Classifications

• • 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
  • C08G59/40—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 curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• • 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
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/50—Amines
  • C08G59/56—Amines together with other curing agents
  • C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • 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

Definitions

• the present invention is suitable for use in electrical and electronic materials, and includes a polyvalent carboxylic acid composition, a curing agent composition, and a curable resin composition containing the polyvalent carboxylic acid composition or the curing agent composition as a curing agent for epoxy resin. About.
• the polyvalent carboxylic acid has excellent performance as a crosslinking agent, a condensing agent and the like, such as high heat stability, good electrical properties, chemical resistance, and the like, as well as formation of a condensate and good reactivity. For this reason, in recent years, it has attracted a great deal of attention as a raw material for polymer production and has come to be widely used. It is also known that polyvalent carboxylic acids can be used as curing agents for epoxy resins.
• curable resin compositions containing epoxy resins have been conventionally used in the fields of architecture, civil engineering, automobiles, aircraft, etc. as resins having excellent heat resistance. Is attracting attention. Conventional signal transmission using electric wiring has been changed to signal transmission using optical signals in order to smoothly transmit and process a large amount of information as information is advanced. For this reason, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, it is desired to develop a resin composition that gives a cured product having excellent transparency.
• Epoxy resins used in these electronic devices have been required to have very high characteristics as packaging materials.
• liquid curing has become more important in the package of cutting-edge fields, especially than in molding methods such as transfer molding using solid resin.
• a molding method using a conductive resin composition is preferably used.
• epoxy resin curing agents for liquid compositions include polyvalent amine compounds, but amine compounds are difficult to use because of intense coloring.
• epoxy resin curing agents it is known that phenolic resins and polyvalent carboxylic acid resins can also give a reliable cured product, but since the shape thereof is solid, such a liquid composition It is difficult to use as a product.
• acid anhydride compounds are generally used as curing agents for epoxy resins in such fields, and in particular, acid anhydrides formed with saturated hydrocarbons are often used because the cured product has excellent light resistance. It's being used.
• alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, etc. are common, and in particular, methylhexahydrophthalic anhydride, methyl which is liquid at room temperature. Tetrahydrophthalic anhydride and the like are mainly used because of easy handling.
• these curing agents have high vapor pressure and partly evaporate at the time of curing, so they are thermally cured in an open system using them as a curing agent for epoxy resin.
• the product itself volatilizes in the atmosphere, which may cause not only environmental pollution and harmful effects on the human body due to the release of harmful substances to the atmosphere, but also contamination of the production line.
• the characteristics of the curable resin composition may be poorly cured due to the absence of a predetermined amount of carboxylic acid anhydride (curing agent) in the cured product, and the characteristics may vary greatly depending on the curing conditions. Therefore, there is a problem that it is difficult to obtain a cured product having the intended performance stably.
• a resin in which a siloxane skeleton such as a silicone resin or a silicone-modified epoxy resin is introduced.
• Patent Document 4 a resin in which a siloxane skeleton introduced therein is more stable to heat and light than an epoxy resin. Therefore, when applied to the sealing material of LED products, it was said that it was superior to epoxy resin in terms of coloring on the LED chip.
• resins incorporating the siloxane skeleton are inferior in resistance to corrosive gases such as sulfur as compared with epoxy resins.
• the present invention has been made in view of the above-mentioned problems of the prior art, and reduces the volatilization of the curing agent at the time of curing, and further provides a cured product having excellent heat resistance, optical properties, and moldability.
• An object of the present invention is to provide a curing agent composition. Furthermore, it aims at providing the curable resin composition which contains this polyhydric carboxylic acid composition or this hardening
• the present invention [1] Following formula (1) (Wherein a plurality of R and Q are independently present and each represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a carboxyl group) and an acid anhydride A curing agent composition that is a mixture with the product, [2]
• a plurality of Qs are each independently selected from any one of a hydrogen atom, a methyl group, and a carboxyl group (provided that only Q is a compound having all hydrogen atoms), 1]
• the curing agent composition according to the above, [3] The method for producing a curing agent composition according to the above [1] or [2], which is obtained by reacting the raw material at 40 to 150 ° C.
• a polyvalent carboxylic acid composition which is a mixture of the polyvalent carboxylic acid resin represented by the formula (1) and a bifunctional or higher carboxylic acid; [5] The polyfunctional carboxylic acid composition according to the above [4], wherein the viscosity of the bifunctional or higher carboxylic acid resin is 10,000 Pa ⁇ s or less at 25 ° C., [6]
• a plurality of Qs are each independently selected from any one of a hydrogen atom, a methyl group, and a carboxyl group (provided that only Q is a compound having all hydrogen atoms), 4] or [5], the polyvalent carboxylic acid composition, [7] The polyvalent compound according to any one of the above [4] to [6] obtained by reacting the raw material at 40 to 150 ° C.
• a method for producing a carboxylic acid composition [8] The molar ratio of the raw material bis (dimethylol) dialkyl ether to the acid anhydride is 1.0 to 10.0 mol of carboxylic acid anhydride group with respect to 1 mol of hydroxyl group of bis (dimethylol) dialkyl ether.
• curable resin composition Containing curable resin composition, [10] The curable resin composition according to [9] above, wherein the epoxy resin is an alicyclic epoxy resin, [11] A cured product obtained by curing the curable resin composition according to the above [9] or [10], About.
• the polyvalent carboxylic acid composition or the curing agent composition of the present invention is useful as a curing agent for an epoxy resin, and in particular, a curable resin composition containing a polyvalent carboxylic acid resin is usually employed for curing an epoxy resin.
• the volatility in the temperature range is extremely low. Furthermore, it is excellent in moldability and gives a cured product with excellent optical properties.
• the polyvalent carboxylic acid composition or the curing agent composition of the present invention is a raw material or modification of a paint, an adhesive, a molded article, a semiconductor, a resin for an optical semiconductor encapsulant, a resin for an optical semiconductor die bond material, a polyimide resin, etc.
• the polyvalent carboxylic acid composition or the curing agent composition has an ability to cure an epoxy resin. Since the cured product obtained from this is excellent in transparency, it is extremely useful as a curing agent for epoxy resin for sealing an optical semiconductor such as a high-brightness white LED or the like.
• the polyvalent carboxylic acid composition or the curing agent composition of the present invention is obtained by reacting a bis (dimethylol) dialkyl ether with a specific acid anhydride (hereinafter referred to as the polyvalent carboxylic acid resin of the present invention). Is included as an essential component.
• Bis (dimethylol) dialkyl ether is not particularly limited as long as it is a tetraol compound having an ether bond in the molecule, but specifically, the following formula (2)
• R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or a carboxyl group).
• the group R is preferably an alkyl group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
• a compound having such a structure can be produced by dimerization of a triol compound synthesized by utilizing an aldol-Kanitzaro reaction at the intersection of an aldehyde compound and formaldehyde.
• a triol compound synthesized by utilizing an aldol-Kanitzaro reaction at the intersection of an aldehyde compound and formaldehyde.
• 2,2'-bis (dimethylol) dipropyl ether 2,2'-bis (dimethylol) diethyl ether, 2,2'-bis (dimethylol) dibutyl ether, 2,2'-bis (dimethylol) dipentyl And ether, 2,2′-bis (dimethylol) dihexyl ether, and the like.
• the polyvalent carboxylic acid resin of the present invention is produced by an addition reaction between an acid anhydride and bis (dimethylol) dialkyl ether.
• an acid anhydride an acid anhydride having a saturated hydrocarbon structure is used.
• hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3- Examples thereof include dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.
• an acid anhydride having a cyclohexane structure having an alkyl substituent and / or a carboxyl group as a substituent is particularly preferable.
• 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride, methylhexahydro Examples include phthalic anhydride.
• hexahydrophthalic anhydride may be used in combination.
• the reaction between an acid anhydride and a bis (dimethylol) dialkyl ether is generally an addition reaction using an acid or a base as a catalyst, but in the present invention, a reaction without a catalyst is particularly preferable.
• a catalyst examples of the catalyst that can be used include hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, hydroxide Metal hydroxides such as potassium, calcium hydroxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7 -Heterocyclic compounds such as ene, imidazole, triazole, tetrazole,
• the amount of the catalyst used is not particularly limited, but it is preferably 0.001 to 5 parts by weight based on the total weight of the raw material of 100 parts by weight.
• a reaction without a solvent is preferable, but an organic solvent may be used.
• the amount of the organic solvent used is 0.005 to 1, preferably 0.005 to 0.7, in a weight ratio with respect to the total amount of acid anhydride and bis (dimethylol) dialkyl ether as reaction substrates.
• it is 0.005 to 0.5 (that is, 50% by weight or less).
• the weight ratio exceeds 1, the progress of the reaction is extremely slow, which is not preferable.
• organic solvents examples include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, diethyl ether , Ethers such as tetrahydrofuran and dioxane, and ester compounds such as ethyl acetate, butyl acetate and methyl formate can be used.
• an acid anhydride or a liquid carboxylic acid resin (or compound) can be used in place of the solvent.
• a method for obtaining the polyvalent carboxylic acid composition of the present invention will be described.
• a liquid polycarboxylic acid resin can be used instead of the solvent, and the liquid carboxylic acid resin is a bifunctional or higher functional carboxylic acid resin from the viewpoint of curability and viscosity adjustment,
• a polyvalent carboxylic acid resin having a viscosity of 10,000 Pa ⁇ s or less at °C is preferable.
• a reaction product of an acid anhydride and a carbinol-modified silicone compound as described above is preferable.
• the carbinol-modified silicone compound can be synthesized using a technique described in, for example, Japanese Patent Application Laid-Open No. 2007-508424.
• a compound having a weight average molecular weight of 500 to 10000 is particularly preferred, more preferably 600 to 6000, and particularly preferably 600 to 2000. The most preferable range is 600-1500. Specifically, the following formula (3)
• n of the repeating unit is preferably 2 to 130, more preferably 3.5 to 8.0, and particularly preferably 3.5 to 25.
• the most preferable range is 3.5 to 17.0.
• the reaction temperature is preferably 40 to 200 ° C, particularly preferably 40 to 150 ° C.
• the reaction at 100 ° C. or lower is preferred, and the reaction at 40 to 100 ° C. is particularly preferred because of the volatilization of the acid anhydride.
• the reaction temperature is too low, there is a problem that it takes time until the reaction, and if the reaction temperature is too high, a reaction other than the target proceeds, which may cause coloring.
• a reaction method a method in which bis (dimethylol) dialkyl ether is added gradually or in a divided manner while heating in an acid anhydride or keeping a constant temperature, and after charging in a lump, the temperature is adjusted.
• the reaction can also be reacted.
• the reaction when the reaction is carried out without a solvent, it is preferably carried out by the above method from the viewpoint of safety.
• the reaction can be carried out under the conditions described later to obtain the polyvalent carboxylic acid composition of the present invention.
• After obtaining the polyvalent carboxylic acid resin of the present invention it is mixed with a liquid polyvalent carboxylic acid.
• the polyvalent carboxylic acid composition may be used.
• the reaction ratio between the acid anhydride and the hydroxyl group of the bis (dimethylol) dialkyl ether is theoretically preferably a reaction in the equimolar or combined vicinity of the functional group equivalents, but can be changed as necessary.
• the hydroxyl group of the bis (dimethylol) dialkyl ether is 0.9 to 1.1, preferably 0.9 to 1.05 equivalent.
• the carboxylic acid anhydride group is 1.0 to 10.0 moles per mole of hydroxyl group of bis (dimethylol) dialkyl ether. It is desirable to adjust the molar ratio.
• the proportion of the polyvalent carboxylic acid resin of the present invention is 1 to 40 wt% relative to the total weight of the polyvalent carboxylic acid resin and the other bifunctional or higher carboxylic acid compound. %, Preferably 1 to 20% by weight.
• the method for obtaining the curing agent composition of the present invention will be described. That is, in the curing agent composition of the present invention, when the acid anhydride to be used is the same as the acid anhydride to be used here, it is produced. The reaction is sometimes carried out in an excess of acid anhydride, and when the reaction between the acid anhydride and bis (dimethylol) dialkyl ether is completed, a mixture (curing agent composition) of the acid anhydride and the polyvalent carboxylic acid of the present invention is obtained. You can also In this case, excess acid anhydride is preferable because it can also serve as a solvent for the reaction.
• the specific reaction ratio is compared with the functional group equivalent, and when the acid anhydride is 1, the molar ratio is bis (dimethylol) dialkyl.
• the ether has a hydroxyl group of 0.001 to 0.9, more preferably 0.01 to 0.8, still more preferably 0.01 to 0.7, and particularly preferably 0.01 to 0.4. .
• curing agent composition of this invention may be sufficient. That is, when the polyvalent carboxylic acid resin of the present invention is used as a curing agent for an epoxy resin, particularly as a liquid composition, it can be mixed with an acid anhydride to form the curing agent composition of the present invention.
• an acid anhydride that can be used an acid anhydride having a saturated ring structure and having no aromatic ring in its structure is used.
• the ratio of the polyvalent carboxylic acid resin of the present invention is 5 to 80% by weight, preferably 5 to 65% by weight, based on the total weight of the acid anhydride and the polyvalent carboxylic acid resin. It is.
• 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.
• An excessively short reaction time means that the reaction is abrupt and is not preferable from the viewpoint of safety.
• a preferred range is 1 to 48 hours, preferably 1 to 36 hours, and more preferably 1 to 24 hours.
• the target polycarboxylic acid resin is obtained by removing the catalyst by neutralization, washing with water, adsorption, etc., and distilling off the solvent.
• the solvent can be distilled off if necessary, and in the case of a solventless or catalyst-free reaction, the product can be taken out without any special purification.
• the most preferable production method is a method in which an acid anhydride and a diol are reacted at 40 to 100 ° C. under conditions of no catalyst and no solvent, and taken out as they are after the reaction is completed.
• the polyvalent carboxylic acid resin of the present invention thus obtained usually shows a colorless to pale yellow solid resinous form (which may crystallize in some cases). In addition, when reacted in an excess of acid anhydride, the shape often shows a liquid state.
• a polyvalent carboxylic acid resin in which at least one of a plurality of Qs is a methyl group or a carboxyl group is preferable. More preferably, a plurality of Qs are each independently selected from any one of a hydrogen atom, a methyl group, and a carboxyl group (except that the compound is composed only of a compound in which all Qs are hydrogen atoms).
• a polyvalent carboxylic acid resin consisting only of a methyl group and / or a carboxyl group.
• the polyvalent carboxylic acid resin is preferably used in a liquid state, and a curing agent composition configured as a mixture of the polyvalent carboxylic acid resin and the acid anhydride, or the polyvalent carboxylic acid resin and the liquid form. It is preferably used in the form of a polyvalent carboxylic acid composition configured as a mixture with a carboxylic acid.
• the polyvalent carboxylic acid resin of the present invention is obtained in a solid form, it is preferably used by mixing with an acid anhydride or liquid carboxylic acid at a temperature of 150 ° C. or lower and making them compatible.
• the content of the polyvalent carboxylic acid resin of the present invention in the curable resin composition is the resin component 1.
• the weight ratio is usually 0.02 to 0.5, preferably 0.02 to 0.4. If the weight ratio is less than 0.02, demolding from the mold becomes worse, and if the weight ratio exceeds 0.5, the fluidity becomes too low at room temperature, making it difficult to handle.
• the polycarboxylic acid composition and the curing agent composition of the present invention are excellent in transparency, epoxy resin curing agent, paint, adhesive, molded article, semiconductor, optical semiconductor encapsulant resin, optical semiconductor die bond material It is useful as a raw material for resin, polyamide resin, polyimide resin, etc., modifier, plasticizer and lubricating oil raw material, medical and agrochemical intermediate, raw material for paint resin, and toner resin. Especially when used as a curing agent for epoxy resins, it has excellent curability and the transparency of the resulting cured product is excellent, so it is extremely useful as a curing agent for epoxy resins used for encapsulating high-intensity white LEDs and other optical semiconductors. It is.
• curable resin composition of the present invention including the polyvalent carboxylic acid composition or the curing agent composition of the present invention will be described.
• curing agent composition you may contain the curing catalyst, additive, inorganic filler, etc. which are described below.
• the curable resin composition of the present invention including the polycarboxylic acid composition or the curing agent composition of the present invention will be described.
• the curable resin composition of the present invention can contain an epoxy resin.
• Examples of the epoxy resin that can be used in the curable resin composition of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins.
• bisphenol A bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxy
• the curable resin composition of the present invention when used for optical applications, it is preferably used in combination with an alicyclic epoxy resin or an epoxy group-containing silicone resin, preferably an epoxy resin having a silsesquioxane structure.
• an alicyclic epoxy resin a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
• These alicyclic epoxy resins include esterification reaction of cyclohexene carboxylic acid with alcohols or esterification reaction of cyclohexene methanol with carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) ), Or Tyschenco reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and transesterification of cyclohexene carboxylic acid ester Examples thereof include an oxidized product of a compound that can be produced by a reaction (a method described in Japanese Patent Application Laid-Open No.
• the 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-pentane.
• carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.
• an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol is exemplified.
• a reaction method it can be produced by applying a general acetalization reaction.
• a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium US Pat. No. 2,945,008
• concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the mixture and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No.
• reaction A method using an organic solvent as a medium Japanese Patent Laid-open No. 7-215979
• a method using a solid acid catalyst Japanese Patent Laid-Open No. 2007-230992
• a cyclic acetal structure is preferable from the viewpoint of structural stability.
• oxidized cycloaliphatic polyolefin such as vinylcyclohexene, limonene, dicyclopentadiene, tricyclopentadiene, methyldicyclopentadiene, bicyclohexene, octadiene, etc. are mentioned.
• epoxy resins include ERL-4221, ERL-4299 (all trade names, all manufactured by Dow Chemical), Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all manufactured by Daicel Chemical Industries) and dicyclo Examples include, but are not limited to, pentadiene diepoxide (Reference: Review Epoxy Resin Basic Edition I p76-85). These may be used alone or in combination of two or more.
• the epoxy resin having a silsesquioxane structure is not particularly specified as long as it is an organopolysiloxane having an epoxycyclohexane structure, but in the present invention, it is obtained by a sol-gel reaction using an alkoxysilane having an epoxycyclohexyl group as a raw material.
• Compounds Specifically, Japanese Unexamined Patent Publication No. 2004-256609, Japanese Unexamined Patent Publication No. 2004-346144, International Publication No. 2004/072150, Japanese Unexamined Patent Publication No. 2006-8747, International Publication No. 2006/003990, Japanese Unexamined Patent Publication No. 2006-104248, International Publication No.
• Japanese Unexamined Patent Publication No. 2004-10849 Japanese Unexamined Patent Publication No. 2004-359933, International Publication No. 2005/100445, Japanese Unexamined Patent Publication No.
• Examples thereof include silsesquioxane type organopolysiloxane having a three-dimensional network structure described in JP-A-2008-174640.
• the silsesquioxane structure is not particularly limited. However, since a siloxane compound having a simple three-dimensional network structure is too hard, a structure that relaxes the hardness is desired.
• a block structure having a silicone segment and the aforementioned silsesquioxane structure obtained by a sol-gel reaction in one molecule is particularly preferable.
• Examples of a method for producing such a compound include a production method and a structure as described in WO2010 / 026714.
• the polyvalent carboxylic acid composition or the curing agent composition of the present invention may be used in combination with other curing agents.
• the proportion of the polyvalent carboxylic acid resin of the present invention in the total curing agent is preferably 20% by weight or more, particularly preferably 30% by weight or more.
• the curing agent that can be used in combination with the polyvalent carboxylic acid resin of the present invention include amine compounds, acid anhydride compounds having an unsaturated ring structure, amide compounds, phenol compounds, and carboxylic acid compounds. .
• the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, 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, cyclo
• the ratio of the curing agent to the epoxy resin is 0.5 to 1.5 equivalents (one functional carboxylic acid and one functional anhydride) with respect to 1 equivalent of the epoxy group of all epoxy resins. It is preferably 0.5 to 1.2 equivalents. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
• a curing accelerator may be used in combination with a curing agent.
• the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole.
• the curing accelerator is usually used in the range of 0.001 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin.
• the curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component.
• the phosphorus-containing compound may be a reactive type or an additive type.
• Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-pho
• Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
• antioxidant to the curable resin composition of this invention as needed.
• Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more.
• the amount of the antioxidant used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the resin component in the curable resin composition of the present invention. It is.
• antioxidants examples include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.
• phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl- ⁇ - (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl
• sulfur antioxidant examples include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like.
• phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Phosphites such as -di-t-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl
• antioxidants can be used alone, but two or more kinds may be used in combination.
• a phosphorus-based antioxidant is particularly preferable.
• a light stabilizer may be added to the curable resin composition of the present invention as necessary.
• the light stabilizer hindered amine-based light stabilizers, particularly HALS and the like are suitable.
• HALS is not particularly limited, but typical examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-te
• a binder resin can be blended with the curable resin composition of the present invention as required.
• the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins.
• the blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.
• An inorganic filler can be added to the curable resin composition of the present invention as necessary.
• inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like.
• the present invention is not limited to these. These may be used alone or in combination of two or more.
• the content of these inorganic fillers is used in an amount of 0 to 95% by weight in the curable resin composition of the present invention.
• the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers.
• agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers.
• a compounding agent and various thermosetting resins can be added.
• a fluorescent substance can be added as needed.
• the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed.
• fluorescent substance A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated.
• phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO 3 : Ce, Y 3 Al 5 O 12 : Ce, Y 4 Al 2 O 9 : Ce, Y 2 O 2 S: Eu, Sr 5 (PO 4 ) 3 Cl: Eu, (SrEu) O.Al 2 O 3 and the like are exemplified.
• the particle size of the phosphor those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 ⁇ m, particularly preferably 2 to 50 ⁇ m. When these phosphors are used, the addition amount thereof is 1 to 80 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the resin component.
• the curable resin composition of the present invention can be obtained by uniformly mixing each component.
• the curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method.
• the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are sufficient until uniform using an extruder, kneader, roll, etc. as necessary.
• a curable resin composition If the curable resin composition is liquid, it is potted, casted, impregnated into a base material, poured into a mold, cast, and cured by heating.
• a technique of casting after melting or molding using a transfer molding machine or the like and further curing by heating.
• the curing temperature and time are 80 to 200 ° C. and 2 to 10 hours.
• a curing method it can be hardened at a high temperature at a stretch, but it is preferable to raise the temperature stepwise to advance the curing reaction.
• initial curing is performed at 80 to 150 ° C.
• post-curing is performed at 100 to 200 ° C.
• the temperature is preferably increased in 2 to 8 stages, more preferably 2 to 4 stages.
• the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, glass fiber,
• a prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heat-dried is subjected to hot press molding to obtain a cured product of the curable resin composition of the present invention. can do.
• the solvent is used in an amount usually accounting for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent.
• cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.
• the curable resin composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used to improve the flexibility of the B stage.
• a film-type resin composition is formed by applying the curable resin composition of the present invention on the release film as the curable resin composition varnish, removing the solvent under heating, and then performing B-stage. To obtain a sheet-like adhesive.
• This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
• curable resin composition of the present invention is used as an optical semiconductor sealing material or die bond material.
• the curing agent composition or the polyvalent carboxylic acid containing the polyvalent carboxylic acid resin of the present invention is prepared by sufficiently mixing the acid composition and an epoxy resin, and other additives such as a curing accelerator, a coupling material, an antioxidant, or a light stabilizer, and used as a sealing material. Or used as both a die bond material and a sealing material.
• a mixing method kneading, three rolls, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, or the like is used to mix at room temperature or warm.
• Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like.
• Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material).
• a wire such as a gold wire is connected to pass an electric current.
• the semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and play a role of a lens.
• the curable resin composition of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the curable resin composition of the present invention for both the die bond material and the sealing material.
• the curable resin composition of the present invention is applied by dispenser, potting, or screen printing, and then heated by placing the semiconductor chip thereon. Curing can be performed to bond the semiconductor chip.
• methods such as hot air circulation, infrared rays and high frequency can be used.
• the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours.
• post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
• a compression molding method or the like in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from a mold is used.
• the injection method include dispenser, transfer molding, injection molding and the like.
• methods such as hot air circulation, infrared rays and high frequency can be used.
• the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours.
• post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
• the curable resin composition of the present invention can be used for general applications in which thermosetting resins such as epoxy resins are used.
• thermosetting resins such as epoxy resins
• adhesives, paints, coating agents, molding materials (sheets) , Film, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions for substrates, and acrylate esters as resist curing agents examples thereof include additives to other resins and the like.
• adhesives examples include civil engineering, architectural, automotive, general office, and medical adhesives, as well as electronic material adhesives.
• adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).
• sealing agents As sealing agents, potting, dipping, transfer mold sealing used for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, potting sealings used for COB, COF, TAB, etc. of ICs and LSIs, flip Examples include underfill used for chips and the like, and sealing (including reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.
• the cured product of the present invention obtained by curing the curable resin composition of the present invention can be used for various applications including optical component materials.
• the optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field.
• color PDP plasma display
• antireflection films antireflection films
• optical correction films housing materials
• front glass protective films front glass replacement materials
• adhesives and LED displays that are expected as next-generation flat panel displays
• LED molding materials LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate
• PLC plasma addressed liquid crystal
• VD video disc
• CD / CD-ROM CD-R / RW
• DVD-R / DVD-RAM MO / MD
• PD phase change disc
• disc substrate materials for optical cards Pickup lenses, protective films, sealing materials, adhesives and the like.
• optical equipment In the field of optical equipment, they are steel camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor parts. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices.
• optical components In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like.
• OEIC optoelectronic integrated circuit
• automotive lamp reflectors In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plate, interior panel, interior material, wire harness for protection / bundling, fuel hose, automobile lamp, glass substitute.
• it is a multilayer glass for railway vehicles.
• they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wire harnesses, and corrosion resistant coatings.
• it In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film.
• Next generation optical / electronic functional organic materials include peripheral materials for organic EL elements, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical computing elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.
• the measurement by gel permeation chromatography is as follows.
• the column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 ( ⁇ 2), KF-802), the coupled eluent is tetrahydrofuran, and the flow rate is 1 ml / min.
• the column temperature was 40 ° C.
• the detection was performed by RI (Reflective index), and a standard polystyrene made by Shodex was used for the calibration curve.
• the functional group equivalent was calculated from the ratio calculated from GPC, and the value was determined with 1 equivalent each of carboxylic acid and acid anhydride.
• Example 1 A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen, and at room temperature, 10 parts of 2,2′-bis (dimethylol) dipropyl ether (Di-TMP manufactured by Perstorp), methylhexahydrophthalic anhydride (Hereinafter, 95 parts of acid anhydride H1) and 5 parts of hexahydrophthalic anhydride (hereinafter referred to as acid anhydride H2) are charged all at once, and heated and stirred at 80 ° C. for 8 hours, whereby the polyvalent carboxylic acid resin of the present invention.
• Di-TMP 2,2′-bis (dimethylol) dipropyl ether
• acid anhydride H2 methylhexahydrophthalic anhydride
• acid anhydride H2 hexahydrophthalic anhydride
• Example 2 A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 100 parts of acid anhydride (H1) while purging with nitrogen, heated to 90 ° C., and then 2,2′-bis (dimethylol) dipropyl ether. (Di-TMP made by Perstorp) 10 parts were added in 4 portions over 2 hours, and then heated and stirred at 80 ° C. for 5 hours, so that the polyvalent carboxylic acid resin (A2) and acid anhydride ( 110 parts of a curing agent composition (B2) containing H1) was obtained. The obtained resin was a colorless liquid resin. The viscosity at 25 ° C. was 118 Pa ⁇ s.
• the molar ratio of the raw material 2,2′-bis (dimethylol) dipropyl ether and the acid anhydride during the reaction was carboxylic to 1 mol of 2,2′-bis (dimethylol) dipropyl ether hydroxyl group.
• the acid anhydride group is 3.7 moles.
• Example 3 168 parts of acid anhydride (H1), carbinol-modified silicone (X-22-160-AS manufactured by Shin-Etsu Chemical Co., Ltd., the following general formula (3 )) After charging 488 parts and reacting at 70 ° C.
• C1 liquid carboxylic acid
• H1 acid anhydride
• Si-TMP 2,2′-bis (dimethylol) dipropyl ether
• the obtained resin was a colorless liquid resin.
• the viscosity at 25 ° C. was 2960 mPa ⁇ s.
• the molar ratio of the raw material 2,2′-bis (dimethylol) dipropyl ether and the acid anhydride during the reaction was carboxylic to 1 mol of 2,2′-bis (dimethylol) dipropyl ether hydroxyl group.
• the acid anhydride group is 1.0 mole.
• n represents the average number of repetitions, and the value of n calculated from the measurement result of gel permeation chromatography is approximately 8.6.
• Example 4 In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 201.6 parts of acid anhydride (H1) and 488 parts of carbinol-modified silicone (X-22-160-AS manufactured by Shin-Etsu Chemical Co., Ltd.) with nitrogen purging, First, 12.5 parts of 2,2′-bis (dimethylol) dipropyl ether (Di-TMP manufactured by Perstorp) was added and reacted at 80 ° C. for 8 hours to react with the polyvalent carboxylic acid resin (A2) of the present invention in a liquid polyvalent state. 702.1 parts of polyvalent carboxylic acid composition (B4) containing carboxylic acid (C1) was obtained.
• the obtained resin was a colorless liquid resin.
• the viscosity at 25 ° C. was 2880 mPa ⁇ s.
• the molar ratio of the raw material 2,2′-bis (dimethylol) dipropyl ether and the acid anhydride during the reaction was carboxylic to 1 mol of 2,2′-bis (dimethylol) dipropyl ether hydroxyl group.
• the acid anhydride group is 1.0 mole.
• Synthesis example 1 To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 10 parts of 1,4-cyclohexanedimethanol (SKY-CDM manufactured by Shin Nippon Chemical Co., Ltd.) and 100 parts of acid anhydride (H1) were added while purging with nitrogen. 110 parts of curing agent compositions (B5) for comparative examples were obtained by heating and stirring at 60 ° C. for 4 hours.
• SKY-CDM 1,4-cyclohexanedimethanol
• H1 acid anhydride
• Synthesis example 2 To a flask equipped with a stirrer, reflux condenser, and stirrer, add 10 parts of 1,6-hexanediol and 100 parts of acid anhydride (H1) while purging with nitrogen, and heat and stir at 60 ° C. for 4 hours. Thus, 110 parts of a curing agent composition (B6) for a comparative example was obtained.
• Synthesis example 3 In a flask equipped with a stirrer, reflux condenser, and stirrer, while purging with nitrogen, 10 parts of water, 110 parts of cyclohexenylmethylcyclohexenecarboxylate, 140 parts of toluene, 1 part of 12-tungstophosphoric acid, 1 part of sodium tungstate 0.5 part, 1.5 parts of disodium hydrogen phosphate and 1.5 parts of 50% xylene solution of trioctylammonium acetate, the temperature of the solution was raised to 45 ° C., and 110 parts of 35% by weight hydrogen peroxide solution was added for 20 minutes. And then kept at 45 ⁇ 5 ° C. and stirred for 12 hours.
• the obtained filtrate was washed with 100 parts of water three times, and toluene was distilled off from the obtained organic layer to obtain 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (EP1) 111. Got a part.
• the epoxy equivalent of the obtained epoxy resin is 130 g / eq. Met.
• the viscosity at 25 ° C. was 211 mPa ⁇ s. (E-type viscometer)
• Synthesis example 4 ⁇ - (3,4 epoxy cyclohexyl) ethyltrimethoxysilane 106 parts, weight average molecular weight 1700 (GPC measured value) silanol-terminated methylphenyl silicone oil 234 parts (silanol equivalent 850, weight average molecular weight 1 measured using GPC) ), 18 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into the reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
• KOH potassium hydroxide
• Synthesis example 5 A flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube was purged with nitrogen, and 140 parts of dimethyl 1,4-cyclohexanedicarboxylate (DMCD-p manufactured by Iwatani Gas Co., Ltd.), cyclohexene-4-methanol 314 Part, tetrabutoxytitanium 0.07 part, 120 ° C 1 hour, 150 ° C 1 hour, 170 ° C 1 hour, 190 ° C 12 hours, while removing methanol produced by the reaction, cooled to 50 ° C .
• DMCD-p dimethyl 1,4-cyclohexanedicarboxylate
• cyclohexene-4-methanol 314 Part, tetrabutoxytitanium 0.07 part, 120 ° C 1 hour, 150 ° C 1 hour, 170 ° C 1 hour, 190 ° C 12 hours, while removing methanol produced by
• Synthesis Example 6 In a flask equipped with a stirrer, reflux condenser, and stirrer, 15 parts of water, 0.95 part of 12-tungstophosphoric acid, 0.78 part of disodium hydrogen phosphate, 50% xylene trioctylammonium acetate while purging with nitrogen 2.7 parts of a solution, 180 parts of toluene, and 118 parts of the compound (D-1) obtained in Synthesis Example 5 were added, and this solution was heated to 60 ° C. and stirred with vigorous stirring, and 35 wt% aqueous hydrogen peroxide. 70 parts were added in 1 hour, and it stirred at 60 degreeC as it was for 13 hours. When the progress of the reaction was confirmed by gas chromatography, the raw material peak disappeared.
• Synthesis example 7 After adding 20 parts of methyl ethyl ketone to 50 parts of the curing agent composition (B2) and dissolving it uniformly, using a rotary evaporator, the methyl hexahydrophthalic anhydride (H1) present in excess with the methyl ethyl ketone added at 100 to 150 ° C. is added.
• the polycarboxylic acid resin (A2 was removed by removing (the acid anhydride was sufficiently removed by flowing in nitrogen gas for 40 minutes under the condition of heating and depressurization from the time when the outflow of methylhexahydrophthalic anhydride disappeared). 16.2 parts were taken out.
• the shape was a colorless solid resin.
• the resulting resin had a softening point (based on JIS K-7234) of 90.1 ° C. and a melt viscosity at 150 ° C. of 0.64 Pa ⁇ s.
• This carboxylic acid resin had very low fluidity unless it was at a high temperature of 90 ° C. or higher, and was difficult to handle.
• Melt viscosity Melt viscosity in cone plate method at 150 ° C Measuring machine: Cone plate (ICI) high temperature viscometer (manufactured by RESEARCH EQUIIPMENT (LONDON) LTD.) Corn No. : 4 (measurement range 0 to 4.00 Pa ⁇ s)
• Example 7 Comparative Examples 2, 3 Epoxy resins (EP1, EP3) obtained in Synthesis Examples 3 and 6 as epoxy resins, curing agent composition (B2) obtained in Example 2 as curing agents, and curing agents obtained in Synthesis Examples 1 and 2
• a composition (B5, B6), a quaternary phosphonium salt (manufactured by Nippon Chemical Industry Co., Ltd., Hishicolin PX4MP, hereinafter referred to as K2) is used as a curing accelerator, and blended at a blending ratio (parts by weight) shown in Table 2 below. 20 Defoaming was performed for a minute to obtain a curable resin composition of the present invention or for comparison.
• the obtained curable resin composition was gently poured into a test piece mold, and the cast was cured under conditions of 150 ° C. ⁇ 1 hour after pre-curing at 120 ° C. ⁇ 3 hours for various tests. A cured product was obtained. The following heat durability transmittance
• Heat test condition left in an oven at 150 ° C. for 96 hours
• Test piece size measured at a thickness of 0.8 mm, converted to a transmittance of 1.0 mm
• Evaluation condition a transmittance of 400 nm was measured with a spectrophotometer. Calculate the rate of change.
• Example 8 Comparative Examples 4, 5
• the obtained curable resin composition was gently poured into a test piece mold, and the cast was cured under conditions of 150 ° C. ⁇ 1 hour after pre-curing at 120 ° C. ⁇ 3 hours for various tests. A cured product was obtained. The following heat durability transmittance
• Heat test condition left in an oven at 150 ° C. for 96 hours
• Test piece size measured at a thickness of 0.8 mm, converted to a transmittance of 1.0 mm
• Evaluation condition a transmittance of 400 nm was measured with a spectrophotometer. Calculate the rate of change.
• the curable resin composition using the curing agent composition of the present invention has optical characteristics excellent in heat resistance.
• Example 9 Comparative Examples 6, 7, 8
• the curable resin composition for the present invention or for comparison was obtained.
• the obtained curable resin composition was gently poured into a test piece mold, and the cast was cured under conditions of 150 ° C. ⁇ 1 hour after pre-curing at 120 ° C. ⁇ 3 hours for various tests.
• a cured product was obtained.
• the obtained cured product was evaluated for the following hardness and heat resistance (Tg). The results are also shown in Table 4 below. (However, in order to remove the parameter of the curing failure of the cured product due to volatilization, an imide film was placed on the mold surface, and the volatilization was sufficiently suppressed for curing.)
• the curable resin compositions obtained in the examples and comparative examples were cast using a ⁇ 5 mm tube made of Teflon (registered trademark), and the cast was cured under the conditions described above to obtain a test piece. Using this test piece, a heat resistance test was performed under the conditions shown below. Measurement conditions Dynamic viscoelasticity measuring device: manufactured by TA-instruments, DMA-2940 Measurement temperature range: 40 ° C-250 ° C Temperature increase rate: 2 ° C./min Test piece size: ⁇ 2 mm A material cut into 15 mm was used.
• the curable resin composition containing the curing agent composition of the present invention has Tg and hardness as compared with the cured product of Comparative Example 6 using the acid anhydride L1 that is usually used as a curing agent for epoxy resins. It is clear that there is a remarkable effect of further improving the heat resistance while maintaining.
• the cured products of Comparative Example 7 and Comparative Example 8 have higher performance in both hardness and heat resistance than the cured product of Comparative Example 6 using acid anhydride L1 that is usually used as a curing agent for epoxy resins. It turns out that it has fallen.
• Corrosion gas 20% aqueous solution of ammonium sulfide (discolors black when sulfur component reacts with silver)
• Contact method A container of an ammonium sulfide aqueous solution and the LED package were mixed in a wide-mouth glass bottle, and the wide-mouth glass bottle was covered and the volatilized ammonium sulfide gas and the LED package were contacted for 10 hours in a sealed state.
• Corrosion determination Judgment was made based on whether or not the lead frame inside the LED package was discolored black (referred to as blackening).
• the curable resin composition containing the polyvalent carboxylic acid resin composition of the present invention is excellent in lighting test illuminance retention, and also has excellent effects on gas permeability resistance without discoloring the lead frame. It is clear that it is obtained.

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