate in the modified resin composition are specifically described below by referring to examples and comparative examples.
First, methods for evaluating physical properties in examples 27 to 35 and comparative examples 10 to 14 are described below.
The residual alkoxy group amount, epoxy equivalent (WPE), viscosity, and mixing index α to η of the modified resin composition were determined by the same methods as described above.
< calculation of condensation Rate of intermediate >
The condensation rate of the intermediate was determined from the Si-NMR measurement results of the collected sample solution (intermediate) after the completion of the reflux step in the following order.
(1) Preparation of Cr solution: chloroform-d (Wako pure chemical industries, Ltd.) was added to 6.3 mass% of chromium acetylacetonate (manufactured by Sigma-Aldrich Co., Ltd.) and dissolved therein.
(2) 200mg of the sample solution after the completion of the refluxing step was weighed in a sample bottle, and the Cr solution was added thereto to adjust the amount to 1 g.
(3) Transferring the solution of (2) to the diameter
Figure BDA0000041312520000781
Si-NMR was measured under the following conditions in the NMR tube (1).
Fourier transform nuclear magnetic resonance apparatus: "alpha-400 type" manufactured by Nippon electronic Co., Ltd.,
and (4) nuclear seed: the amount of Si is controlled by the control system,
cumulative number of times: 4000 times
(4) The condensation rate K of the intermediate was determined according to the following formula.
A condensation ratio (%) (D1X 1+ D2X 2+ T1X 1+ T2X 2+ T3X 3) </or
{(D0+D1+D2)×2+(T0+T1+T2+T3)×3}×100…(10)
Wherein,
d0: the total of integrated values of signals derived from the D0 structure represented by formula (11) below of an alkoxysilane compound having n ═ 1 in formula (1).
D1: the total of integrated values of signals derived from the D1 structure represented by formula (12) below of an alkoxysilane compound having n ═ 1 in formula (1).
D2: the total of integrated values of signals derived from the D2 structure represented by formula (12) below of an alkoxysilane compound having n ═ 1 in formula (1).
T0: the total of integrated values of signals derived from the T0 structure represented by formula (13) below of the alkoxysilane compound represented by formula (1) wherein n is 2.
T1: the total of integrated values of signals derived from the T1 structure represented by formula (14) below of the alkoxysilane compound represented by formula (1) wherein n is 2.
T2: the total of integrated values of signals derived from the T2 structure represented by formula (14) below of the alkoxysilane compound represented by formula (1) wherein n is 2.
T3: the total of integrated values of signals derived from the T3 structure represented by formula (14) below of the alkoxysilane compound represented by formula (1) wherein n is 2.
Chemical formula 8
Figure BDA0000041312520000791
D0 structure
In the formula (11), R is any organic group or H.
Chemical formula 9
Figure BDA0000041312520000792
D1 Structure D2 Structure
In the formula (12), R is any organic group or H.
Chemical formula 10
Figure BDA0000041312520000793
T0 structure
In the formula (13), R is any organic group or H.
Chemical formula 11
Figure BDA0000041312520000794
T1 structure T3 structure T2 structure
In the formula (14), R is any organic group or H.
< calculation of condensation Rate of alkoxysilane Compound of modified resin composition >
The condensation rate of the alkoxysilane compound in the modified resin composition is determined as the condensation rate L (%) from the Si-NMR measurement result of the sample solution collected after the completion of the dehydration condensation step, by the same method as the method for calculating the condensation rate of the intermediate.
< calculation of storage stability index θ and storage stability of resin composition >
The storage stability in the resin composition was evaluated by the storage stability index θ shown in the following formula (9).
Storage stability index θ (storage viscosity)/(initial viscosity) … (9)
The container containing the resin composition immediately after the production was sealed, and after adjusting the temperature at 25 ℃ for 2 hours, the viscosity at 25 ℃ was measured and used as the "initial viscosity".
Further, the container containing the resin composition was sealed, and stored in a constant temperature incubator at 60 ℃ for 16.5 days. After storage, the viscosity at 25 ℃ was measured and used as "storage viscosity".
When the resin composition had fluidity (viscosity of 1000Pa · s or less) and the storage stability index θ was 6 or less, it was judged to have storage stability, and the judgment was made as follows.
0≤θ≤4 ◎
4<θ≤6 ○
< test on light resistance of cured product >
The light resistance of the cured product of the resin composition was evaluated by the following method.
(1) A cured product prepared by the method described below was cured in a solution to prepare a cured product having a thickness of 20 mm. times.10 mm. times.3 mm.
(2) The cured product was covered with a black mask having a hole diameter of 5.5mm of 25 mm. times.15 mm. times.1.2 mm thick to prepare a sample for light resistance test.
(3) An apparatus was prepared so that the above-mentioned sample in an incubator thermostatically maintained at 50 ℃ could be irradiated with UV light from a UV irradiation apparatus (manufactured by Ushio inc. "Spot Cure SP7-250 DB") via an optical fiber.
(4) The sample was placed in a 50 ℃ incubator with a black mask on top.
(5) 2W/cm was irradiated from the upper part of the black mask in such a manner that UV light could be irradiated into a hole having a diameter of 5.5mm2UV light for 96 hours.
(6) The sample after UV irradiation was measured by a spectrocolorimeter ("SD 5000", manufactured by Nippon Denshoku industries Co., Ltd.) in which the opening of the integrating sphere was modified to have a diameter of 10 mm.
(7) According to "ASTM D1925-70 (1988): the Test Method for Yellowness Index of Plastics (Test Method for Yellowness Index of Plastics) "determines the Yellowness Index (YI). When YI is 13 or less, it is judged to have light resistance.
< Cold thermal shock test of cured product >
The cold and heat shock properties of the cured product of the resin composition were evaluated by the following methods.
(1) The following substrate and silicon chip were prepared.
(1-1) substrate: manufactured by Solvay Advanced Polymers K.K. "AMODEL A-4122NL WH 905" (having a depression of diameter 10mm X depth 1.2mm in the center of a plate of 15mm X thickness 2 mm)
(1-2) silicon chips (commercial silicon wafers were cut into 5 mm. times.5 mm. times.200 μm in thickness)
(2) The solution for curing material prepared by the method described later was poured onto the substrate to prepare 10 substrates each containing 1 silicon chip, and the substrates were cured to prepare samples for a thermal shock test.
(3) The above sample was set in a cold-hot impact device ("TSE-11-A" manufactured by ESPEC CORP. to obtain a cold-hot impact material having a temperature of "(-40 ℃ to 120 ℃)/cycle: the exposure time was 14 minutes and the warming and cooling time was 1 minute ".
(4) After 50 cycles of thermal cycles, the samples were taken out, and the number of specimens was recorded by spraying a penetrant liquid ("MICRO CHECK") under a magnifying glass to visually observe the presence or absence of abnormalities (peeling or cracks).
(5) The sample in which abnormality was not confirmed in (4) above was again placed in the apparatus, and the evaluation was performed in the same manner after 50 cycles of thermal cycling, and then the evaluation was performed in the same manner after 100 cycles of thermal cycling. These operations were repeated to evaluate.
(6) The evaluation was interrupted when abnormality was observed in 2 out of 10 samples, and the "number of thermal shock resistance" was obtained (number of interrupted thermal cycles) - (50) ".
When the number of times of the thermal shock resistance is 50 or more, it is determined that the thermal shock resistance is sufficient for practical use.
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)
Trade name: "AER 2600" manufactured by Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described methods are as follows.
Epoxy equivalent (WPE): 187g/eq
Viscosity (25 ℃): 14.3 pas
(1-2) epoxy resin B: 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate (hereinafter, referred to as alicyclic epoxy resin)
Trade name: "CEL 2021P" manufactured by Daicel Chemical Industries, Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described methods are as follows.
Epoxy equivalent (WPE): 131g/eq
Viscosity (25 ℃): 227mPa · s
(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter, GPTMS)
Trade name: KBM-403 manufactured by shin-Etsu chemical industries, Ltd "
(3) Alkoxysilane compound I: phenyltrimethoxysilane (hereinafter referred to as PTMS)
Trade name: KBM-103, manufactured by shin-Etsu chemical industries, Ltd "
(4) Alkoxysilane compound J: dimethyldimethoxysilane (hereinafter referred to as DMDMS)
Trade name: KBM-22, manufactured by shin-Etsu chemical industries, Ltd "
(5) Alkoxysilane compound K: tetraethoxysilane (hereinafter, referred to as TEOS)
Trade name: KBE-04, manufactured by shin-Etsu chemical industries, Ltd "
(6) Solvent(s)
(6-1) tetrahydrofuran: wako pure chemical industries, Ltd., a stabilized form (hereinafter referred to as THF) was not contained
(6-2) tert-Butanol: "Heguang pure chemical" manufactured by Heguang pure chemical industries, Ltd. (hereinafter referred to as "t-BuOH")
(7) Hydrolytic condensation catalyst
(7-1) dibutyl dimethoxy tin (hereinafter, referred to as DBTDM): manufactured by Sigma-Aldrich Co
(7-2) dioctyltin diacetate (hereinafter, referred to as DOTDA): "Neostann U-820" manufactured by Nidong Kabushiki Kaisha "
(7-3) dibutyltin dilaurate (hereinafter, referred to as DBTDL): wako pure chemical industries, Ltd
(8) Curing agent: "4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride ═ 70/30"
Trade name: manufactured by Nissan chemical and physical Co., Ltd. "RIKACID MH-700G"
(9) Curing accelerator: amine compound
Trade name: "U-CAT 18X" manufactured by San-Apro Ltd "
(10) Silicone resin: "SCR-1012 (solutions A and B)" manufactured by shin-Etsu chemical industries, Ltd "
(11) Internal standard substance
1, 1, 2, 2-tetrabromoethane: manufactured by Tokyo chemical industry Co Ltd
[ example 27]
The resin composition was prepared by the following procedure.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) The Bis-a epoxy resin, the alkoxysilane compound, and THF were charged into a flask charged with a stirrer in accordance with the composition ratios shown in table 4 below under an atmosphere of 25 ℃ and mixed and stirred, and then water and a hydrolytic condensation catalyst were added and mixed and stirred.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 25 hours while refluxing (refluxing step).
(4) After the reaction was completed, the temperature was cooled to 25 ℃, and then the cooling tube was removed from the flask, and after the reflux step was completed, a sample solution (intermediate) was collected.
(5) After the reflux step was completed, Si-NMR of the sample solution was measured, and the condensation rate K1 of the intermediate was determined from the above formula (10). The condensation rate K1 (%) of the intermediate is 80.1% or more and 78% or less.
(6) After the solution after the reflux step was distilled off at 400Pa and 50 ℃ for 1 hour using an evaporator, a dehydration condensation reaction was carried out while further distilling off at 80 ℃ for 10 hours (dehydration condensation step).
(7) And after the dehydration condensation reaction is finished, cooling to 25 ℃ to obtain a resin composition, and collecting a sample solution.
(8) After the completion of the dehydration condensation step, Si-NMR of the sample solution was measured, and the condensation rate L1 of the modified resin composition was determined from the above formula (10). The condensation rate L1 (%) -86.6% or more of the modified resin composition was 80% or more. In addition, the modified resin composition has a residual alkoxy group content of 0% to 5%.
(9) The mixing indices α 34 to ∈ 34 of the resin compositions are shown in table 6 below.
(10) Further, the epoxy equivalent Weight (WPE), initial viscosity, and storage viscosity of the resin composition obtained in (6) were measured by the above-mentioned methods. Further, the storage stability index θ 34 was obtained and is shown in table 6.
The epoxy equivalent Weight (WPE) of the resin composition of example 27 was 220g/eq, which is an appropriate value. The initial viscosity was 12.7Pa · s < 1000Pa · s, and the storage viscosity was 32.5Pa · s < 1000Pa · s, both of which were liquid having fluidity. The resin composition was judged to have improved storage stability because the storage stability index θ 34 was 2.6. ltoreq.4, and the flowability was excellent.
Next, using the resin composition, a cured product was produced in the following order and evaluated.
(11) The resin composition, the curing agent and the curing accelerator were mixed and stirred at a composition ratio shown in table 5 below in an atmosphere of 25 ℃, and degassed under vacuum to obtain a solution for a cured product.
(12) A molding jig was prepared by sandwiching silicone rubber having a thickness of 3mm and a shape of コ with 2 stainless steel plates coated with a release agent so that a cured product prepared by the molding jig was about 50mm × about 20mm × 3mm thick.
(13) The molding jig and the 10 substrates for the cold-hot impact test were filled with the solution for a cured product, and 1 silicon chip was put into each substrate.
(14) The molding jig and the substrate for the cold thermal shock test were placed in a furnace, and curing treatment was performed at 120 ℃ for 1 hour and further at 150 ℃ for 1 hour to prepare a cured product.
(15) After the temperature in the furnace was lowered to 30 ℃ or lower, the cured product was taken out, and a sample for light resistance test and a sample for cold thermal shock test were prepared according to the above-mentioned methods.
(16) Using the above samples, a light resistance test and a thermal shock test were performed by the above methods, and the results are shown in table 6 below. The index YI of the cured product in the light resistance test was 11.9. ltoreq. 13, and it was judged that the cured product had sufficient light resistance in practical use. In addition, the number of cold and hot impact tests was 350 or more and 50 or less, and it was judged that the test had sufficient cold and hot impact resistance in practical use.
From the above results, it is understood that the resin composition of example 27 has good fluidity and excellent storage stability, and that the cured product of the resin composition has sufficient light resistance and thermal shock resistance in practical use, and is judged as being acceptable in all cases.
[ example 28]
Resin compositions and cured products thereof were prepared in the same manner as in example 27, as shown in tables 4 and 5 below.
The resin composition and the cured product thereof were evaluated in the same manner as in example 27. The evaluation results, blend indices α 35 to ∈ 35, and storage stability index θ 35 are shown in table 6 below.
The condensation rate K2 (%) of the intermediate is 78.2% or more and 78% or less.
The condensation rate L2 (%) > 81.8% or more of the modified resin composition was 80% or more.
The modified resin composition has a residual alkoxy group content of 0% to 5%.
As shown in table 6 below, the resin composition of example 28 had an epoxy equivalent Weight (WPE) of 233g/eq, which is an appropriate value.
The initial viscosity was 15.9 pas < 1000 pas, and the storage viscosity was 53.8 pas < 1000 pas, which gave good fluidity. The resin composition having an improved storage stability, which is excellent in fluidity and has a storage stability index θ 35 of 3.4. ltoreq.4, is known.
Further, YI as an index of the light resistance test of the cured product was 8.1. ltoreq.13, and it was judged that the cured product had sufficient light resistance in practical use. The number of times of the cold and hot shock test is more than or equal to 50 times, and the cold and hot shock resistance is judged to be sufficient in practical application.
From the above results, it was confirmed that the resin composition of example 28 was excellent in fluidity, improved in storage stability, and the cured product of the resin composition had sufficient light resistance and thermal shock resistance in practical use, and was judged to be acceptable in total.
[ example 29]
Resin compositions and cured products thereof were prepared in the same manner as in example 27, as shown in tables 4 and 5 below.
The resin composition and the cured product thereof were evaluated in the same manner as in example 26. The evaluation results, blend indices α 36 to ∈ 36, and storage stability index θ 36 are shown in table 6.
The condensation rate K3 (%) of the intermediate is 85.3% or more and 78%.
The condensation rate L3 (%) -86.8% or more of the modified resin composition was 80% or more.
The modified resin composition has a residual alkoxy group content of 0% to 5%.
As shown in table 6 below, the resin composition of example 29 had an epoxy equivalent Weight (WPE) of 242g/eq, which is a suitable value.
The initial viscosity was 14.3Pa · s < 1000Pa · s, and the storage viscosity was 41.0Pa · s < 1000Pa · s, both of which were liquid having fluidity. The resin composition having an improved storage stability, which is excellent in fluidity and has a storage stability index θ 36 of 2.9. ltoreq.4, is known.
The YI as an index of the light resistance test of the cured product was 8.9. ltoreq.13, and it was judged that the cured product had sufficient light resistance in practical use.
The number of times of the cold and hot shock test is more than or equal to 50 times, and the cold and hot shock resistance is judged to be sufficient in practical application.
From the above results, it was confirmed that the resin composition of example 29 was excellent in fluidity, improved in storage stability, and the cured product of the resin composition had sufficient light resistance and thermal shock resistance in practical use, and thus was judged to be acceptable in total.
[ example 30]
Resin compositions and cured products thereof were prepared in the same manner as in example 27, as shown in tables 4 and 5 below.
The resin composition and the cured product thereof were evaluated in the same manner as in example 27. The evaluation results, blend indices α 37 to ∈ 37, and storage stability index θ 37 are shown in table 6.
The condensation rate K4 (%) of the intermediate is 87.4% or more than 78%.
The condensation rate L4 (%) > 88.8% or more of the modified resin composition was 80% or more.
The modified resin composition has a residual alkoxy group content of 0% to 5%.
As shown in table 6 below, the epoxy equivalent Weight (WPE) of the resin composition of example 30 was 238g/eq, which is an appropriate value.
The initial viscosity was 15.6Pa · s < 1000Pa · s, and the storage viscosity was 24.9Pa · s < 1000Pa · s, both of which were liquid having fluidity. The resin composition having an improved storage stability, i.e., a storage stability index θ 37 of 1.6. ltoreq.4, is known to have excellent fluidity.
The YI as an index of the light resistance test of the cured product was 8.8. ltoreq.13, and it was judged that the cured product had sufficient light resistance in practical use.
The number of cold and hot impact tests is 150 or more than 50, and the test result is judged to have sufficient cold and hot impact resistance in practical application.
From the above results, it was confirmed that the resin composition of example 30 was excellent in fluidity, improved in storage stability, and the cured product of the resin composition had sufficient light resistance and thermal shock resistance in practical use, and was judged to be acceptable in total.
[ example 31]
Resin compositions and cured products thereof were prepared in the same manner as in example 27, as shown in tables 4 and 5 below.
The resin composition and the cured product thereof were evaluated in the same manner as in example 27. The evaluation results, blend indices α 38 to ∈ 38, and storage stability index θ 38 are shown in table 6 below.
The condensation rate K5 (%) of the intermediate is 82.6% or more and 78% or less.
The condensation rate L5 (%) -87.2% or more of the modified resin composition was 80% or more.
The modified resin composition has a residual alkoxy group content of 0% to 5%.
As shown in table 6 below, the resin composition of example 31 had an epoxy equivalent Weight (WPE) of 245g/eq, which is an appropriate value.
The initial viscosity was 17.3Pa · s < 1000Pa · s, and the storage viscosity was 50.2Pa · s < 1000Pa · s, both of which were liquid having fluidity. The resin composition having an improved storage stability, which is excellent in fluidity and has a storage stability index θ 38 of 2.9. ltoreq.4, is known.
The YI as an index of the light resistance test of the cured product was 8.2. ltoreq.13, and it was judged that the cured product had sufficient light resistance in practical use.
The number of cold and hot impact tests is 150 or more than 50, and the test result is judged to have sufficient cold and hot impact resistance in practical application.
From the above results, it was confirmed that the resin composition of example 31 was excellent in fluidity, improved in storage stability, and the cured product of the resin composition had sufficient light resistance and thermal shock resistance in practical use, and was judged to be acceptable in total.
[ example 32]
Resin compositions and cured products thereof were prepared in the same manner as in example 27, as shown in tables 4 and 5 below.
The resin composition and the cured product thereof were evaluated in the same manner as in example 27. The evaluation results, blend indices α 39 to ∈ 39, and storage stability index θ 39 are shown in table 6 below.
The condensation rate K6 (%) of the intermediate is 82.8% or more and 78% or less.
The condensation rate L6 (%). cndot.83.2% or more of the modified resin composition was 80% or more.
The modified resin composition has a residual alkoxy group content of 0% to 5%.
As shown in table 6 below, the resin composition of example 32 had an epoxy equivalent Weight (WPE) of 253g/eq, which is an appropriate value.
The initial viscosity was 24.3Pa · s < 1000Pa · s, and the storage viscosity was 86.3Pa · s < 1000Pa · s, both of which were liquid having fluidity. The resin composition having an improved storage stability, i.e., a storage stability index θ 39 of 3.6. ltoreq.4, is known to have excellent fluidity.
YI as an index of the light resistance test of the cured product was 9.7. ltoreq.13, and it was judged that the cured product had sufficient light resistance in practical use. In addition, the number of times of the cold and hot impact test was not less than 250 times and not less than 50 times, and it was judged that the test had sufficient cold and hot impact resistance in practical use.
From the above results, it was confirmed that the resin composition of example 32 was excellent in fluidity, improved in storage stability, and the cured product of the resin composition had sufficient light resistance and thermal shock resistance in practical use, and was judged to be acceptable in total.
[ example 33]
Resin compositions and cured products thereof were prepared in the same manner as in example 27, as shown in tables 4 and 5 below.
The resin composition and the cured product thereof were evaluated in the same manner as in example 27. The evaluation results, blend indices α 40 to ∈ 40, and storage stability index θ 40 are shown in table 6 below.
The condensation rate K7 (%) of the intermediate is 83.5% or more and 78%.
The condensation rate L7 (%) -84.4% or more of the modified resin composition was 80% or more.
The modified resin composition has a residual alkoxy group content of 0% to 5%.
As shown in table 6 below, the resin composition of example 33 had an epoxy equivalent Weight (WPE) of 210g/eq, which is an appropriate value.
The initial viscosity was 12.8Pa · s < 1000Pa · s, and the storage viscosity was 39.8Pa · s < 1000Pa · s, both of which were liquid having fluidity. The resin composition having an improved storage stability, i.e., a storage stability index θ 33 of 3.1. ltoreq.4, is known to have excellent fluidity.
YI as an index of the light resistance test of the cured product was 7.5. ltoreq.13, and it was judged that the cured product had sufficient light resistance in practical use. In addition, the number of cold and hot impact tests was 350 or more and 50 or less, and it was judged that the test had sufficient cold and hot impact resistance in practical use.
From the above results, it was confirmed that the resin composition of example 33 was excellent in fluidity, improved in storage stability, and the cured product of the resin composition had sufficient light resistance and thermal shock resistance in practical use, and was judged to be acceptable in total.
[ example 34]
Resin compositions and cured products thereof were prepared in the same manner as in example 27, as shown in tables 4 and 5 below.
The resin composition and the cured product thereof were evaluated in the same manner as in example 27, and the evaluation results, the blending indices α 41 to ∈ 41, and the storage stability index θ 41 are shown in table 6 below.
The condensation rate K8 (%) of the intermediate is 84.2% or more and 78%.
The condensation rate L8 (%) -84.4% or more of the modified resin composition was 80% or more.
The modified resin composition has a residual alkoxy group content of 0% to 5%.
As shown in table 6 below, the resin composition of example 33 had an epoxy equivalent Weight (WPE) of 233g/eq, which is an appropriate value.
The initial viscosity was 13.2Pa · s < 1000Pa · s, and the storage viscosity was 46.8Pa · s < 1000Pa · s, both of which were liquid having fluidity. The resin composition having an improved storage stability, i.e., a storage stability index θ 41 of 3.5. ltoreq.4, is known to have excellent fluidity.
The cured product was judged to have light resistance when YI, which is an index for the light resistance test, was 7.3. ltoreq.13. The number of cold and hot impact tests was 150 or more and 50 or less, and it was judged that the steel had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 34 was excellent in fluidity, improved in storage stability, and the cured product of the resin composition had sufficient light resistance and thermal shock resistance in practical use, and was judged to be acceptable in total.
[ example 35]
The time for distilling off at 80 ℃ for 5 hours in the dehydration condensation step was changed to 2.5 hours. Other conditions were the same as in example 27, resin compositions were prepared according to table 4, and evaluated by the same method as in example 27.
The evaluation results, blend indices α 42 to ∈ 42, and storage stability index θ 42 are shown in table 6 below.
The condensation rate K9 (%) of the intermediate is 78.2% or more and 78% or less.
The condensation rate L9 (%) < 79.0% < 80% of the modified resin composition.
The modified resin composition has a residual alkoxy group content of 4% to 5%.
As shown in table 6 below, the resin composition of example 35 had an epoxy equivalent Weight (WPE) of 230g/eq, which is an appropriate value. The initial viscosity was 15.1Pa · s < 1000Pa · s, and the storage viscosity was 68.0Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 42 is 4.5 or less and 6, the condensation ratio of the modified resin is less than 80%, and the resin composition is excellent in fluidity and storage stability.
The cured product was judged to have light resistance when YI, which is an index for the light resistance test, was 8.1. ltoreq.13. In addition, the number of cold and hot impact tests was 250 or more and 50 or less, and it was judged that the test had cold and hot impact resistance.
From the above results, it was confirmed that the resin composition of example 35 was excellent in fluidity, improved in storage stability, and the cured product of the resin composition had sufficient light resistance and thermal shock resistance in practical use, and thus was judged to be acceptable in total.
Comparative example 10
The curing temperature of (14) in example 27 was changed to 110 ℃ for 4 hours and further 150 ℃ for 1 hour. Other conditions were the same as in example 27, and resin compositions and cured products were prepared according to the following tables 4 and 5, and evaluated by the same method as in example 27.
The evaluation results, blend indices α 43 to ∈ 43, and storage stability index θ 43 are shown in table 6 below.
The condensation rate of the intermediate K10 (%) < 71.1% < 78%.
The condensation rate L10 (%) < 75.4.0% < 80% of the modified resin composition.
The modified resin composition has a residual alkoxy group content of 21% to 5%.
As shown in table 6 below, the resin composition of comparative example 10 had an epoxy equivalent Weight (WPE) of 200g/eq, which is an appropriate value.
Further, the initial viscosity was 11.7 pas < 1000 pas. However, the storage viscosity was > 1000 pas, fluidity was not shown, and the storage stability index θ 43 was > 85, resulting in poor storage stability.
As shown in table 6, it was found that the cured product obtained by using the resin composition of comparative example 10 was excellent in light resistance and thermal shock resistance, but the storage stability of the resin composition was poor, and the overall evaluation was no good.
Comparative example 11
In the same manner as in example 27, cured products were prepared as shown in Table 5. The cured product was evaluated in the same manner as in example 27. The evaluation results are shown in table 6 below.
YI as an index of the light resistance test of the cured product was 16.9 > 13, and it was judged that the cured product had insufficient light resistance in practical use. In addition, the number of cold and hot impact tests is 500 or more and 50 or more, and it is judged that the cold and hot impact resistance is sufficient in practical use.
From the above results, it was confirmed that the cured product of comparative example 11 was judged to be unsatisfactory in total because it had no light resistance, although it had thermal shock resistance.
Comparative example 12
A solution for a cured product was prepared in the same manner as in example 26, using the mixture obtained by mixing and stirring liquid A and liquid B of a silicone resin ("SCR-1012 (liquids A and B)" manufactured by shin-Etsu chemical Co., Ltd.) in a mass ratio of 1: 1, according to the following Table 5.
The curing solution was poured into the molding jig and the 10 substrates for the cold-hot impact test in the same manner as in example 27, and 1 silicon chip was further put into each substrate.
The molding jig and the substrate for the cold thermal shock test were placed in a furnace, and curing was performed at 70 ℃ for 1 hour and at 150 ℃ 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.
When YI, which is an index of the light resistance test of the cured product, is 2.0. ltoreq.13, it is judged that the cured product has sufficient light resistance in practical use. However, the number of hot and cold shock tests was 0 times < 50 times, and it was judged that the hot and cold shock resistance was not sufficient for practical use.
From the above results, it was judged that the cured product of comparative example 12 was not heat and cold shock resistant although it had light resistance, and thus was judged to be a total failure.
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, resin compositions were prepared according to table 4, and evaluated by the same method as in example 27.
The evaluation results, blend indices α 44 to ∈ 44, and storage stability index θ 44 are shown in table 6 below.
The condensation rate of the intermediate K11 (%) < 64.8% < 78%.
The condensation rate L11 (%) < 80% of the modified resin composition was 68.0%.
The modified resin composition has a residual alkoxy group content of 7% to 5%.
As shown in table 6 below, the resin composition of comparative example 13 had an epoxy equivalent Weight (WPE) of 233g/eq, which is an appropriate value. The initial viscosity was 15.2 pas < 1000 pas. However, the storage viscosity was > 1000 pas, the fluidity was not exhibited, the storage stability index θ 44 was > 66, the storage stability was poor, and the overall judgment was that the storage stability was insufficient.
As is clear from the above, even if the time for performing the dehydration condensation step is extended, the storage stability of the resin composition does not reach the pass line, and the properties of the resin composition greatly depend on the condensation rate (chemical structure) of the intermediate in the reflow step.
Comparative example 14
The temperature of the oil bath in the reflux step was changed to 60 ℃. Other conditions were the same as in example 27, resin compositions were prepared according to table 4, and evaluated by the same method as in example 27.
The evaluation results, blend indices α 45 to ∈ 45, and storage stability index θ 45 are shown in table 6 below.
The condensation rate K12 (%) of the intermediate was 63.6% < 78%.
The condensation rate L12 (%) < 80% of the modified resin composition was 65.4%.
The modified resin composition has a residual alkoxy group content of 12% to 5%.
As shown in table 6 below, the resin composition of comparative example 14 had an epoxy equivalent Weight (WPE) of 238g/eq, which is an appropriate value. The initial viscosity was 16.4 pas < 1000 pas. However, the storage viscosity was > 1000 pas, the fluidity was not exhibited, the storage stability index θ 44 was > 61, the storage stability was poor, and the overall judgment was that the storage stability was insufficient.
As shown in tables 4 to 6, it is understood that the resin compositions of examples 27 to 35 produced by mixing an epoxy resin and a specific alkoxysilane compound at a specific ratio, particularly defining the condensation rate of an intermediate in the reflux step of cohydrolytic condensation, and then performing dehydration condensation, particularly defining the condensation rate of a modified resin composition, have excellent flowability and storage stability, and the cured products of these resin compositions have excellent light resistance and thermal shock resistance.
Figure BDA0000041312520000921
TABLE 5
Unit: mass%
Figure BDA0000041312520000941
Next, a resin composition obtained by adding an oxetane compound to the modified resin composition of the present embodiment will be specifically described by referring to examples and comparative examples.
The epoxy equivalent (WPE), viscosity, and mixing indices α to η were determined by the same methods as described above.
The evaluation of physical properties in examples 36 to 38 and comparative examples 15 to 16 was carried out as follows.
< measurement of viscosity of composition >
The vessel containing the resin composition immediately after the production was sealed, and after adjusting the temperature at 25 ℃ for 2 hours, the viscosity at 25 ℃ was measured.
When the viscosity is 1000 pas or less, it is judged to have fluidity.
< test on light resistance of cured product >
The light resistance of the cured product was evaluated by the following method.
(1) A cured product prepared by the method described below was cured in a solution to prepare a cured product having a thickness of 20 mm. times.10 mm. times.3 mm.
(2) The cured product was covered with a black mask having a hole diameter of 5.5mm of 25 mm. times.15 mm. times.1.2 mm thick to prepare a sample for light resistance test.
(3) An apparatus was prepared so that the above-mentioned sample in an incubator thermostatically maintained at 50 ℃ could be irradiated with UV light from a UV irradiation apparatus (manufactured by Ushio inc. "Spot Cure SP7-250 DB") via an optical fiber.
(4) The sample was placed in a 50 ℃ incubator with a black mask on top.
(5) 2W/cm was irradiated from the upper part of the black mask in such a manner that UV light could be irradiated into a hole having a diameter of 5.5mm2UV light for 96 hours.
(6) The sample after UV irradiation was measured by a spectrocolorimeter ("SD 5000", manufactured by Nippon Denshoku industries Co., Ltd.) in which the opening of the integrating sphere was modified to have a diameter of 10 mm.
(7) According to "ASTM D1925-70 (1988): the Test Method for Yellowness Index of Plastics (Test Method for Yellowness Index of Plastics) "determines the Yellowness Index (YI). When YI is 11 or less, it is judged to have light resistance.
< crack test of cured product >
The presence or absence of cracks in the cured product was evaluated by the following method.
(1) Substrates shown below were prepared.
Substrate: manufactured by Solvay Advanced Polymers K.K. "AMODEL A-4122NL WH 905" (having a depression of diameter 10mm X depth 1.2mm in the center of a plate of 15mm X thickness 2 mm)
(2) 5 samples were prepared by pouring a solution for curing prepared by the method described below into the substrate, and the samples were cured to prepare samples for crack testing.
(3) The sample was sprayed with a penetrant (manufactured by KOHZAI CORPORATION, "MICRO CHECK") and the presence or absence of cracks was visually observed under a magnifying glass, and the number of cracks was recorded.
(4) In the case where no crack was observed in 4 out of 5 samples, it was judged to have crack resistance.
< surface tack test of cured product >
The surface tackiness of the cured product was evaluated by the following method.
(1) A cured product prepared by the method described below was cured in a solution to prepare a cured product having a thickness of 20 mm. times.10 mm. times.3 mm.
(2) The surface of the obtained cured product was lightly pressed with a thumb wearing a latex glove, and it was judged that the surface tackiness was good when no stickiness was observed.
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)
Trade name: "AER" manufactured by Ltd, Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 187g/eq
Viscosity (25 ℃): 14.3 pas
(1-2) epoxy resin B: 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate (hereinafter, referred to as alicyclic epoxy resin)
Trade name: "CEL 2021P" manufactured by Daicel Chemical Industries, Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 131g/eq
Viscosity (25 ℃): 227mPa · s
(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter, GPTMS)
Trade name: KBM-403 manufactured by shin-Etsu chemical industries, Ltd "
(3) Alkoxysilane compound I: phenyltrimethoxysilane (hereinafter referred to as PTMS)
Trade name: KBM-103, manufactured by shin-Etsu chemical industries, Ltd "
(4) Alkoxysilane compound J: dimethyldimethoxysilane (hereinafter referred to as DMDMS)
Trade name: KBM-22, manufactured by shin-Etsu chemical industries, Ltd "
(5) Alkoxysilane compound K: tetraethoxysilane (hereinafter, referred to as TEOS)
Trade name: KBE-04, manufactured by shin-Etsu chemical industries, Ltd "
(6) Solvent(s)
(6-1) tetrahydrofuran: wako pure chemical industries, Ltd., a stabilized form (hereinafter referred to as THF) was not contained
(7) Hydrolysis condensation catalyst: dibutyltin dilaurate (product of Wako pure chemical industries, Ltd., hereinafter referred to as DBTDL)
(8) Oxetane compound: 3-Ethyl-3 { [ (3-ethyloxetan-3-yl) methoxy ] methyl } OXETANE (manufactured by Toyo Kabushiki Kaisha, "ARON OXETANE OXT-221")
(9) Cationic polymerization initiator
Trade name: San-Aid SI-100L, a product of Sanxin chemical industries, Ltd "
(10) Curing agent: "4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride ═ 70/30"
Trade name: manufactured by Nissan chemical and physical Co., Ltd. "RIKACID MH-700G"
(11) Curing accelerator: amine compound
Trade name: "U-CAT 18X" manufactured by San-Apro Ltd "
(12) Silicone resin
Trade name: "EG 6301 (solution A/solution B)", manufactured by Dow Corning Toray Co., Ltd "
[ Synthesis example 1]
Resin composition A: resin composition a was produced and evaluated in the following order.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) According to the composition ratio shown in table 7, an alicyclic epoxy resin, an alkoxysilane compound and THF were charged into a flask charged with a stirrer in an atmosphere of 25 ℃ and mixed and stirred, and then water and a hydrolytic condensation catalyst were added and mixed and stirred.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 8 hours while refluxing.
(4) After the reaction was completed, the temperature was cooled to 25 ℃, and then the cooling tube was removed from the flask, and the sample solution was collected after the reflux process was completed.
(5) After the solution after the completion of the refluxing step was distilled off at 400Pa and 50 ℃ for 1 hour using an evaporator, the solution was further distilled off at 80 ℃ for 5 hours, and a dehydration condensation reaction was carried out.
(6) After the reaction, the reaction mixture was cooled to 25 ℃ to obtain a resin composition A.
(7) The mixing indices α 46 to ∈ 46 in this resin composition are shown in table 9.
(8) Further, the epoxy equivalent (WPE) of the resin composition A obtained in the above (6) was measured according to the above-mentioned method.
The epoxy equivalent Weight (WPE) of the resin composition was 158g/eq, which is an appropriate value.
[ Synthesis example 2]
Resin composition B: resin composition B was synthesized and evaluated in the same manner as in synthesis example 1, based on the composition ratios shown in table 7. The mixing indices α 47 to ∈ 47 are shown in table 9.
The epoxy equivalent Weight (WPE) of the resin composition B was 163g/eq, which is an appropriate value.
[ Synthesis example 3]
Resin composition C: resin composition C was synthesized and evaluated in the same manner as in synthesis example 1, based on the composition ratios shown in table 7. The mixing indices α 48 to ε 48 are shown in Table 9.
The epoxy equivalent Weight (WPE) of the resin composition C was 160g/eq, which is an appropriate value.
[ example 36]
Composition 1 was produced and evaluated in the following order.
(1) 75% by mass of the resin composition A of Synthesis example 1 and 25% by mass of the oxetane compound were mixed and stirred, and then degassed under vacuum, and the degassed mixture was used as composition 1. The composition 1 had a viscosity of 1.82 pas and was a liquid having excellent fluidity.
(2) A cationic polymerization initiator was added in an amount of 0.8 mass% to 99.2 mass% of composition 1, followed by mixing, and degassing was performed under the same conditions as in (1) to prepare a solution for a cured product.
(3) A molding jig was prepared by sandwiching silicone rubber having a thickness of 3mm and a shape of コ with 2 stainless steel plates coated with a release agent so that a cured product prepared by the molding jig had a thickness of about 50mm × about 20mm × 30 mm.
(4) A sample was prepared by injecting the solution for a cured product into the molding jig and the 5 substrates for a crack test.
(5) The molding jig and the substrate for crack test were placed in a furnace, and curing treatment was performed at 85 ℃ for 1 hour and at 150 ℃ for 3 hours to prepare a cured product.
(6) Using the above samples, the light resistance test, crack resistance test, and surface tackiness test were performed by the methods described above, and the results are shown in table 9. The cured product was judged to have light resistance when YI, which is an index for the light resistance test, was 6.8. ltoreq.11. In addition, in 5 samples, no crack was generated in 5 samples, and it was judged that the sample had crack resistance. Further, no stickiness was observed, and the surface tackiness was also good.
From the above results, it was confirmed that the composition 1 of example 36 had fluidity, and the cured product of the composition had light resistance, crack resistance and good surface tackiness, and thus was judged to be acceptable in total.
[ example 37]
Composition 2 was produced and evaluated in the following order.
(1) Composition 2 was prepared by mixing and stirring 70 mass% of resin composition B of synthesis example 2 and 30 mass% of an oxetane compound, and degassing the mixture in the same manner as in example 36. The viscosity of composition 2 was 2.78 pas, and it was a liquid having excellent fluidity.
(2) To 99.4% by mass of composition 2, 0.6% by mass of a cationic polymerization initiator was added and mixed, and degassing treatment was performed 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 curing treatment was performed in the same manner as in example 36 to prepare a cured product.
The cured product was judged to have light resistance when YI, which is an index for the light resistance test, was 7.9. ltoreq.11. In addition, in 5 samples, no crack was generated in 5 samples, and it was judged that the sample had crack resistance. Further, no stickiness was observed, and the surface tackiness was also good.
From the above results, it was confirmed that the composition 2 of example 35 had fluidity, and the cured product of the composition had light resistance, crack resistance and good surface tackiness, and thus was judged to be acceptable in total.
[ example 38]
Composition 3 was produced and evaluated in the following order.
(1) 80 mass% of the resin composition C of Synthesis example 3 and 20 mass% of the oxetane compound were mixed and stirred, and the mixture was degassed by the same method as in example 36 to obtain composition 3. The composition 3 had a viscosity of 2.27 pas and was a liquid having excellent fluidity.
(2) 99.3% by mass of composition 3 was mixed with 0.7% by mass of a cationic polymerization initiator, and the mixture was degassed 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 curing treatment was performed in the same manner as in example 36 to prepare a cured product.
The cured product was judged to have light resistance when YI, which is an index for the light resistance test, was 8.8. ltoreq.11. In addition, in all 4 of the 5 samples, no cracks were generated, and it was judged that the samples had crack resistance. Further, no stickiness was observed, and the surface tackiness was also good.
From the above results, it was confirmed that the composition 3 of example 38 had fluidity, and the cured product of the composition had light resistance, crack resistance and good surface tackiness, and thus was judged to be acceptable in total.
Comparative example 15
In the Bis-a epoxy resin and the alicyclic epoxy resin, a curing agent and a curing accelerator were added in the composition ratios shown in table 8 in place of the cationic polymerization initiator, and the mixture was mixed and stirred, and degassed under vacuum to obtain a solution for a cured product. Next, in the same manner as in example 36, the above-mentioned solution for a cured product was injected into the molding jig and the above-mentioned 5 substrates for crack test, and curing treatment was performed at 110 ℃ for 4 hours to prepare a cured product.
The results of evaluation by the same method as in example 36 are shown in table 9.
YI as an index of the light resistance test of the cured product was 13.9 > 11, and it was judged that the cured product had no light resistance. In addition, no crack was observed in 4 out of 5 samples, and the samples had crack resistance. Further, no stickiness was observed, and the surface tackiness was good.
From the above results, it was judged that the cured product of comparative example 15 did not have light resistance, and thus was judged to be failed in total.
Comparative example 16
The mixture obtained by mixing the solution a and the solution B of the silicone resin at a mass ratio of 1: 1 was mixed and stirred, and degassed under vacuum, and the degassed mixture was used as a solution for a cured product.
Next, in the same manner as in example 36, the solution for a cured product was injected into the molding jig and the 5 substrates for a crack test, and the curing treatment was performed at 150 ℃ for 1 hour to prepare a cured product.
The results of evaluation by the same method as in example 36 are shown in table 9.
The cured product was judged to have light resistance when YI, which is an index for the light resistance test, was 2.3. ltoreq.11. In addition, no crack was observed in 5 out of 5 samples, and the sample had crack resistance. However, stickiness and poor surface tack were observed. From the above results, it was found that the cured product of comparative example 16 had light resistance and crack resistance, but had poor surface tackiness, and was judged to be totally defective.
As shown in tables 7 to 9, resin compositions obtained by mixing an epoxy resin and a specific alkoxysilane compound at a specific ratio and cohydrolytic condensation, and resin compositions containing an oxetane compound are excellent in flowability. In addition, cured products using these resin compositions have excellent light resistance, crack resistance, and surface tackiness.
Figure BDA0000041312520001011
Figure BDA0000041312520001021
Figure BDA0000041312520001031
Next, a photosensitive resin composition obtained by adding a photoacid generator to the modified resin composition of the present embodiment will be specifically described with reference to examples and comparative examples.
The epoxy equivalent (WPE), viscosity, and mixing indices α to η were determined by the same methods as described above.
The evaluation of physical properties in examples 39 to 41 and comparative examples 17 to 19 was carried out as follows.
< measurement of viscosity of photosensitive resin composition >
The container containing the composition immediately after the production was sealed, and after temperature adjustment was performed at 25 ℃ for 1 hour, the viscosity at 25 ℃ was measured.
When the viscosity is 1000 pas or less, it is judged to have fluidity.
< method a for producing coating film >
The coating film was prepared in the following procedure under the conditions of air temperature 23 ℃ and humidity 55% RH.
(1) The following substrates were prepared, and the surfaces thereof were wiped with ethanol (99.5% manufactured by Wako pure chemical industries, Ltd.) and dried.
Substrate: polyethylene terephthalate resin (hereinafter referred to as PET)
Polycarbonate resin (hereinafter referred to as PC)
Polymethyl methacrylate resin (hereinafter, referred to as PMMA)
(2) The photosensitive composition of example or the composition of comparative example was applied onto the substrate using a bar coater (# 3).
(3) The substrate was set in a UV curing apparatus (manufactured by Fusion UV Systems Japan k.k.) and cured by repeating the conditions 3 times or less.
Light source and amount of light: high-pressure mercury lamp (120W/cm2)
Speed of belt conveyor: 10 m/min
(4) Further, the substrate was heat-treated at 100 ℃ for 1 hour and then cured.
< method b for producing coating film >
A coating film was formed in the following manner under the conditions of air temperature of 23 ℃ and humidity of 55% RH.
(1) The following substrates were prepared, and the surfaces thereof were wiped with ethanol (99.5% manufactured by Wako pure chemical industries, Ltd.) and dried.
Substrate: PET
(2) The photosensitive composition of example or the composition of comparative example was applied onto the substrate using a bar coater (# 3).
(3) The substrate was set in a UV curing apparatus (manufactured by Fusion UV Systems Japan k.k.) and cured by repeating the conditions 5 times or less.
Light source and amount of light: high-pressure mercury lamp (120W/cm2)
Speed of belt conveyor: 5 m/min
< photocurability of coating film >
According to "JIS K5600-5-4: 1999 general test methods for coatings-part 5: mechanical properties of the coating film-section 4: scratch strength (pencil method) ", and it was judged that the photocurability was good when the coating film was measured and found to be 3B to 6H.
< adhesion of coating film >
According to "JIS K5600-5-6: 1999 general test methods for coatings-part 5: mechanical properties of the coating film-section 6: adhesion (cross cut method) ", the coating film was measured.
The results were evaluated on the following 3-point scale: o: substantially no peeling was observed, Δ: partial peeling, x: and substantially peeled off. When a result more favorable than the standard was shown, the adhesiveness was judged to be favorable.
< comprehensive judgment >
The photosensitive resin composition is judged to be acceptable overall when it has fluidity and the coating film has good photocurability and adhesion.
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.)
Trade name: "AER" manufactured by Ltd, Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 187g/eq
Viscosity (25 ℃): 14.3 pas
(1-2) epoxy resin B: 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate (hereinafter, referred to as alicyclic epoxy resin.)
Trade name: "CEL 2021P" manufactured by Daicel Chemical Industries, Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 131g/eq
Viscosity (25 ℃): 227mPa · s
(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter, referred to as GPTMS.)
Trade name: KBM-403 manufactured by shin-Etsu chemical industries, Ltd "
(3) Alkoxysilane compound I: phenyltrimethoxysilane (hereinafter referred to as PTMS.)
Trade name: KBM-103, manufactured by shin-Etsu chemical industries, Ltd "
(4) Alkoxysilane compound J: dimethyldimethoxysilane (hereinafter referred to as DMDMDMS)
Trade name: KBM-22, manufactured by shin-Etsu chemical industries, Ltd "
(5) Alkoxysilane compound K: tetraethoxysilane (hereinafter, referred to as TEOS.)
Trade name: KBE-04, manufactured by shin-Etsu chemical industries, Ltd "
(6) Solvent(s)
(6-1) tetrahydrofuran: wako pure chemical industries, Ltd., and containing no stabilizer (hereinafter, referred to as THF.)
(7) Hydrolysis condensation catalyst: dibutyl tin dilaurate (product of Wako pure chemical industries, Ltd., hereinafter referred to as DBTDL.)
(8) Photoacid generators
(8-1) hexafluorophosphate salt mixture of triarylsulfonium
Trade name: manufactured by Union Carbide Corporation, "UVI-6990" (hereinafter, referred to as UVI-6900.)
(8-2) hexafluoroantimonate salt of aromatic sulfonium
Trade name: sanxin chemical industry Co., Ltd, "San-Aid SI-80L" (hereinafter referred to as SI-80L.)
(9) Oxetane compounds
(9-1) 3-Ethyl-3- (phenoxymethyl) oxetane
Trade name: "OXT-211" (hereinafter referred to as POX.) manufactured by Toyo Synthesis Co., Ltd
[ Synthesis example 4]
Resin composition D: resin composition D was produced and evaluated in the following order.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) According to the composition ratio shown in table 10, an alicyclic epoxy resin, an alkoxysilane compound, and THF were charged into a flask charged with a stirrer in an atmosphere of 25 ℃ and mixed and stirred, and then water and a hydrolytic condensation catalyst were added and mixed and stirred.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 8 hours while refluxing.
(4) After the reaction was completed, the temperature was cooled to 25 ℃, and then the cooling tube was removed from the flask to collect the solution.
(5) The solution was distilled off at 400Pa and 50 ℃ for 1 hour using an evaporator, and then distilled off at 80 ℃ for 5 hours, and a dehydration condensation reaction was carried out.
(6) After the reaction, the reaction mixture was cooled to 25 ℃ to obtain a resin composition D.
(7) Table 12 shows mixing indexes α 49 to ∈ 49 in the resin composition.
(8) Further, the epoxy equivalent Weight (WPE) of the resin composition D obtained in the above (6) was measured according to the above method.
The epoxy equivalent Weight (WPE) of the resin composition was 193g/eq, which is an appropriate value. Further, the viscosity was 12.7 pas < 1000 pas, and good fluidity was exhibited.
[ Synthesis example 5]
Resin composition E: resin composition E was synthesized and evaluated in the same manner as in synthesis example 4, based on the composition ratios shown in table 10. The mixing indices α 50 to ∈ 50 are shown in table 12.
The epoxy equivalent Weight (WPE) of the resin composition E was 152g/eq, which is an appropriate value. Further, the viscosity was 0.93 pas < 1000 pas, and good fluidity was exhibited.
[ example 39]
The photosensitive resin composition 1 and the coating film thereof were produced and evaluated in the following procedure.
(1) The resin composition D of synthesis example 4 was mixed and stirred in the proportions shown in table 11, and then degassed under vacuum, and the degassed mixture was used as the photosensitive resin composition 1. The photosensitive resin composition 1 has a viscosity of 12.6 pas < 1000 pas and is a liquid having excellent fluidity.
(2) According to the "method a for producing a coating film", the photosensitive resin composition 1 was applied to the 3 kinds of substrates (PET, PC, PMMA) and a coating film was produced using a UV curing apparatus.
(3) According to "JIS K5600-5-4: 1999 general test methods for coatings-part 5: mechanical properties of the coating film-section 4: scratch strength (pencil method) ", the results of the measurement of the coating film are shown in table 12.
(4) According to "JIS K5600-5-6: 1999 general test methods for coatings-part 5: mechanical properties of the coating film-section 6: the results of the measurement of the above coating film (adhesion (cross cut method)') are shown in table 12.
As described above, the photosensitive resin composition 1 was judged to be acceptable overall because it had excellent fluidity, good photocurability of the coating film, and better adhesiveness than comparative example 17 as a standard.
[ example 40]
Photosensitive resin composition 2 was produced in the same manner as in example 39, based on the compounding ratios shown in table 11. Wherein the belt conveyor speed of the UV curing apparatus was set to 10 m/min. The evaluation results are shown in Table 12.
The photosensitive resin composition 2 has a viscosity of 3.2 pas < 1000 pas and is a liquid having excellent fluidity.
As described above, the photosensitive resin composition 2 was judged to be acceptable overall because it had excellent fluidity, good photocurability of the coating film, and better adhesiveness than comparative example 17 as a standard.
[ example 41]
Photosensitive resin composition 3 was produced in accordance with the compounding ratio shown in table 11, and evaluated in the same manner as in example 39. The photosensitive resin composition 3 has a viscosity of 1.0 pas < 1000 pas and is a liquid having excellent fluidity.
Next, using the photosensitive resin composition 3, a coating film was produced by the above "method for producing a coating film" using PET as a substrate. The results are shown in Table 12.
As described above, the photosensitive resin composition 3 was judged to be acceptable overall because it had excellent fluidity, good photocurability of the coating film, and better adhesiveness than comparative example 19, which is the standard.
Comparative example 17
Photosensitive resin composition 4 was produced in the same manner as in example 39, based on the compounding ratio shown in table 11. The evaluation results are shown in Table 12.
The photosensitive resin composition 4 had a viscosity of 13.8 pas < 1000 pas and was a liquid with excellent fluidity.
However, as shown in table 12, the photosensitive resin composition 4 was judged to be totally defective because the adhesiveness of the coating film was poor although it had excellent fluidity.
Comparative example 18
Photosensitive resin composition 5 was produced in the same manner as in example 39, based on the compounding ratio shown in table 11. As the silane coupling agent, GPTMS was used. The evaluation results are shown in Table 12.
The photosensitive resin composition 5 has a viscosity of 12.1 pas < 1000 pas and is a liquid having excellent fluidity.
However, as shown in table 12, the photosensitive resin composition 5 was judged to be totally defective because no effect of improving the adhesion of the coating film was observed although it had excellent fluidity.
Comparative example 19
Photosensitive resin composition 6 was produced in the same manner as in example 39, based on the compounding ratios shown in table 11. The evaluation results are shown in Table 12.
The photosensitive resin composition 6 has a viscosity of 0.3 pas < 1000 pas and is a liquid having excellent fluidity.
However, as shown in table 12, the photosensitive resin composition 6 was excellent in fluidity, but the adhesiveness of the coating film was poor, and the overall judgment was that it was not good.
From the results in tables 10 to 12, it is understood that when the photosensitive resin composition contains a photoacid generator and a resin composition obtained by cohydrolytic condensation of an epoxy resin and a specific alkoxysilane compound, the photosensitive resin composition has excellent fluidity, and a coating agent and a coating film using the photosensitive resin composition have excellent photocurability and adhesiveness.
Figure BDA0000041312520001091
Figure BDA0000041312520001101
Next, a fluorescent resin composition obtained by adding a fluorescent material to the modified resin composition of the present embodiment will be specifically described with reference to examples and comparative examples.
The evaluation of physical properties in examples 42 to 44 and comparative examples 20 to 23 was carried out as follows.
The epoxy equivalent (WPE), viscosity, and mixing indices α to η were determined by the same methods as described above.
< calculation of storage stability index θ and storage stability of resin composition >
The storage stability of the resin composition was evaluated by a storage stability index θ represented by the following general formula (9).
Storage stability index θ ═ (storage viscosity)/(initial viscosity) (9)
The container containing the resin composition immediately after the production was sealed, and after adjusting the temperature at 25 ℃ for 2 hours, the viscosity at 25 ℃ was measured and used as the "initial viscosity".
Further, the container containing the resin composition was sealed and stored in a thermostatic incubator at 25 ℃ for 2 weeks. After storage, the viscosity at 25 ℃ was measured and used as "storage viscosity".
When the resin composition has fluidity (viscosity of 1000Pa · s or less) and the storage stability index θ is 4 or less, it is judged that the resin composition has storage stability.
< test of Dispersion stability of fluorescent resin composition >
After the production of the fluorescent resin composition, the resultant was placed in a 50mL glass bottle, sealed and stored in a thermostatic incubator at 25 ℃ for 5 hours. After storage, the appearance was observed, and the precipitation and uniformity of the phosphor were visually confirmed. When the precipitation of the phosphor was not observed and the phosphor was uniformly dispersed, the dispersion stability was judged to be acceptable.
< test on light resistance of cured product (cured product of resin composition) >
The cured product having the solid material (phosphor) dispersed therein has a large variation in Yellowness (YI). Therefore, a cured product was produced from the resin composition without adding a phosphor by the following method, and the evaluation was performed, and the result was evaluated as light resistance.
(1) A cured product prepared by the method described below was cured in a solution to prepare a cured product having a thickness of 20 mm. times.10 mm. times.3 mm.
(2) The cured product was covered with a black mask having a hole diameter of 5.5mm of 25 mm. times.15 mm. times.1.2 mm thick to prepare a sample for light resistance test.
(3) An apparatus was prepared so that the above-mentioned sample in an incubator thermostatically maintained at 50 ℃ could be irradiated with UV light from a UV irradiation apparatus (manufactured by Ushio inc. "Spot Cure SP7-250 DB") via an optical fiber.
(4) The sample was placed in a 50 ℃ incubator with a black mask on top.
(5) 2W/cm was irradiated from the upper part of the black mask in such a manner that UV light could be irradiated into a hole having a diameter of 5.5mm2UV light for 96 hours.
(6) The sample after UV irradiation was measured by a spectrocolorimeter ("SD 5000", manufactured by Nippon Denshoku industries Co., Ltd.) in which the opening of the integrating sphere was modified to have a diameter of 10 mm.
(7) According to "ASTM D1925-70 (1988): the Test Method for Yellowness Index of Plastics (Test Method for Yellowness Index of Plastics) "determines the Yellowness Index (YI). When this YI is 13 or less, it is judged as being acceptable.
< test of luminescence of LED >
The LED was turned on, and the color tone was visually confirmed, and the emission was acceptable when the color tone of the LED without the phosphor was changed from blue to white.
< luminescence test (afterglow time measurement) of light-storing Material >
Irradiation of a sample "JIS Z9107: 2008 safety marking-classification of performance, performance benchmark and test method "usual light source fluorescent lamp D6520 minutes. After irradiation, the afterglow luminance was measured with a luminance meter to be 0.3mcd/m2The time until this point is referred to as afterglow time. When the afterglow time was 120 minutes or more, the luminescence was judged to be acceptable.
< reliability test of LED (1) (continuous operation test: hereinafter referred to as "L test") >
The evaluation of 10 LEDs was carried out under the following conditions in accordance with a method 1026.5 (steady state operating life) of "MIL-STD-750E (test method of semiconductor device)" and a method 1005.8 (steady state life) of "MIL-STD-883G (microcircuit)".
The light was turned on at "IF 20mA, Ta 25 ℃, 960 hours", and the total luminous flux (lm) before and after the light was turned on was measured. Further, for each LED, the "total luminous flux maintenance ratio (%) (total luminous flux after lighting)/(total luminous flux before lighting) × 100" was obtained, and when the lowest value of the total luminous flux maintenance ratios (%) of all the LEDs was 90% or more, it was judged as being acceptable.
< reliability test of LED (2) (thermal shock test: hereinafter referred to as "TS test") >
The 10 LEDs were evaluated under the following conditions in accordance with test method 307 (thermal shock test) of "EIAJ ED-4701/300 (environmental and durability test method for semiconductor device (strength test I)".
The lighting of the LED was confirmed after thermal shock was performed for 100 cycles with "-10 ℃ (5 minutes) to 100 ℃ (5 minutes)" as 1 cycle, and when all 10 were lit, the LED was judged to be acceptable.
< test (3) for reliability of LED (temperature cycle test: hereinafter referred to as "TC" test) >
The 10 LEDs were evaluated under the following conditions in accordance with test method 105 (temperature cycle test) of "EIAJ ED-4701/100 (environmental and durability test method for semiconductor devices (life test I)".
The lighting of the LEDs was confirmed after 100 cycles of 1 cycle of "-40 ℃ (30 minutes) -85 ℃ (5 minutes) -100 ℃ (30 minutes) -25 ℃ (5 minutes)", and when all 10 were lit, the LED was judged to be acceptable.
In the above evaluation of the LED, when all of the light resistance and reliability tests (1) to (3) were acceptable, the LED was judged to be acceptable overall.
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: "AER" manufactured by Ltd, Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 188g/eq
Viscosity (25 ℃): 14.8 pas
(1-2) epoxy resin B: 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate (hereinafter, referred to as "alicyclic epoxy resin")
Trade name: "CEL 2021P" manufactured by Daicel Chemical Industries, Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 131g/eq
Viscosity (25 ℃): 227mPa · s
(2) Alkoxysilane compound
(2-1) alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter, referred to as "GPTMS")
Trade name: KBM-403 manufactured by shin-Etsu chemical industries, Ltd "
(2-2) alkoxysilane compound I: phenyltrimethoxysilane (hereinafter, referred to as "PTMS")
Trade name: KBM-103, manufactured by shin-Etsu chemical industries, Ltd "
(2-3) alkoxysilane compound J: dimethyldimethoxysilane (hereinafter, referred to as "DMDMS")
Trade name: KBM-22, manufactured by shin-Etsu chemical industries, Ltd "
(2-4) alkoxysilane compound K: tetraethoxysilane (hereinafter, referred to as "TEOS")
Trade name: KBE-04, manufactured by shin-Etsu chemical industries, Ltd "
(3) Solvent: tetrahydrofuran (manufactured by Wako pure chemical industries, Ltd., containing no stabilizer) (hereinafter, referred to as "THF")
(4) Hydrolysis condensation catalyst: dibutyl tin dilaurate (manufactured by Wako pure chemical industries, Ltd., hereinafter referred to as "DBTDL")
(5) Curing agent: "4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride ═ 70/30"
Trade name: manufactured by Nissan chemical and physical Co., Ltd. "RIKACID MH-700G"
(6) Curing accelerator: amine compound
Trade name: "U-CAT 18X" manufactured by San-Apro Ltd "
(7) Reactive diluents: "1,2: 8, 9-diepoxy-terpene-diene "
Trade name: "CEL 3000" manufactured by Daicel Chemical Industries, Ltd "
(8) Polymerization initiator: aromatic sulfonium salt
Trade name: San-Aid SI-100L, a product of Sanxin chemical industries, Ltd "
(9) Phosphor
(9-1) phosphor A: YAG Ce3+ phosphor (manufactured by Kasei Optonix, LTD.)
(9-2) phosphor B (phosphorescent phosphor): "SrAl 2O4: Eu, Dy phosphor" (manufactured by Special chemical Co., Ltd.)
(10) Silicone resin
Trade name: "EG 6301 (solution A/solution B)", manufactured by Dow Corning Toray Co., Ltd "
[ Synthesis example 6]
The resin composition was produced by the following procedure.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) The Bis-a1 epoxy resin, the alkoxysilane compound, and THF were charged into a flask charged with a stirrer in accordance with the composition ratios shown in table 13 below under an atmosphere of 25 ℃ and mixed and stirred, and then water and the hydrolytic condensation catalyst were added and mixed and stirred.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 20 hours while refluxing (refluxing step).
(4) After the reaction was completed, it was cooled to 25 ℃ and then the cooling tube was removed from the flask.
(5) After the solution after the reflux step was distilled off at 400Pa and 50 ℃ for 1 hour using an evaporator, a dehydration condensation reaction was carried out while further distilling off at 80 ℃ for 10 hours (dehydration condensation step).
(6) And after the dehydration condensation reaction is finished, cooling to 25 ℃ to obtain the resin composition.
(7) The mixing indexes α 51 to ∈ 51 of the resin compositions are shown in table 16 below.
(8) Further, the epoxy equivalent Weight (WPE), initial viscosity and storage viscosity of the resin composition obtained in the above (6) were measured by the above-mentioned methods. Further, the storage stability index θ 51 was obtained and is shown in table 16.
The epoxy equivalent Weight (WPE) of the resin composition of synthesis example 6 was 228g/eq, which is an appropriate value. The initial viscosity was 38.2Pa · s < 1000Pa · s, and the storage viscosity was 61.1Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 51 was 1.6. ltoreq.4, and it was judged as a resin composition having storage stability.
[ Synthesis example 7]
Resin compositions were produced in accordance with tables 13 and 14 by the same method as in synthetic example 6 except that the refluxing step was carried out for 6 hours. The results of evaluation by the same method as in synthesis example 6, the blend indices α 52 to ∈ 52, and the storage stability index θ 52 are shown in table 16.
As shown in table 16, the resin composition of synthesis example 7 had an epoxy equivalent Weight (WPE) of 158g/eq, which is an appropriate value. The initial viscosity was 1.8Pa · s < 1000Pa · s, and the storage viscosity was 3.1Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 52 was 1.72. ltoreq.4, and it was judged as a resin composition having storage stability.
[ example 42]
A cured product was produced using the resin composition of Synthesis example 6 stored at 25 ℃ for 2 weeks, and subjected to a light resistance test. The results are shown in Table 16.
(1) The resin composition, the curing agent and the curing accelerator were mixed and stirred at the composition ratios shown in table 14 in an atmosphere of 25 ℃, and degassed under vacuum to obtain a solution for a cured product.
(2) A molding jig was prepared by holding silicone rubber 3mm thick and shaped like コ between 2 stainless steel plates coated with a release agent.
(3) The solution for a cured product was injected into the molding jig, and curing treatment was performed at 120 ℃ for 1 hour and further at 150 ℃ for 1 hour to prepare a cured product.
(4) After the temperature in the furnace was lowered to 30 ℃ or lower, the cured product was taken out, and a sample for light resistance test was prepared according to the method described above.
(5) Using the above samples, a light resistance test was performed by the above method, and the results are shown in table 16. When YI as an index of the light resistance test of the cured product was 7.5. ltoreq.13, the cured product was judged to be satisfactory in light resistance.
(6) Then, a fluorescent resin composition was prepared by mixing 90 mass% of the resin composition of Synthesis example 6 with 10 mass% of phosphor A, mixing and stirring the mixture for 10 minutes by a planetary mixer (manufactured by Kokai Co., Ltd.), and then subjecting the mixture to a defoaming treatment under vacuum.
(7) The fluorescent resin composition was poured into a 50mL sample bottle and stored at 25 ℃ for 5 hours.
(8) After storage, the side surfaces and the bottom surface were visually checked, and as a result, no precipitation was observed, and the fluorescent material was uniformly dispersed, and it was judged that the dispersion stability of the fluorescent resin composition was satisfactory. The evaluation results are shown in Table 16.
Further, using the fluorescent resin composition stored at 25 ℃ for 2 weeks, a shell-type LED was produced in the following order, and reliability tests (1) to (3) were performed. The results are shown in Table 16.
The shell type LED has a structure comprising 2 lead frames, wherein a cup part for placing an LED chip is formed at the upper end of one lead frame.
(9) Further, the fluorescent resin composition, the curing agent, and the curing accelerator were mixed and stirred in the composition ratios shown in table 15, and degassed under vacuum to obtain an LED sealing material.
(10) And (3) injecting (9) the LED sealing material into the cup part of the projectile-shaped casting frame with the diameter of 5 mm.
(11) LED chips having an emission wavelength of 400nm were die-bonded with silver paste, and a lead frame to which bonding wires (copper wires) were connected was impregnated.
(12) After defoaming in vacuum, the mixture was cured at 90 ℃ for 1 hour and further at 110 ℃ for 5 hours.
(13) Further, as an outer layer resin, 46.6 mass% of a curing agent and 0.2 mass% of a curing accelerator were added to 53.2 mass% of Bis-a epoxy resin, and mixed and stirred, and degassed under vacuum, and the obtained substance was injected into a mold frame, and cured at 130 ℃ for 1 hour, and further cured at 150 ℃ for 6 hours, to obtain a bullet-type LED. The evaluation results are shown in Table 16.
As a result of the above-described "light emission test", the LED of comparative example 20 as a reference emitted blue light, whereas the LED of example 42 emitted white light and was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", the lowest value of all the LEDs was determined to be a total luminous flux maintenance rate (%) of 94% or more and 90% and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
As a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, it was confirmed that all of the dispersion stability test, the light resistance test, the light emission test, and the reliability tests (1) to (3) of the fluorescent resin composition of example 42 were acceptable, and the composition was comprehensively judged to be acceptable.
[ example 43]
Resin compositions, cured products, fluorescent resin compositions, and LEDs were prepared according to tables 13 to 15 in the same manner as in example 40 except that the resin composition of synthesis example 7 was used instead of the resin composition of synthesis example 6, and the curing temperatures of (3) and (12) of example 41 were changed to 110 ℃ for 4 hours and further to 150 ℃ for 1 hour, and the results of the evaluations were shown in table 16.
When YI as an index of the light resistance test was 6.8. ltoreq.13, the light resistance was judged to be acceptable.
The fluorescent resin composition stored at 25 ℃ for 5 hours was judged to have no precipitation and the phosphor was uniformly dispersed, and to have satisfactory dispersion stability.
Subsequently, as a result of the "light emission test" of the LED, white light was emitted and it was judged as being acceptable.
As a result of the "reliability test (1) (L test)", the minimum value of all the LEDs was 95% or more of the total luminous flux maintenance rate (%) and was judged as being acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Next, as a result of performing the "reliability test (3) (TC test)" described above, all the LEDs were turned on and judged to be acceptable even after performing a temperature cycle of 100 cycles.
From the above results, it was confirmed that all of the dispersion stability test, the light resistance test, the light emission test, and the reliability tests (1) to (3) of the fluorescent resin composition of example 43 were acceptable, and the composition was comprehensively judged to be acceptable.
[ example 44]
A fluorescent resin composition was prepared by mixing 60 mass% of the resin composition of synthesis example 7 with 40 mass% of the fluorescent material B in the same manner as in example 42, and evaluated. The dispersion stability test of the fluorescent resin composition of example 44 was carried out, and as a result, no precipitation was observed, and the composition was relatively uniform and was judged to be acceptable.
Then, the fluorescent resin composition, the reaction diluent and the polymerization initiator were mixed at the ratios shown in table 17, and deaerated in vacuo, and the light-storing material (coating film) was produced in the following order under the conditions of air temperature 23 ℃ and humidity 55% RH.
(1) A glass slide of 5 cm. times.5 cm size was prepared, and the surface was wiped with ethanol (99.5% manufactured by Wako pure chemical industries, Ltd.) and dried.
(2) The fluorescent resin composition was coated on the slide glass using a bar coater (# 3).
(3) The above glass slide was cured at 140 ℃ for 10 minutes to form a coating film.
As a luminescence test of the light-storing material (coating film), the afterglow time was measured by the above-mentioned method and the duration was 600 minutes or longer, and it was judged as acceptable.
From the above results, the fluorescent resin composition of example 44 was judged to be acceptable in the dispersion stability test and the light emission test, and was judged to be acceptable in total. The results are shown in Table 18.
[ reference example ]
Resin compositions, cured products, and LEDs were prepared according to tables 13 to 15 using the resin composition of synthesis example 6 in place of the fluorescent resin composition of example 42, and the results of the evaluation are shown in table 16.
When YI as an index of the light resistance test was 7.5. ltoreq.13, the light resistance was judged to be acceptable.
Next, as a result of the "light emission test" of the LED, blue light was emitted, and it was judged that the light emission was not satisfactory.
Further, as a result of performing the "reliability test (1) (L test)", the lowest value of all the LEDs was determined to be a total luminous flux maintenance ratio (%) of 95% or more and 90%, and it was determined to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Next, as a result of performing the "reliability test (3) (TC test)" described above, all the LEDs were turned on and judged to be acceptable even after performing a temperature cycle of 100 cycles.
Comparative example 20
A fluorescent resin composition was produced using an alicyclic epoxy resin instead of the resin composition of synthesis example 6, and the evaluation results are shown in table 16.
When the fluorescent resin composition of comparative example 20 was stored at 25 ℃ for 5 hours, the phosphor precipitated and became inhomogeneous, and it was judged that the dispersion stability was not satisfactory. Further, since a normal fluorescent resin composition cannot be produced, the cured product and the LED are not produced and evaluated, and the overall judgment is failed.
Comparative example 21
In the same manner as in example 42 except that a Bis-a epoxy resin was used in place of the resin composition of synthesis example 6, resin compositions, cured products, fluorescent resin compositions, and LEDs were prepared according to tables 13 to 15, and the evaluation results are shown in table 16.
YI as an index of the light resistance test was 17.2 > 13, and it was judged that the light resistance was not satisfactory.
The fluorescent resin composition stored at 25 ℃ for 5 hours was judged to have no precipitation and the phosphor was uniformly dispersed, and to have satisfactory dispersion stability.
Subsequently, as a result of the "light emission test" of the LED, white light was emitted and it was judged as being acceptable.
Further, as a result of performing the "reliability test (1) (L test)", the lowest value of all the LEDs was 97% or more of the total luminous flux maintenance rate (%) and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Next, as a result of performing the "reliability test (3) (TC test)" described above, all the LEDs were turned on and judged to be acceptable even after performing a temperature cycle of 100 cycles.
From the above results, it was found that all of the dispersion stability test, the luminescence test, and the reliability tests (1) to (3) of the fluorescent resin composition of comparative example 21 were acceptable, but the light resistance was poor, and the composition was totally judged to be unacceptable.
Comparative example 22
The silicone resin obtained by mixing and stirring the solution a and the solution B at a mass ratio of 1: 1 was used instead of the resin composition of synthesis example 6. Resin compositions, cured products, fluorescent resin compositions, and LEDs were prepared according to tables 13 to 15 in the same manner as in example 42 except that the curing temperature of the cured products and the LED sealing materials was changed to 70 ℃ for 1 hour and further 150 ℃ for 5 hours, and the evaluation results are shown in table 16.
When YI as an index of the light resistance test was 2.0. ltoreq.13, the light resistance was judged to be acceptable.
Subsequently, as a result of the "light emission test" of the LED, white light was emitted and it was judged as being acceptable.
As a result of the above-described "reliability test (1) (L test)", 3 LEDs out of 10 were not lit, and the total luminous flux maintenance ratio (%) was not measured and judged as failed.
Next, as a result of performing the "reliability test (2) (TS test)" described above, after performing thermal shock for 100 cycles, only 4 LEDs out of 10 were turned on, and it was determined as a failure.
Further, as a result of performing the "reliability test (3) (TC test)" described above, after performing a temperature cycle of 100 cycles, only 6 LEDs out of 10 were turned on, and it was determined as a failure.
From the above results, it was judged that the fluorescent resin composition of comparative example 22 was acceptable in the dispersion stability test, the light resistance test and the light emission test, but the results of the reliability tests (1) to (3) were not acceptable, and the overall judgment was made to be unacceptable.
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 an alicyclic epoxy resin was used instead of the resin composition of synthesis example 7, and a dispersion stability test and a light emission test were performed by using the formulation shown in table 17. The results are shown in Table 18.
The fluorescent resin composition of comparative example 23 was subjected to a dispersion stability test, and as a result, it was judged as defective because precipitation occurred and unevenness occurred.
As a luminescence test of the light-storing material (coating film), the afterglow time was measured by the above-mentioned method and the duration was 600 minutes or longer, and it was judged as acceptable.
From the above results, it was judged that the fluorescent resin composition of comparative example 23 passed the light emission test, but failed the dispersion stability, and was judged to be failed as a whole.
From the results in tables 13 to 18, it is clear that the fluorescent resin compositions of examples 42 and 43 are excellent in dispersion stability and the cured products thereof are excellent in light resistance. In addition, the LED using the fluorescent resin compositions of examples 42 and 43 as a sealing material had good emission test and excellent reliability test. The fluorescent resin composition of example 44 was excellent in dispersion stability, and the luminescence test of the light-storing material was good. On the other hand, the fluorescent resin compositions of comparative examples 20 and 23 were poor in dispersion stability. Further, at least one of the light resistance when a cured product is obtained, and a light emission test and a reliability test of an LED used as a sealing material is poor.
As described above, the fluorescent resin composition of the present embodiment is excellent in dispersion stability, and the sealing material using the same is excellent in reliability and the light-storing material is excellent in luminescence.
Figure BDA0000041312520001221
TABLE 14
Unit: mass%
Figure BDA0000041312520001231
Figure BDA0000041312520001241
Figure BDA0000041312520001251
TABLE 17
Unit: mass%
Figure BDA0000041312520001261
Next, an insulating resin composition obtained by adding an insulating powder to the modified resin composition of the present embodiment will be specifically described with reference to examples and comparative examples.
The evaluation of 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 indices α to η were determined by the same methods as described above.
< measurement of average particle diameter of fused silica >
The average particle size was measured in a dry mode using a laser diffraction particle size distribution measuring apparatus (manufactured by SYMPATEC, "HELOS system").
< measurement of viscosity of resin composition >
The container containing the composition immediately after the production was sealed, and after temperature adjustment was performed at 25 ℃ for 1 hour, the viscosity at 25 ℃ was measured.
When the viscosity is 1000 pas or less, it is judged to have fluidity.
< measurement of volume resistivity of insulating resin composition >
An insulating resin composition was coated on a glass slide with a bar coater to a thickness of 40 μm, and the resultant was heated at 200 ℃ for 60 minutes to form a coating film.
The coating film was measured by a resistivity meter (DIA INSTRUMENTS co., ltd., product of Loresta) and had a volume resistivity of 1 × 1010When the voltage is not less than Ω · cm, the insulation is judged to be good.
< measurement of adhesive Strength and evaluation of adhesive Properties of insulating resin composition >
The adhesive strength before and after the moisture absorption treatment was measured in the following manner.
(1) An insulating resin composition was applied to a die pad (die pad) portion (9 mm. times.9 mm) of a copper lead frame.
(2) Subsequently, a silicon chip (8mm × 16mm) was mounted on the die pad portion, and the resultant was heated in a furnace at 200 ℃ × 1 hour. (sample before moisture absorption treatment)
(3) The sample prepared in (2) was subjected to moisture absorption in a constant temperature and humidity apparatus set at a temperature of 85 ℃ and a humidity of 85% for 72 hours. (sample after moisture absorption treatment)
(4) The "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" were heated on a hot plate at 250 ℃ for 20 seconds with the silicon chip facing downward, and then the lead of the lead frame was lifted up, and the adhesion strength when the silicon chip and the die pad were peeled off was measured using a push-pull gauge (manufactured by IMADA co., ltd).
(5) When the residual ratio of the adhesive strength represented by the following formula was 80% or more, the adhesiveness was judged to be good.
Residual bonding strength (%) (bonding strength after moisture absorption treatment)/(bonding strength before moisture absorption treatment) × 100
< evaluation of voids in insulating resin composition >
An insulating resin composition was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted thereon, and the glass chip was heated in a furnace at 200 ℃ for 1 hour. The presence or absence of voids in the sample was visually confirmed under a magnifying glass.
The insulating resin compositions of examples and comparative examples were judged to be acceptable overall when the insulating properties and adhesion were good and no voids were observed.
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: "AER" manufactured by Ltd, Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 187g/eq
Viscosity (25 ℃): 14.3 pas
(1-2) epoxy resin F: bisphenol F type epoxy resin (hereinafter referred to as "Bis-F epoxy resin")
Trade name: japan Epoxy Resins Co., Ltd., "JeR 807"
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 169g/eq
Viscosity (25 ℃): 3.2Pa · s
(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter, referred to as "GPTMS")
Trade name: KBM-403 manufactured by shin-Etsu chemical industries, Ltd "
(3) Alkoxysilane compound I: phenyltrimethoxysilane (hereinafter, referred to as "PTMS")
Trade name: KBM-103, manufactured by shin-Etsu chemical industries, Ltd "
(4) Alkoxysilane compound J: dimethyldimethoxysilane (hereinafter, referred to as "DMDMS")
Trade name: KBM-22, manufactured by shin-Etsu chemical industries, Ltd "
(5) Alkoxysilane compound K: tetraethoxysilane (hereinafter, referred to as "TEOS")
Trade name: KBE-04, manufactured by shin-Etsu chemical industries, Ltd "
(6) Solvent(s)
(6-1) tetrahydrofuran: wako pure chemical industries, Ltd., a stabilized form (hereinafter referred to as "THF")
(7) Hydrolysis condensation catalyst: dibutyl tin dilaurate (manufactured by Wako pure chemical industries, Ltd., hereinafter referred to as "DBTDL")
(8) Curing agent: dicyandiamide (pill good medicine industry co., Ltd.)
(9) Diluent agent: O-Toluene glycidyl Ether (trade name "SY-OCG", manufactured by Kagaku Kogyo Co., Ltd.) (epoxy equivalent of 181g/eq, viscosity of 8 mPas)
(10) Insulating powder
(10-1) fused silica (made by Toxinchen Kabushiki Kaisha, average particle diameter 6.1 μm)
(10-2) hydrophobic silica (Wacker Asahikasei Silicone Co., LTD., "H18")
[ Synthesis example 8]
Resin composition F: resin composition F was produced and evaluated in the following order.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) According to the composition ratio shown in table 19, the epoxy resin, the alkoxysilane compound, and THF were charged into a flask charged with a stirrer in an atmosphere of 25 ℃ and mixed and stirred, and then water and the hydrolytic condensation catalyst were added and mixed and stirred.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 10 hours while refluxing.
(4) After the reaction was completed, the temperature was cooled to 25 ℃, and then the cooling tube was removed from the flask, and after the reflux process was completed, a sample solution was collected.
(5) After the solution after the completion of the refluxing step was distilled off at 400Pa and 50 ℃ for 1 hour using an evaporator, the solution was further distilled off at 80 ℃ for 10 hours, and a dehydration condensation reaction was carried out.
(6) After the reaction, the reaction mixture was cooled to 25 ℃ to obtain a resin composition F.
(7) Table 21 shows mixing indices α 54 to ∈ 54 in the resin compositions.
(8) Further, the epoxy equivalent (WPE) of the resin composition F obtained in the above (6) was measured according to the above method.
The epoxy equivalent Weight (WPE) of the resin composition was 195g/eq, which is an appropriate value. The viscosity was 12.7 pas, and the liquid was fluid.
[ Synthesis example 9]
Resin composition G: resin composition G was synthesized and evaluated in the same manner as in synthesis example 8, based on the composition ratios shown in table 19. The mixing indices α 55 to ∈ 55 are shown in table 21.
The epoxy equivalent Weight (WPE) of the resin composition was 228g/eq, which is an appropriate value. The viscosity was 13.8 pas, and the liquid was fluid.
[ Synthesis example 10]
Resin composition H: resin composition H was synthesized and evaluated in the same manner as in synthesis example 8, based on the composition ratios shown in table 19. The mixing indices α 56 to ε 56 are shown in Table 21.
The epoxy equivalent Weight (WPE) of the resin composition was 206g/eq, which is an appropriate value. The viscosity was 18.2 pas, and the liquid was fluid.
[ Synthesis example 11]
Resin composition I: resin composition I was synthesized and evaluated in the same manner as in synthesis example 8 based on the composition ratios shown in table 19. The mixing indices α 57 to ε 57 are shown in Table 21.
The epoxy equivalent Weight (WPE) of the resin composition was 208g/eq, which is an appropriate value. The viscosity was 10.2 pas, and the liquid was fluid.
[ example 45]
The insulating resin composition 1 was produced and evaluated in the following manner. The evaluation results and mixing indices α 54 to ∈ 54 are shown in table 21.
The resin composition F of synthesis example 8 was used, and raw materials were mixed according to the composition shown in table 20, and uniformly kneaded by a three-roll mill (manufactured by mitsunobu co. Further, the resultant was degassed at 400Pa for 30 minutes in a vacuum chamber to obtain insulating composition 1.
The insulating resin composition 1 was coated on a glass slide with a bar coater to a thickness of 40 μm, and the coated glass slide was heated at 200 ℃ for 60 minutes to form a coating film. The coating film was measured by a resistivity meter (DIA INSTRUMENTS co., ltd., product of Loresta)The volume resistivity of (2) was 1X 1010Omega cm or more, the insulation is judged to be good.
The residual ratio of the adhesive strength of the insulating resin composition 1 was determined in the following manner.
(1) The insulating resin composition 1 was applied to a die pad portion (9 mm. times.9 mm) of a copper lead frame to prepare 4 of the above samples.
(2) Subsequently, a silicon chip (8mm × 16mm) was mounted on the die pad portion, and the resultant was heated in a furnace at 200 ℃ × 1 hour.
(3) 2 of the samples prepared in (2) were used as "samples before moisture absorption treatment".
(4) The remaining 2 samples of the sample prepared in (2) were subjected to moisture absorption in a constant temperature and humidity apparatus set at a temperature of 85 ℃ and a humidity of 85% for 72 hours, and the resultant was used as a "post-moisture absorption sample".
(5) Using the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment", the silicon chip was placed downward, heated on a hot plate at 250 ℃ for 20 seconds, and then the lead of the lead frame was lifted up, and the adhesion strength when the silicon chip and the die pad were peeled off was measured using a push-pull force meter (manufactured by IMADA co. The measurement was performed with n being 2, and the average value was obtained.
(6) The average value of the bonding strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" obtained above was substituted into the following formula to obtain the residual ratio of bonding strength, and the adhesiveness was evaluated.
The residual bonding strength (%) is not less than 95% and not more than 80% (bonding strength after moisture absorption)/(bonding strength before moisture absorption) × 100, and it is judged that the insulating resin composition 1 has good adhesiveness.
Next, the insulating resin composition 1 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and no voids were generated.
From the above results, it was judged that the insulating resin composition 1 was excellent in insulating properties and adhesiveness and was judged to be acceptable in total because no voids were generated.
[ example 46]
Insulating resin composition 2 was produced and evaluated in the same manner as in example 45 using resin composition G described above, according to the composition shown in table 20. The evaluation results and mixing indices α 55 to ∈ 55 are shown in table 21.
The volume resistivity of the insulating resin composition 2 was 1X 1010Omega cm or more, the insulation is judged to be good.
The average value of the bonding strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the insulating resin composition 2 was substituted into the following formula to determine the residual ratio of the bonding strength, and the adhesiveness was evaluated.
The residual bonding strength (%) was not less than 92% and not more than 80% (bonding strength after moisture absorption)/(bonding strength before moisture absorption) × 100, and it was judged that the insulating resin composition 2 had good adhesiveness.
Next, the insulating resin composition 2 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and no voids were generated.
From the above results, it was judged that the insulating resin composition 2 was excellent in insulating properties and adhesiveness and no voids were generated, and thus the overall judgment was made as a pass.
[ example 47]
Insulating resin composition 3 was produced and evaluated in the same manner as in example 45 using resin composition H described above, according to the composition shown in table 20. The evaluation results and the mixing indices α 56 to ∈ 56 are shown in table 21.
The volume resistivity of the insulating resin composition 3 was 1X 1010Omega cm or more, the insulation is judged to be good.
The average value of the adhesive strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the insulating resin composition 3 was substituted into the following formula to determine the residual ratio of the adhesive strength, and the adhesiveness was evaluated.
The residual bonding strength (%) is equal to or greater than 89% and 80% of (bonding strength after moisture absorption)/(bonding strength before moisture absorption) × 100, and it is judged that the insulating resin composition 3 has good adhesiveness.
Next, the insulating resin composition 3 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and no voids were generated.
From the above results, it was judged that the insulating resin composition 3 was excellent in insulating properties and adhesiveness and was judged to be acceptable in total because no voids were generated.
[ example 48]
Insulating resin composition 4 was produced and evaluated in the same manner as in example 43 using resin composition I described above, according to the compositions in table 20. The evaluation results and the mixing indices α 57 to ∈ 57 are shown in table 21.
The volume resistivity of the insulating resin composition 4 was 1X 1010Omega cm or more, the insulation is judged to be good.
The average value of the adhesive strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the insulating resin composition 4 was substituted into the following formula to determine the residual ratio of the adhesive strength, and the adhesiveness was evaluated.
The residual bonding strength (%) is not less than 86% and not more than 80% (bonding strength after moisture absorption)/(bonding strength before moisture absorption) × 100, and it is judged that the insulating resin composition 4 has good adhesiveness.
Next, the insulating resin composition 4 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and no voids were generated.
From the above results, it was judged that the insulating resin composition 4 was excellent in insulating properties and adhesiveness and was judged to be acceptable in total because no voids were generated.
Comparative example 24
Based on the composition shown in Table 20, an insulating resin composition 5 was produced and evaluated in the same manner as in example 45, using Bis-A epoxy resin and Bis-F epoxy resin in place of the resin composition F. The results are shown in Table 21.
The volume resistivity of the insulating resin composition 5 was 1X 1010Omega cm or more, the insulation is judged to be good.
The average value of the bonding strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the insulating resin composition 5 was substituted into the following formula to determine the residual ratio of the bonding strength, and the adhesiveness was evaluated.
The residual bonding strength (%) was 63% < 80% of (bonding strength after moisture absorption)/(bonding strength before moisture absorption) × 100, and it was judged that the insulating resin composition 5 had poor adhesion.
Next, an insulating resin composition 5 was applied to a die pad portion of a copper lead frame, a glass chip (8mm × 8mm) was mounted, and the glass chip was heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and no voids were generated.
From the above results, it was judged that the insulating resin composition 5 was satisfactory in insulation property, no voids were generated, but poor in adhesion property, and thus was totally judged to be defective.
Comparative example 25
Based on the composition shown in table 20, an insulating resin composition 6 was produced and evaluated in the same manner as in example 43 using Bis-a epoxy resin, GPTMS, and PTMS in place of resin composition F. The results are shown in Table 21.
The volume resistivity of the insulating resin composition 6 was 1X 10 10Omega cm or more, the insulation is judged to be good.
The average value of the adhesive strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the insulating resin composition 6 was substituted into the following formula to determine the residual ratio of the adhesive strength, and the adhesiveness was evaluated.
The residual bonding strength (%) is equal to or greater than 89% and 80% of (bonding strength after moisture absorption)/(bonding strength before moisture absorption) × 100, and it is judged that the insulating resin composition 6 has good adhesiveness.
Next, the insulating resin composition 6 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and as a result, generation of pores was confirmed.
From the above results, it was judged that the insulating resin composition 6 was satisfactory in insulating property and adhesiveness, but generation of voids was confirmed, and thus the overall judgment was failed.
As shown in tables 19 to 21, when the insulating resin composition contains a resin composition obtained by mixing an epoxy resin and a specific alkoxysilane compound at a specific ratio and performing cohydrolytic condensation, and an insulating powder and a curing agent, the insulating resin composition is excellent in insulating properties and adhesion properties and also does not cause voids.
Figure BDA0000041312520001351
Figure BDA0000041312520001361
Figure BDA0000041312520001371
Next, a semiconductor device using the modified resin composition of the present embodiment will be specifically described by referring to examples and comparative examples.
The evaluation of 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 indices α to η were determined by the same methods as described above.
< calculation of storage stability index θ and storage stability of resin composition >
The storage stability of the resin composition was evaluated by a storage stability index θ represented by the following general formula (9).
Storage stability index θ ═ (storage viscosity)/(initial viscosity) (9)
The container containing the resin composition immediately after the production was sealed, and after adjusting the temperature at 25 ℃ for 2 hours, the viscosity at 25 ℃ was measured and used as the "initial viscosity".
The container containing the resin composition was sealed and stored in a incubator at a constant temperature of 25 ℃ for 2 weeks. After storage, the viscosity at 25 ℃ was measured and used as "storage viscosity".
When the resin composition has fluidity (viscosity of 1000Pa · s or less) and the storage stability index θ is 4 or less, it is judged that the resin composition has storage stability.
< test on light resistance of LED (cured product) >
It is difficult to cut the sample after the LED is manufactured. Therefore, a cured product was produced by the following method, and the evaluation results were used as a substitute for the evaluation of the light resistance of the LED.
(1) A cured product prepared by the method described below was cured in a solution to prepare a cured product having a thickness of 20 mm. times.10 mm. times.3 mm.
(2) The cured product was covered with a black mask having a hole diameter of 5.5mm of 25 mm. times.15 mm. times.1.2 mm thick to prepare a sample for light resistance test.
(3) An apparatus was prepared so that the above-mentioned sample in an incubator thermostatically maintained at 50 ℃ could be irradiated with UV light from a UV irradiation apparatus (manufactured by Ushio inc. "Spot Cure SP7-250 DB") via an optical fiber.
(4) The sample was placed in a 50 ℃ incubator with a black mask on top.
(5) 2W/cm was irradiated from the upper part of the black mask in such a manner that UV light could be irradiated into a hole having a diameter of 5.5mm2UV light for 96 hours.
(6) The sample after UV irradiation was measured by a spectrocolorimeter ("SD 5000", manufactured by Nippon Denshoku industries Co., Ltd.) in which the opening of the integrating sphere was modified to have a diameter of 10 mm.
(7) According to "ASTM D1925-70 (1988): the Test Method for Yellowness Index of Plastics (Test Method for Yellowness Index of Plastics) "determines the Yellowness Index (YI). When this YI is 13 or less, it is judged as being acceptable.
< reliability test of LED (1) (continuous operation test: hereinafter referred to as "L test") >
The evaluation of 10 LEDs was carried out under the following conditions in accordance with a method 1026.5 (steady state operating life) of "MIL-STD-750E (test method of semiconductor device)" and a method 1005.8 (steady state life) of "MIL-STD-883G (microcircuit)".
The light is turned on under the conditions that the forward current IF is 20mA, the ambient temperature Ta is 25 ℃, and 960 hours, and the total luminous flux (lm) before and after the light is turned on is measured. Further, for each LED, the "total luminous flux maintenance ratio (%) (total luminous flux after lighting)/(total luminous flux before lighting) × 100" was obtained, and when the lowest value of the total luminous flux maintenance ratios (%) of all the LEDs was 90% or more, it was judged as being acceptable.
< reliability test of LED (2) (thermal shock test: hereinafter referred to as "TS test") >
The 10 LEDs were evaluated under the following conditions in accordance with test method 307 (thermal shock test) of "EIAJ ED-4701/300 (environmental and durability test method for semiconductor device (strength test I)".
The lighting of the LED was confirmed after thermal shock was performed for 100 cycles with "-10 ℃ (5 minutes) to 100 ℃ (5 minutes)" as 1 cycle, and when all 10 were lit, the LED was judged to be acceptable.
< test (3) for reliability of LED (temperature cycle test: hereinafter referred to as "TC" test) >
The 10 LEDs were evaluated under the following conditions in accordance with test method 105 (temperature cycle test) of "EIAJ ED-4701/100 (environmental and durability test method for semiconductor devices (life test I)".
The lighting of the LEDs was confirmed after 100 cycles of 1 cycle of "-40 ℃ (30 minutes) -85 ℃ (5 minutes) -100 ℃ (30 minutes) -25 ℃ (5 minutes)", and when all 10 were lit, the LED was judged to be acceptable.
In the above evaluation of the LED, when all of the light resistance and reliability tests (1) to (3) were acceptable, the LED was judged to be acceptable overall.
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")
Trade name: "AER 2600" manufactured by Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 188g/eq
Viscosity (25 ℃): 14.8 pas
(1-2) epoxy resin A2: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as "Bis-A2 epoxy resin")
Trade name: "AER 2500" by Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 186g/eq
Viscosity (25 ℃): 10.2 pas
(1-3) epoxy resin A3: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter, referred to as "Bis-A3 epoxy resin")
Trade name: "AER 6071" made by Ltd, Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) measured by the above method is as follows. Among them, the epoxy resin a3 was solid at 25 ℃, and thus the viscosity could not be measured.
Epoxy equivalent (WPE): 470g/eq
(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter, referred to as "GPTMS")
Trade name: KBM-403 manufactured by shin-Etsu chemical industries, Ltd "
(3) Alkoxysilane compound L: 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter, referred to as "ECETMS")
Trade name: KBM-303, manufactured by shin-Etsu chemical industries, Ltd "
(4) Alkoxysilane compound I: phenyltrimethoxysilane (hereinafter, referred to as "PTMS")
Trade name: KBM-103, manufactured by shin-Etsu chemical industries, Ltd "
(5) Alkoxysilane compound J: dimethyldimethoxysilane (hereinafter, referred to as "DMDMS")
Trade name: KBM-22, manufactured by shin-Etsu chemical industries, Ltd "
(6) Alkoxysilane compound K: tetraethoxysilane (hereinafter, referred to as "TEOS")
Trade name: KBE-04, manufactured by shin-Etsu chemical industries, Ltd "
(7) Solvent(s)
(7-1) tetrahydrofuran: wako pure chemical industries, Ltd., a stabilized form (hereinafter referred to as "THF")
(7-2) tert-Butanol: : wako pure chemical industries, Ltd., and containing no stabilizer (hereinafter referred to as "t-BuOH")
(8) Hydrolytic condensation catalyst
(8-1) Dibutyltin dilaurate (manufactured by Wako pure chemical industries, Ltd., hereinafter referred to as "DBTDL")
(8-2) dibutyl dimethoxy tin (manufactured by Sigma-Aldrich Co., Ltd., hereinafter referred to as "DBTDM")
(9) Curing agent: "4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride ═ 70/30"
Trade name: manufactured by Nissan chemical and physical Co., Ltd. "RIKACID MH-700G"
(10) Curing accelerator: amine compound
Trade name: "U-CAT 18X" manufactured by San-Apro Ltd "
(11) Silicone resin
Trade name: "EG 6301 (solution A/solution B)", manufactured by Dow Corning Toray Co., Ltd "
[ Synthesis example 12]
The resin composition was produced by the following procedure.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) The Bis-a1 epoxy resin, the alkoxysilane compound, and THF were charged into a flask charged with a stirrer in accordance with the composition ratios shown in table 22 below under an atmosphere of 25 ℃ and mixed under stirring, and then water and the hydrolytic condensation catalyst were added thereto and mixed under stirring.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 20 hours while refluxing (refluxing step).
(4) After the reaction was completed, it was cooled to 25 ℃ and then the cooling tube was removed from the flask.
(5) After the solution after the reflux step was distilled off at 400Pa and 50 ℃ for 1 hour using an evaporator, a dehydration condensation reaction was carried out while further distilling off at 80 ℃ for 10 hours (dehydration condensation step).
(6) And after the dehydration condensation reaction is finished, cooling to 25 ℃ to obtain the resin composition.
(7) The mixing indices α 58 to ∈ 58 in the resin composition are shown in table 24 below.
(8) Further, the epoxy equivalent Weight (WPE), initial viscosity and storage viscosity of the resin composition obtained in the above (6) were measured by the above-mentioned methods. Further, the storage stability index θ 58 was obtained and shown in table 24.
The epoxy equivalent Weight (WPE) of the resin composition of synthesis example 12 was 230g/eq, which is an appropriate value. The initial viscosity was 33.7Pa · s < 1000Pa · s, and the storage viscosity was 47.0Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 58 was 1.39. ltoreq.4, and it was judged as a resin composition having storage stability.
[ Synthesis example 13]
Resin compositions were produced in the same manner as in synthesis example 12, based on tables 22 and 23. The results of evaluation by the same method as in synthesis example 12, mixing indices α 59 to ∈ 59, and storage stability index θ 59 are shown in table 24.
As shown in table 24, the resin composition of synthesis example 13 had an epoxy equivalent Weight (WPE) of 231g/eq, which is an appropriate value. The initial viscosity was 13.2Pa · s < 1000Pa · s, and the storage viscosity was 19.1Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 59 was 1.45 ≦ 4, and it was determined as a resin composition having storage stability.
[ Synthesis example 14]
Resin compositions were produced in the same manner as in synthesis example 12, based on tables 22 and 23. The results of evaluation by the same method as in synthesis example 12, the blend indices α 60 to ∈ 60, and the storage stability index θ 60 are shown in table 24.
As shown in table 24, the resin composition of synthesis example 14 had an epoxy equivalent Weight (WPE) of 242g/eq, which is an appropriate value. The initial viscosity was 14.5Pa · s < 1000Pa · s, and the storage viscosity was 16.2Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 60 was 1.12. ltoreq.4, and it was judged as a resin composition having storage stability.
[ Synthesis example 15]
Resin compositions were produced in the same manner as in synthesis example 12, based on tables 22 and 23. The results of evaluation by the same method as in synthesis example 12, the blend indices α 61 to ∈ 61, and the storage stability index θ 61 are shown in table 24.
As shown in table 24, the resin composition of synthesis example 15 had an epoxy equivalent Weight (WPE) of 245g/eq, which is an appropriate value. The initial viscosity was 14.8Pa · s < 1000Pa · s, and the storage viscosity was 21.0Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 61 was 1.42. ltoreq.4, and it was judged as a resin composition having storage stability.
[ Synthesis example 16]
Resin compositions were produced in the same manner as in synthesis example 12, based on tables 22 and 23. The results of evaluation by the same method as in synthesis example 12, the blend indices α 62 to ∈ 62, and the storage stability index θ 62 are shown in table 24.
As shown in table 24, the resin composition of synthesis example 16 had an epoxy equivalent Weight (WPE) of 228g/eq, which is an appropriate value. The initial viscosity was 44.0Pa · s < 1000Pa · s, and the storage viscosity was 61.1Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 62 was 1.39. ltoreq.4, and it was judged as a resin composition having storage stability.
[ Synthesis example 17]
Resin compositions were produced in accordance with tables 22 and 23 by the same method as in synthesis example 12 except that the time for the reflux step was set to 7 hours. The results of evaluation by the same method as in synthesis example 12, mixing indices α 63 to ∈ 63, and storage stability index θ 63 are shown in table 24.
As shown in table 24, the resin composition of synthesis example 17 had an epoxy equivalent Weight (WPE) of 214g/eq, which is an appropriate value. The initial viscosity was 4.9Pa · s < 1000Pa · s, and the storage viscosity was 9.4Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 63 was 1.91. ltoreq.4, and it was judged as a resin composition having storage stability.
[ Synthesis example 18]
Resin compositions were produced in the same manner as in synthesis example 12, based on tables 22 and 23. The results of evaluation by the same method as in synthesis example 12, the blend indices α 64 to ∈ 64, and the storage stability index θ 64 are shown in table 24.
As shown in table 24, the resin composition of synthesis example 18 had an epoxy equivalent Weight (WPE) of 214g/eq, which is an appropriate value. The initial viscosity was 13.1Pa · s < 1000Pa · s, and the storage viscosity was 15.9Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 7 was 1.21. ltoreq.4, and it was judged as a resin composition having storage stability.
[ Synthesis example 19]
Resin compositions were produced in the same manner as in synthesis example 12, based on tables 22 and 23. The results of evaluation by the same method as in synthesis example 12, the blend indices α 65 to ∈ 65, and the storage stability index θ 65 are shown in table 24.
As shown in table 24, the epoxy equivalent Weight (WPE) of the resin composition of synthesis example 19 was 238g/eq, which is an appropriate value. The initial viscosity was 18.9Pa · s < 1000Pa · s, and the storage viscosity was 28.7Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 65 was 1.52. ltoreq.4, and was judged to be a resin composition having storage stability.
[ Synthesis example 20]
Resin compositions were produced in the same manner as in synthesis example 12, based on tables 22 and 23. The results of evaluation by the same method as in synthesis example 12, mixing indices α 66 to ∈ 66, and storage stability index θ 66 are shown in table 24.
As shown in table 24, the resin composition of synthesis example 20 had an epoxy equivalent Weight (WPE) of 213g/eq, which is an appropriate value. The initial viscosity was 11.2Pa · s < 1000Pa · s, and the storage viscosity was 16.1Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 66 was 1.44. ltoreq.4, and was judged to be a resin composition having storage stability.
[ Synthesis example 21]
Resin compositions were produced in the same manner as in synthesis example 12, based on tables 22 and 23. The results of evaluation by the same method as in synthesis example 12, the blend indices α 67 to ∈ 67, and the storage stability index θ 67 are shown in table 24.
As shown in table 24, the resin composition of synthesis example 21 had an epoxy equivalent Weight (WPE) of 253g/eq, which is an appropriate value. The initial viscosity was 26.8Pa · s < 1000Pa · s, and the storage viscosity was 39.1Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 67 was 1.46. ltoreq.4, and was judged to be a resin composition having storage stability.
[ comparative Synthesis example 1]
Resin compositions were produced in the same manner as in synthesis example 12, based on tables 22 and 23. The results of evaluation by the same method as in synthesis example 12, mixing indices α 68 to ∈ 68, and storage stability index θ 68 are shown in table 24.
As shown in table 24, the epoxy equivalent Weight (WPE) of the resin composition of comparative synthesis example 1 was 295g/eq, which is an appropriate value. The initial viscosity was 33.4Pa · s < 1000Pa · s, and the storage viscosity was 48.2Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 68 was 1.44. ltoreq.4, and it was judged as a resin composition having storage stability.
[ comparative Synthesis example 2]
Resin compositions were produced in the same manner as in synthesis example 12, based on tables 22 and 23. The results of evaluation by the same method as in synthesis example 12, mixing indices α 69 to ∈ 69, and storage stability index θ 69 are shown in table 24.
As shown in table 24, the epoxy equivalent Weight (WPE) of the resin composition of comparative synthesis example 2 was 295g/eq, which is an appropriate value. The initial viscosity was 29.0Pa · s < 1000Pa · s, and the liquid was fluid. However, the storage viscosity was > 1000 pas, the fluidity was not observed, the storage stability index θ 69 was > 35, and the storage stability of the resin composition of comparative synthesis example 2 was poor, and a sample for LED evaluation could not be prepared.
[ 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 ℃ and stirred to dissolve, and then P-MS and DBTDL were added and mixed.
Further, while purging with nitrogen, the temperature of the oil bath was raised to 105 ℃ to carry out dealcoholization reaction for 8 hours.
Subsequently, the mixture was cooled to 60 ℃ and then reduced in pressure to 12000Pa, and the dissolved alcohol was removed to obtain a resin composition. Table 24 shows the results of evaluation by the same method as in synthesis example 12 and the storage stability index θ 70.
The epoxy equivalent Weight (WPE) of the resin composition of comparative synthesis example 3 was 282g/eq, which is an appropriate value. Further, the initial viscosity was 1.89Pa · s < 1000Pa · s, and the storage viscosity was 2.03Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 70 was 1.07 or less and 4, and it was judged as a resin composition having storage stability.
[ example 49]
A cured product was produced using the resin composition of Synthesis example 12 stored at 25 ℃ for 2 weeks, and subjected to a light resistance test. The results are shown in Table 24.
(1) The resin composition, the curing agent and the curing accelerator were mixed and stirred at the composition ratios shown in table 23 in an atmosphere of 25 ℃, and degassed under vacuum to obtain a solution for a cured product.
(2) A molding jig was prepared by holding silicone rubber 3mm thick and shaped like コ between 2 stainless steel plates coated with a release agent.
(3) The solution for a cured product was injected into the molding jig, and curing treatment was performed at 120 ℃ for 1 hour and further at 150 ℃ for 1 hour to prepare a cured product.
(4) After the temperature in the furnace was lowered to 30 ℃ or lower, the cured product was taken out, and a sample for light resistance test was prepared according to the method described above.
(5) Using the above samples, a light resistance test was performed by the above method, and the results are shown in table 24.
When YI as an index of the light resistance test of the cured product was 10.1. ltoreq.13, the cured product was judged to be satisfactory in light resistance.
Next, using the resin composition of synthesis example 12, a shell-type LED having a structure shown in fig. 1 was produced in the following order, and reliability tests (1) to (3) were performed. The results are shown in Table 24.
(6) The solution for curing the sealing resin (1) was injected into the cup of a projectile-type cast frame having a diameter of 5 mm.
(7) An LED chip having an emission wavelength of 400nm was die-bonded with silver paste, and a lead frame to which bonding wires (gold wires) were connected was dipped.
(8) After defoaming in vacuum, the mixture was cured at 90 ℃ for 1 hour and further at 110 ℃ for 5 hours.
(9) Further, as an outer layer resin, 46.6 mass% of a curing agent and 0.2 mass% of a curing accelerator were added to 53.2 mass% of Bis-a epoxy resin, and mixed and stirred, and degassed under vacuum, and the degassed mixture was injected into a mold frame, and cured at 130 ℃ for 1 hour, and further cured at 150 ℃ for 6 hours, to obtain a bullet-type LED.
As a result of the above-described "reliability test (1) (L test)", the lowest value of all the LEDs was determined to be a total luminous flux maintenance rate (%) of 94% or more and 90% and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, the LED of example 49 was judged to be acceptable in all of the light resistance tests and reliability tests (1) to (3), and was judged to be acceptable in all.
[ example 50]
A cured product and an LED were produced in the same manner as in example 49 using the resin composition of synthesis example 13 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 8.1. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", the lowest value of all the LEDs was determined to be a total luminous flux maintenance rate (%) of 96% or more and 90%, and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, the LED of example 50 was judged to be acceptable in all of the light resistance tests and reliability tests (1) to (3), and was judged to be acceptable in all.
[ example 51]
A cured product and an LED were produced in the same manner as in example 49 using the resin composition of synthesis example 14 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 8.9. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", the minimum value of all LEDs was 95% or more of the total luminous flux maintenance rate (%) and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, the LED of example 51 was judged to be acceptable in all of the light resistance tests and reliability tests (1) to (3), and was judged to be acceptable in all.
[ example 52]
A cured product and an LED were produced in the same manner as in example 49 using the resin composition of synthesis example 15 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 8.3. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", the lowest value of all the LEDs was determined to be a total luminous flux maintenance rate (%) of 92% or more and 90%, and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, the LED of example 52 was judged to be acceptable in all of the light resistance tests and reliability tests (1) to (3), and was judged to be acceptable in all.
[ example 53]
A cured product and an LED were produced in the same manner as in example 49 using the resin composition of synthesis example 16 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 7.5. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", the lowest value of all the LEDs was determined to be a total luminous flux maintenance rate (%) of 96% or more and 90%, and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, the LED of example 53 was judged to be acceptable in all of the light resistance tests and reliability tests (1) to (3), and was judged to be acceptable in all.
[ example 54]
Cured products and LEDs were produced in the same manner as in example 49 except that the resin composition of synthesis example 17 was used instead of the resin composition of synthesis example 12, and the curing treatment temperature of the cured product and the sealing resin for LEDs was changed to 110 ℃ for 4 hours, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 8.8. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", the lowest value of all the LEDs was determined to be a total luminous flux maintenance rate (%) of 96% or more and 90%, and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, the LED of example 54 was judged to be acceptable in all of the light resistance tests and reliability tests (1) to (3), and was judged to be acceptable in all.
[ example 55]
A cured product and an LED were produced in the same manner as in example 49 using the resin composition of synthesis example 18 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 12.4. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", the minimum value of all the LEDs was 97% or more and 90% of the total luminous flux maintenance rate (%), and it was judged as being acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, the LED of example 55 was judged to be acceptable in all of the light resistance tests and reliability tests (1) to (3), and was judged to be acceptable in all.
[ example 56]
A cured product and an LED were produced in the same manner as in example 49 using the resin composition of synthesis example 19 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 7.2. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", the lowest value of all the LEDs was determined to be a total luminous flux maintenance rate (%) of 92% or more and 90%, and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, the LED of example 56 was judged to be acceptable in all of the light resistance tests and reliability tests (1) to (3), and was judged to be acceptable in all.
[ example 57]
A cured product and an LED were produced in the same manner as in example 49 using the resin composition of synthesis example 20 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 7.8. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", the lowest value of all the LEDs was determined to be a total luminous flux maintenance rate (%) of 93% or more and 90%, and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, the LED of example 57 was judged to be acceptable in all of the light resistance tests and reliability tests (1) to (3), and was judged to be acceptable in all.
[ example 58]
A cured product and an LED were produced in the same manner as in example 49 using the resin composition of synthesis example 21 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 9.2. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", the lowest value of all the LEDs was determined to be a total luminous flux maintenance rate (%) of 92% or more and 90%, and was judged to be acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, the LED of example 58 was judged to be acceptable in all of the light resistance tests and reliability tests (1) to (3), and was judged to be acceptable in all.
[ example 59]
An SMD type LED having a structure shown in fig. 2 was manufactured in the following procedure using the resin composition of synthesis example 13, and it was confirmed that the LED was turned on, with a size of 2.5mm × 2.5 mm.
(1) A silver paste was coated on the glass fiber epoxy substrate on which the metal pattern was formed, and the LED chip was die-bonded.
(2) The substrate was put into an electric furnace and cured.
(3) Bonding wires (gold wires) are bonded to the die-bonded LED chips to form a circuit.
(4) A substrate was placed on the mold, and the resin composition of Synthesis example 13 was injected and cured at 90 ℃ for 1 hour and further at 110 ℃ for 5 hours.
(5) The LEDs on the substrate are cut one by one to manufacture SMD type LEDs.
From the above results, it was found that the LEDs of examples 49 to 59 were excellent in light resistance and reliability, and were judged to be acceptable in total.
Comparative example 26
A cured product and an LED were produced in the same manner as in example 49 using the resin composition of comparative synthesis example 1 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 8.4. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", 2 LEDs out of 10 LEDs were not turned on, and the total luminous flux maintenance rate (%) could not be measured, and it was judged as failed.
Next, as a result of performing the "reliability test (2) (TS test)" described above, only 6 LEDs out of 10 LEDs were turned on after performing thermal shock for 100 cycles, and it was determined as a failure.
Further, as a result of performing the "reliability test (3) (TC test)" described above, only 6 LEDs out of 10 LEDs were turned on after performing a temperature cycle of 100 cycles, and it was determined as a failure.
From the above results, it was found that the LED of comparative example 26 was good in light resistance, but all of the reliability tests (1) to (3) were failed, and the LED was totally determined to be failed.
Comparative example 27
An attempt was made to produce a cured product and an LED by the same method as in example 49 using the resin composition of comparative synthesis example 2 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were carried out. Therefore, the overall judgment is failed.
Comparative example 28
A cured product and an LED were produced in the same manner as in example 49 using Bis-a1 epoxy resin instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
YI as an index of the light resistance test was 17.2 > 13, and it was judged that the light resistance was not satisfactory.
As a result of the above-described "reliability test (1) (L test)", the minimum value of all the LEDs was 97% or more and 90% of the total luminous flux maintenance rate (%), and it was judged as being acceptable.
Next, as a result of the above-described "reliability test (2) (TS test)", all the LEDs were turned on and judged to be acceptable even after the thermal shock was performed for 100 cycles.
Further, as a result of the above-described "reliability test (3) (TC test)", all the LEDs were turned on and judged to be acceptable even after the temperature cycle of 100 cycles.
From the above results, it was found that the LED of comparative example 28 was excellent in reliability, but poor in light resistance, and was judged to be defective overall.
Comparative example 29
The silicone resin obtained by mixing and stirring the solution a and the solution B at a mass ratio of 1: 1 was used instead of the resin composition of synthesis example 12. Cured products and LEDs were produced in the same manner as in example 49 except that the curing temperature of the cured product and the sealing resin for LEDs was changed to 70 ℃ for 1 hour and further 150 ℃ for 5 hours, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
When YI as an index of the light resistance test was 2.0. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described "reliability test (1) (L test)", 3 LEDs out of 10 LEDs were not turned on, and the total luminous flux maintenance ratio (%) was not measured and judged as a failure.
Next, as a result of performing the "reliability test (2) (TS test)" described above, only 4 LEDs out of 10 LEDs were turned on after performing thermal shock for 100 cycles, and it was determined as a failure.
Further, as a result of performing the "reliability test (3) (TC test)" described above, only 6 LEDs out of 10 LEDs were turned on after performing a temperature cycle of 100 cycles, and it was determined as a failure.
From the above results, it was confirmed that the LED of comparative example 29 was good in light resistance, but all of the reliability tests (1) to (3) were failed, and the LED was totally determined to be failed.
Comparative example 30
A cured product and an LED were produced in the same manner as in example 49 using the resin composition of comparative synthesis example 3 instead of the resin composition of synthesis example 12, and light resistance tests and reliability tests (1) to (3) were performed. The results are shown in Table 24.
Although a cured product for light resistance test was produced, cracks were generated and could not be measured, and it was judged that the light resistance was not satisfactory.
As a result of the above-described "reliability test (1) (L test)", 4 LEDs out of 10 LEDs were not turned on, and the total luminous flux maintenance ratio (%) was not measured and judged as a failure.
Next, as a result of performing the "reliability test (2) (TS test)" described above, only 5 LEDs out of 10 LEDs were turned on after performing thermal shock for 100 cycles, and it was determined as a failure.
Further, as a result of performing the "reliability test (3) (TC test)" described above, only 7 LEDs out of 10 LEDs were turned on after performing a temperature cycle of 100 cycles, and it was determined as a failure.
From the above results, it was judged that all of the light resistance and reliability tests (1) to (3) of the LED of comparative example 32 were failed, and the LED was comprehensively judged as failed.
As is clear from the results in tables 22 to 24, the LEDs of examples 49 to 59 are excellent in light resistance, L test, TS test and TC test. On the other hand, comparative examples 26 to 30 were poor in at least one of storage stability, light resistance, L test, TS test and TC test.
As described above, the LED manufactured using the modified resin composition of the present embodiment is excellent in light resistance and reliability.
Figure BDA0000041312520001531
TABLE 23
Unit: mass%
Figure BDA0000041312520001541
Figure BDA0000041312520001551
Next, the optical lens manufactured by using the modified resin composition of the present embodiment will be specifically described by referring to examples and comparative examples.
The evaluation of physical properties in examples 60 to 63 and comparative examples 31 to 35 was carried out as follows.
< calculation of storage stability index θ and storage stability of resin composition >
The storage stability of the resin composition was evaluated by a storage stability index θ represented by the following general formula (9).
Storage stability index θ ═ (storage viscosity)/(initial viscosity) (9)
The container containing the resin composition immediately after the production was sealed, and after adjusting the temperature at 25 ℃ for 2 hours, the viscosity at 25 ℃ was measured and used as the "initial viscosity".
Further, the container containing the resin composition was sealed and stored in a thermostatic incubator at 25 ℃ for 2 weeks. After storage, the viscosity at 25 ℃ was measured and used as "storage viscosity".
When the resin composition has fluidity (viscosity of 1000Pa · s or less) and the storage stability index θ is 4 or less, it is judged that the resin composition has storage stability.
< test on light resistance of optical lens (cured product) >
Since it was difficult to cut a sample after the optical lens was manufactured, a cured product was produced by the following method, and the evaluation result was substituted for the evaluation of the light resistance of the optical lens.
(1) A cured product prepared by the method described below was cured in a solution to prepare a cured product having a thickness of 20 mm. times.10 mm. times.3 mm.
(2) The cured product was covered with a black mask having a hole diameter of 5.5mm of 25 mm. times.15 mm. times.1.2 mm thick to prepare a sample for light resistance test.
(3) An apparatus was prepared so that the above-mentioned sample in an incubator thermostatically maintained at 50 ℃ could be irradiated with UV light from a UV irradiation apparatus (manufactured by Ushio inc. "Spot Cure SP7-250 DB") via an optical fiber.
(4) The sample was placed in a 50 ℃ incubator with a black mask on top.
(5) 2W/cm was irradiated from the upper part of the black mask in such a manner that UV light could be irradiated into a hole having a diameter of 5.5mm2UV light for 96 hours.
(6) The sample after UV irradiation was measured by a spectrocolorimeter ("SD 5000", manufactured by Nippon Denshoku industries Co., Ltd.) in which the opening of the integrating sphere was modified to have a diameter of 10 mm.
(7) According to "ASTM D1925-70 (1988): the Test Method for Yellowness Index of Plastics (Test Method for Yellowness Index of Plastics) "determines the Yellowness Index (YI). When this YI is 13 or less, it is judged as being acceptable.
< Cold thermal shock test of optical lens >
(1) 10 optical lenses manufactured by the method described below were placed in a cold-thermal shock device ("TSE-11-A" manufactured by ESPEC CORP.) and the temperature was measured at a temperature of "(-40 ℃ to 120 ℃) per cycle: the exposure time was 14 minutes and the warming and cooling time was 1 minute ".
(2) After 100 cycles of thermal cycles, the samples were taken out, and the number of specimens was recorded by spraying a penetrant liquid ("MICRO CHECK" manufactured by KOHZAI CORPORATION) and visually observing the presence or absence of an abnormality (peeling or cracking) under a magnifying glass.
(3) The sample in which abnormality was not confirmed in (4) above was again placed in the apparatus, and further subjected to 100 cycles of thermal cycling and evaluated by the same method. These operations were repeated to evaluate.
(4) The evaluation was interrupted when abnormality was observed in 1 of the 10 samples, and the "number of times of thermal shock resistance (the number of interrupted thermal cycles) - (100)" was determined.
When the number of times of the thermal shock resistance was 200 or more, the thermal shock resistance was judged to be acceptable.
< surface tackiness test of optical lens >
When the surface of an optical lens manufactured by the method described later was lightly pressed with a thumb wearing a latex glove, the surface was judged to have a satisfactory tackiness without confirming tackiness.
< porosity test of optical lens >
The 10 optical lenses manufactured by the method described later were visually confirmed under a magnifying glass, and when 10 lenses had no void, the lenses were judged to be acceptable.
When all of the above-mentioned light resistance test, thermal shock resistance test, surface tackiness test and porosity test were acceptable, the test was judged to be 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)
Trade name: "AER" manufactured by Ltd, Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 187g/eq
Viscosity (25 ℃): 14.3 pas
(1-2) epoxy resin B: 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexylcarboxylate (hereinafter, referred to as alicyclic epoxy resin)
Trade name: "CEL 2021P" manufactured by Daicel Chemical Industries, Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 131g/eq
Viscosity (25 ℃): 227mPa · s
(2) Alkoxysilane compound
(2-1) alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter, GPTMS)
Trade name: KBM-403 manufactured by shin-Etsu chemical industries, Ltd "
(2-2) alkoxysilane compound I: phenyltrimethoxysilane (hereinafter referred to as PTMS)
Trade name: KBM-103, manufactured by shin-Etsu chemical industries, Ltd "
(2-3) alkoxysilane compound J: dimethyldimethoxysilane (hereinafter referred to as DMDMS)
Trade name: KBM-22, manufactured by shin-Etsu chemical industries, Ltd "
(2-4) alkoxysilane compound K: tetraethoxysilane (hereinafter, referred to as TEOS)
Trade name: KBE-04, manufactured by shin-Etsu chemical industries, Ltd "
(3) Solvent: tetrahydrofuran (Heguang pure chemical industry Co., Ltd., containing no stabilizer) (hereinafter, referred to as THF)
(4) Hydrolytic condensation catalyst
(4-1) Dibutyltin dilaurate (hereinafter referred to as DBTDL, manufactured by Wako pure chemical industries, Ltd.)
(4-2) dibutyl dimethoxy tin (manufactured by Sigma-Aldrich Co., Ltd., hereinafter referred to as DBTDM)
(5) Curing agent: "4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride ═ 70/30"
Trade name: manufactured by Nissan chemical and physical Co., Ltd. "RIKACID MH-700G"
(6) Curing accelerator: amine compound
Trade name: "U-CAT 18X" manufactured by San-Apro Ltd "
(7) Silicone resin
Trade name: "EG 6301 (solution A/solution B)", manufactured by Dow Corning Toray Co., Ltd "
[ Synthesis example 22]
The resin composition was produced by the following procedure.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) The Bis-a1 epoxy resin, the alkoxysilane compound, and THF were charged into a flask charged with a stirrer in accordance with the composition ratios shown in table 25 below, and mixed and stirred at 25 ℃.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 20 hours while refluxing (refluxing step).
(4) After the reaction was completed, it was cooled to 25 ℃ and then the cooling tube was removed from the flask.
(5) After the solution after the reflux step was distilled off at 400Pa and 50 ℃ for 1 hour using an evaporator, a dehydration condensation reaction was carried out while further distilling off at 80 ℃ for 10 hours (dehydration condensation step).
(6) And after the dehydration condensation reaction is finished, cooling to 25 ℃ to obtain the resin composition.
(7) The mixing indices α 71 to ∈ 71 of the obtained resin compositions are shown in table 27 below.
(8) Further, the epoxy equivalent Weight (WPE), initial viscosity and storage viscosity of the resin composition obtained in the above (6) were measured by the above-mentioned methods. Further, the storage stability index θ 71 was obtained and shown in table 27.
As shown in table 27, the resin composition of synthesis example 22 had an epoxy equivalent Weight (WPE) of 230g/eq, which is an appropriate value. The initial viscosity was 33.7Pa · s < 1000Pa · s, and the storage viscosity was 47.0Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 71 was 1.39. ltoreq.4, and it was judged as a resin composition having storage stability.
[ Synthesis example 23]
Resin compositions were produced in accordance with tables 25 and 26 by the same method as in synthetic example 22 except that the time for the reflux step was set to 25 hours. Evaluation was performed by the same method as in synthesis example 22, and the evaluation results, blend indices α 72 to ∈ 72, and storage stability index θ 72 were shown in 27.
As shown in table 27, the epoxy equivalent Weight (WPE) of the resin composition of synthesis example 23 was 238g/eq, which is an appropriate value. The initial viscosity was 15.2Pa · s < 1000Pa · s, and the storage viscosity was 20.3Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 72 was 1.33. ltoreq.4, and it was judged as a resin composition having storage stability.
[ Synthesis example 24]
Resin compositions were prepared according to tables 25 and 26 by the same method as in synthetic example 22. The evaluation was carried out by the same method as in synthesis example 22, and the evaluation results, the blend indices α 73 to ∈ 73, and the storage stability index θ 73 are shown in table 27.
As shown in table 27, the resin composition of synthesis example 24 had an epoxy equivalent Weight (WPE) of 228g/eq, which is an appropriate value. The initial viscosity was 38.2Pa · s < 1000Pa · s, and the storage viscosity was 61.1Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 73 was 1.60. ltoreq.4, and was judged to be a resin composition having storage stability.
[ Synthesis example 25]
Resin compositions were produced in accordance with tables 25 and 26 by the same method as in synthetic example 22 except that the time for the reflux step was set to 7 hours. The evaluation was carried out by the same method as in synthesis example 22, and the evaluation results, blend indices α 74 to ∈ 74, and storage stability index θ 74 are shown in table 27.
As shown in table 27, the resin composition of synthesis example 25 had an epoxy equivalent Weight (WPE) of 214g/eq, which is an appropriate value. The initial viscosity was 4.9Pa · s < 1000Pa · s, and the storage viscosity was 9.4Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 74 was 1.91. ltoreq.4, and was judged to be a resin composition having storage stability.
[ comparative Synthesis example 4]
Resin compositions were prepared in accordance with tables 25 and 26 by the same method as in synthesis example 22. The results of the evaluation by the same method as in synthesis example 22, the blend indices α 75 to ∈ 75, and the storage stability index θ 75 are shown in table 27.
As shown in table 27, the epoxy equivalent (WPE) of the resin composition of comparative synthesis example 4 was 295g/eq, which is an appropriate value. The initial viscosity was 33.4Pa · s < 1000Pa · s, and the storage viscosity was 48.2Pa · s < 1000Pa · s, both of which were liquid having fluidity. The storage stability index θ 75 was 1.44. ltoreq.4, and it was judged as a resin composition having storage stability.
[ comparative Synthesis example 5]
Resin compositions were prepared in accordance with tables 25 and 26 by the same method as in synthesis example 22. The results of the evaluation by the same method as in synthesis example 22, mixing indices α 76 to ∈ 76, and storage stability index θ 76 are shown in table 27.
As shown in table 27, the epoxy equivalent (WPE) of the resin composition of comparative synthesis example 5 was 295g/eq, which is an appropriate value. The initial viscosity was 29.0Pa · s < 1000Pa · s, and the liquid was fluid. However, the storage viscosity was > 1000 pas, the fluidity was not observed, and the storage stability index θ 76 was > 35, the storage stability was poor, and a sample for evaluating an optical lens could not be produced.
[ example 60]
Using the resin composition of Synthesis example 22 stored at 25 ℃ for 2 weeks, a cured product was produced by the following procedure, and a light resistance test was performed. The results are shown in Table 27.
(1) The resin composition, the curing agent and the curing accelerator were mixed and stirred in the composition ratios shown in table 26 at 25 ℃ and degassed under vacuum to prepare a solution for a cured product.
(2) A molding jig was prepared by holding silicone rubber 3mm thick and shaped like コ between 2 stainless steel plates coated with a release agent.
(3) The solution for a cured product was injected into the molding jig, and curing treatment was performed at 120 ℃ for 1 hour and further at 150 ℃ for 1 hour to prepare a cured product.
(4) After the temperature in the furnace was lowered to 30 ℃ or lower, the cured product was taken out, and a sample for light resistance test was prepared according to the method described above.
(5) Using the above samples, a light resistance test was performed by the above method, and the test results are shown in table 27. When YI as an index of the light resistance test of the cured product was 10.1. ltoreq.13, the cured product was judged to be satisfactory in light resistance.
Next, using the resin composition of synthesis example 22, an optical lens was produced by the following procedure, and a thermal shock test, a surface tackiness test, and a void test were performed. The results are shown in Table 27.
(6) The raw materials were mixed in the ratios shown in table 26, defoamed in vacuum, and then set in an injection molding machine (manufactured by Sodick co.
(7) Further, the mixture was cured at 140 ℃ for 15 minutes, cooled to room temperature, and then released from the mold to obtain an optical lens having a diameter of about 1 cm.
As a result of the cold and hot impact test performed by the above method, the cold and hot impact resistance was judged to be acceptable when the number of cold and hot impact tests was 400 or more times and 200 or more times.
As a result of the surface tackiness test by the above method, no stickiness was observed, and it was judged as being acceptable.
As a result of the porosity test by the above method, no pores were confirmed, and it was judged as being acceptable.
From the above results, the optical lens of example 60 was judged to be acceptable in all of the light resistance test, the cold and hot shock test, the surface tackiness test and the void test, and was judged to be acceptable in total.
[ example 61]
A cured product and an optical lens were produced in the same manner as in example 60 using the resin composition of synthesis example 23 instead of the resin composition of synthesis example 22, and a light resistance test, a cold thermal shock test, a surface tackiness test, and a void test were performed. The results are shown in Table 27.
The light resistance was judged to be acceptable when YI, which is an index of the light resistance test, was 8.1. ltoreq.13.
As a result of the cold and hot impact test performed by the above method, the cold and hot impact test was carried out 300 times or more and 200 times or more, and it was judged that the cold and hot impact resistance was acceptable.
As a result of the surface tackiness test by the above method, no stickiness was observed, and it was judged as being acceptable.
As a result of the porosity test by the above method, no pores were confirmed, and it was judged as being acceptable.
From the above results, it was found that all of the light resistance test, the cold and hot shock test, the surface tackiness test and the void test of the optical lens of example 61 were acceptable, and the total was judged to be acceptable.
[ example 62]
A cured product and an optical lens were produced in the same manner as in example 60 using the resin composition of synthesis example 24 instead of the resin composition of synthesis example 22, and a light resistance test, a cold thermal shock test, a surface tackiness test, and a void test were performed. The results are shown in Table 27.
When YI as an index of the light resistance test was 8.9. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the above-described cold and hot impact test, the number of cold and hot impact tests was 500 or more and 200 or more, and it was judged that the cold and hot impact resistance was satisfactory.
As a result of the surface tackiness test by the above method, no stickiness was observed, and it was judged as being acceptable.
As a result of the porosity test by the above method, no pores were confirmed, and it was judged as being acceptable.
From the above results, it was found that all of the light resistance test, the cold and hot shock test, the surface tackiness test and the void test of the optical lens in example 62 were acceptable, and the total was judged to be acceptable.
[ example 63]
A cured product and an optical lens were produced in the same manner as in example 60 using the resin composition of synthesis example 25 instead of the resin composition of synthesis example 22, and a light resistance test, a cold thermal shock test, a surface tackiness test, and a void test were performed. The results are shown in Table 27.
When YI as an index of the light resistance test was 8.3. ltoreq.13, the light resistance was judged to be acceptable.
As a result of the cold and hot impact test performed by the above method, the cold and hot impact test was carried out 300 times or more and 200 times or more, and it was judged that the cold and hot impact resistance was acceptable.
As a result of the surface tackiness test by the above method, no stickiness was observed, and it was judged as being acceptable.
As a result of the porosity test by the above method, no pores were confirmed, and it was judged as being acceptable.
From the above results, the optical lens of example 63 was judged to be acceptable in all of the light resistance test, the thermal shock test, the surface tackiness test and the void test, and was judged to be acceptable in all.
Comparative example 31
A cured product and an optical lens were produced in the same manner as in example 60 using the resin composition of comparative synthesis example 4 instead of the resin composition of synthesis example 22, and a light resistance test, a cold thermal shock test, a surface tackiness test, and a void test were performed. The results are shown in Table 27.
When YI as an index of the light resistance test was 8.4. ltoreq.13, the light resistance was judged to be acceptable.
The results of the thermal shock resistance tests performed by the above method were that the thermal shock resistance was judged to be unsatisfactory when the number of thermal shock tests was 100 times or less and 200 times or less.
As a result of the surface tackiness test by the above method, no stickiness was observed, and it was judged as being acceptable.
As a result of the porosity test by the above method, no pores were confirmed, and it was judged as being acceptable.
From the above results, it was found that the optical lens of comparative example 31 was acceptable in the light resistance test, the surface tackiness test and the void test, but was not acceptable in the thermal shock test, and was therefore judged to be acceptable in total.
Comparative example 32
In place of the resin composition of synthesis example 22, the resin composition of comparative synthesis example 5 was used, and an attempt was made to produce a cured product and an optical lens by the same method as in example 60, and a light resistance test, a cold thermal shock test, a surface tack test, and a void test were carried out. Therefore, the overall judgment is failed.
Comparative example 33
A cured product and an optical lens were produced in the same manner as in example 60 using a Bis-a epoxy resin instead of the resin composition of synthesis example 22, and a light resistance test, a surface tack test, and a void test were performed. The results are shown in Table 27.
YI as an index of the light resistance test was 17.2 > 13, and it was judged that the light resistance was not satisfactory.
As a result of the thermal shock resistance test performed by the above method, the thermal shock resistance was judged to be acceptable when the number of times of the thermal shock resistance test was 500 or more and not less than 200 times.
As a result of the surface tackiness test by the above method, no stickiness was observed, and it was judged as being acceptable.
As a result of the porosity test by the above method, no pores were confirmed, and it was judged as being acceptable.
From the above results, the optical lens of comparative example 35 was judged to be acceptable in the thermal shock test, the surface tackiness test and the void test, but not acceptable in the light resistance, and therefore, was judged to be acceptable in total.
Comparative example 34
A cured product and an optical lens were produced in the same manner as in example 60 using the silicone resin obtained by mixing and stirring the solution a and the solution B in a mass ratio of 1: 1 instead of the resin composition of synthesis example 22, and a light resistance test, a surface tack test, and a void test were performed. The results are shown in Table 27.
When YI as an index of the light resistance test was 2.0. ltoreq.13, the light resistance was judged to be acceptable.
The results of the thermal shock resistance tests performed by the above method were that the thermal shock resistance was judged to be unsatisfactory when the number of thermal shock tests was 100 times or less and 200 times or less.
As a result of the surface tackiness test by the above method, no stickiness was observed, and it was judged as being acceptable.
As a result of the porosity test by the above method, no pores were confirmed, and it was judged as being acceptable.
From the above results, it was found that the optical lens of comparative example 34 was acceptable in the light resistance test, the surface tackiness test and the void test, but was not acceptable in the thermal shock test, and therefore was judged to be acceptable in total.
Comparative example 35
A cured product and an optical lens were produced in the same manner as in example 60 using a composition obtained by mixing Bis-a epoxy resin, GPTMS, and PTMS in the formulation shown in table 25 instead of the resin composition of synthesis example 22, and a light resistance test, a surface tack test, and a void test were performed. The results are shown in Table 27.
In the light resistance test, a plurality of voids were generated in the test sample, and the light resistance could not be measured.
As a result of the cold and hot impact test performed by the above method, the cold and hot impact resistance was judged to be acceptable when the number of cold and hot impact tests was 200 or more times.
As a result of the surface tackiness test by the above method, stickiness was confirmed and it was judged as a failure.
As a result of the porosity test by the above method, the porosity was confirmed in 8 samples out of the 10 samples, and the sample was judged to be failed.
From the above results, it was found that the optical lens of comparative example 35 was acceptable in the thermal shock test, but failed in the light resistance test, the surface tackiness test and the void test, and thus was judged to be generally unacceptable.
Figure BDA0000041312520001651
Watch 26
Unit: mass%
Figure BDA0000041312520001671
Next, a conductive resin composition obtained by adding conductive metal powder to the modified resin composition of the present embodiment will be specifically described with reference to examples and comparative examples.
The evaluation of physical properties in examples 64 to 67 and comparative examples 36 to 38 was carried out as follows.
The epoxy equivalent (WPE), viscosity, and mixing indices α to η were determined by the same methods as described above.
< measurement of average particle diameter of conductive Metal powder >
The average particle size was measured in a dry mode using a laser diffraction particle size distribution measuring apparatus (manufactured by SYMPATEC, "HELOS system").
< measurement of viscosity of conductive resin composition >
The container containing the composition immediately after the production was sealed, and after temperature adjustment was performed at 25 ℃ for 1 hour, the viscosity at 25 ℃ was measured.
When the viscosity is 1000 pas or less, it is judged to have fluidity.
< measurement of softening Point of novolak-type phenol resin >
According to "JIS K6910: 2007 (phenol resin test method) "item 5.8 was measured.
< measurement of hydroxyl equivalent weight of novolak-type phenol resin >
According to "JIS K0070: 1002 (test methods for acid value, saponification value, ester value, iodine value, hydroxyl value, and unsaponifiable matter of chemical) "the hydroxyl value was measured and converted to a hydroxyl equivalent.
< measurement of volume resistivity of conductive resin composition >
The conductive resin composition was coated on a glass slide with a bar coater to a thickness of 40 μm, and the coated film was heated at 200 ℃ for 60 minutes.
The coating film was measured by a resistivity meter (DIA INSTRUMENTS CO., LTD., manufactured by Loresta) and had a volume resistivity of 9X 10-4When Ω · cm or less, the conductivity was judged to be good.
< measurement of adhesion Strength and evaluation of adhesion of conductive resin composition >
The adhesive strength before and after the moisture absorption treatment was measured in the following manner.
(1) A conductive resin composition was applied to a chip pad portion (9 mm. times.9 mm) of a copper lead frame.
(2) Subsequently, a silicon chip (8mm × 16mm) was mounted on the die pad portion, and the resultant was heated in a furnace at 200 ℃ × 1 hour. (sample before moisture absorption treatment)
(3) The sample prepared in (2) was subjected to moisture absorption in a constant temperature and humidity apparatus set at a temperature of 85 ℃ and a humidity of 85% for 72 hours. (sample after moisture absorption treatment)
(4) The "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" were heated on a hot plate at 250 ℃ for 20 seconds with the silicon chip facing downward, and then the lead of the lead frame was lifted up, and the adhesion strength when the silicon chip and the die pad were peeled off was measured using a push-pull force meter (manufactured by IMADA co.
(5) When the residual ratio of the adhesive strength represented by the following formula was 80% or more, the adhesiveness was judged to be good.
Residual bonding strength (%) (bonding strength after moisture absorption treatment)/(bonding strength before moisture absorption treatment) × 100
< evaluation of voids in conductive resin composition >
A conductive resin composition was applied to the chip pad portion of the copper lead frame, a glass chip (8 mm. times.8 mm) was mounted thereon, and the glass chip was heated in a furnace at 200 ℃ for 1 hour. The presence or absence of voids in the sample was visually confirmed under a magnifying glass.
The resin compositions of examples and comparative examples were judged to be acceptable overall when they had good flowability, conductivity and adhesion and no voids were observed.
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: "AER" manufactured by Ltd, Asahi Kasei Epoxy Co., Ltd "
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 187g/eq
Viscosity (25 ℃): 14.3 pas
(1-2) epoxy resin F: bisphenol F type epoxy resin (hereinafter referred to as "Bis-F epoxy resin")
Trade name: japan Epoxy Resins Co., Ltd., "JeR 807"
The epoxy equivalent Weight (WPE) and viscosity measured by the above-described method are as follows.
Epoxy equivalent (WPE): 169g/eq
Viscosity (25 ℃): 3.2Pa · s
(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter, referred to as "GPTMS")
Trade name: KBM-403 manufactured by shin-Etsu chemical industries, Ltd "
(3) Alkoxysilane compound I: phenyltrimethoxysilane (hereinafter, referred to as "PTMS")
Trade name: KBM-103, manufactured by shin-Etsu chemical industries, Ltd "
(4) Alkoxysilane compound J: dimethyldimethoxysilane (hereinafter, referred to as "DMDMS")
Trade name: KBM-22, manufactured by shin-Etsu chemical industries, Ltd "
(5) Alkoxysilane compound K: tetraethoxysilane (hereinafter, referred to as "TEOS")
Trade name: KBE-04, manufactured by shin-Etsu chemical industries, Ltd "
(6) Solvent(s)
(6-1) tetrahydrofuran: wako pure chemical industries, Ltd., a stabilized form (hereinafter referred to as "THF")
(7) Hydrolysis condensation catalyst: dibutyl tin dilaurate (manufactured by Wako pure chemical industries, Ltd., hereinafter referred to as "DBTDL")
(8) Curing agent
(8-1) curing agent A: novolac type phenol resin (trade name "Phenolite" manufactured by DIC K.K.; hydroxyl equivalent 104g/eq, softening point 100 ℃ C.) (hereinafter referred to as "NP resin")
(8-2) curing agent B: 1, 8-diazabicyclo [5.4.0] undec-7-ene (product name "DBU" manufactured by San-Apro Ltd.) (hereinafter, referred to as "DBU")
(9) Diluent agent: O-Toluene glycidyl Ether (trade name "SY-OCG" manufactured by Kagaku chemical Co., Ltd.; epoxy equivalent 181g/eq, viscosity 8 mPas)
(10) Silver powder
(10-1) Scale-like silver powder (average particle diameter 6.3 μm)
(10-2) spherical silver powder (average particle diameter 1.2 μm)
[ Synthesis example 26]
Resin composition J: resin composition J was produced and evaluated in the following order.
(1) Preparing: the circulating constant temperature water tank was set to 5 ℃ and the cooling tube was refluxed. Further, an oil bath at 80 ℃ was placed on the magnetic stirrer.
(2) According to the composition ratio shown in table 28, the epoxy resin, the alkoxysilane compound, and THF were charged into a flask charged with a stirrer in an atmosphere of 25 ℃ and mixed and stirred, and then water and the hydrolytic condensation catalyst were further added and mixed and stirred.
(3) Subsequently, the flask was equipped with a cooling tube, and the flask was quickly immersed in an oil bath at 80 ℃ to start stirring, and reacted for 10 hours while refluxing.
(4) After the reaction was completed, the temperature was cooled to 25 ℃, and then the cooling tube was removed from the flask to collect the sample solution after the completion of the refluxing step.
(5) After the solution after the completion of the refluxing step was distilled off at 400Pa and 50 ℃ for 1 hour using an evaporator, the solution was further distilled off at 80 ℃ for 5 hours, and a dehydration condensation reaction was carried out.
(6) After the reaction, the reaction mixture was cooled to 25 ℃ to obtain resin composition J.
(7) Table 30 shows mixing indexes α 77 to ∈ 77 in the resin compositions.
(8) Further, the epoxy equivalent (WPE) of the resin composition J obtained in the above (6) was measured according to the above method.
The epoxy equivalent Weight (WPE) of the resin composition was 195g/eq, which is an appropriate value. The viscosity was 12.7 pas, and the liquid was fluid.
[ Synthesis example 27]
Resin composition K: resin composition K was synthesized and evaluated in the same manner as in synthesis example 26, based on the composition ratios shown in table 28. The mixing indices α 78 to ε 78 are shown in Table 30.
The epoxy equivalent Weight (WPE) of the resin composition was 228g/eq, which is an appropriate value. The viscosity was 13.8 pas, and the liquid was fluid.
[ Synthesis example 28]
Resin composition L: resin composition L was synthesized and evaluated in the same manner as in synthesis example 26, based on the composition ratios shown in table 28. The mixing indices α 79. epsilon. 79 are shown in Table 30.
The epoxy equivalent Weight (WPE) of the resin composition was 206g/eq, which is an appropriate value. The viscosity was 18.2 pas, and the liquid was fluid.
[ Synthesis example 29]
Resin composition M: resin composition M was synthesized and evaluated in the same manner as in synthesis example 26, based on the composition ratios shown in table 28. The mixing indices α 80 to ε 80 are shown in Table 30.
The epoxy equivalent Weight (WPE) of the resin composition was 208g/eq, which is an appropriate value. The viscosity was 10.2 pas, and the liquid was fluid.
[ example 64]
The conductive resin composition 1 was produced and evaluated in the following manner. The evaluation results and mixing indices α 77 to ∈ 77 are shown in table 30.
Using resin composition J of Synthesis example 26, raw materials were mixed in accordance with the composition shown in Table 29, and uniformly kneaded by a three-roll mill (manufactured by Kokai Co., Ltd.). Further, the resultant was degassed at 400Pa for 30 minutes using a vacuum chamber to obtain a conductive resin composition 1. The conductive resin composition 1 had a viscosity of 21.5 pas and was a liquid having excellent fluidity.
The conductive resin composition 1 was coated on a glass slide with a bar coater to a thickness of 40 μm, and the coated glass slide was heated at 200 ℃ for 60 minutes to form a coating film. The volume resistivity of the coating film was measured by a resistivity meter (DIA INSTRUMENTS co., ltd., product of "Loresta"), and was 2 × 10-4Omega cm, judged as good conductivity.
The residual ratio of the adhesive strength of the conductive resin composition 1 was determined in the following manner.
(1) The conductive resin composition 1 was applied to a chip pad portion (9 mm. times.9 mm) of a copper lead frame to prepare a 4-point sample.
(2) Subsequently, a silicon chip (8mm × 16mm) was mounted on the die pad portion, and the resultant was heated in a furnace at 200 ℃ × 1 hour.
(3) The sample prepared in (2) was designated as "sample before moisture absorption treatment" at 2 points.
(4) The remaining 2 points of the sample prepared in (2) were subjected to moisture absorption in a constant temperature and humidity apparatus set at a temperature of 85 ℃ and a humidity of 85% for 72 hours, and this was used as a "post-moisture-absorption-treatment sample".
(5) Using the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment", the silicon chip was placed downward, heated on a hot plate at 250 ℃ for 20 seconds, and then the lead of the lead frame was lifted up, and the adhesion strength when the silicon chip and the die pad were peeled off was measured using a push-pull force meter (manufactured by IMADA co. The measurement was performed with n being 2, and the average value was obtained.
(6) The average value of the bonding strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" obtained above was substituted into the following formula to obtain the residual ratio of bonding strength, and the adhesiveness was evaluated.
The residual adhesive strength (%) was (adhesive strength after moisture absorption)/(adhesive strength before moisture absorption) × 100 was (148mN)/(151mN) × 100 was 98% or more and 80%, and it was judged that the adhesiveness of the conductive resin composition 1 was good.
Next, the conductive resin composition 1 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and no voids were generated.
From the above results, it was judged that the conductive resin composition 1 was excellent in fluidity, conductivity and adhesiveness and was judged to be acceptable in total because no voids were generated.
[ example 65]
Using the resin composition K described above in accordance with the composition in table 29, conductive resin composition 2 was produced and evaluated in the same manner as in example 64. The evaluation results and mixing indices α 78 to ∈ 78 are shown in table 30.
The conductive resin composition 2 had a viscosity of 23.7Pa · s and was a liquid having excellent fluidity.
The volume resistivity of the conductive resin composition 2 was 3X 10-4Omega cm, judged as good conductivity.
The average value of the bonding strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the conductive resin composition 2 was substituted into the following formula to determine the residual ratio of the bonding strength, and the adhesiveness was evaluated.
The residual adhesive strength (%) was (adhesive strength after moisture absorption)/(adhesive strength before moisture absorption) × 100 was (138mN)/(145mN) × 100 was 95% or more and 80%, and it was judged that the adhesiveness of the conductive resin composition 2 was good.
Next, the conductive resin composition 2 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and no voids were generated.
From the above results, it was judged that the conductive resin composition 2 was excellent in fluidity, conductivity and adhesiveness and was judged to be acceptable in all cases because no voids were generated.
[ example 66]
Using the resin composition L described above in accordance with the composition in table 29, conductive resin composition 3 was produced and evaluated in the same manner as in example 64. The evaluation results and the mixing indices α 79 to ∈ 79 are shown in table 30.
The conductive resin composition 3 had a viscosity of 28.2Pa · s and was a liquid having excellent fluidity.
The volume resistivity of the conductive resin composition 3 was 3X 10-4Omega cm, judged as good conductivity.
The average value of the bonding strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the conductive resin composition 3 was substituted into the following formula to obtain the residual bonding strength ratio, and the adhesiveness was evaluated.
The residual adhesive strength (%) is (adhesive strength after moisture absorption)/(adhesive strength before moisture absorption) × 100 is (124mN)/(136mN) × 100 is 91% or more and 80%, and it is judged that the adhesiveness of the conductive resin composition 3 is good. Further, it is presumed that the conductive resin composition 4 of example 65, which was produced with the same composition except that the ratio of NP resin to DBU was changed, exhibited more excellent adhesiveness, and that a multiplier effect was exhibited by using 2 kinds of curing agents in combination.
Next, the conductive resin composition 3 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and no voids were generated.
From the above results, it was judged that the conductive resin composition 3 was excellent in fluidity, conductivity and adhesiveness and was judged to be acceptable in total because no voids were generated.
[ example 67]
Using the resin composition M described above in accordance with the composition in table 29, a conductive resin composition 4 was produced and evaluated in the same manner as in example 64. The evaluation results and mixing indices α 80 to ∈ 80 are shown in table 30.
The conductive resin composition 4 had a viscosity of 19.1 pas and was a liquid having excellent fluidity.
The volume resistivity of the conductive resin composition 4 was 3X 10-4Omega cm, judged as good conductivity.
The average value of the bonding strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the conductive resin composition 4 was substituted into the following formula to obtain the residual bonding strength ratio, and the adhesiveness was evaluated.
The residual adhesive strength (%) is (adhesive strength after moisture absorption)/(adhesive strength before moisture absorption) × 100 is (108mN)/(128mN) × 100 is 84% or more and 80%, and it is judged that the adhesiveness of the conductive resin composition 4 is good.
Next, the conductive resin composition 4 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and no voids were generated.
From the above results, it was judged that the conductive resin composition 4 was excellent in fluidity, conductivity and adhesiveness and was judged to be acceptable in total because no voids were generated.
Comparative example 36
Conductive resin composition 5 was produced and evaluated in the same manner as in example 64, using Bis-a epoxy resin and Bis-F epoxy resin in place of resin composition J, according to the compositions in table 29. The results are shown in Table 30.
The conductive resin composition 5 had a viscosity of 26.4Pa · s and was a liquid having excellent fluidity.
The volume resistivity of the conductive resin composition 5 was 3X 10-4Omega cm, judged as good conductivity.
The average value of the bonding strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the conductive resin composition 5 was substituted into the following formula to obtain the residual bonding strength ratio, and the adhesiveness was evaluated.
The residual bonding strength (%) is (bonding strength after moisture absorption)/(bonding strength before moisture absorption) × 100 is (81mN)/(132mN) × 100 is 61% < 80%, and the conductive resin composition 5 has poor adhesiveness.
Next, the conductive resin composition 5 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and no voids were generated.
From the above results, it was judged that the conductive resin composition 5 was satisfactory in fluidity and conductivity and was not defective in adhesiveness although no voids were generated, and thus the overall judgment was failed.
Comparative example 37
Based on the composition shown in table 29, a conductive resin composition 6 was produced and evaluated in the same manner as in example 1, using Bis-a epoxy resin, GPTMS, and PTMS in place of the resin composition J. The results are shown in Table 30.
The conductive resin composition 6 had a viscosity of 18.2 pas and was a liquid having excellent fluidity.
The volume resistivity of the conductive resin composition 6 was 42X 10-4Omega cm, judged as poor conductivity.
The average value of the bonding strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the conductive resin composition 6 was substituted into the following formula to obtain the residual ratio of the bonding strength, and the adhesiveness was evaluated.
The residual adhesive strength (%) is (adhesive strength after moisture absorption)/(adhesive strength before moisture absorption) × 100 is (120mN)/(134mN) × 100 is 89% or more and 80%, and the adhesiveness of the conductive resin composition 6 is good.
Next, the conductive resin composition 6 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and as a result, generation of pores was confirmed.
From the above results, it was judged that the conductive resin composition 6 was satisfactory in fluidity and adhesiveness, but poor in conductivity, and was also judged to be defective in general by the occurrence of voids.
Comparative example 38
Conductive resin composition 7 was produced and evaluated in the same manner as in example 62 using Bis-a epoxy resin, Bis-F epoxy resin, and TEOS in place of resin composition J in accordance with the compositions in table 29. The results are shown in Table 30.
The conductive resin composition 7 had a viscosity of 16.3Pa · s and was a liquid having excellent fluidity.
The volume resistivity of the conductive resin composition 7 was 3X 10-4Omega cm, judged as good conductivity.
The average value of the bonding strength of the "sample before moisture absorption treatment" and the "sample after moisture absorption treatment" of the conductive resin composition 7 was substituted into the following formula to determine the residual ratio of the bonding strength, and the adhesiveness was evaluated.
The residual adhesive strength (%) is (adhesive strength after moisture absorption)/(adhesive strength before moisture absorption) × 100 is (131mN)/(140mN) × 100 is 94% or more and 80%, and the adhesiveness of the conductive resin composition 7 is good.
Next, the conductive resin composition 7 was applied to the die pad portion of the copper lead frame, and a glass chip (8mm × 8mm) was mounted and heated in a furnace under conditions of 200℃ × 1 hour. The sample was visually confirmed under a magnifying glass, and as a result, generation of pores was confirmed.
From the above results, it was found that the conductive resin composition 7 was satisfactory in fluidity, conductivity and adhesiveness, but voids were observed, and thus the overall judgment was failed.
As shown in tables 28 to 30, if the conductive resin composition contains a resin composition obtained by mixing an epoxy resin and a specific alkoxysilane compound at a specific ratio in the present embodiment and cohydrolytic condensation, a conductive metal powder, and a curing agent, the conductive resin composition has excellent fluidity.
The conductive resin composition of the present embodiment is excellent in conductivity and adhesiveness, and does not cause voids.
Figure BDA0000041312520001761
Figure BDA0000041312520001771
Figure BDA0000041312520001781
The present application is based on Japanese patent application (Japanese patent application No. 2008-175096) filed on 3.7.2008 to the Japanese franchise and Japanese patent application (Japanese patent application No. 2008-314273) filed on 10.12.2008 to the Japanese franchise, the contents of which are incorporated herein by reference.
Industrial applicability
According to the present invention, a modified resin composition which can form a cured product having excellent transparency and excellent heat resistance, heat discoloration resistance, light resistance, and thermal shock resistance and which has excellent storage stability can be provided.
Further, by using the modified resin composition of the present invention, it is possible to provide: a light-emitting component such as an LED which has excellent adhesion to an element or a sealing material, does not crack, and has a small decrease in long-term luminance; and an optical lens which can be injection molded, has a hard texture after curing and excellent dimensional stability, and has light resistance; and a semiconductor device using the light emitting member and/or the optical lens. By using the modified resin composition of the present invention, it is also possible to provide: a photosensitive composition which can suppress the inhibition of the generation of oxygen and has excellent adhesion, a coating agent containing the composition, and a coating film formed by curing the coating agent; a fluorescent resin composition having excellent dispersion stability of a fluorescent material, and a light storage material using the fluorescent resin composition; < d > an electrically conductive resin composition which is excellent in fluidity, electrical conductivity and adhesiveness and does not cause voids; and (e) an insulating resin composition which is excellent in fluidity, insulating properties and adhesion properties and does not cause voids.

Claims (33)

1. A modified resin composition obtained by reacting an epoxy resin (A) with an alkoxysilane compound represented by the following general formula (1),
(R1)n-Si-(OR2)4-n (1)
wherein n represents an integer of 0 to 3 inclusive; in addition, R1Each independently represents at least 1 or more organic groups selected from the group consisting of hydrogen atoms, the following a), the following b), the following c), and R2Respectively independent earth surfaceRepresents 1 or more organic groups selected from the group consisting of hydrogen atoms and d) below,
a) an organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms,
b) a 1-valent aliphatic organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more kinds of structures selected from the group consisting of a chain, a branched chain and a ring, the 1-valent aliphatic organic group having 1 or more carbon atoms and 24 or less and an oxygen atom number of 0 or more and 5 or less,
c) A 1-valent aromatic organic group, wherein the 1-valent aromatic organic group is an unsubstituted or substituted aromatic hydrocarbon unit, and optionally has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 to 24 carbon atoms and 0 to 5 oxygen atoms,
d) a 1-valent organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, wherein the number of carbon atoms in the 1-valent organic group is 1 to 8;
the alkoxysilane compound includes:
(B) n is 1 or 2 and has at least 1 cyclic ether group as R1At least 1 alkoxysilane compound, and
(C) n is 1 or 2 and has at least 1 aromatic organic group as R1At least 1 kind of alkoxysilane compound of (a),
the alkoxysilane compound represented by the general formula (2) has a mixing index alpha of 0.001 to 19 inclusive,
mixing index α ═ (α c)/(α b) … (2)
Wherein, in the formula (2), α B represents the content (mol%) of the component (B) in the alkoxysilane compound represented by the general formula (1), and α C represents the content (mol%) of the component (C) in the alkoxysilane compound represented by the general formula (1);
And the modified resin composition has a residual alkoxy group content of 5% or less.
2. The modified resin composition according to claim 1, having a viscosity of 1000 Pa-s or less at 25 ℃.
3. The modified resin composition according to claim 1 or 2, wherein the epoxy equivalent of the modified resin composition is 100g/eq or more and 700g/eq or less.
4. The modified resin composition according to any one of claims 1 to 3, wherein the condensation rate of the alkoxysilane compound is 80% or more.
5. The modified resin composition according to any one of claims 1 to 4, wherein the viscosity of the epoxy resin (A) at 25 ℃ is 500 Pa-s or less.
6. The modified resin composition according to any one of claims 1 to 5, wherein the epoxy equivalent of the epoxy resin (A) is 100g/eq or more and 300g/eq or less.
7. The modified resin composition according to any one of claims 1 to 6, wherein the epoxy resin (A) is a polyfunctional epoxy resin comprising a glycidyl etherate of a polyphenol compound.
8. The modified resin composition according to any one of claims 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 claims 1 to 8, wherein the alkoxysilane compound represented by the general formula (3) has a mixing index β of 0.01 or more and 1.4 or less,
mixing index β { (β n2)/(β nO + β n1) } (3)
In the formula (3), β n2 represents the content (mol%) of the alkoxysilane compound represented by the general formula (1) in which n is 2, β n0 represents the content (mol%) of the alkoxysilane compound represented by the general formula (1) in which n is 0, β n1 represents the content (mol%) of the alkoxysilane compound represented by the general formula (1) in which n is 1, and β n2, β n0, and β n1 are values satisfying 0 ≦ { (β n0)/(β n0+ β n1+ β n2) } ≦ 0.1.
10. The modified resin composition according to any one of claims 1 to 9, wherein a mixing index γ of the epoxy resin (A) represented by the following general formula (4) and the alkoxysilane compound is 0.02 to 15,
mixing index γ ═ (γ a)/(γ s) (4)
Wherein in formula (4), γ a represents the mass (g) of the epoxy resin (a), and γ s represents the mass (g) of an alkoxysilane compound in which n is 0 to 2 among the alkoxysilane compounds represented by general formula (1).
11. A process for producing a modified resin composition according to any one of claims 1 to 10, which comprises reacting an alkoxysilane compound comprising at least (B) and (C) represented by the following general formula (1) in the presence of an epoxy resin (A), the process comprising the following steps (a) and (B):
a step (a): a step of co-hydrolyzing an alkoxysilane compound containing at least (B) and (C) represented by the general formula (1) in the presence of an epoxy resin (A) through a reflux step without dehydration to produce an intermediate;
a step (b): a step of subjecting the intermediate produced in the step (a) to a dehydration condensation reaction;
(R1)n-Si-(OR2)4-n (1)
wherein n represents an integer of 0 to 3 inclusive; in addition, R1Each independently represents at least 1 or more organic groups selected from the group consisting of hydrogen atoms, the following a), the following b), the following c), and R2Each independently represents 1 or more organic groups selected from the group consisting of a hydrogen atom and d),
a) an organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms,
b) A 1-valent aliphatic organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more kinds of structures selected from the group consisting of a chain, a branched chain and a ring, the 1-valent aliphatic organic group having 1 or more carbon atoms and 24 or less and an oxygen atom number of 0 or more and 5 or less,
c) a 1-valent aromatic organic group, wherein the 1-valent aromatic organic group is an unsubstituted or substituted aromatic hydrocarbon unit, and optionally has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 to 24 carbon atoms and 0 to 5 oxygen atoms,
d) a 1-valent organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, wherein the number of carbon atoms in the 1-valent organic group is 1 to 8;
(B) n is 1 or 2 and has at least 1 cyclic ether group as R1At least 1 kind of alkoxysilane compound of (a),
(C) n is 1 or 2 and has at least 1 aromatic organic group as R 1At least 1 kind of alkoxysilane compound of (a),
and the mixing index alpha of the alkoxysilane compound represented by the general formula (2) is 0.001 to 19,
mixing index α ═ (α c)/(α b) … (2)
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).
12. A process for producing a modified resin composition according to any one of claims 1 to 10, which comprises reacting an alkoxysilane compound comprising at least (B) and (C) represented by the following general formula (1) in the presence of an epoxy resin (A), the process comprising the following steps (C) and (d):
a step (c): a step of producing an intermediate by cohydrolyzing an alkoxysilane compound containing at least (B) and (C) represented by general formula (1) in a reflux step without dehydration;
step (d): a step of allowing the intermediate produced in the step (c) to coexist with the epoxy resin (a) to perform a dehydration condensation reaction;
(R1)n-Si-(OR2)4-n (1)
wherein n represents an integer of 0 to 3 inclusive; in addition, R1Each independently represents at least 1 or more organic groups selected from the group consisting of hydrogen atoms, the following a), the following b), the following c), and R 2Each independently represents 1 or more organic groups selected from the group consisting of a hydrogen atom and d),
a) an organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, and containing a cyclic ether group having 4 to 24 carbon atoms and 1 to 5 oxygen atoms,
b) a 1-valent aliphatic organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more kinds of structures selected from the group consisting of a chain, a branched chain and a ring, the 1-valent aliphatic organic group having 1 or more carbon atoms and 24 or less and an oxygen atom number of 0 or more and 5 or less,
c) a 1-valent aromatic organic group, wherein the 1-valent aromatic organic group is an unsubstituted or substituted aromatic hydrocarbon unit, and optionally has an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of chain, branched and cyclic structures, and the 1-valent aromatic organic group has 6 to 24 carbon atoms and 0 to 5 oxygen atoms,
d) A 1-valent organic group having an unsubstituted or substituted aliphatic hydrocarbon unit containing 1 or more structures selected from the group consisting of a chain, a branched chain and a ring, wherein the number of carbon atoms in the 1-valent organic group is 1 to 8;
(B) n is 1 or 2 and has at least 1 cyclic ether group as R1At least 1 kind of alkoxysilane compound of (a),
(C) n is 1 or 2 and has at least 1 aromatic organic group as R1At least 1 kind of alkoxysilane compound of (a),
and the mixing index alpha of the alkoxysilane compound represented by the general formula (2) is 0.001 to 19,
mixing index α ═ (α c)/(α b) … (2)
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).
13. The method for producing a modified resin composition according to claim 11 or 12, wherein the alkoxysilane compound represented by the general formula (3) has a mixing index β of 0.01 to 1.4,
mixing index β { (β n2)/(β n0+ β n1) } (3)
In the formula (3), β n2 represents the content (mol%) of the alkoxysilane compound represented by the general formula (1) in which n is 2, β n0 represents the content (mol%) of the alkoxysilane compound represented by the general formula (1) in which n is 0, β n1 represents the content (mol%) of the alkoxysilane compound represented by the general formula (1) in which n is 1, and β n2, β n0, and β n1 are values satisfying 0 ≦ { (β n0)/(β n0+ β n1+ β n2) } ≦ 0.1.
14. The method for producing a modified resin composition according to any one of claims 11 to 13, wherein a mixing index γ between the epoxy resin (A) represented by the following general formula (4) and the alkoxysilane compound is 0.02 to 15,
mixing index γ ═ (γ a)/(γ s) (4)
Wherein in formula (4), γ a represents the mass (g) of the epoxy resin (a), and γ s represents the mass (g) of an alkoxysilane compound in which n is 0 to 2 among the alkoxysilane compounds represented by general formula (1).
15. The method for producing a modified resin composition according to any one of claims 11 to 14, wherein the temperature in the reflux step without dehydration is 50 to 100 ℃.
16. The method for producing a modified resin composition according to any one of claims 11 to 15, wherein a condensation rate of an intermediate obtained by cohydrolysis in a reflux step without dehydration is 78% or more.
17. The method for producing the modified resin composition according to any one of claims 11 to 16, wherein an alkoxide-based organotin is used as a catalyst in the cohydrolysis.
18. A resin composition obtained by further adding an oxetane compound (D) to the modified resin composition as claimed in claim 1.
19. A fluorescent resin composition obtained by further adding a fluorescent material (E) to the modified resin composition according to claim 1.
20. A conductive resin composition obtained by further adding a conductive metal powder (F) to the modified resin composition according to claim 1.
21. An insulating resin composition obtained by further adding an insulating powder (G) to the modified resin composition according to claim 1.
22. A resin composition obtained by further adding an epoxy resin (A') to the modified resin composition as described in claim 1.
23. A curable resin composition obtained by further adding a curing agent (H) to the resin composition according to any one of claims 1, 18 and 19.
24. A curable resin composition obtained by further adding a curing accelerator (I) to the resin composition according to claim 23.
25. A photosensitive resin composition, which is obtained by adding a photoacid generator (J) to the resin composition according to any one of claims 1, 18 and 19.
26. A light-emitting component produced using the resin composition according to claim 24 or 25.
27. An optical lens produced by using the resin composition according to claim 24 or 25.
28. A light-storing material produced using the resin composition according to claim 24 or 25.
29. A semiconductor device comprising the light-emitting component according to claim 26 and/or the optical lens according to claim 27.
30. A curable resin composition obtained by adding a curing accelerator (I) to the resin composition according to any one of claims 20 to 22.
31. A photosensitive resin composition, which is obtained by adding a photoacid generator (J) to the resin composition according to any one of claims 20 to 22.
32. A coating agent comprising the resin composition of any one of claims 24, 25, 30, and 31.
33. A coating film produced by using the coating agent according to claim 32.
CN2009801247757A 2008-07-03 2009-07-03 Modified resin composition, method for producing the same, and curable resin composition containing the same Active CN102076734B (en)

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