WO2015041325A1 - シリコーン変性エポキシ樹脂およびその組成物と硬化物 - Google Patents
シリコーン変性エポキシ樹脂およびその組成物と硬化物 Download PDFInfo
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- WO2015041325A1 WO2015041325A1 PCT/JP2014/074864 JP2014074864W WO2015041325A1 WO 2015041325 A1 WO2015041325 A1 WO 2015041325A1 JP 2014074864 W JP2014074864 W JP 2014074864W WO 2015041325 A1 WO2015041325 A1 WO 2015041325A1
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- 0 CCC*(CCC1)(C1[S+](*)*)[S+](*)(*)C(C)CC Chemical compound CCC*(CCC1)(C1[S+](*)*)[S+](*)(*)C(C)CC 0.000 description 2
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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
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
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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
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
Definitions
- Examples of the resin composition for sealing an optical semiconductor element include a bisphenol A type epoxy resin excellent in adhesiveness and mechanical strength, and an epoxy resin having no UV absorption, such as a hydrogenated bisphenol A type epoxy resin or an alicyclic epoxy resin.
- a composition containing a curing agent and a curing catalyst is frequently used.
- the luminance and output of the LED element increase, there are problems of discoloration and cracking due to light, heat, etc. from the LED element.
- a resin in which an epoxy group is introduced into a silicone resin that does not absorb UV and gives a flexible cured product is known.
- a cyclic ether such as a glycidyl group or an epoxycyclohexyl group.
- Silicone resin having at least one containing group Patent Document 1
- reaction product of epoxyalkoxysilane and silanol Patent Document 2
- Patent Document 3 Silicone resin having a combination of alicyclic epoxy-modified silicone resin and alicyclic epoxy resin
- Patent Document 4 an addition reaction type phenyl silicone resin composition has been disclosed as a resin composition having low gas permeability (Patent Document 4), but it is still not satisfactory in terms of low gas permeability and adhesiveness. Absent.
- the present invention has been made in view of the above circumstances, and provides a silicone-modified epoxy resin composition that gives a cured product excellent in low gas permeability and strength, and an epoxy resin cured product obtained by curing the composition.
- the purpose is to do.
- a silicone-modified epoxy resin represented by the following formula (1). (Wherein R 1 represents an alkylene group having 2 to 6 carbon atoms which may contain an ester or ether bond, R 2 represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or 6 to 12 carbon atoms) A monovalent aromatic hydrocarbon group, R 3 represents an oxygen atom or a phenylene group, k represents an average value of 1 to 10, m represents an integer of 0 to 2, and n represents an average value of 0 to 10.
- R 4 represents an alkylene group having 0 to 4 carbon atoms which may contain an ester or ether bond.
- R 2 , R 3 and k each have the same meaning as described above.
- m and R 4 represent the same meaning as described above.
- the silicone-modified epoxy resin according to (1) obtained by reacting a compound represented by the formula: (4)
- the silicone-modified epoxy resin according to (1) obtained by oxidizing a diolefin compound of the following formula (4).
- R 1 to R 3 , k, m, and n each have the same meaning as described above.
- An epoxy resin composition comprising (A) the silicone-modified epoxy resin according to any one of (1) to (4) and (B) an epoxy resin curing agent.
- the epoxy resin composition according to (5) further comprising (C) an epoxy resin curing catalyst.
- the epoxy resin curing agent according to (5) which is selected from an amine curing agent, a phenol curing agent, an acid anhydride curing agent, and a polyvalent carboxylic acid resin. .
- Example 2 is a 1H-NMR spectrum of the silicone-modified epoxy resin (A-1) obtained in Example 1.
- 2 is a GPC chart of the silicone-modified epoxy resin (A-1) obtained in Example 1.
- the silicone-modified epoxy resin of the present invention can be obtained by oxidizing the diolefin resin that is a precursor of the silicone-modified epoxy resin of the present invention.
- the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
- Specific examples of the method of oxidative epoxidation with peracid include the method described in Japanese Patent Application Laid-Open No. 2006-52187.
- peracids examples include organic acids such as formic acid, acetic acid, propionic acid, maleic acid, benzoic acid, m-chlorobenzoic acid, and phthalic acid, and acid anhydrides thereof.
- organic acids such as formic acid, acetic acid, propionic acid, maleic acid, benzoic acid, m-chlorobenzoic acid, and phthalic acid
- acid anhydrides thereof it is preferable to use formic acid, acetic acid, and phthalic anhydride from the viewpoint of the efficiency of reacting with hydrogen peroxide to produce an organic peracid, the reaction temperature, the ease of operation, and the economy.
- Formic acid or acetic acid is more preferably used from the viewpoint of simplicity of reaction operation.
- Various methods can be applied to the epoxidation method using hydrogen peroxide solution. Specifically, Japanese Patent Application Laid-Open No.
- Non-Patent Document 1 James V. Crivello and Ramesh Narayan, Novell Epoxynorbornane Monomers. 1. Synthesis and Characterization, Macromolecules 1996, 29, pages 433 to 438) can also be described. . Specifically, the olefin group can be obtained by epoxidation using oxone.
- the polyacid used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, but polyacids containing tungsten or molybdenum are preferred, polyacids containing tungsten are more preferred, and tungstates are particularly preferred.
- Specific polyacids and polyacid salts included in the polyacids include tungsten acids selected from tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, 12-tungstosilicic acid, and the like. Examples thereof include molybdenum-based acids selected from molybdic acid and phosphomolybdic acid, and salts thereof.
- Examples of the counter cation of these salts include ammonium ions, alkaline earth metal ions, and alkali metal ions. Specific examples include alkaline earth metal ions such as calcium ions and magnesium ions, alkali metal ions such as sodium, potassium and cesium, but are not limited thereto. Particularly preferred counter cations are sodium ion, potassium ion, calcium ion and ammonium ion.
- the amount of the polyacid used is 1.0 to 20 mmol in terms of metal element (tungstenic acid is tungsten atom, molybdic acid is molybdenum atom) to 1 mol of olefin (functional group equivalent) in the diolefin compound of the present invention. , Preferably 2.0 to 20 mmol, more preferably 2.5 to 10 mmol.
- quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be preferably used, and in particular, the alkyl chain is preferably an aliphatic chain. .
- tridecanylmethylammonium salt dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt
- trihexa examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt.
- the anion species of these salts use carboxylate ions.
- carboxylate ion acetate ion, carbonate ion and formate ion are preferable. In particular, acetate ion is preferred.
- acetate ion is preferred.
- the quaternary ammonium salt has more than 100 carbon atoms, the hydrophobicity may become too strong and the solubility in the organic layer may deteriorate.
- the carbon number of the quaternary ammonium salt is less than 10, the hydrophilicity becomes strong, and the compatibility with the organic layer may be similarly deteriorated. In general, halogen remains in the quaternary ammonium salt.
- the amount of tungstic acid and quaternary ammonium carboxylate used is preferably 0.01 to 0.8 times equivalent, or 1.1 to 10 times equivalent to the valence of the tungstic acid used. More preferably 0.05 to 0.7 times equivalent, or 1.2 to 6.0 times equivalent, still more preferably 0.05 to 0.5 times equivalent, or 1.3 to 4.5 times equivalent. is there.
- tungstic acid is divalent with H 2 WO 4
- the quaternary ammonium carboxylate is 0.02 to 1.6 mol, or 2.2 to 20 mol, per mol of tungstic acid.
- a range is preferred.
- tungstophosphoric acid is trivalent, it is similarly 0.03 to 2.4 mol, or 3.3 to 30 mol, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 3.2. Mole or 4.4 to 40 mol is preferred.
- the amount of the quaternary ammonium carboxylate is lower than 1.1 times equivalent of the valence of tungstic acids, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and a by-product is produced.
- the problem is that things are easy to make.
- the amount is more than 10 times the equivalent, not only is the treatment of the excess quaternary ammonium carboxylate difficult, but it also serves to suppress the reaction, which is not preferable.
- a commercially available product may be used as the quaternary ammonium salt having a carboxylate ion as an anion.
- the raw material quaternary ammonium salt is treated with a metal hydroxide or an ion exchange resin to be converted into a quaternary ammonium hydroxide. Further, it may be produced by a method of reacting with various carboxylic acids. Examples of the raw material quaternary ammonium salt include quaternary ammonium halides and various metal salts. If there is a suitable quaternary ammonium hydroxide, it may be used.
- any buffer can be used, but it is preferable to use an aqueous phosphate solution in this reaction.
- the pH is preferably adjusted between pH 4 and 10, more preferably pH 5-9. When the pH is less than 4, the hydrolysis reaction and polymerization reaction of the epoxy group easily proceed. Moreover, when pH10 is exceeded, reaction will become extremely slow and the problem that reaction time is too long will arise. In particular, in the present invention, it is preferable to adjust the pH to be between 5 and 9 when the tungstic acid as a catalyst is dissolved.
- a buffer solution is used in an amount of 0.1 to 10 mol% of phosphoric acid (or phosphorous such as sodium dihydrogen phosphate) with respect to hydrogen peroxide.
- Acid salt and adjusting the pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.).
- a basic compound for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.
- the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added.
- a preferable phosphate concentration is 0.1 to 60% by mass, preferably 5 to 45% by mass.
- a buffer such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate or sodium tripolyphosphate (or its hydrate) is not used without adjusting the pH. It may be added directly. In the sense of simplifying the process, there is no troublesome pH adjustment, and direct addition is particularly preferred.
- the amount of phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol% equivalent to hydrogen peroxide. It is. In this case, if the amount exceeds 5 mol% equivalent to hydrogen peroxide, pH adjustment is required. If the amount is less than 0.1 mol% equivalent, the resulting epoxy resin hydrolyzate tends to proceed or the reaction is slow. The bad effect of becoming.
- This reaction is oxidative epoxidation using hydrogen peroxide.
- hydrogen peroxide used in this reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by mass is preferable because of easy handling. When the concentration exceeds 40% by mass, it is not preferable because the handling becomes difficult and the decomposition reaction of the produced silicone-modified epoxy resin easily proceeds.
- This reaction uses an organic solvent.
- the amount of the organic solvent to be used is 0.3 to 10, preferably 0.3 to 5, more preferably 0.5 to 2.5 by mass ratio with respect to the diolefin compound 1 as the reaction substrate. is there. When the mass ratio exceeds 10, it is not preferable because the progress of the reaction becomes extremely slow.
- organic solvents include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. It is done.
- ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone
- ethers such as diethyl ether, tetrahydrofuran and dioxane
- ester compounds such as ethyl acetate, butyl acetate and methyl formate
- nitriles such as acetonitrile Compounds and the like can also be used.
- reaction operation method for example, when the reaction is performed in a batch-type reaction kettle, a diolefin compound, hydrogen peroxide (aqueous solution), polyacids (catalyst), a buffer solution, a quaternary ammonium salt, and an organic solvent are added. In addition, stir in two layers. There is no specific designation for the stirring speed. Since heat is often generated when hydrogen peroxide is added, a method of gradually adding hydrogen peroxide after each component may be added.
- the reaction temperature is not particularly limited, but is preferably 0 to 90 ° C, more preferably 0 to 75 ° C, particularly preferably 15 ° C to 60 ° C.
- the reaction temperature is too high, the hydrolysis reaction tends to proceed, and when the reaction temperature is low, the reaction rate becomes extremely slow.
- reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long reaction time is not preferable because it consumes a great deal of energy.
- a preferred range is 1 to 48 hours, preferably 3 to 36 hours, and more preferably 4 to 24 hours.
- the quenching treatment is preferably performed using a basic compound. It is also preferable to use a reducing agent and a basic compound in combination.
- a preferred treatment method there is a method of quenching residual hydrogen peroxide using a reducing agent after neutralization adjustment to pH 6 to 12 with a basic compound. If the pH is less than 6, the heat generated during the reduction of excess hydrogen peroxide is large, which may cause decomposition products.
- the reducing agent examples include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C and the like.
- the reducing agent is used in an excess amount of hydrogen peroxide of usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, and still more preferably 0.05 to 3 times mol with respect to the number of moles. is there.
- Basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphorus such as sodium phosphate and sodium hydrogen phosphate. Examples thereof include basic solids such as acid salts, ion exchange resins, and alumina.
- the amount used is water or organic solvents (for example, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, hydrocarbons such as cyclohexane, heptane and octane, methanol, ethanol, isopropyl alcohol, etc.
- the amount used is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times the number of moles of excess hydrogen peroxide. Mole, more preferably 0.05 to 3 times mole. These may be added as water or a solution of the above-mentioned organic solvent, or may be added alone.
- a solid base that does not dissolve in water or an organic solvent it is preferable to use a mass ratio of 1 to 1000 times the amount of hydrogen peroxide remaining in the system. More preferably, it is 10 to 500 times, and further preferably 10 to 300 times.
- the treatment may be carried out after separation of an aqueous layer and an organic layer described later.
- the above-mentioned organic solvent is added and the operation is performed.
- the reaction product is extracted from the layer.
- the organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times in mass ratio with respect to the raw material diolefin compound. This operation is repeated several times as necessary, and then the organic layer is separated. If necessary, the organic layer is washed with water and purified.
- the obtained organic layer may be an ion exchange resin or a metal oxide (especially silica gel or alumina is preferred), activated carbon (especially a chemical activated carbon is particularly preferred), or a composite metal salt (especially a basic composite metal salt).
- a metal oxide especially silica gel or alumina is preferred
- activated carbon especially a chemical activated carbon is particularly preferred
- a composite metal salt especially a basic composite metal salt.
- a mineral with a viscosity especially, a layered viscosity mineral such as montmorillonite is preferred
- the solvent is distilled off to obtain the desired epoxy compound. In some cases, it may be further purified by column chromatography or distillation.
- the diolefin compound which is a precursor of the silicone modified epoxy resin (A) of the present invention is represented by the general formula (4).
- R 1 represents an alkyl group having 0 to 6 carbon atoms which may contain an ester or ether bond
- R 2 represents an alkyl group or aromatic group having 1 to 6 carbon atoms
- R 3 represents an oxygen atom or
- k represents an average value of 1 to 10
- m represents an integer of 0 to 2
- n represents an average value of 0 to 10.
- a plurality of R 1 to R 3 , k, m, May be the same or different.
- R 1 is an alkylene group having 2 to 6 carbon atoms which may contain an ester or ether bond.
- Examples thereof include an ester group, an ethylene ether group, a propylene ether group, a butylene ether group, a pentylene ether group, and a hexylene ether group.
- an ethylene group and a propylene group are particularly preferable from the viewpoint of low gas permeability and strength of the cured product.
- R 2 is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms.
- Specific examples of the monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms are as follows. Is a saturated monovalent aliphatic such as an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, heptyl, 2-ethylhexyl, heptyl, octyl, etc.
- Examples thereof include unsaturated monovalent aliphatic hydrocarbon groups such as hydrocarbon groups, vinyl groups, allyl groups, isopropenyl groups, butenyl groups and the like, preferably methyl groups, ethyl groups, n-propyl groups, isopropyl groups, etc. Group, n-butyl group, t-butyl group and heptyl group, more preferably methyl group.
- Specific examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group, benzyl group, 2-phenylethyl group and 2-phenylpropylene group.
- An aralkyl group such as an alkyl group, preferably a phenyl group, a benzyl group, a 2-phenylethyl group, or a 2-phenylpropyl group, and more preferably a phenyl group.
- R 3 is an oxygen atom or a phenylene group.
- a phenylene group is preferable from the viewpoint of low gas permeability.
- M is an integer from 0 to 2, preferably 1 or 2.
- n is an average value of 0 to 10, preferably 0 to 5, and more preferably 0 to 2.
- k is an average value of 1 to 10, and preferably 1 to 2 from the viewpoint of low gas permeability of the cured product.
- silicone-modified epoxy resin (A) is an epoxidized product of a diolefin compound that includes the following formula (5).
- Me represents a methyl group.
- R 1 , R 3 , k, and n represent the same meaning as described above.
- the diolefin body is, for example, the following general formula (6): (Wherein R 2 , R 3 and k are the same as above) At least one organosilicon compound having a SiH group at the end of the molecule represented by the following general formula (8): (Wherein R 4 is an alkylene group having 0 to 4 carbon atoms which may contain an ester or ether bond.)
- a compound having a terminal alkenyl group represented by can be produced by a hydrosilylation reaction in the presence of a platinum catalyst.
- Specific examples of the compound having a terminal alkenyl group include the following formulas (9) to (11): The compound represented by these can be mentioned.
- the diolefin body of the said Formula (4) description can be obtained.
- the silicone-modified epoxy resin of the present invention can be obtained by oxidizing the obtained diolefin body by the diolefin resin oxidation method described above.
- the silicone-modified epoxy resin of the present invention has the following formula (2): (Wherein R 4 and m are the same as above)
- the epoxy group-containing compound containing a terminal alkenyl group can be obtained by hydrosilylation reaction with one or more organic silicon compounds having a SiH group at the terminal in the molecule.
- R 4 is an alkylene group having 0 to 4 carbon atoms which may contain an ester or ether bond, and specifically includes a methylene group, an ethylene group, a propylene group, a butylene group, an isopropylene group, a methyl ester. Groups, methyl ether groups and the like.
- Compounds represented by the formula (2) include the following formulas (12) to (14) An epoxy group-containing compound containing a terminal alkenyl group represented by
- the organosilicon compound having a SiH group at the terminal can be obtained by reacting the compound of the above formula (6) with the compound of the above formula (8).
- the above formula (6) can also be used as it is.
- the following formula (3) In the formula, R 2 , R 3 , k, m, and n each have the same meaning as described above.) The compound represented by these is mentioned.
- the reaction ratio between the organosilicon compound having a SiH group at the terminal and the compound having a terminal alkenyl group is such that the SiH group / alkenyl group molar ratio (H / Vi) is 0.1 to 3.0, particularly 0.
- the reaction is preferably carried out at a ratio of 5 to 1.5.
- the hydrosilylation reaction may be performed according to a conventionally known method.
- an epoxy group-containing compound containing a terminal alkenyl group is converted to a compound represented by the above formula (8) in the same manner as above.
- a compound represented by the above formula (2) may be reacted to obtain an epoxy resin.
- the above formula (6), the above formula (8), the above formula (2) may be used.
- the target epoxy resin may be obtained by reacting the compound represented by the formula (6) with the compound represented by the formula (2).
- the epoxy group-containing compound containing a terminal alkenyl group can be obtained by oxidizing the compound having a terminal alkenyl group by the diolefin resin oxidation method described above.
- a curing agent having a functional group reactive with an epoxy group is used.
- amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and polyvalent carboxylic acid resins can be mentioned, among which acid anhydride-based curing agents and polyvalent carboxylic acid resins are preferable.
- acid anhydride curing agents examples include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, Mixtures of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2 , 3-dicarboxylic acid anhydride, 2,4-diethylglutaric acid anhydride, etc., among which hexahydrophthalic anhydride and its derivatives are preferred.
- the polyvalent carboxylic acid resin (B) is a compound having at least two or more carboxyl groups and having an aliphatic hydrocarbon group or a siloxane skeleton as a main skeleton.
- the polyvalent carboxylic acid resin is not only a polyvalent carboxylic acid compound having a single structure, but also a mixture of a plurality of compounds having different substituent positions or different substituents, that is, a polyvalent carboxylic acid.
- a composition is also included, and in the present invention, they are collectively referred to as a polyvalent carboxylic acid resin.
- the polycarboxylic acid resin (B) a bi- to hexa-functional carboxylic acid is particularly preferable, and a reaction between a polyhydric alcohol having 5 or more carbon atoms or a polyhydric alcohol having a siloxane structure and an acid anhydride.
- the compound obtained by is more preferable.
- the polycarboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable.
- the bifunctional to hexafunctional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, Diols such as tricyclodecane dimethanol and norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, ditrimethylol group Tetraols such as bread,
- Particularly preferred alcohols are alcohols having 5 or more carbon atoms, particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, And compounds such as 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornene diol, and the like.
- 2-ethyl-2-butyl-1 3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol, and other alcohols having a branched or cyclic structure are more preferable.
- 2,4-diethylpentanediol and tricyclodecane dimethanol are particularly preferable.
- the polyhydric alcohol which has a siloxane structure is not specifically limited,
- the silicone oil represented by a following formula can be used.
- a 1 represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond
- a 2 represents a methyl group or a phenyl group
- n represents a repeating number, which means an average value.
- Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane- 2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and the like are preferable, Of these, methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are preferable.
- cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferable for increasing the hardness
- methylhexahydrophthalic anhydride is preferable for increasing the illuminance retention.
- one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted at 40 to 150 ° C. under non-catalytic and solvent-free conditions and heated. After completion, take it out as it is. It is a technique. However, it is not limited to this reaction condition.
- the polycarboxylic acid thus obtained is particularly represented by the following formula
- a 3 represent at least one of a hydrogen atom, a methyl group, and a carboxyl group.
- a 4 represents a chain-like, cyclic aliphatic group having 2 to 20 carbon atoms derived from the aforementioned polyhydric alcohol. M is 2-4.
- the compound represented by these is preferable.
- the resin composition of the present invention preferably contains an acid anhydride.
- acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3- And acid anhydrides such as dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.
- methyltetrahydrophthalic anhydride methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid
- An acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and the like are preferable.
- a 5 present represents at least one of a hydrogen atom, a methyl group, and a carboxyl group.
- the polyvalent carboxylic acid resin (B) and the acid anhydride are preferably used in combination, and when used in combination, the use ratio is preferably in the following range.
- W1 shows the mixing
- W2 shows the mixing
- the range of W1 / (W1 + W2) is more preferably 0.05 to 0.60, still more preferably 0.10 to 0.55, and particularly preferably 0.15 to 0.4. If it is less than 0.05, there is a strong tendency of acid volatilization to increase during curing, which is not preferable. If it exceeds 0.70, the viscosity becomes high and handling becomes difficult.
- the polyvalent carboxylic acid resin (B) and the acid anhydride are used in combination, the polyvalent carboxylic acid resin (B) and the acid anhydride are produced in an excess of the acid anhydride when the polyvalent carboxylic acid resin (B) is produced.
- the method of making a mixture of these is also preferable from the viewpoint of the ease of operation.
- the blending amount of the curing agent of the component (B) is a functional group reactive with the epoxy group (-CO in the case of an acid anhydride curing agent) with respect to a total of 1 mol of the epoxy groups in the component (A).
- the amount of the acid anhydride group represented by —O—CO— is 0.3 to 1.0 mol, preferably 0.4 to 0.8 mol. If the functional group having reactivity with the epoxy group is 0.3 mol or more, the heat resistance and transparency of the cured product are improved, and if it is 1.0 mol or less, the mechanical properties of the cured product are improved. Therefore, it is preferable.
- “functional group having reactivity with epoxy group” means an amino group possessed by an amine curing agent, a phenolic hydroxyl group possessed by a phenol curing agent, an acid anhydride group possessed by an acid anhydride curing agent, It is a carboxyl group possessed by a polyvalent carboxylic acid resin.
- Curing catalysts include quaternary phosphonium salts such as tetrabutylphosphonium / O, O-diethyl phosphorodithioate, tetraphenylphosphonium tetraphenylborate, and organic phosphine-based curing catalysts such as triphenylphosphine and diphenylphosphine, , 8-diazabicyclo (5,4,0) undecene-7, tertiary amine-based curing catalyst such as triethanolamine, benzyldimethylamine, 1,8-diazabicyclo (5,4,0) undecene-7 phenol salt, , 8-diazabicyclo (5,4,0) undecene-7 octylate, 1,8-diazabicyclo (5,4,0) undecene-7 p-toluenesulfonate, 1,8-diazabicyclo (5,4 0) Unde
- the blending amount of (C) curing catalyst is 0.01 to 3 parts by mass, preferably 0.05 to 1.5 parts by mass with respect to 100 parts by mass in total of components (A) and (B). If the amount of the curing catalyst is less than the lower limit, the effect of promoting the reaction between the epoxy resin and the curing agent may not be sufficient. On the contrary, if the amount of the curing catalyst is larger than the upper limit value, it may cause discoloration during curing or reflow test.
- Antioxidants include phosphorous acid compounds and hindered phenol antioxidants, with hindered phenol antioxidants being preferred. Moreover, as an ultraviolet absorber, a hindered amine type ultraviolet absorber is preferable.
- the amount of component (D) is 0.1 to 0.5 parts by weight, preferably 0.1 to 0.3 parts by weight, per 100 parts by weight of component (A). When the blending amount of the antioxidant exceeds the upper limit of the previous period, the remaining antioxidant is not preferable because it is deposited on the surface of the cured resin, and when it is less than the lower limit of the previous period, the heat resistance and transparency are lowered.
- the resin composition for encapsulating an optical semiconductor element of the present invention can be produced by blending the above components and various additives as necessary, and dissolving or melting and mixing them.
- Melt mixing may be a known method.
- the above components may be charged into a reactor and melt-mixed in a batch manner, or each of the above components may be charged into a kneader such as a kneader or a heat triple roll. And can be continuously melt-mixed.
- the (C) curing catalyst is previously heated and dissolved and mixed in the (B) curing agent, and dispersed and mixed with the component (A), the component (D), and the like at the final stage of mixing.
- GPC GPC was measured under the following conditions.
- Various conditions of GPC Manufacturer Waters column: SHODEX GPC LF-G (guard column), KF-603, KF-602.5, KF-602, KF-601 (2) Flow rate: 0.4 ml / min.
- the obtained toluene solution was distilled under reduced pressure to obtain a diolefin compound 1 containing the following compound (15) as a main component.
- the olefin equivalent was 0.319 mol / 100 g.
- Example 1 Synthesis of a silicone-modified epoxy resin stirring apparatus, a flask equipped with a reflux condenser, 157 parts (olefin equivalent 0.319 mol / 100 g) of the diolefin compound 1 obtained in Synthesis Example 1, 150 parts of toluene, 5.4 parts of trioctylmethylammonium acetate (50% by weight xylene solution from Lion Akzo, TOMAA-50), 9 parts of water, 2.6 parts of 12-tungstophosphoric acid, 0.9 part of sodium tungstate, dihydrogen phosphate While adding 1.4 parts of sodium and stirring at 50 ⁇ 3 ° C., 63 parts of 35% by mass hydrogen peroxide was added, and the mixture was stirred as it was at 50 ⁇ 3 ° C.
- the epoxy resins used in the comparative examples are as follows.
- the reactor is charged with MeO (Me) 2 SiO (Me 2 SiO) m Si (Me) 2 OMe (m is an integer from 1 to 8, average is 1.5) (1.0 mol, 306 g), ⁇ - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-303) (1.0 mol, 246 g), 500 g of isopropyl alcohol, 12 g of a 25% by weight tetramethylammonium hydroxide a
- GPC confirmed 1 area% or less of tricyclodecane dimethanol, and 100 parts of a curing agent (B) that was a mixture of a polycarboxylic acid resin and an acid anhydride compound was obtained.
- the colorless liquid resin thus obtained has a GPC purity of 37 area% for the polycarboxylic acid resin (formula P below) and 11 area% for cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.
- Methyl hexahydrophthalic anhydride was 52% by area.
- the functional group equivalent was 171 g / eq. Met.
- composition- A resin composition was prepared with the formulation (parts by mass) shown in Table 1 below. As a result, the epoxy resin compositions of Examples 2 and 3 and Comparative Examples 1 and 2 were obtained. Each component in these tables is as follows. In the table, a blank column means “0”.
- Curing catalyst quaternary phosphonium salt (manufactured by San Apro, U-CAT5003)
- Antioxidant Pentaerythritol tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] (manufactured by ADEKA Corporation, ADK STAB AO-60)
- compositions of Examples 2 and 3 are excellent in low gas permeability and strength.
- composition of Comparative Example 1 is excellent in strength, it is inferior in low gas permeability.
- silicone-modified epoxy resin of Comparative Example 2 is inferior in both low gas permeability and strength.
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Abstract
Description
すなわち本発明は、下記(1)~(8)に関する。
(1)下記式(1)で表されるシリコーン変性エポキシ樹脂。
(2)下記式(2)、下記式(6)に記載の化合物の反応物である、(1)に記載のシリコーン変性エポキシ樹脂。
(3)下記式(2)、下記式(6)及び下記式(8)
で表される化合物を反応させて得られる(1)に記載のシリコーン変性エポキシ樹脂。
(4)下記式(4)のジオレフィン化合物を酸化することにより得られる(1)に記載のシリコーン変性エポキシ樹脂。
(5)(1)~(4)のいずれか一項に記載の(A)シリコーン変性エポキシ樹脂と(B)エポキシ樹脂硬化剤を含有するエポキシ樹脂組成物。
(6)さらに、(C)エポキシ樹脂硬化触媒を含有する(5)に記載のエポキシ樹脂組成物。
(7)(5)記載のエポキシ樹脂硬化剤がアミン系硬化剤、フェノール系硬化剤、酸無水物系硬化剤、多価カルボン酸樹脂のいずれかから選ばれることを特徴とするエポキシ樹脂組成物。
(8)(5)~(7)のいずれか一項に記載のエポキシ樹脂組成物を硬化してなる硬化物。
過酸による酸化エポキシ化の手法としては具体的には日本国特開2006-52187号公報に記載の手法などが挙げられる。使用できる過酸としては、例えばギ酸、酢酸、プロピオン酸、マレイン酸、安息香酸、m-クロロ安息香酸、フタル酸などの有機酸およびそれらの酸無水物が挙げられる。これらの中でも、過酸化水素と反応して有機過酸を生成する効率、反応温度、操作の簡便性、経済性などの観点からは、ギ酸、酢酸、無水フタル酸を使用するのが好ましく、特に反応操作の簡便性の観点から、ギ酸または酢酸を使用するのがより好ましい。
過酸化水素水によるエポキシ化の手法においては種々の手法が適応できるが、具体的には、日本国特開昭59-108793号公報、日本国特開昭62-234550号公報、日本国特開平5-213919号公報、日本国特開平11-349579号公報、日本国特公平1―33471号公報、日本国特開2001-17864号公報、日本国特公平3-57102号公報等に挙げられるような手法が適応できる。
他にも、非特許文献1(James V.Crivello and Ramesh Narayan、Novel Epoxynorbornane Monomers. 1. Synthesis and Characterization、Macromolecules 1996、29巻、433~438頁)に記載されている方法も適用することができる。具体的には、オキソンを使用して、オレフィン基をエポキシ化して得ることができる。
<(A)シリコーン変性エポキシ樹脂>
まず、本発明のシリコーン変性エポキシ樹脂の前駆体であるジオレフィン化合物、ポリ酸類及び4級アンモニウム塩を有機溶剤と過酸化水素水との二層で反応を行う。
ポリ酸類に含まれる具体的なポリ酸及びポリ酸塩としては、タングステン酸、12-タングストリン酸、12-タングストホウ酸、18-タングストリン酸及び12-タングストケイ酸等から選ばれるタングステン系の酸、モリブデン酸及びリンモリブデン酸等から選ばれるモリブデン系の酸、ならびにそれらの塩等が挙げられる。
これらの塩のカウンターカチオンとしては、アンモニウムイオン、アルカリ土類金属イオン、アルカリ金属イオン等が挙げられる。
具体的にはカルシウムイオン、マグネシウムイオン等のアルカリ土類金属イオン、ナトリウム、カリウム、セシウム等のアルカリ金属イオン等が挙げられるがこれらに限定されない。特に好ましいカウンターカチオンとしては、ナトリウムイオン、カリウムイオン、カルシウムイオン、アンモニウムイオンである。
具体的にはトリデカニルメチルアンモニウム塩、ジラウリルジメチルアンモニウム塩、トリオクチルメチルアンモニウム塩、トリアルキルメチル(アルキル基がオクチル基である化合物とデカニル基である化合物の混合タイプ)アンモニウム塩、トリヘキサデシルメチルアンモニウム塩、トリメチルステアリルアンモニウム塩、テトラペンチルアンモニウム塩、セチルトリメチルアンモニウム塩、ベンジルトリブチルアンモニウム塩、ジセチルジメチルアンモニウム塩、トリセチルメチルアンモニウム塩、ジ硬化牛脂アルキルジメチルアンモニウム塩などが挙げられるがこれらに限定されない。
またこれら塩のアニオン種は、カルボン酸イオンを使用する。カルボン酸イオンとしては、酢酸イオン、炭酸イオン、ギ酸イオンが好ましい。また、特に酢酸イオンが好ましい。
4級アンモニウム塩の炭素数が100を上回ると、疎水性が強くなりすぎて有機層への溶解性が悪くなる場合がある。一方、4級アンモニウム塩の炭素数が10未満であると、親水性が強くなり、同様に有機層への相溶性が悪くなる場合がある。
4級アンモニウム塩には一般にハロゲンが残存する。本発明においては特に、1質量%以下、より好ましくは1000ppm以下、さらに好ましくは700ppm以下である。総ハロゲン量が1質量%を超える場合、生成物に多量にハロゲンが残存するため好ましくない。
タングステン酸類と4級アンモニウムのカルボン酸塩の使用量は使用するタングステン酸類の価数倍の0.01~0.8倍当量、あるいは1.1~10倍当量が好ましい。より好ましくは0.05~0.7倍当量、あるいは1.2~6.0倍当量であり、さらに好ましくは0.05~0.5倍当量、あるいは1.3~4.5倍当量である。
例えば、タングステン酸であればH2WO4で2価であるので、タングステン酸1モルに対し、4級アンモニウムのカルボン酸塩は0.02~1.6モル、もしくは2.2~20モルの範囲が好ましい。またタングストリン酸であれば3価であるので、同様に0.03~2.4モル、もしくは3.3~30モル、ケイタングステン酸であれば4価であるので0.04~3.2モル、もしくは4.4~40モルが好ましい。
4級アンモニウムのカルボン酸塩の量が、タングステン酸類の価数倍の1.1倍当量よりも低い場合、エポキシ化反応が進行しづらい(場合によっては反応の進行が早くなる)、また副生成物ができやすいという問題が生じる。10倍当量よりも多い場合、過剰の4級アンモニウムのカルボン酸塩の処理が大変であるばかりか、反応を抑制する働きがあり、好ましくない。
特に本発明においては触媒であるタングステン酸類を溶解した際に、pH5~9の間になるように調整されることが好ましい。
緩衝液の使用方法は、例えば好ましい緩衝液であるリン酸-リン酸塩水溶液の場合は過酸化水素に対し、0.1~10モル%当量のリン酸(あるいはリン酸二水素ナトリウム等のリン酸塩)を使用し、塩基性化合物(たとえば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム等)でpH調整を行うという方法が挙げられる。ここでpHは過酸化水素を添加した際に前述のpHになるように添加することが好ましい。また、リン酸二水素ナトリウム又はリン酸水素二ナトリウム等を用いて調整することも可能である。好ましいリン酸塩の濃度は0.1~60質量%、好ましくは5~45質量%である。
また、本反応においては緩衝液を使用せず、pH調整無しに、リン酸水素二ナトリウム、リン酸二水素ナトリウム、リン酸ナトリウムあるいはトリポリリン酸ナトリウム等(またはその水和物)のリン酸塩を直接添加しても構わない。工程の簡略化、という意味合いではpH調整のわずらわしさが無く、直接の添加が特に好ましい。この場合のリン酸塩の使用量は、過酸化水素に対し、通常0.1~5モル%当量、好ましくは0.2~4モル%当量、より好ましくは、0.3~3モル%当量である。この際、過酸化水素に対し、5モル%当量を超えるとpH調整が必要となり、0.1モル%当量未満の場合、生成したエポキシ樹脂の加水分解物が進行しやすくなる、あるいは反応が遅くなる等の弊害が生じる。
その使用量としては水、あるいは有機溶剤(例えば、トルエン、キシレン等の芳香族炭化水素、メチルイソブチルケトン、メチルエチルケトン等のケトン類、シクロヘキサン、ヘプタン、オクタン等の炭化水素、メタノール、エタノール、イソプロピルアルコール等のアルコール類等の各種溶剤)に溶解するものであれば、その使用量は過剰分の過酸化水素のモル数に対し、通常0.01~20倍モル、より好ましくは0.05~10倍モル、さらに好ましくは0.05~3倍モルである。これらは水、あるいは前述の有機溶剤の溶液として添加しても単体で添加しても構わない。
水や有機溶剤に溶解しない固体塩基を使用する場合、系中に残存する過酸化水素の量に対し、質量比で1~1000倍の量を使用することが好ましい。より好ましくは10~500倍、さらに好ましくは10~300倍である。水や有機溶剤に溶解しない固体塩基を使用する場合は、後に記載する水層と有機層の分離の後、処理を行っても構わない。
得られた有機層は必要に応じてイオン交換樹脂や金属酸化物(特に、シリカゲルやアルミナ等が好ましい)、活性炭(中でも特に薬品賦活活性炭が好ましい)、複合金属塩(中でも特に塩基性複合金属塩が好ましい)、粘度鉱物(中でも特にモンモリロナイト等層状粘度鉱物が好ましい)等により、不純物を除去し、さらに水洗及びろ過等を行った後、溶剤を留去し、目的とするエポキシ化合物を得る。場合によってはさらにカラムクロマトグラフィーや蒸留により精製しても構わない。
で表される。
で示される分子中の末端にSiH基を有する有機ケイ素化合物の1種以上と、下記一般式(8)
で示される末端アルケニル基を有する化合物を、白金触媒存在下、ヒドロシリル化反応によって製造することができる。
末端アルケニル基を有する化合物の具体例としては、下記式(9)~(11)
このようにして、上記式(4)記載のジオレフィン体を得ることができる。
の末端アルケニル基を含有するエポキシ基含有化合物を上記と同様、分子中の末端にSiH基を有する有機ケイ素化合物の1種以上とヒドロシリル化反応することでも得られる。
式(2)で表される化合物としては下記式(12)~(14)
で表される化合物が挙げられる。
<(B)硬化剤>
硬化剤としては、エポキシ基と反応性の官能基を有する硬化剤が使用される。例えば、アミン系硬化剤、フェノール系硬化剤、酸無水物系硬化剤、多価カルボン酸樹脂が挙げられ、そのうち酸無水物系硬化剤、多価カルボン酸樹脂が好ましい。酸無水物系硬化剤としては、無水フタル酸、無水マレイン酸、無水トリメリット酸、無水ピロメリット酸、ヘキサヒドロ無水フタル酸、3-メチル-ヘキサヒドロ無水フタル酸、4-メチル-ヘキサヒドロ無水フタル酸、3-メチル-ヘキサヒドロ無水フタル酸と4-メチル-ヘキサヒドロ無水フタル酸との混合物、テトラヒドロ無水フタル酸、無水ナジック酸、無水メチルナジック酸、ノルボルナン-2,3-ジカルボン酸無水物、メチルノルボルナン-2,3-ジカルボン酸無水物、2,4-ジエチルグルタル酸無水物などを挙げることができ、これらのうち、ヘキサヒドロ無水フタル酸及びその誘導体が好ましい。
多価カルボン酸樹脂(B)は少なくとも2つ以上のカルボキシル基を有し、脂肪族炭化水素基またはシロキサン骨格を主骨格とすることを特徴とする化合物である。本発明においては多価カルボン酸樹脂とは単一の構造を有する多価カルボン酸化合物だけでなく、置換基の位置が異なる、あるいは置換基の異なる複数の化合物の混合体、すなわち多価カルボン酸組成物も含包し、本発明においてはそれらをまとめて多価カルボン酸樹脂と称す。
多価カルボン酸樹脂(B)としては、特に2~6官能のカルボン酸が好ましく、炭素数5以上の2~6官能の多価アルコールまたはシロキサン構造を有する多価アルコールと酸無水物との反応により得られた化合物がより好ましい。さらには上記酸無水物が飽和脂肪族環状酸無水物であるポリカルボン酸が好ましい。
2~6官能の多価アルコールとしてはアルコール類としては、アルコール性水酸基を有する化合物であれば特に限定されないがエチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、シクロヘキサンジメタノール、2,4-ジエチルペンタンジオール、2-エチル-2-ブチル-1.3-プロパンジオール、ネオペンチルグリコール、トリシクロデカンジメタノール、ノルボルネンジオール等のジオール類、グリセリン、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、2-ヒドロキシメチル-1,4-ブタンジオール等のトリオール類、ペンタエリスリトール、ジトリメチロールプロパン等のテトラオール類、ジペンタエリスリトールなどのヘキサオール類等が挙げられる。
特に好ましいアルコール類としては炭素数が5以上のアルコールであり、特に1,6-ヘキサンジオール、1,4-シクロヘキサンジメタノール、1,3-シクロヘキサンジメタノール、1,2-シクロヘキサンジメタノール、2,4-ジエチルペンタンジオール、2-エチル-2-ブチル-1,3-プロパンジオール、ネオペンチルグリコール、トリシクロデカンジメタノール、ノルボルネンジオール等の化合物が挙げられ、中でも2-エチル-2-ブチル-1,3-プロパンジオール、ネオペンチルグリコール、2,4-ジエチルペンタンジオール、1,4-シクロヘキサンジメタノール、トリシクロデカンジメタノール、ノルボルネンジオール等の分岐鎖状構造や環状構造を有するアルコール類がより好ましい。高い照度保持率を付与する観点から、2,4-ジエチルペンタンジオール、トリシクロデカンジメタノールが特に好ましい。
シロキサン構造を有する多価アルコールは特に限定されないが、例えば下記式で表されるシリコーンオイルを使用することができる。
酸無水物としては特にメチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ブタンテトラカルボン酸無水物、ビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、メチルビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、シクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物等が好ましく、中でもメチルヘキサヒドロ無水フタル酸、シクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物が好ましい。ここで、硬度を上げるためには、シクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物が好ましく、照度保持率を上げるためにはメチルヘキサヒドロ無水フタル酸無水物が好ましい。
付加反応の条件としては特に指定はないが、具体的な反応条件の1つとしては酸無水物、多価アルコールを無触媒、無溶剤の条件下、40~150℃で反応させ加熱し、反応終了後、そのまま取り出す。という手法である。ただし、本反応条件に限定されない。
で表される化合物が好ましい。
特にメチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ブタンテトラカルボン酸無水物、ビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、メチルビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、シクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物等が好ましい。
特に好ましくは下記式
で表されるヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、シクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物が好ましく、中でもメチルヘキサヒドロ無水フタル酸、シクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物が好ましい。
多価カルボン酸樹脂(B)と酸無水物を併用する場合、多価カルボン酸樹脂(B)の製造時に過剰の酸無水物の中で製造し、多価カルボン酸(B)と酸無水物の混合物を作るという手法も操作の簡便性の面から好ましい。
硬化触媒としては、テトラブチルホスホニウム・O,O-ジエチルホスホロジチオエート、テトラフェニルホスホニウムテトラフェニルボレートなどの第四級ホスホニウム塩、トリフェニルフォスフィン、ジフェニルフォスフィン等の有機フォスフィン系硬化触媒、1,8-ジアザビシクロ(5,4,0)ウンデセン-7、トリエタノールアミン、ベンジルジメチルアミン等の三級アミン系硬化触媒、1,8-ジアザビシクロ(5,4,0)ウンデセン-7 フェノール塩、1,8-ジアザビシクロ(5,4,0)ウンデセン-7 オクチル酸塩、1,8-ジアザビシクロ(5,4,0)ウンデセン-7 p-トルエンスルホン酸塩、1,8-ジアザビシクロ(5,4,0)ウンデセン-7 ギ酸塩等の第四級アンモニウム塩、オクチル酸亜鉛、ナフチル酸亜鉛等の有機カルボン酸塩、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート、アルミニウムエチルアセトアセテート・ジイソプロピレート等のアルミキレート化合物、2-メチルイミダゾール、2-フェニル-4-メチルイミダゾールなどのイミダゾール類などを挙げられ、望ましくは第四級ホスホニウム塩、第四級アンモニウム塩である。
酸化防止剤としては、亜リン酸化合物、ヒンダードフェノール系酸化防止剤等があり、ヒンダードフェノール系酸化防止剤が好ましい。また、紫外線吸収剤としては、ヒンダードアミン系紫外線吸収剤が好ましい。(D)成分の配合量は、(A)成分100質量部に対して、0.1~0.5質量部、好ましくは0.1~0.3質量部である。酸化防止剤の配合量が前期上限値を超えると、残存した酸化防止剤が硬化後の樹脂の表面に析出するため好ましくなく、前期下限値未満では耐熱性、透明性が低下する。
上記各成分に加えて、慣用の添加剤、例えば、紫外線吸収剤、劣化防止剤、蛍光体、熱可塑剤、希釈剤などを必要に応じて併用しても差し支えない。
○GPC:GPCは下記条件にて測定した。
GPCの各種条件
メーカー:ウォーターズ
カラム:SHODEX GPC LF-G(ガードカラム)、KF-603、KF-602.5、KF-602、KF-601(2本)
流速:0.4ml/min.
カラム温度:40℃
使用溶剤:THF(テトラヒドロフラン)
検出器:RI(示差屈折検出器)
○NMR:日本電子株式会社製 JNM-ECS400を用いて、重クロロホルム溶媒で測定した。
○エポキシ当量:JIS K7236に記載の方法で測定した。
1Lのセパラブルフラスコに5-ビニル-2-ノルボルネン(1.3mоl、156g)、トルエン200g、0.5質量%塩化白金酸トルエン溶液0.20gを加え、内温を80℃まで上昇させた。次に1,4-ビス(ジメチルシリル)べンゼン(1mоl、194g)を混合した溶液を1時間かけて滴下した。滴下終了後、110℃で4時間反応させた。得られたトルエン溶液を減圧蒸留することで下記化合物(15)を主成分とするジオレフィン化合物1を得た。得られたジオレフィン化合物1を1H-NMRにて確認したところ、オレフィン当量は0.319mol/100gであった。
実施例1;シリコーン変性エポキシ樹脂の合成
撹拌装置、還流冷却管を備えたフラスコに、合成例1で得られたジオレフィン化合物1を157部(オレフィン当量0.319mol/100g)、トルエン150部、トリオクチルメチルアンモニウムアセテート5.4部(ライオンアクゾ製50質量%キシレン溶液、TOMAA-50)、水9部、12-タングストリン酸2.6部、タングステン酸ナトリウム0.9部、リン酸二水素ナトリウム1.4部を加え、50±3℃に昇温攪拌しながら、35質量%過酸化水素水63部を加え、そのまま50±3℃で24時間攪拌した。1H-NMRにて反応の進行を確認したところ、反応終了後のオレフィンからエポキシへのコンバージョン率は>99%であり、原料オレフィンピークは消失(1%以下)していた。
ついで30質量%水酸化ナトリウム水溶液でpH9とした後、20質量%チオ硫酸ナトリウム水溶液25部を加え30分攪拌を行い、静置した。2層に分離した有機層を取り出し、ここに活性炭(味の素ファインテクノ製CP)12.5部を加え、室温で4時間攪拌後、ろ過した。得られたろ液の有機溶剤を留去することで、下記式(16)
を主成分とする本発明のシリコーン変性エポキシ樹脂(A-1)を162部得た。
1H-NMRの測定結果より、式(16)の骨格の化合物を>98%含有していることを確認した。さらに、GPC測定においては純度>99%であった。エポキシ当量はJIS K7236に記載の方法では正確に測定することができなかった(オレフィン当量から計算した理論エポキシ当量は330g/eq)。シリコーン変性エポキシ樹脂(A-1)の1H-NMRスペクトルを図1に、GPCチャートを図2にそれぞれ示す。
[比較例1]
・3’-4’-エポキシシクロヘキシルメチル 3,4-エポキシシクロヘキサンカルボキシレート(ダイセル化学工業(株)社製、CEL2021P)
[比較例2]
[脂環式エポキシ基を含有するオルガノポリシロキサンの合成]
反応器にMeO(Me)2SiO(Me2SiO)mSi(Me)2OMe(mは1~8の整数で、平均は1.5)(1.0mol、306g)、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン(信越化学工業(株)製、KBM―303)(1.0mol、246g)、イソプロピルアルコール500gを仕込んだ後、水酸化テトラメチルアンモニウムの25質量%水溶液12g、水110gを添加し室温で3時間攪拌した。次いで、系内にトルエン500mlを入れ、リン酸二水素ナトリウム水溶液で中和した。分液漏斗を用いて分離した有機層(トルエン溶液)を熱水にて洗浄した後、減圧下トルエンを溜去したところ、下記平均組成式(20)で示される構造を有する、シリコーン変性エポキシ樹脂(A-3)を得た。シリコーン変性エポキシ樹脂(A-3)のGPCで測定されたポリスチレン換算の重量平均分子量は4300であり、エポキシ当量(滴定法(JIS K7236)により測定、以下同様)は403g/eqであった。
[硬化剤として使用した多価カルボン酸樹脂と酸無水物化合物の混合物の合成]
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらトリシクロデカンジメタノール15部、メチルヘキサヒドロフタル酸無水物(新日本理化(株)製、リカシッドMH)70部、シクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物(三菱ガス化学製 H-TMAn)15部を加え、40℃で3時間反応後、70℃で1時間加熱撹拌を行った。GPCによりトリシクロデカンジメタノールの1面積%以下を確認し、多価カルボン酸樹脂と酸無水物化合物の混合物である硬化剤(B)が100部得られた。得られた無色の液状樹脂であり、GPCによる純度は多価カルボン酸樹脂(下記式P)が37面積%、シクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物が11面積%、メチルヘキサヒドロフタル酸無水物が52面積%であった。また、官能基当量は171g/eq.であった。
下記表1に示す配合(質量部)で樹脂組成物を調製した。その結果、実施例2及び3、比較例1~2のエポキシ樹脂組成物を得た。これらの表中の各成分は以下のとおりである。また、表中、空欄は「0」を意味する。
(C)硬化触媒:第四級ホスホニウム塩(サンアプロ(株)製、U-CAT5003)
(D)酸化防止剤:ペンタエリスリトールテトラキス[3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオナート](株式会社ADEKA社製、アデカスタブAO-60)
得られた組成物及び硬化物の特性評価を以下の方法で行なった。硬化は、組成物を100℃で1時間、次いで150℃で4時間加熱して行なった。結果を表1に示す。
(1)粘度
東機産業製E型回転粘度計にて、23℃で測定した。
(2)硬度
JIS K6301に準拠して棒状硬化物について測定した(タイプD)。
(3)TMA(Tg,CTE)
5mm×15mm、厚さ4mmを有する試験片を用いてエスアイアイ・ナノテクノロジー社製TMA/SS-6100を用いて測定した。
(4)水蒸気透過率
厚さ0.5mmを有する各硬化物の水蒸気透過率をJIS K 7129に準拠して測定した。
Claims (8)
- 請求項1~4のいずれか一項に記載の(A)シリコーン変性エポキシ樹脂と(B)エポキシ樹脂硬化剤を含有するエポキシ樹脂組成物。
- さらに、(C)エポキシ樹脂硬化触媒を含有する請求項5に記載のエポキシ樹脂組成物。
- 請求項5記載のエポキシ樹脂硬化剤がアミン系硬化剤、フェノール系硬化剤、酸無水物系硬化剤、多価カルボン酸樹脂のいずれかから選ばれることを特徴とするエポキシ樹脂組成物。
- 請求項5~7のいずれか一項に記載のエポキシ樹脂組成物を硬化してなる硬化物。
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KR20180027491A (ko) * | 2015-07-10 | 2018-03-14 | 스미토모 세이카 가부시키가이샤 | 에폭시 수지 조성물, 그 제조 방법 및 해당 조성물의 용도 |
KR102534679B1 (ko) | 2015-07-10 | 2023-05-19 | 스미토모 세이카 가부시키가이샤 | 에폭시 수지 조성물, 그 제조 방법 및 해당 조성물의 용도 |
US11066510B2 (en) | 2015-07-10 | 2021-07-20 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition, process for producing same, and uses of said composition |
CN108291075A (zh) * | 2015-11-18 | 2018-07-17 | 住友精化株式会社 | 环氧树脂组合物、其制造方法及该组合物的用途 |
WO2017086368A1 (ja) * | 2015-11-18 | 2017-05-26 | 住友精化株式会社 | エポキシ樹脂組成物、その製造方法、及び該組成物の用途 |
JPWO2017086368A1 (ja) * | 2015-11-18 | 2018-09-06 | 住友精化株式会社 | エポキシ樹脂組成物、その製造方法、及び該組成物の用途 |
JPWO2018131570A1 (ja) * | 2017-01-10 | 2019-06-27 | 住友精化株式会社 | エポキシ樹脂組成物 |
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WO2018131569A1 (ja) * | 2017-01-10 | 2018-07-19 | 住友精化株式会社 | エポキシ樹脂組成物 |
JPWO2018131571A1 (ja) * | 2017-01-10 | 2019-06-27 | 住友精化株式会社 | エポキシ樹脂組成物 |
JPWO2018131569A1 (ja) * | 2017-01-10 | 2019-07-11 | 住友精化株式会社 | エポキシ樹脂組成物 |
US11603466B2 (en) | 2017-01-10 | 2023-03-14 | Sumitomo Seika Chemicals Co.. Ltd. | Epoxy resin composition |
US11292872B2 (en) | 2017-01-10 | 2022-04-05 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition |
US11091627B2 (en) | 2017-01-10 | 2021-08-17 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition |
US11111382B2 (en) | 2017-01-10 | 2021-09-07 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition |
WO2018181719A1 (ja) * | 2017-03-31 | 2018-10-04 | 住友精化株式会社 | エポキシ樹脂、エポキシ樹脂組成物、並びに、その硬化物、用途及び製造方法 |
WO2019026822A1 (ja) * | 2017-07-31 | 2019-02-07 | 住友精化株式会社 | エポキシ樹脂組成物 |
JP7146766B2 (ja) | 2017-07-31 | 2022-10-04 | 住友精化株式会社 | エポキシ樹脂組成物 |
JPWO2019026822A1 (ja) * | 2017-07-31 | 2020-07-16 | 住友精化株式会社 | エポキシ樹脂組成物 |
WO2024043038A1 (ja) * | 2022-08-22 | 2024-02-29 | 信越化学工業株式会社 | カチオン硬化型組成物、硬化物、及び光半導体装置 |
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US9777107B2 (en) | 2017-10-03 |
JPWO2015041325A1 (ja) | 2017-03-02 |
JP6397823B2 (ja) | 2018-09-26 |
WO2015041325A8 (ja) | 2015-06-18 |
TW201518393A (zh) | 2015-05-16 |
US20160237202A1 (en) | 2016-08-18 |
TWI629307B (zh) | 2018-07-11 |
CN105873976B (zh) | 2018-07-03 |
CN105873976A (zh) | 2016-08-17 |
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