CN112029071B - Light-resistant epoxy resin and application thereof - Google Patents
Light-resistant epoxy resin and application thereof Download PDFInfo
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- CN112029071B CN112029071B CN201910492265.0A CN201910492265A CN112029071B CN 112029071 B CN112029071 B CN 112029071B CN 201910492265 A CN201910492265 A CN 201910492265A CN 112029071 B CN112029071 B CN 112029071B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates 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
- C08G59/18—Macromolecules 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
- C08G59/20—Macromolecules 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
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates 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
- C08G59/18—Macromolecules 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
- C08G59/20—Macromolecules 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
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates 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
- C08G59/18—Macromolecules 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
- C08G59/20—Macromolecules 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
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
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Abstract
The invention provides an epoxy resin and application thereof, wherein the epoxy resin uses nuclear magnetic resonance hydrogen spectrum @, the method is characterized in that 1 H-NMR) is 0.15 to 0.29 in terms of the number ratio (B/A) of aromatic protons (B) to aliphatic protons (A). The epoxy resin has a specific amount ratio of aromatic protons to aliphatic protons, and the epoxy resin provides a packaging material having suitable mechanical strength and excellent light resistance and heat resistance.
Description
Technical Field
The present invention relates to an epoxy resin, and more particularly, to a light-resistant epoxy resin having a specific quantitative ratio of aromatic protons to aliphatic protons. The epoxy resins of the present invention can be used to prepare an encapsulating composition to provide an encapsulating material that is particularly useful for light emitting diodes (light emitting diode, LEDs).
Background
With the development of technology, photoelectric materials have been widely studied and applied in various fields. For example, LEDs are one of the dominant studies in optoelectronic materials and can be used in outdoor devices such as electronic signs, indicator lights, detectors, and the like. However, the packaging material of the LED of the aforementioned outdoor device is susceptible to the problem of light transmittance degradation due to the influence of weather (e.g., temperature) and light irradiation due to long-term exposure to outdoor environment. Therefore, in addition to the high requirements for light transmittance, the packaging materials for LEDs are becoming more and more stringent in terms of weather resistance and light resistance.
At present, the packaging material of the LED mainly comprises epoxy resin and silicone, but the silicone has high cost and the prepared packaging material has the problem of poor mechanical strength generally, so the packaging material of the LED still takes the epoxy resin as the main material. However, the existing epoxy resin still has the problem of insufficient weather resistance and light resistance, and the transmittance of the prepared packaging material is obviously attenuated after the packaging material is exposed to high temperature or ultraviolet light for a long time.
Disclosure of Invention
The present invention is directed to a light-resistant epoxy resin (also referred to herein as "first epoxy resin"). In particular, the present invention relates to a light-resistant epoxy resin having a specific quantitative ratio of aromatic protons to aliphatic protons. The invention achieves the aim of improving the light resistance and the heat resistance of the packaging material prepared by using the epoxy resin by controlling the quantity ratio of aromatic protons to aliphatic protons in the epoxy resin; in addition, the packaging material prepared has proper mechanical strength. The epoxy resins of the present invention are therefore particularly suitable for LED packaging applications.
It is therefore an object of the present invention to provide an epoxy resin which exhibits hydrogen nuclear magnetic resonance spectrum 1 H-NMR) is 0.15 to 0.29 in terms of the number ratio (B/A) of aromatic protons (B) to aliphatic protons (A).
In some embodiments of the invention, the epoxy resin also has a Weight Per Epoxy (WPE) of 500 to 2000 g/eq.
In some embodiments of the invention, the epoxy resin comprises structural units derived from a cycloaliphatic compound (alicyclic compound) having two carboxyl groups and structural units derived from an aromatic epoxide (aromatic epoxide) having two epoxide groups. More specifically, the alicyclic compound having two carboxyl groups may have the structure of the following formula (I):
in formula (I), R 1 Is thatR 2 Each independently is H or methyl, and m is an integer from 0 to 2, wherein x represents a bonding position. Examples of the aromatic epoxide having two epoxy groupsSuch as may be selected from the group of: bisphenol a diglycidyl ether (bisphenol A diglycidyl ether), bisphenol F diglycidyl ether (bisphenol F diglycidyl ether), and combinations thereof.
In some embodiments of the invention, the epoxy resin comprises structural units derived from an aromatic compound having two-OH groups (aromatic compound) and structural units derived from a cycloaliphatic epoxide having two epoxy groups (alicyclic epoxide). More specifically, the aromatic compound having two-OH groups may have the structure of the following formula (II):
in formula (II), X 1 To X 8 、R 11 R is R 12 Each independently is H or CH 3 . The cycloaliphatic epoxide having two epoxide groups may be selected, for example, from the group consisting of: and combinations thereof, wherein n is an integer from 1 to 30.
It is a further object of the present invention to provide the use of an epoxy resin as described above for the preparation of an encapsulating composition.
It is still another object of the present invention to provide an encapsulating composition comprising a first epoxy resin and a hardener, wherein the first epoxy resin is an epoxy resin as described above. The hardener may be selected, for example, from the group: anhydrides, phenolic resins, imidazoles, and combinations thereof.
In some embodiments of the present invention, the encapsulating composition further comprises a second epoxy resin selected from the group consisting of: isocyanurate-based epoxy resins, cycloaliphatic epoxy resins, and combinations thereof.
It is still another object of the present invention to provide an encapsulating material which is prepared by curing the encapsulating composition as described above, and which has a transmittance after baking at 150 ℃ for 168 hours of preferably less than 23% as compared to the attenuation value of the transmittance before baking.
In order to make the above objects, technical features and advantages of the present invention more comprehensible, a detailed description of some embodiments accompanied with figures is provided below.
Detailed Description
Some specific embodiments according to the present invention will be specifically described below; however, the invention may be embodied in many different forms without departing from the spirit thereof and should not be construed as limited to the specific embodiments set forth herein.
As used in this specification (particularly in the claims), the singular and plural forms "a," "an," and "the" are to be construed as including the singular and plural forms, unless the context clearly dictates otherwise.
The term "normal temperature and pressure" herein means an environment having a temperature of 25℃and a pressure of 1 atm.
Herein, the term "light attenuation" refers to the attenuation of light transmittance. The term "light attenuation-resistant" means that the transmittance of a material is attenuated to a low degree after being subjected to heat or light. Herein, the transmittance is a transmittance value measured under light of 400 nm.
Unless otherwise indicated, in this specification (particularly in the claims), the use of "first," "second," and similar terms are used merely to distinguish between components or elements described, do not themselves have a special meaning, and are not intended to refer to a sequential order.
The present invention has an effect of providing an epoxy resin having a specific quantitative ratio of aromatic protons to aliphatic protons, and providing an encapsulating material having suitable mechanical strength and excellent light resistance and heat resistance using the epoxy resin. The following provides a detailed description of the epoxy resins of the present invention and their related applications.
1. Epoxy resin (first epoxy resin)
Herein, the epoxy resin is a thermosetting resin having an epoxy functional group. The epoxy resin of the present invention (i.e. "first epoxy resin") has the following features: hydrogen nuclear magnetic resonance spectrum 1 H-NMR) is 0.15 to 0.29, for example 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27 or 0.28. As for the light attenuation resistance, the epoxy resin of the invention adopts nuclear magnetic resonance hydrogen spectrum 1 The quantitative ratio (B/A) of the aromatic proton (B) to the aliphatic proton (A) as determined by H-NMR) is preferably 0.15 to 0.21. In addition, the epoxy resins of the present invention further may have an epoxy equivalent Weight (WPE) of 500 to 2000g/eq, such as 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, or 1950g/eq.
As will be described below, the epoxy resin of the present invention may be produced by reacting an alicyclic compound having two carboxyl groups with an aromatic epoxide having two epoxy groups, or may be produced by reacting an aromatic compound having two-OH groups with an alicyclic epoxide having two epoxy groups, so that the epoxy resin of the present invention may comprise or consist of structural units derived from an alicyclic compound having two carboxyl groups and structural units derived from an aromatic epoxide having two epoxy groups, or structural units derived from an aromatic compound having two-OH groups and structural units derived from an alicyclic epoxide having two epoxy groups.
1.1. Alicyclic compound having two carboxyl groups
Herein, the alicyclic compound having two carboxyl groups is a compound having two carboxyl groups and at least one aliphatic ring in one molecule. The number of carbon atoms of the aliphatic ring is at least 3, preferably 3 to 16, more preferably 3 to 8, and may be saturated or unsaturated, preferably saturated. In addition, the aliphatic ring may be substituted or unsubstituted, and hetero atoms, such as oxygen, sulfur, and the like, may be contained in the aliphatic ring.
In a preferred embodiment of the present invention, the alicyclic compound having two carboxyl groups has the structure of the following formula (I):
in formula (I), R 1 Is thatR 2 Each independently is H or methyl, and m is an integer from 0 to 2, wherein x represents a bonding position.
The compound having the structure of formula (I) can be obtained by reacting a cycloaliphatic anhydride with a cycloaliphatic diol. Examples of cycloaliphatic anhydrides include, but are not limited to, hexahydrophthalic anhydride (hexahydrophthalic anhydride), methyl hexahydrophthalic anhydride, dimethyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, and dimethyl tetrahydrophthalic anhydride. Examples of cycloaliphatic diols include, but are not limited to, 1, 4-cyclohexanedimethanol, tricyclo [5.2.1.0 2,6 ]Decanedimethanol (tricyclo [ 5.2.1.0) 2,6 ]decanedimethanol), 2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A), bis (4-hydroxycyclohexyl) methane (hydrogenated bisphenol F), 4' -bis (hydroxymethyl) dicyclohexyl, 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5 ]]Undecane (spiroglycerol) and 5-ethyl-2- (2-hydroxy-1, 1-dimethylethyl) -5-hydroxymethyl-1, 3-dioxane. In the latter examples, in the preparation of the compounds having the structure of formula (I), hexahydrophthalic anhydride and methylhexahydrophthalic anhydride were used as cycloaliphatic anhydrides, and 1, 4-cyclohexanedimethanol, tricyclo [5.2.1.0 were used 2,6 ]Decanedimethanol (tricyclo [ 5.2.1.0) 2,6 ]decanedimethanol), 2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol a) as cycloaliphatic diol.
1.2. Aromatic epoxides having two epoxide groups
Herein, an aromatic epoxide having two epoxy groups is an epoxide having two epoxy groups and at least one aromatic ring in one molecule. The number of carbon atoms of the aromatic ring is at least 4, preferably 6 to 24, more preferably 6 to 18. The aromatic ring may be substituted or unsubstituted, and hetero atoms, such as oxygen, sulfur, nitrogen, and the like may be contained in the aromatic ring.
In some embodiments of the present invention, the aromatic epoxide having two epoxide groups is a diglycidyl ether of a difunctional phenol compound, examples of which include, but are not limited to, bisphenol a (bisphenol a, BPA), tetramethyl bisphenol a, dimethyl bisphenol a, bisphenol F, tetramethyl bisphenol F, dimethyl bisphenol F, bisphenol S, tetramethyl bisphenol S, dimethyl bisphenol S, 4 '-biphenol, 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-tertiary butylphenol), resorcinol, hydroquinone, 9-bis (4-hydroxyphenyl) -9H-fluorene, and 9, 9-bis (4-hydroxy-3-methylphenyl) -9H-fluorene.
In a preferred embodiment of the present invention, the aromatic epoxide having two epoxide groups is selected from the group consisting of: bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, and combinations thereof.
1.3. Aromatic compounds having two-OH groups
As used herein, an aromatic compound having two-OH groups is a compound having two-OH groups and at least one aromatic ring in one molecule. In some embodiments of the invention, the aromatic compound having two-OH groups has the structure of formula (II):
in formula (II), X 1 To X 8 、R 11 R is R 12 Each independently is H or CH 3 . In a preferred embodiment of the invention, X 1 To X 8 Are all H, and R 11 R is R 12 Are all CH 3 . In the latter examples bisphenol A is used (i.e., in formula (II), X 1 To X 8 Are all H, and R 11 R is R 12 Are allCH 3 ) As aromatic compounds having two-OH groups.
1.4. Cycloaliphatic epoxides having two epoxide groups
Herein, the alicyclic epoxy having two epoxy groups is an epoxy having two epoxy groups and at least one aliphatic ring in one molecule. The alicyclic epoxide having two epoxy groups may be diglycidyl ether of the aforementioned alicyclic diol, but the present invention is not limited thereto. Specifically, examples of cycloaliphatic epoxides having two epoxide groups include, but are not limited to, dicyclopentadiene type epoxy resin (dicyclopentadienyl-based epoxy resin), hydrogenated bisphenol A type epoxy resin (hydrogenated bisphenol A-based epoxy resin), and 7-oxabicyclo [4.1.0] heptane type epoxy resin (7-oxacicyclo [4.1.0] heptane-based epoxy resin).
In some embodiments of the present invention, one or more 7-oxabicyclo [4.1.0] heptane-type epoxy resins having the structure of formula (III) below are used:
in formula (III), R 21 Is H or CH 3 Y is a covalent bond, -CH (CH) 3 )-、-CH 2 CH 2 -、-CH 2 CH(CH 3 )-、-CH 2 CH 2 CH 2 -、-C(＝O)OCH 2 -、-OC(＝O)(CH 2 ) 4 C(＝O)O-、-CH 2 OC(＝O)(CH 2 ) 4 C(＝O)OCH 2 -、 Wherein n is an integer of 1 to 30, and represents a bonding position.
Specific examples of 7-oxabicyclo [4.1.0] heptane type epoxy resins having the structure of formula (III) include, but are not limited to, the following group:
a kind of electronic device with high-pressure air-conditioning system
1.5. Preparation and Properties of epoxy resin
The epoxy resins of the present invention having a specific B/A value can be obtained by reacting an alicyclic or aromatic compound having two-OH groups with an aromatic or alicyclic epoxide having at least two epoxy groups in the presence of a catalyst, and formulating the ratio of these components to obtain the epoxy resins having the desired B/A value. The kind of the foregoing catalyst is not particularly limited as long as it can promote ring opening of the epoxy functional group and reduce the reaction temperature. Suitable catalysts include, but are not limited to, amines, imidazoles, and phosphorous-containing compounds. Examples of amines include, but are not limited to, 1,8-diazabicyclo [5.4.0] undec-7-ene (1, 8-diazabicyclo [5.4.0] undec-7-ene), triethylenediamine and 2,4,6-tris (dimethylaminomethyl) phenol (2, 4,6-tris (dimethylaminomethyl) phenol). Examples of imidazoles include, but are not limited to, 2-ethyl-4-methylimidazole and 2-methylimidazole. Examples of phosphorus-containing compounds include, but are not limited to, triphenyl-n-butyl phosphonium bromide (TBP), triphenylphosphine, tetraphenyl phosphonium-tetraphenyl borate (tetraphenyl phosphonium-tetraphenyl borate), tetra-n-butyl phosphonium-o, o-diethyl phosphorodithioate (tetra-n-butyl phosphonium-o, o-diethyl phosphorodithioate). The above-mentioned catalysts may be used alone or in combination of two or more.
In a preferred embodiment of the present invention, the epoxy resin is obtained by reacting an alicyclic compound having two carboxyl groups with an aromatic epoxide having two epoxy groups. First, a cycloaliphatic diol and a cycloaliphatic anhydride are mixed, heated to 90 ℃ to 110 ℃, and then subjected to an exothermic reaction so that the temperature reaches 160 ℃ to 180 ℃, and after the exothermic reaction is completed, the temperature is lowered to 140 ℃ to 150 ℃ and maintained at that temperature for 2 hours, thereby producing a cycloaliphatic compound (intermediate) having two carboxyl groups. Then, the intermediate product is cooled to 100 ℃ to 120 ℃ and aromatic epoxide with two epoxide groups is added, and the catalyst is added after uniform mixing. Then, after the temperature is raised to 150 to 160 ℃, an exothermic reaction is performed so that the temperature reaches 180 to 200 ℃, and after the exothermic reaction is completed, the temperature is lowered to 150 to 170 ℃ and maintained at that temperature for 2 hours, thereby producing the epoxy resin of the present invention. In this case, the amount of the alicyclic compound having two carboxyl groups and the aromatic epoxide having two epoxy groups is preferably controlled so that the number ratio (B/A) of the aromatic proton (B) to the aliphatic proton (A) of the produced epoxy resin is not more than 0.21. As shown in the examples below, the most excellent light-deterioration resistance (heat light deterioration value of less than 15%; UV light deterioration value of less than 3%)
In another embodiment of the present invention, the epoxy resin is obtained by reacting an aromatic compound having two-OH groups with a cycloaliphatic epoxide having two epoxide groups. First, after heating the alicyclic epoxide having two epoxy groups to 80 to 100 ℃, an aromatic compound having two-OH groups is added, and after mixing uniformly, a catalyst is added. Thereafter, the temperature is raised to 130 to 150 ℃, an exothermic reaction is performed so that the temperature reaches 180 to 200 ℃, and after the exothermic reaction is completed, the temperature is lowered to 150 to 170 ℃ and maintained at that temperature for 2 hours. Next, the alicyclic epoxy having two epoxy groups is added again and maintained at 150 to 170℃for 2 hours to effect a reaction, thereby obtaining the epoxy resin of the present invention.
In addition to the foregoing 1 The epoxy resin of the present invention preferably has a softening point (softening point) of 60 to 115℃in addition to the quantitative ratio (B/A) of the aromatic proton (B) to the aliphatic proton (A) and the epoxy equivalent value as measured by H-NMR, for example, 65℃68℃70℃75℃80℃81℃85℃89 DEG C90 ℃, 92 ℃, 96 ℃, 100 ℃, 105 ℃, 108 ℃, 110 ℃, or 113 ℃. The epoxy resin of the present invention is preferably a liquid epoxy resin at normal temperature and pressure, and specifically, the epoxy resin of the present invention preferably has a viscosity of less than 1000 pa·s at normal temperature and pressure.
2. Encapsulation composition
The epoxy resins of the present invention are useful in preparing potting compositions. Accordingly, the present invention also provides an encapsulating composition comprising a first epoxy resin and a hardener, and optionally other components, wherein the first epoxy resin is an epoxy resin having a specific B/a value as described above.
In the encapsulating composition of the present invention, the first epoxy resin may be present in an amount of 45 wt% to 65 wt%, such as 47 wt%, 50 wt%, 52 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, or 63 wt%, based on the total weight of the encapsulating composition.
2.1. Hardening agent
Herein, the hardener refers to a component that can initiate a ring-opening reaction of an epoxy functional group and undergo a crosslinking curing reaction with an epoxy resin. The kind of the hardener is not particularly limited as long as it can initiate a ring-opening reaction of the epoxy functional group and carry out a crosslinking curing reaction together with the epoxy resin. Examples of hardeners include, but are not limited to, anhydrides, phenolic resins (phenolic resins) and imidazoles. The above-mentioned hardening agents may be used alone or in combination of two or more.
Anhydrides include, but are not limited to, monoanhydrides, acid dianhydrides, polyanhydrides, and copolymers of the foregoing with other copolymerizable monomers. Examples of monoanhydrides include, but are not limited to, acetic anhydride, maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, or 4-methylhexahydrophthalic anhydride. Examples of acid dianhydrides include, but are not limited to, naphthalene tetracarboxylic dianhydride (naphthalene tetracarboxylic dianhydride) or pyromellitic dianhydride (pyromellitic dianhydride). Examples of polyanhydrides include, but are not limited to, mellitic anhydride (mellitic trianhydride). Examples of copolymers of anhydride with other copolymerizable monomers include, but are not limited to, styrene-maleic anhydride copolymers (copolymer of styrene and maleic anhydride).
Examples of phenolic resins include, but are not limited to, novolac phenolic resins (novolac phenolic resin) and resole phenolic resins (resol phenolic resin). Examples of novolak-type phenol resins include, but are not limited to, phenol novolak resins, phenol aralkyl resins, cresol novolak resins, tertiary butyl phenol novolak resins, and nonylphenol novolak resins.
Examples of imidazoles include, but are not limited to, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 1-benzyl-2-phenylimidazole.
In a preferred embodiment of the present invention, the hardener is a hardener which is in a liquid state at normal temperature and pressure, specifically a hardener having a viscosity of less than 1000 pa·s at normal temperature and pressure. In the latter examples, an acid anhydride in a liquid state at normal temperature and pressure was used as the hardener.
In the encapsulating composition of the present invention, the content of the hardener is not particularly limited as long as a desired hardening effect can be provided. Generally, the hardener can be present in an amount of 20 wt% to 35 wt%, such as 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 30 wt%, or 33 wt%, based on the total weight of the encapsulating composition.
2.2. Second epoxy resin
In the encapsulating composition of the present invention, a second epoxy resin may be optionally further included as an auxiliary hardener (auxiliary hardener) in addition to the first epoxy resin to aid in curing of the encapsulating composition. The second epoxy resin may be any existing epoxy resin such as, but not limited to, an epoxy resin having a triazine ring, a cycloaliphatic epoxy resin, a phenol-based epoxy resin (phenol epoxy resin), a cresol-based epoxy resin (cresol epoxy resin), a naphthalene-based epoxy resin (naphthalene phenolic epoxy resin), and a bisphenol-based epoxy resin (bisphenol phenolic epoxy resin). Examples of epoxy resins having a triazine ring include, but are not limited to, isocyanurate-based epoxy resins such as triglycidyl isocyanurate (triglycidyl isocyanurate). Examples of cycloaliphatic epoxy resins include, but are not limited to, the aforementioned cycloaliphatic epoxides such as (3 ',4' -epoxycyclohexane) methyl-3, 4-epoxycyclohexyl carboxylate ((3 ',4' -epoxycyclohexane) methyl 3,4-epoxycyclohexyl carboxylate). Examples of the cresol-based epoxy resin include, but are not limited to, o-cresol-based epoxy resin (ortho-cresol epoxy resin), m-cresol-based epoxy resin (meta-cresol epoxy resin), and p-cresol-based epoxy resin (para-cresol epoxy resin). Examples of bisphenol-based epoxy resins include, but are not limited to, bisphenol A-type epoxy resins (bisphenol A epoxy resin) and bisphenol F-type epoxy resins (bisphenol F epoxy resin). The epoxy resins may be used alone or in combination of two or more. In the latter examples triglycidyl isocyanurate or (3 ',4' -epoxycyclohexane) methyl-3, 4-epoxycyclohexyl carboxylate was used as the second epoxy resin.
In a preferred embodiment of the present invention, the second epoxy resin is an epoxy resin that is liquid at normal temperature and pressure, specifically an epoxy resin having a viscosity of less than 1000 Pa.s at normal temperature and pressure, or an epoxy resin that is liquid at least at the preparation temperature of the encapsulating composition. For example, in the latter embodiment, the encapsulating composition is prepared at a temperature of 120 ℃, and the melting point of the second epoxy resin is preferably lower than 120 ℃ in order to facilitate the liquid state during the preparation process.
In the encapsulating composition of the present invention, the content of the second epoxy resin is not particularly limited as long as it can provide a desired auxiliary effect without adversely affecting the light attenuation resistance and mechanical strength of the resulting encapsulating material. In general, the second epoxy resin may be present in an amount of 10 wt% to 20 wt%, such as 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, or 19 wt%, based on the total weight of the encapsulating composition.
2.3. Other optional ingredients
Other optional ingredients, such as catalysts as will be exemplified below and additives known in the art, may be further included in the encapsulating composition of the present invention as needed to adaptively improve the processability of the encapsulating composition during manufacture or to improve the physical and chemical properties of the material after curing of the encapsulating composition. Examples of additives known in the art include, but are not limited to, inorganic fillers, flame retardants, carbon black, colorants, defoamers, dispersants, viscosity modifiers, thixotropic agents (thixotropic agent), leveling agents (leveling agents), coupling agents, mold release agents, mold inhibitors, stabilizers, antioxidants, and antimicrobial agents. The additives may be used alone or in any combination.
In some embodiments of the present invention, the encapsulating composition further adds a catalyst to promote the epoxy functional group reaction and to reduce the curing reaction temperature of the encapsulating composition. The kind of the catalyst is not particularly limited as long as it can promote ring opening of the epoxy functional group and reduce the curing reaction temperature. Suitable catalysts include, but are not limited to, amines, imidazoles, phosphorus-containing compounds, and derivatives of the foregoing. The foregoing catalysts may be used alone or in any combination. In the examples which follow, triphenyl-n-butylphosphonium bromide (TBP) was used.
2.4. Preparation of encapsulation composition
Regarding the preparation of the encapsulating composition of the present invention, the components of the encapsulating composition may be prepared in a form of a varnish by uniformly mixing and dissolving or dispersing them in a solvent by a stirrer for use in subsequent processing. The solvent may be any inert solvent that can dissolve or disperse the components of the encapsulating composition, but that does not react with such components, such as toluene, gamma butyrolactone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, methyl isobutyl ketone, N-dimethylformamide (N, N-dimethyl formamide, DMF), N-dimethylacetamide (N, N-dimethyl acetamide, DMAc), and N-methylpyrrolidone (NMP).
However, the solvent is easily volatilized during the heat curing to generate defects such as bubbles and voids (void) in the material obtained after the curing of the encapsulating composition, which is disadvantageous for the application of the encapsulating material. Therefore, in order to avoid the occurrence of bubbles or voids in the cured product due to the volatilization of the solvent during the heat curing, the encapsulating composition is not usually prepared by using a solvent, so as to be beneficial for application as an encapsulating material, and is more suitable for environmental requirements of low VOC (volatile organic compound ). In view of this, the solvent-free encapsulating composition of the present invention can be prepared as follows. First, the first epoxy resin and the second epoxy resin were placed in a glass retort and uniformly mixed at 110 to 130 ℃ for 30 minutes. Then, the temperature was lowered to 90 to 110 ℃, and then, a hardener and a catalyst were added and uniformly mixed at the temperature for 30 minutes, thereby obtaining an encapsulating composition in a semi-cured state (B-stage).
3. Encapsulating material
The present invention also provides an encapsulating material provided by the above-described encapsulating composition, which is formed by curing the above-described encapsulating composition, that is, a material obtained after the encapsulating composition is completely cured (also referred to as C-stage). The curing method of the encapsulating composition is not particularly limited, and in some embodiments of the present invention, the encapsulating composition is cured by heating and pressurizing.
The encapsulation material of the present invention may be used for encapsulation of optoelectronic components, examples of which include, but are not limited to, LEDs, laser diodes, and photodetectors. The encapsulation material of the present invention is not limited to the above encapsulation applications, but may be used for encapsulation of any other object that needs to provide surface protection, such as encapsulation of wind turbine blades.
The encapsulant of the present invention has excellent light decay resistance, and in particular, the encapsulant of the present invention has a light transmittance after 168 hours of baking at 150 ℃ of less than 23%, such as 22%, 21%, 20%, 19%, 18%, 16%, 14%, 12%, 11%, 10%, 9%, 8%, 7%, 5% or 3%, in some embodiments, particularly less than 15%, of the light transmittance before baking. In addition, the encapsulating material of the present invention was used at 200 milliwatts per square centimeter (mW/cm) 2 ) And the attenuation value of the transmittance after 336 hours of continuous irradiation with a UV light source having a wavelength of 365 nm is less than 5%, such as 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1% or 0.5%, in some embodiments particularly less than 3%, compared to the transmittance before irradiation.
In addition, the packaging material of the invention has sufficient bending strength (flexural strength, FS) and bending modulus [ ], the packaging material is made of the materialflexal modules, FM). In particular, the packaging material of the present invention has a bending strength of up to 8 kg force/square millimeter (kgf/mm) 2 ) To 12 kg force/square mm, for example 8.5 kg force/square mm, 9 kg force/square mm, 9.5 kg force/square mm, 10 kg force/square mm, 10.5 kg force/square mm, 11 kg force/square mm or 11.5 kg force/square mm. In addition, the flexural modulus of the packaging material of the invention can reach 230 kg force/square millimeter (kgf/mm) 2 ) To 300 kg force/square millimeter, for example 235 kg force/square millimeter, 240 kg force/square millimeter, 245 kg force/square millimeter, 250 kg force/square millimeter, 255 kg force/square millimeter, 260 kg force/square millimeter, 265 kg force/square millimeter, 270 kg force/square millimeter, 275 kg force/square millimeter, 280 kg force/square millimeter, 285 kg force/square millimeter, 290 kg force/square millimeter or 295 kg force/square millimeter. For the encapsulation material of the present invention, the flexural modulus can be considered to be comparable to the Elastic Modulus (EM), which is proportional to the internal stress. Therefore, the lower the flexural modulus of the material, the lower the internal stress thereof, and the material having low internal stress is less likely to generate a fracture phenomenon due to a drastic change in temperature.
4. Examples
4.1. Description of measurement modes
The invention will now be further illustrated by the following specific embodiments, in which the measuring apparatus and method employed are each as follows:
[ Nuclear magnetic resonance Hydrogen Spectrum ] 1 H-NMR) test]
Nuclear magnetic resonance hydrogen Spectroscopy of epoxy resin using Nuclear magnetic resonance Spectroscopy (model: unity 400, available from Varian) 1 H-NMR). In the epoxy resin of the present invention, peaks between 0.5ppm and 5.5ppm (i.e., zone A) represent aliphatic protons, while peaks between 6.5ppm and 7.5ppm (i.e., zone B) represent aromatic protons. The aliphatic protons (a) may be obtained by summing the integrated values of all peaks of the a region, and the aromatic protons (B) may be obtained by summing the integrated values of all peaks of the B region.
[ epoxy equivalent Weight (WPE) test ]
0.15 g to 0.17 g of epoxy resin is taken as a sample in a beaker, 55 ml of the corresponding solvent (e.g. methyl ethyl ketone or toluene) is added and an indicator (e.g. crystal violet) is added. Titration was performed by potentiometric titration, and the titration solution used was a 0.1N HBr-glacial acetic acid solution. The titration end point is the reverse curve point in the potential change curve, and the WPE is calculated according to the following formula.
Where W is the sample weight, V is the titration volume of HBr, and N is the concentration of HBr.
[ softening Point test ]
The softening point test method was the ring and ball method (ring and ball method), and the test specification according to which was JIS K7232, and the related test methods are summarized as follows. First, 2.02 g of epoxy resin was taken as a sample and poured into a preheated copper ring, which was melted and bubble removed at a temperature of +70℃. Then, the copper ring containing the sample is cooled at room temperature for at least 30 minutes. Then, a beaker containing glycerin was prepared and placed on a heater, a copper ring containing a sample was placed in glycerin in a hanging manner, an iron ball was placed on the sample, and an infrared detector was set. The temperature rising rate of the heater was set to 5 ℃ per minute and heating was started, and the falling of the iron ball was confirmed by the infrared detector, and the temperature at which the iron ball fell was the softening point.
[ preparation of cured product sample ]
46.+ -.2 g of encapsulating composition (B-stage) was taken and granulated. The mold temperature of the molding machine (model: ST-75, purchased from a high-speed company) was set at 150.+ -. 2 ℃. After the ingot particles are preheated to 80+/-2 ℃, the ingot particles are put into a feed hole of a forming machine. Then, the resulting sample was cured in the mold for 4 minutes by maintaining the pressure with a punch (punching and holding) for 1 minute, and then the molded sample (molded specimen) was taken out. The molded sample may optionally be post-cured at 150℃for 4 hours to give a post-cured sample.
[ glass transition temperature (Tg) test ]
4 to 6 mg of the post-cured sample were taken and placed in a sample tray. Tg of the samples was determined using a differential scanning calorimeter (differential scanning calorimeter, DSC) (model: DSC 2910, available from TA instruments). The test conditions were as follows: the temperature parameters are set to 50-250 ℃ and the temperature rising rate is 20 ℃/min. And searching an inflection point in the obtained curve of the temperature and the heat flow (heat flow), wherein the temperature of the inflection point corresponding to the temperature axis is Tg.
[ thermal light decay test ]
The molded test pieces were cut into samples having a length of 60 mm, a width of 14 mm and a thickness of 1 mm. The sample was placed in a UV-visible light spectrometer (model: UV-1700, available from Shimadzu) to measure the transmittance at 400 nm (hereinafter referred to as "initial transmittance value"). Thereafter, the samples were placed in an oven and continuously baked at 150.+ -. 2 ℃ for 168 hours. After the sample was taken out and cooled to room temperature, the sample was placed in a UV-visible spectrometer to measure the transmittance in the 400 nm band (hereinafter referred to as "heat-resistant transmittance"). The heat-resistant light value minus the initial transmittance value is the heat light attenuation value.
[ Ultraviolet (UV) light decay test ]
The molded test pieces were cut into samples having a length of 60 mm, a width of 14 mm and a thickness of 1 mm. The sample was placed in a UV-visible spectrometer to measure the transmittance at the 400 nm wavelength band (hereinafter referred to as "initial transmittance"). Thereafter, the sample was placed at a distance of 5 cm at an intensity of 200 milliwatts per square centimeter (mW/cm) 2 ) And a UV light source having a wavelength of 365 nm was continuously irradiated with UV light for 336 hours. Next, the sample was further subjected to UV-visible light spectrometer to measure the transmittance in the 400 nm band (hereinafter referred to as "UV-resistant transmittance"). The value obtained by subtracting the initial transmittance value from the UV light resistance value is the UV light attenuation value.
[ test of flexural Strength and flexural modulus ]
Measurement of flexural Strength and flexural modulusThe test specification is JIS K6911, and the relevant test methods are summarized below. First, the post-cured sample was cut into a sample having a length of 80 mm or more, a width of 10.+ -. 0.2 mm and a thickness of 4.+ -. 0.2 mm. Next, the sample was placed in a universal material tester for a three-point bending test, in which the distance of the lower two fulcrums was set to 64 mm, and the moving speed of the upper jig was 2 mm/min. The flexural strength and flexural modulus were measured at the time of sample fracture. The unit of the bending strength is kilogram force/square millimeter (kgf/mm) 2 ). The unit of flexural modulus is kilogram force/square millimeter (kgf/mm) 2 )。
4.2. Raw material information list for examples and comparative examples
Table 1: raw material information list
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4.3. Preparation of epoxy resin and measurement of Properties
The epoxy resins of Synthesis examples 1 to 9 and comparative Synthesis examples 1 to 3 were prepared in accordance with the proportions shown in tables 2-1 to 2-3, and the preparation methods are described below.
With regard to synthesis examples 1 to 8 and comparative synthesis examples 1 to 3, first, an alicyclic diol and an alicyclic acid anhydride were mixed, heated to 100 ℃, then, an exothermic reaction was performed so that the temperature reached 170 ℃, and after the completion of the exothermic reaction, the temperature was lowered to 145 ℃ and maintained at that temperature for 2 hours, whereby an alicyclic compound (intermediate) having two carboxyl groups was produced. Then, the intermediate product is cooled to 110 ℃ and diglycidyl ether of a difunctional phenol compound is added, and after uniform mixing, the catalyst is added. Then, after the temperature was raised to 155 ℃, an exothermic reaction was performed so that the temperature reached 190 ℃, and after the completion of the exothermic reaction, the temperature was lowered to 160 ℃ and maintained at that temperature for 2 hours, whereby the epoxy resins of synthesis examples 1 to 8 and comparative synthesis examples 2 and 3 were obtained, and the epoxy resin of comparative synthesis example 1 was not successfully synthesized.
With respect to synthesis example 9, after first heating 100 parts by weight of the alicyclic epoxy to 90 ℃, 53.8 parts by weight of the bifunctional phenol compound was added, and after mixing uniformly, 0.1 part by weight of the catalyst was added. Thereafter, the temperature was raised to 140℃and an exothermic reaction was performed so that the temperature reached 190℃and after the exothermic reaction was completed, the temperature was lowered to 160℃and maintained at that temperature for 2 hours. Next, 7.6 parts by weight of a cycloaliphatic epoxide was added and kept at 160℃for 2 hours to effect a reaction, thereby obtaining an epoxy resin of Synthesis example 9.
In addition, commercially available epoxy resins 1 and 2 were prepared, wherein commercially available epoxy resin 1 was BE504H and commercially available epoxy resin 2 was BE503L.
The epoxy resins of Synthesis examples 1 to 9, the epoxy resins of comparative Synthesis examples 1 to 3, and the commercial epoxy resins 1 and 2 were measured for B/A value, softening point, and WPE according to the measurement methods described above, and the results were recorded in tables 2-1 to 2-3.
Table 2-1: composition and Properties of the epoxy resins of Synthesis examples 1 to 5
Table 2-2: composition and Properties of the epoxy resins of Synthesis examples 6 to 9
Table 2-3: comparative Synthesis examples 1 to 3 epoxy resins and compositions and Properties of commercially available epoxy resins 1 and 2
4.4. Preparation of the encapsulation composition and measurement of Properties (one)
The encapsulating compositions of examples 1 to 9 and comparative examples 1 to 6 were formulated in the proportions shown in tables 3-1 to 3-3. First, the first epoxy resin and the second epoxy resin were placed in a glass retort and uniformly mixed at 120℃for 30 minutes. Next, after cooling to 100 ℃, a hardener and a catalyst were added, and uniformly mixed at that temperature for 30 minutes, thereby obtaining each encapsulating composition (B stage).
Tg, heat light attenuation value, UV light attenuation value, flexural strength and flexural modulus of the cured products of the encapsulating compositions of examples 1 to 9 and comparative examples 1 to 6 were measured in accordance with the measurement methods described above and are recorded in tables 4-1 to 4-3.
Table 3-1: components and proportions of the encapsulation compositions of examples 1 to 5
Table 3-2: components and proportions of the encapsulation compositions of examples 6 to 9
Table 3-3: composition of encapsulation compositions of comparative examples 1 to 6
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Table 4-1: properties of cured products of the encapsulation compositions of examples 1 to 5
Table 4-2: properties of cured products of the encapsulation compositions of examples 6 to 9
Table 4-3: properties of cured products of the encapsulation compositions of comparative examples 1 to 6
As shown in tables 4-1 and 4-2, the cured product formed from the encapsulating composition comprising the epoxy resin having a specific B/A value of the present invention has a low heat light attenuation value, a low UV light attenuation value, a suitable Tg, a sufficient flexural strength and flexural modulus. In other words, the encapsulating material obtained from the resin composition of the present invention can have particularly excellent light-failure resistance properties while maintaining sufficient mechanical strength. Examples 1 to 3, 7 and 8 show that even if the proportions of the respective components used for preparing the epoxy resin are different, the obtained encapsulating material can obtain excellent light-failure resistance and sufficient mechanical strength as long as the B/a value of the epoxy resin is within the specified range. Examples 4 to 6 and 9 show that even if each component used for preparing the epoxy resin is different, the obtained encapsulating material can obtain excellent light-failure resistance and sufficient mechanical strength as long as the B/a value of the epoxy resin is within the specified range. Further, the results of examples 1 to 7 show that in the case where the epoxy resin of the present invention comprises a structural unit derived from an alicyclic compound having the structure of formula (I) and a structural unit derived from an aromatic epoxide having two epoxy groups, and the number ratio (B/a) of aromatic protons (B) to aliphatic protons (a) is not more than 0.21, the most excellent light-aging resistance property (heat light aging value less than 15%; UV light aging value less than 3%) can be provided.
In contrast, as shown in tables 4 to 3, the cured product formed from the encapsulating composition not containing the epoxy resin having a specific B/A value of the present invention cannot have a low heat light attenuation value, a low UV light attenuation value, a suitable Tg, a good flexural strength and a good flexural modulus at the same time. In particular, comparative examples 1 to 6 show that when the B/a value of the epoxy resin is not within the specified range, the thermal light attenuation value and the UV light attenuation value of the obtained encapsulating material are greatly improved, showing that the encapsulating material is poor in light resistance and does not have the light attenuation resistance characteristics.
4.5. Preparation of the encapsulation composition and measurement of Properties (II)
The encapsulating compositions of examples 10 to 11 and comparative example 7 were formulated in the proportions shown in table 5. First, the first epoxy resin and the solvent were placed in a glass retort and uniformly mixed at 120℃for 30 minutes. Next, after cooling to 100 ℃, a hardener and a catalyst were added, and uniformly mixed at that temperature for 30 minutes, thereby obtaining each encapsulating composition (B stage). After the encapsulation composition was coated on a glass plate to form a film, it was baked at 100℃for 2 hours to remove the solvent, and then baked at 150℃for 4 hours to perform post-curing, and cut into a sample having a length of 60 mm, a width of 14 mm and a thickness of 100. Mu.m. Next, the thermo-optical attenuation values of the encapsulation compositions of examples 10 to 11 and comparative example 7 were measured according to the measurement methods described above, and are recorded in table 5.
Table 5: composition of the encapsulation compositions of examples 10 and 11 and comparative example 7 and properties of the cured products produced
As shown in table 5, even though the encapsulating composition of the present invention does not contain the second epoxy resin, as long as the encapsulating composition contains the epoxy resin having a specific B/a value of the present invention, the resulting cured product can have excellent light-failure resistance properties as well.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and illustrate the technical features of the present invention, not intended to limit the scope of the protection of the present invention. Any person skilled in the art can easily accomplish the changes or arrangements without departing from the technical principle and spirit of the present invention, and the present invention is claimed. Accordingly, the scope of the invention is set forth in the following claims.
Claims (8)
1. An epoxy resin characterized in that the number ratio (B/A) of aromatic protons (B) to aliphatic protons (A) as measured by nuclear magnetic resonance hydrogen spectrometry is 0.15 to 0.21,
wherein the epoxy resin is obtained by reacting an alicyclic compound having two carboxyl groups with an aromatic epoxide having two epoxy groups to contain a structural unit derived from the alicyclic compound having two carboxyl groups and a structural unit derived from the aromatic epoxide having two epoxy groups, or
The epoxy resin is obtained by reacting an aromatic compound having two-OH groups with an alicyclic epoxy compound having two epoxy groups to contain a structural unit derived from the aromatic compound having two-OH groups and a structural unit derived from the alicyclic epoxy compound having two epoxy groups,
wherein the alicyclic compound having two carboxyl groups has the structure of the following formula (I):
in formula (I), R 1 Is thatR 2 Each independently is H or methyl, and m is an integer from 0 to 2, wherein x represents a bonding position;
the aromatic epoxide having two epoxide groups is selected from the group consisting of: bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, and combinations thereof;
the aromatic compound having two-OH groups has the structure of the following formula (II):
in formula (II), X 1 To X 8 、R 11 R is R 12 Each independently of the otherIs H or CH 3 ；
The cycloaliphatic epoxide having two epoxide groups is selected from the group consisting of: and combinations thereof, wherein n is an integer from 1 to 30.
2. The epoxy resin of claim 1, further having an epoxy equivalent weight of 500 to 2000 g/eq.
3. Use of the epoxy resin according to claim 1 or 2 for the preparation of an encapsulating composition.
4. An encapsulating composition comprising a first epoxy resin and a hardener, wherein the first epoxy resin is an epoxy resin according to claim 1 or 2.
5. The encapsulating composition of claim 4 further comprising a second epoxy resin selected from the group consisting of: isocyanurate-based epoxy resins, cycloaliphatic epoxy resins, and combinations thereof.
6. The encapsulating composition of claim 4 wherein the hardener is selected from the group consisting of: anhydrides, phenolic resins, imidazoles, and combinations thereof.
7. Encapsulating material, characterized in that it is prepared by curing the encapsulating composition according to any of claims 4 to 6.
8. The encapsulating material of claim 7 wherein the light transmittance after baking at 150 ℃ for 168 hours has a decay value of less than 23% compared to the light transmittance before baking.
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| JPS6136320A (en) * | 1984-07-30 | 1986-02-21 | Toshiba Corp | Photo-setting composition |
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| JPS6136320A (en) * | 1984-07-30 | 1986-02-21 | Toshiba Corp | Photo-setting composition |
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